ProceedingsBook SIMI2018

PENTRU ECOLOGIE INDUSTRIALĂ
2018
SIMI
Proceedings Book
Bucharest
20-21 September 2018
National Research and Development Institute for

Industrial Ecology - ECOIND
INTERNATIONAL SYMPOSIUM “THE ENVIRONMENT AND THE INDUSTRY”,
SIMI 2018, PROCEEDINGS BOOK
21st INTERNATIONAL SYMPOSIUM

“THE ENVIRONMENT AND THE INDUSTRY”
PROCEEDINGS BOOK
Bucharest, Romania
September 20-21, 2018
1
2
21st International Symposium “The Environment and the Industry” –

SIMI 2018
Editors:
Ph.D. Chem. Luoana Florentina PASCU

Ph.D. Eng. Carol Blaziu LEHR
Ph.D. Catalina STOICA
Ph.D. Eng. Gabriela Geanina VASILE
Ph.D. Eng. Alina Mirela CONSTANTIN
PhD. Eng. Ioana Alexandra IONESCU
Proofing:
Ph.D. Student Ecaterina Anca SERBAN
Ph.D. Eng. Adriana CUCIUREANU
Ph.D. Andreea COZEA
Graphic design Alina TANASESCU
Publisher: National Research and Development Institute for Industrial

Ecology ECOIND, Drumul Podu Dambovitei Street no. 71-73, district 6,
Bucharest, Romania
www.simiecoind.ro
ISSN-L: 1843-5831
DOI: http://doi.org/10.21698/simi.2018
The authors assumed full responsibility for the information presented in the paper.
2017 SYMPOSIUM PROCEEDINGS IS INDEXED IN WEB OF SCIENCE –

CONFERENCE PROCEEDINGS CITATION INDEX-SCIENCE
2015, 2016, 2017
Symposium Proceedings are

indexed in:
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Organizers
International Symposium
“The Environment and the Industry” SIMI 2018
under Honorary Patronage of:

Romanian Academy
under Coordination of:

Ministry of Research and Innovation
Minister of National Education
Ministry of Environment
Ministry of Water and Forests
Ministry of Economy
Organized by:
National Research and Development Institute for Industrial Ecology –
ECOIND
Co-organized by:
Romanian Society of Chemistry
Romanian Water Association
Romanian Environment Association 1998
Faculty of Agro-Food Economy and Environment – Academy of Economic
Studies Bucharest
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Welcome
Dear colleagues,
Welcome to the 21st edition of the International Symposium “The
environment and the industry” to be held in Bucharest on September 20-21,
2018.
The symposium is aiming to bring together scientists, professors,
consultants representing research and educational organizations, economic
units, environmental authorities from all over the world in order to
exchange their results, propose potential solutions to environmental issues
and contribute to the integration of environmental dimension in the decision
making process.
Do not miss the opportunity to exchange your works results with other
environmental specialists from Romania and abroad.
We wish you a pleasant and fruitful stay in Bucharest.
Ph.D. Chem. Luoana Florentina Pascu

Chair of SIMI 2018
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Honorific Committee
Acad. Ioan-Aurel Pop, President of Romanian Academy

Acad. Marius Andruh, President of “Chemical Sciences Section” of
the Romanian Academy
Acad. Gheorghe Duca President of Academy of Sciences of
Moldova
Acad. Tudor Lupascu, President of “Chemistry Institute” of
Academy of Sciences of Moldova
Emeritus Prof. Ph.D. Eng. Sorin Rosca, President of Romanian
Society of Chemistry
Prof. Ph.D. Eng. Puiu Lucian Georgescu, State Secretary –
Ministry of Research and Innovation
Prof. Ph.D. Eng. Tudor Prisecaru, University Politechnica of
Bucharest, Romania
Prof. Ph.D. Eng. Vladimir Rojanschi, President of Romanian
Environmental Association 1998
Felix Stroe, President of Romanian Water Association
Emeritus Prof. Ph.D. Eng. Gheorghita Jinescu, Vice-President of
Romanian Society of Chemistry
Prof. Ph.D. eng. Cristina Orbeci, Faculty of Applied Chemistry and
Materials Science Dean, University Politechnica of Bucharest,
Romania
Prof. Ph.D. eng. Dobre Tanase, President of Romanian Society of
Chemical Engeneering
Ph.D. Eng. Caner Zanbak, Environmental Advisor, Mining
Engineer at Turkish Chemical Manufacturers Association
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Scientific Committee
Chair: Ph.D. Chem. Luoana Florentina Pascu, INCD-ECOIND, Romania

Co-Chair: Ph.D. Eng. Carol Blaziu Lehr, INCD-ECOIND, Romania
Sustainable Environmental Technologies
Ph.D. Eng. Costel Bumbac, INCD-ECOIND, Romania

Prof. Ph.D. Eng. Cristina Costache, University Politehnica Bucharest,
Romania
Ph.D. Eng. Gheorghe Batrinescu, INCD-ECOIND, Romania
SR Chem. Cristiana Cosma, INCD-ECOIND, Romania
Prof. Tim Grotehnuis, WUR Holland
Honored Prof. Ph.D. Eng. Gheorghita Jinescu, University Politehnica
Bucharest, Romania
Ph.D. Mykola Kartel, CISC, Ukraine
Ph.D. Pawel Krzeminski, NIVA, Norway
Ph.D. Michela Langone, Trento University, Italy
Acad. Ph.D. Tudor Lupascu, ICA, Moldova
Prof. Ph.D.Ying Ma, Coimbra University, Portugal
Prof. Ph.D. Eng. Ileana Nistor, University of Bacau, Romania
Ph.D.Eng. Ines Nitoi, INCD-ECOIND, Romania
Prof. Ph.D. Ovidiu Popa, USAMV Bucharest, Romania
Prof. Ph.D. Eng. Mircea Teodorescu, University Politehnica Bucharest,
Romania
Prof. Ph.D. Giuliano Tevi, Ecological University, Romania
Ph.D. Eng. Valentin Vladut, INMA, Bucharest, Romania
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Pollution Assessment & Management System
Prof. Ph.D. Eng. Ioan Bica, UTC Bucharest, Romania

Ph.D. Eng. Lucian Constantin, INCD-ECOIND, Romania
SR Eng. Virgil Criste, INCD-ECOIND, Romania
Prof. Ph.D. Tiago Natal da Luz, Coimbra University, Portugal
Ph.D. Eng. Carol Blaziu Lehr, INCD-ECOIND, Romania
SR biochem. Irina Lucaciu, ECOIND, Romania
Prof. Ph.D. Rui S. Oliveira, Coimbra University, Portugal
Ph.D. Robert Raschman, Dekonta, Czech Republic
Prof. Ph.D. Eng. Geta Rasnoveanu, University of Bucharest, Romania
Prof. Ph.D. Eng. Vladimir Rojanschi, Ecological University, Romania
Prof. Ph.D. Daniel Scradeanu, University of Bucharest, Romania
Prof. Ph.D. Jose Paulo Sousa, Coimbra University, Portugal
SR Eng. Cristian Teodorescu, International Development, Norway
Ph.D. Eng. Gabriela Geanina Vasile, INCD-ECOIND, Romania
Ph.D. Caner Zanbak, TCMA, Turkey
Pollution Control and Monitoring
Prof. Dr. Irinel Adriana Badea, University of Bucharest, Romania

SR Chem. Elena Bucur, INCD-ECOIND, Romania
Ph.D. Marius Bumbac,Valahia University, Romania
SR Chem. Liliana Cruceru, INCD-ECOIND, Romania
Academ. Gheorghe Duca, ASRM, Moldova
Prof. Margarita Filipova, Rousse University, Bulgaria
Ph.D. Chem. Toma Galaon, INCD-ECOIND, Romania
Prof. Ph.D. Jean Louis Marty, Perpignan University, France
Prof. Ph.D. Eng. Aurelia Meghea
Prof. Ph.D. Eng. Gheorghe Nechifor, University Politehnica Bucharest,
Romania
Ph.D. Biolog. Mihai Nita-Lazar, INCD-ECOIND, Romania
Ph.D. Chem. Luoana Florentina Pascu, INCD-ECOIND, Romania
Ph.D. Chem Jana Petre, INCD-ECOIND, Romania
Prof. Ph.D. Eng. Gabriel–Lucian Radu, University Politehnica Bucharest,
Romania
Prof. Ph.D. Lucica Tofan, Ovidius University, Romania
Prof. Ph.D. Chem. Luminita Valdescu, University of Bucharest, Romania
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Sponsors
9
Content
Sustainable Environmental Technologies
A VARIANT OF GREEN CONCRETE WITH INDUSTRIAL AND 17
AGRICULTURAL WASTE
Catalina Mihaela Helepciuc (Gradinaru), Marinela Barbuta, Adrian
Alexandru Serbanoiu, Andrei Burlacu
ADSORPTION OF Sr2+ IONS FROM AQUEOUS SOLUTIONS ON 23
THE ACTIVATED CARBON CAN-7 UNDER DYNAMIC
CONDITIONS
Mihai Ciobanu, Tudor Lupascu, Tatiana Mitina, Igor Povar
ANALYSING WOOD DENSITY AND BIOMASS: A CASE STUDY 31
OF FOREST PLANTATIONS FROM MOLODOVA NOUA
WASTE HEAPS, ROMANIA
Ilie-Cosmin Cantar, Ion Chisalita, Lucian Dinca
GROWTH ACTIVATION OF SACCHAROMYCOPSIS 38
(ENDOMYCOPSIS) FIBULIGERA Y-436 STRAIN BY SQUALENE
AND ANOLYTE WATER IN LABORATORY EXPERIMENTS
Irina Senicovscaia, Tatiana Grozova, Georgiy Poleshchuk
INQUIRY INTO THE POTENTIAL USE OF IONIC LIQUIDS 46
INSTEAD OF INORGANIC ACIDSIN HYDROTHERMAL
HYDROLYSIS OF MACROALGAE
Konstantza Tonova, Madlena Lazarova
KINETIC ANALYSIS OF MANGANESE REMOVAL FROM 54
MINE WATER - CONTINUOUS FLOW REACTION SYSTEM
Laurentiu Razvan Dinu, Valeriu Robert Badescu, Viorel Ion Patroescu,
Gabriela Geanina Vasile, Voicu Oncu
NANOSCALE IRON PARTICLES FOR WASTEWATER 61
DECONTAMINATION
Eugenia Panturu, Razvan Ioan Panturu, Gheorghita Jinescu, Antoaneta
Filcenco-Olteanu, Aura Daniela Radu
NEW LABORATORY TECHNIQUES ON SOIL 69
DECONTAMINATION
Maria Popa, Loredana Irena Negoita
NUMERICAL MODELING OF FLOW OVER AN OGEE 76
SPILLWAY AND INVESTIGATION OF EFFECT OF
DOWNSTREAM INFLUENCES ON DISCHARGE
Ali Yıldız, Alpaslan Yarar, ŞerifeYurdagül Kumcu
OXIDATION OF SULPHUR SPECIES ON ACTIVE CARBONS: 84
THE SUGGESTED MECHANISM
Raisa Nastas, Vasile Rusu, Tudor Lupascu
PHOSPHATE REMOVAL FROM WASTEWATER BY USING 92
LOW-COST ADSORBENT MATERIALS
Oanamari Daniela Orbulet, Cristina Modrogan, Cristina Orbeci, Dancila
Madelene
10
PHOTODEGRADATION OF RHODAMINE 6G IN PRESENCE 99

OF Ag/TiO2 PHOTOCATALYST
Maria Harja, Amalia Maria Sescu, Lidia Favier, Doina Lutic, Gabriela Ciobanu
PHYSICAL MODELING OF FLOW OVER AN OGEE 105
SPILLWAY AND INVESTIGATION OF SCALE EFFECTS BY
USING FROUDE SIMILARITY
Ali Yıldız, Alpaslan Yarar
REMOVAL OF HEXAVALENT CHROMIUM IONS FROM THE 111
SIMULATED WASTEWATER USING
ELECTROCOAGULATION PROCESS
Firas Hashim Kamar, Karim Khalifa Esgair, Baker M. Abod, Aurelia Cristina
Nechifor
REMOVAL OF NITRITEIONS FROM WATER IN DYNAMIC 119
AND OXIC CONDITIONS
Tatiana Goreacioc, Raisa Nastas, Maria Sandu, Tudor Lupascu, Anatolie
Tarita
SEEDLINGS PLANTING INNOVATIVE TECHNOLOGY 127
DEDICATED FOR SLOPE DEGRADED TERRAINS AND HARD
ENVIRONMENTAL CONDITIONS
Constantin Gabriel Bogdanof, Alexandra Liana Visan, Dumitru Milea, Radu
Ciuperca, Alexandru-Ionut Petrisor
SLUDGE DRYING IN TUNNELS USING PHOTOVOLTAIC 135
PANELS
Cornel Sava, Marius-Daniel Roman, Elena Maria Pica
SYNTHESIS OF ZnO/CuO NANOCOMPOSITES WITH CNF 145
AND Ag BY GEL SOL
Catalina Nutescu Duduman, María Gómez De Salazar Y Caso De Los Cobos
José, Consuelo Gómez De Castro, Marius Niculaua, Gabriela Ciobanu, Maria
Harja
THE INFLUENCE OF TEMPERATURE ON SO2 RETENTION 153
FROM RESIDUAL GASES BY ABSORPTION INTO DILUTE
BASIC SOLUTIONS
Annette Madelene Dancila, Cristina Modrogan, Cristian Onose, Oanamari
Orbulet, Cristina Orbeci
THE SOLUTION CHEMISTRY OF THE COPPER (II) - 162
AMMONIA - THIOSULFATE AQUEOUS SYSTEM
Igor Povar, Stefano Ubaldini, Tudor Lupascu, Oxana Spinu, Boris Pintilie
USING THE LECHATE TREATMENT TECHNOLOGIES FOR 170
FERTILIZERS
Casen Panaitescu, Cristinel Constandache
Pollution Assessment & Management Systems

APPROACHES TO PREDICT THE IMPACT OF AIR 177
ATMOSPHERIC COMPONENT IN ENVIRONMENTAL IMPACT
ASSESSMENT REPORTS IN ASSESSING EXTENSIONS TO
ACTIVE INDUSTRIAL OBJECTS
Antoaneta Stefanova, Margarita Filipova
11
ASSESSMENT TERMS FOR LOCAL SUSTAINABILITY 186

MANAGEMENT
Ildiko Tulbure
CHARACTERIZATION OF MINERAL SPRINGS FROM THE 195
BUILA-VANTURARITA NATURAL PARK AREA
Ovidiu Teodor Matica, Luisa Roxana Popescu
END OF WASTE CRITERIA FOR OIL WASTES 206
Georgeta Madalina Arama, Lidia Kim, Adriana Cuciureanu, Agnes
Serbanescu, Ileana Nicolescu, Mona Barbu, Bogdan Stanescu, Gina Traistaru
ENVIRONMENTAL ISSUES RESULTING FROM THE 215
EXCAVATION OF ALLUVIAL SOIL IN PROTECTED AREAS,
CASE STUDY IN ROSCI 0103 LUNCA BUZAULUI
Giuliano Tevi, Alexandra Stoica
EXPLORING THE POSSIBILITIES OF AIR PURIFICATION IN 223
URBAN ENVIRONMENTS USING GREEN ROOFING
Irina Tsvetanova, Ivanka Zhelev
IDENTIFYING AND DESCRIBING THE MAIN CLIMATIC AND 232
STRESS FACTORS THAT ARE AFFECTING FOREST AND
VITICULTURAL ECOSYSTEMS
Diana Elena Vizitiu, Lucian Dinca, Viorica Enache, Alina Donici, Lucretia
Popa, Danut Cociorva, Gabriel Murariu
LOW HEATING VALUE PREDICTION FROM PROXIMATE 242
ANALYSIS FOR SEWAGE SLUDGE SAMPLES
Agnes Serbanescu, Mona Barbu, Ileana Nicolescu, Georgeta Madalina Arama
NEW APPROCHES REGARDING BAT CONCLUSION 250
IMPLEMENTATION
Valeriu Danciulescu, Andreea Cozea, Mihaela Petrescu, Raluca Diodiu,
Gheorghita Tanase, Andrei Vasile
NEW ECOLOGICAL SOLUTION TO COMBAT THE 258
VEGETATION IN EXCESS IN NATURAL AND HYDROPOWER
LAKES
Victorita Radulescu
OPTIMAL POLICY OF IRRIGATION AND DRAINAGE WELLS 267
SYSTEMS IN AFFECTED AGRICULTURAL LANDS
Victorita Radulescu
PROTECTING SURFACE WATER RESOURCES THROUGH 276
SILVICULTURAL METHODS
Cristinel Constandache, Lucian Dinca, Nicu Constantin Tudose, Casen
Panaitescu
THE BEST PRACTICES FOR THE ASSESSMENT OF THE 285
RAINWATER DRAINED BY THE URBAN SEWERAGE
SYSTEMS
Daniel Scradeanu, Giuliano Tevi, Alexandru Balint
THE INDEXES IN ESTIMATING RAINFALL EROSIVITY – 294
CASE STUDY BUCHAREST
Marin Rusanescu, Ion Durbaca, Elena Valentina Stoian
TRANSITION OF INCD ECOIND SIMCM TO THE 304
REQUIREMENTS OF THE NEW STANDARDS ISO 9001: 20015
AND ISO 14001: 2015
Virgil Criste
12
USE OF REMOTE SENSING DATA IN INVESTIGATIONS OF 311

ECOLOGICAL STATE OF WATER BODIES IN URBAN AREA
OF KYIV CITY
Viktor Vyshnevskyi, Sergiy Shevchuk
WATER QUALITY ASSESSMENT USING PHYSICAL- 318
CHEMICAL PARAMETERS OF THE DANUBE RIVER
(DELTAIC AREA) INCLUDING RAZIM AND GOLOVITA
LAKES, ROMANIA
Irina Catianis, Gabriel Iordache, Dumitru Grosu, Marian Malageanu, Iulian
Pojar, Ana Bianca Pavel
Pollution Control and Monitoring
A BASELINE ASSESSMENT OF WATER QUALITY FROM 333

PRIVATE WELLS LOCATED IN CONSTANTA COUNTY AND
RISK IMPLICATIONS FOR COMMUNITY HEALTH
Gina Vasile Scaeteanu, Roxana Maria Madjar
ASSESSMENT OF DRINKING WATER QUALITY FROM 341
TREATMENT PLANTS AND CONSUMERS
Mariana Popescu, Diana Puiu, Madalina Mihalache, Vasile Ion Iancu, Marius
Simion, Marcela Antoaneta Niculescu, Daniel Manolache, Liliana Cruceru
COMPARATIVE STUDY REGARDING THE ANALYSIS OF THE 347
METALS CONTENTS FROM BIOMASS WASTES
THROUGH DIFFERENT METHODS OF DIGESTION
Gina Alina Traistaru (Catrina), Agnes Serbanescu, Mona Barbu, Ileana
Nicolescu, Nicolae Ionut Cristea, Bogdan Stanescu, Ileana Cristina Covaliu
CONSIDERATIONS REGARDING THE CONTROL OF 354
BIOCHEMICAL OXYGEN DEMAND AND CHEMICAL
OXYGEN DEMAND FROM DEJ WASTEWATER TREATMENT
PLANT
Marius-Daniel Roman, Roxana Mare, Adriana Hadarean
DESTRUCTION CAVITATION ACTION ON THE MICROBIAL 362
CELLS SIZES
Iryna Z. Koval
DETERMINATION OF RHODIUM FROM WASTEWATER 366
SAMPLES USING ICP-EOS TECHNIQUE
Anda Tenea, Cristina Dinu,Eleonora-Mihaela Ungureanu, Gabriela-Geanina
Vasile, Marius Simion
DETERMINATION OF SULFUR COMPOUNDS WITH A 373
STRONG OLFACTORY IMPACT ON THE POPULATION
Raluca Diodiu, Toma Galaon, Vasile Iancu, Mihaela Petrescu, Mihai Bratu,
Valeriu Danciulescu, Andreea Cozea
HEAVY METALS EMISSIONS TO AIR FROM INDUSTRIAL 378
PLANTS: CRITICALITIES AND SOLUTIONS
Elena Cristina Rada
INTERDISCIPLINARY STUDY REGARDING THE COLOIDAL 384
SILVERSOLUTIONS EFFECT ON MOMORDICA CHARANTIA L.
DEVELOPMENT
Adriana Bira, Zoltán Marosy, Cristian Ion
13
MEMBRANE FILTRATION EFFICIENCY ON TRIAZINE 392

HERBICIDES IN ORGANIC AND AQUEOUS SOLUTIONS
Roxana-Elena Scutariu, Vasile Ion Iancu, Gheorghe Nechifor, Gabriel-Lucian
Radu, Marius Simion, Marcela Niculescu
MICROSTRUCTURAL AND CHEMICAL 400
CHARACTERIZATION OF SOME WESTES FOR
PHONOABSORBANT MATERIALS OBTAINING
Mihai Bratu, Luoana Florentina Pascu, Cristea Nicolae Ionut, Nicolescu Ileana
ORGANIZATION OF HYDROGEOLOGICAL MONITORING 409
WITHIN THE UKRAINIAN PART OF THE TISZA RIVER BASIN
Lidiia Davybida
PHYSICO–CHEMICAL CHARACTERISTICS AND 417
WASTEWATERQUALITY INDEX FOR EVALUETING THE
EFFICIENCY OF TREATMENT PROCESS EFFLUENT
Florinela Pirvu, Jana Petre, Liliana Cruceru, Iuliana Paun, Marcela Niculescu,
Luoana Florentina Pascu, Nicoleta Vasilache, Florentina Laura Chiriac
QUANTIFICATION OF ANIONIC AND NONIONIC 426
SURFACTANTS IN DOMESTIC WASTEWATER SAMPLES
COLLECTED FROM ROMANIA
Daniel Mitru, Catalina Stoica, Mihai Nita-Lazar
THE REMOVAL OF NITRATE FROM DRINKING WATER, 432
NATURAL WATER BY ION EXCHANGE USING ION
EXCHANGE RESIN, PUROLITE A520E AND A500
Nicoleta Vasilache, Liliana Cruceru, Jana Petre, Laura Florentina Chiriac,
Iuliana Claudia Păun, Marcela Niculescu, Florinela Pîrvu, Giovanina Lupu
THE USE OF CORTICOLOUS LICHEN SPECIES TO ASSESS 443
THE LEVEL OF AIR POLLUTION WITH HEAVY METALS
Dorian-Gabriel Neidoni, Ladislau Andres, Valeria Nicorescu, Carol Blaziu
Lehr, Elena Bucur, Adrian Sinitean
VERIFYING THE HEIGHT OF THE DISCHARGE CHIMNEY 451
FOR EMISSIONS RESULTING FROM HAZARDOUS WASTE
INCINERATION INSTALLATIONS
Loredana Irena Negoita, Maria Popa
14
SUSTAINABLE ENVIRONMENTAL TECHNOLOGIES
15
Section Sustainable Environmental Technologies 16

DOI: http://doi.org/10.21698/simi.2018.fp01
A VARIANT OF GREEN CONCRETE WITH INDUSTRIAL AND

AGRICULTURAL WASTE
Catalina Mihaela Helepciuc (Gradinaru), Marinela Barbuta, Adrian Alexandru Serbanoiu,

Andrei Burlacu
”Gheorghe Asachi” Technical University of Iasi, Faculty of Civil Engineering and Building
Services, 1 Mangeron Blvd., 700050, Iasi, serbanoiu.adrian@tuiasi.ro, Romania
Abstract
The research presented in this paper aim to analyze the effects of cement
replacement by fly ash in 10 vol. %, 20 vol. %, and 30 vol. % and, afterwards, the
effects of mineral aggregates substitution by 50 vol. % with vegetal aggregates. The
used vegetal aggregates were shredded corn cobs, and were investigated the density,
the compressive and split tensile strength of concrete. The results revealed that fly
ash, as cement partial replacement, decreased the compressive strength comparing to
the reference concrete, meanwhile, the splitting tensile strength was improved when
were used 10% and 20% vol. of fly ash. Fly ash had a positive effect on the
compressive strength of the vegetal concrete, in the case of the composition with
10% and 30% vol. of industrial waste, and also on splitting tensile strength in the
case of 10% and 20% vol. of replacement rate. The concrete density diminished
with 1.67%, 3.12% and 3.82% in the case of 10%, 20% and 30% vol. cement
replacement by fly ash, respectively. Corn cob aggregates led to a concrete density
decreasing with almost 25% compared to reference concrete.
Keywords: corn cob, density, fly ash, mechanical properties
Introduction
Today, in our society, the accent is put more and more on sustainability,
environment protection and CO2 emissions decreasing. That is why, in terms of
concrete production, the most used material in the construction industry, has become
a must to make it as environmentally friendly as possible. This can be achieved by
partially replace the cement and/or aggregates from its composition by industrial and
agricultural waste. Fly ash, because there are very high quantities of waste disposed
as landfill, and corn cobs, because they represent an easy renewable natural
resource.
Fly ash is an industrial waste generated by the thermal plants, in quantities equal to
30-40% of the burned coal (Sun et al 2003), that is usually placed into landfills and
becoming, in this way, a threaten for the environment (Aprianti 2017).
The concrete with fly ash represents an ecologic material that has been studied a lot
up to now, but in this paper it is presented as reference for a concrete with vegetal
aggregates and fly ash. Fly ash was used in the corn cob concrete in order to
enhance its properties.
Used as cement partial replacement, fly ash has, in general, positive effects on the
strength, sulphate action resistance, permeability and workability of the concrete
(Badur & Chaudhary 2008), but this depends on its properties derived from the
combustion method and type of coal used (Aprianti 2017). Also, it decrease the
hydration heat, this being an advantage for the mass structures (Meyer 2009).
Corn cobs represent an agricultural waste that is, either burned on the field (Pinto et
al 2012a), either used as such as fertilizer on the harvested field (Ashour et al 2013).
The corn cob aggregates can be used for obtaining a lightweight and sustainable
ecoconcrete, they having a density of only 212 kg/m3 (Pinto et al 2012a). The use of
different kind of vegetal aggregates for such purposes is the subject of many
researches all over the world. The advantages of vegetals in concrete composition
are represented by their renewability, low cost and sustainability (Saxena et al
2011). They also ensure thermal (Paiva et al 2012) and acoustic (Asdrubali 2007)
insulation properties. The concrete with corn cobs as conventional aggregates
replacement, in particular, has not been very studied up to now. Faustino et al (2015)
used corn cob granules coated with cement paste in concrete composition, and
obtained a lightweight material with a density of 1680 kg/m³; this low density was
accompanied by compressive strength decrease compared to normal concrete made
with conventional aggregates, sand and gravel. Pinto et al (2012b) studied the
concrete with granulated corn cobs with bigger dimensions than those used by
Faustino et al (2015), in a ratio of 6/1/1 (corn cob granules/ Portland cement/ water),
obtaining a material with a density of 382.2 kg/m3, and a compressive strength of
120 kN/m2.
The research presented in this paper aim to analyse the effects of cement
replacement by fly ash in 10 vol. %, 20 vol. %, and 30 vol. % and, afterwards, the
effects of mineral aggregates substitution by 50 vol.% with vegetal aggregates.
Materials and Methods

The start point of the research was a reference concrete of 25/30 strength class, and
on this basis, were developed concrete recipes with 10 vol. %, 20 vol. % and 30 vol.
% cement replacement by FA, a concrete recipe with 50 vol. % of mineral
aggregates replacement by corn cob aggregates and than these two variants were
combined in order to study interconnection between fly ash and corn cobs.
The ingredients of the studied concrete recipes were as follows:
- natural sand (diameter 0–4 mm);
- river gravel (diameter 4–8 mm);
- cement type CEM II, with mineral additives and of 42.5R MPa strength,
- fly ash from CET Holboca, Iasi;
- two types of additives (a super plasticizer and an accelerator for concrete
hardening);
- vegetal aggregates of corn cobs, shredded in granules smaller than 5-6 mm in
diameter.
The developed variants of concrete were:
- RC – a reference concrete of 25/30 strength Class (manufactured according to
NE012-1:2007);
- CFA10 – a concrete with 10 vol.% of FA as cement partial replacement;
- CCC50 – a concrete with 50 vol.% of corn cob granules as partial replacement of
mineral aggregates;

- CCCFA 50-10 – a concrete with 50 vol.% of corn cob granules as partial

replacement of mineral ones and 10 vol.% of FA as partial replacement of cement;
replacement of mineral ones and 20 vol.% of FA as partial replacement of cement;
replacement of mineral ones and 30 vol. % of FA as partial replacement of cement.
The concrete was poured into cylinder moulds with 100 mm diameter and 200 mm
length and were made three samples for each recipe. On the resulted samples was
measured the apparent density and than were performed tests to determine
compressive and splitting tensile strength, according to the norms in force (SR EN
12350-6:2010); (SR EN 12390-3:2009/AC:2011); (SR EN 12390-6:2010); (SR EN
12390-7/AC:2006). Provide sufficient detail to allow the work to be reproduced.
Methods already published should be indicated by a reference: only relevant
modifications should be described.
Results and Discussion

Concrete density
Regarding the evolution of concrete density from casting till 28 days of curing
(Figure 1), RC registered a 1.2% density decreasing and the CCC50 a 8.42% smaller
density. The smallest density decrease of all was registered by CFA10, with 0.58%,
and the biggest one by CCC50, with 8.42%. From the CFA category, the highest
diminish was of CFA20, with 3.74%, and from the CCCFA group, the smallest
diminish was of CCCFA50-10, with 4.99%.
Figure 1. The evolution of concrete density, from casting till 28 days of curing
[kg/m3].

Figure 2. Concrete density at 28days, [kg/m3].
The cement replacement by fly ash determined the density decreasing of the
concrete, the smallest density from the CFA group being registered by CFA30 with
a value of 2118, 47 kg/m3, with 3.82% smaller than of the RC (Figure 2). The
concrete recipe with corn cobs only registered a density diminish with 24.56%
compared to RC. The group of CCCFA registered density values smaller than 1750
kg/m³, the decrease being between 25,59% and 21.25 % compared to RC (Figure 2).
Compressive strength of the concrete
From compressive strength point of view (Figure 3), FA led to the decreasing of this
property with 7.98%, 17.47% and 34.19% for 10 vol. %, 20 vol. % and 30 vol. % of
cement replacement, respectively. The 50 vol. % of mineral aggregates replaced by
corn cob ones determined a strong compressive strength diminish, with 85.90%.
Figure 3. Compressive strength of the concrete [N/mm2].
Fly ash association with corn cob aggregates revealed an improvement of the
compressive strength in the case of 10 vol. % and 30 vol. % cement replacement,
than CCC50, with 43.66% and 11.83%, respectively.
Tensile strength of the concrete

Regarding the tensile strength of the studied concrete recipes (Figure 4), FA led to
the increase of the splitting tensile strength with 9.39%, 15.96% for 10 vol. % and
20 vol. % of cement replacement, respectively. The 50 vol. % of mineral aggregates
replaced by corn cob ones determined a strong splitting tensile strength diminish,
with 76.05%.
Figure 4. Splitting tensile strength of the concrete [N/mm2].
Fly ash association with corn cob aggregates revealed an improvement of splitting
tensile strength in the case of 10 vol. % and 20 vol. % cement replacement, with
62.19% and 15.68%, respectively, than CCC50.
Conclusions
A source of vegetable waste for building materials is represented by corn cobs.
Analyzing the mechanical properties of concretes with corn cob aggregates, these
had values much lower compared to the standard concrete. It seems that the
association of fly ash with corn cobs aggregates had very positive effects on the
vegetal concrete. In conclusion, the use of vegetable waste is adequate to achieve
sustainable development in the constructions field. An advantage of these concretes
is their weight, the obtained densities fitting them into the category of lightweight
concrete which may have non-structural applications such as screeds, plasters or
closures in the form of masonry blocks or panels.
Acknowledgements
The first author is grateful to Sika Romania representatives for their technical support and for
providing the necessary additives in order to accomplish the presented research.
References
Aprianti, ES 2017, ‘A huge number of artificial waste material can be
supplementary cementitious material (SCM) for concrete production - a
review part II’, Journal of Cleaner Production, vol. 142, pp. 4178-4194.
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19th International Congress on Acoustics, PACS, Madrid, pp. 43-55.

Ashour, A, Amer, M, Marzouk, A, Shimizu, K, Kondo, R & El-Sharkawy, S 2013,

‘Corncobs as a Potential Source of Functional Chemicals’, Molecules, vol.18,
pp.13823-13830.
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‘Lightweight concrete masonry units based on processed granulate of corn cob
as aggregate’, Materiales de Construcción, vol. 65, no. 318, pp. e055.
Meyer, C 2009, ‘The greening of the concrete industry’, Cement & Concrete
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2012(a), ‘Characterization of corn cob as a possible raw building material’,
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structural applications’, Construction and Building Materials, vol. 34, pp.
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Materials, Pavla Těšinova Editor, InTech, Rijeka, Croatia.
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test specimens.
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ADSORPTION OF Sr2+ IONS FROM AQUEOUS SOLUTIONS ON THE

ACTIVATED CARBON CAN-7 UNDER DYNAMIC CONDITIONS
Mihai Ciobanu, Tudor Lupascu, Tatiana Mitina, Igor Povar
Institute of Chemistry, 3 Academiei Street, MD2028, Chisinau, ipovar@yahoo.ca, Republic of

Moldova
Abstract
In the paper the eliminating strontium ions from groundwater by using the CAN-7
activated carbon under dynamic conditions has been studied. The activated carbon
CAN-7 is obtained by the chemical method, through the treatment with ortho-
phosphoric acid at distinct temperatures. It has been proved that by the reduction of
the filtration rate of the solution containing strontium ions through the adsorbent
column, the strontium ion adsorption is increased. The adsorption of strontium ions
from aqueous solutions on the CAN-7 activated carbon has been measured at
different lengths of working layer of the adsorbent column and at different filtration
rates of the solution. The length of working layer of the column with CAN-7 has
been determined as a function of the initial concentration of strontium ions and
filtration rates. The activated carbon CAN-7 with adsorbed strontium ions is
completely regenerated by 0.36% of hydrochloric acid. The obtained results for the
process of adsorption of strontium ions from aqueous solutions on the CAN-7
activated carbon under dynamic conditions has demonstrated the option of removing
this pollutant from the deep waters.
Keywords: activated carbon, adsorption, aqueous solution, chemical activation,

dynamic conditions, nut shells
Introduction
Heavy metals penetrate the life form through water, air and food. If their amount
exceeds the maximum admissible concentration, then there are health problems in
the human body. Most heavy metal ions interact with N, S, O and P electron donors
from the chemical structure of proteins in living organisms by forming coordinating
compounds. The initiated reactions take place in the cell membrane and are followed
by the penetration of toxic substances into the cells, which in turn lead to their
physiological modification.
Presently there are a series of papers on the adsorption of Sr2+ ions from aqueous
solutions on different types of adsorbents (Chegrouche et al 2009, Hasany &
Chandhary1981, Mitina et al 2015, Moon et al 2011, Shawabkeh et al 2002,Wang et
al 2009,Yavari et al 2010, Zhang et al 2004). Scientific studies on the study of
adsorption of strontium ions from solutions in dynamic conditions are limited
(Mohamed-Ibrahim et al 2011, Yuko et al 2014).
The purpose of this paper is to evaluate the possibility of removing strontium ions
from groundwater by using the CAN-7 activated carbon under dynamic conditions.
The use of CAN-7 activated carbon under static conditions previously demonstrated
a good adsorption capacity compared to other modified activated carbons, obtained
from the same raw material (nut shells), but by using a physicochemical method
(Ciobanu et al 2016). The activated carbon CAN-7 was obtained by the chemical
method, through the treatment with ortho-phosphoric acid at distinct temperatures.

The CAN-7 activated carbon was obtained from nut shells by treatment with ortho-
phosphoric acid at 80°C and subsequent activation at 460°C. The activated carbon
fraction studied was 0.8-1.0 mm. As adsorbent, strontium nitrate, pure for analysis,
was used. The adsorption isotherms were determined at various concentrations of
strontium ions in solution, using the same mass of activated carbon at 20°C. The
equilibrium concentrations of strontium ions in solutions were determined on the
AAS-1 spectrophotometer. One of the efficient methods of removing Sr2+ ions from
deep water is the adsorption method using modified activated carbon. The study of
the process of adsorption (a) of strontium ions from aqueous solutions on the CAN-
7 activated carbon under static conditions proved the possibility of removing this
pollutant from deep waters (Figure 1) (Ciobanu et al 2016).
Figure 1. Adsorption isotherm (adsorption a versus equilibrium concentration Ce) of

Sr2+ions from aqueous solutions on the CAN-7 activated carbon under static
conditions, t = 200C.
Figure 1 demonstrates that the activated carbon CAN-7, obtained from nut shells by
chemical activation with ortho-phosphoric acid, can bind strontium ions in much
greater amounts than it can be present in deep waters. As an example, in the artesian
fountain of the Mandra village of the Calarasi district the concentration of strontium
ions is 48 mg/L, the maximum admissible concentration being 7 mg/L. It is easy to
assume that the value of adsorption of strontium ions on this adsorbent will be
higher under dynamic conditions, obviously at reasonable filter rates.
Figure 2 shows the curve of the Sr2+ ions adsorption dynamics from aqueous
solutions on the fractionated CAN-7 activated carbon (2.0-3.0 mm) at a filtration
rate of 6.7 m/hr. The initial concentration of the solution was 100 mg/L. The
adsorption column had a length of 91 cm and its diameter was 1.8 cm. From the data
presented in Figure 2, it can be seen that at a filtration rate of 6.7 m/hr, the adsorbent
column practically does not work, since the contact time of the activated carbon
granules and Sr2+ ions is too low.

Figure 2. Dynamics of the adsorption of Sr2+ ions from aqueous solutions on the
CAN-7 activated carbon. Rate of filtration is 6.7 m/hr, the filtration volume Vfil is in
L.
The decrease of the filtration rate to 5.75 m/hr (Figure 3) demonstrates a

modification of the curve allure of the adsorption dynamics, but without yielding
results that could be used for practical removal of Sr2+ ions.
Figure 3. Dynamics of adsorption of Sr2+ ions from aqueous solutions on the CAN-
7 activated carbon. Rate of filtration Vfil is 5.75m/hr.
Figure 4. Adsorption isotherm of Sr2+ ions from aqueous solutions on the CAN-7
activated carbon under the dynamic conditions. Rate of filtration Vfil is 1.9m/hr.

At a filtration rate Vfil of 1.9 m/hr (Figure 4) there is a significant change in the curve
of the adsorption dynamics of the strontium ion on the CAN-7 activated carbons at
relatively low values of the filtrate volumes.
Figure 5. Adsorption isotherm of Sr2+ ions from aqueous solution on the CAN-7
activated carbon under dynamic conditions. The filtering rateVfil is 0.95m/hr.
Figure 5 shows an increase in the adsorption value compared to Figure 4, the

filtration rate being 1.9 m/hr. Indeed, from Figure 5 at filtrate volume of 0.1L, C/Co
is of 0.06, and from Figure 4 at the same volume, C/Co is equal to 0.03.
The measured adsorption of strontium ions from aqueous solutions on the CAN-7
activated carbon as afunction of the length of adsorbent layer in the column (L) is
shown in Figure 6 and Figure 7.
Figure 6. Adsorption isotherms of Sr2+ ions from aqueous solutions on the CAN-7
activated carbon under dynamic conditions. The filtering rate is 0.85m/hr. Length of
the adsorbent layer, l: 80mm (■), 130mm (●), 190 mm (▲).

Figure 7. Adsorption isotherms of Sr2+ ions from aqueous solutions on the CAN-7
activated carbon under dynamic conditions. The filtering rate is 0.85m/hr. Length of
the adsorbent layer, L: 250 mm (■), 300 mm (●), 360 mm (▲).
Based on the data from Figure 6 and Figure 7 (Sr2+ ion permeation concentrations),
Figure 8 shows the dependence of the loss of the directional effect of the adsorption
layer (τ) on the length of the adsorbent layer (L, mm).
Figure 8. The dependence of the loss of the directional effect of the adsorption layer
(τ) on the length of the adsorbent layer (L).
From the data presented in Figure 8, the working length layer of column with the
CAN-7 activated carbon (lo), which is equal to 185mm, is determined.
Further, the column containing CAN-7with strontium ions adsorbed was subjected
to the regeneration process with 0.36% hydrochloric acid. The acid solution was
filtered through a column with the same filtration rate of 0.85 m/hr. The obtained
data are shown in Figure 9. This figure shows the complete removal of strontium
ions from the porous structure of the adsorbent after filtration of 2 liters of 0.36%
hydrochloric acid. Thus, the CAN-7 activated carbon was completely regenerated.
Consequently, strontium ions were adsorbed on the inner surface of activated carbon
and thus it was possible its removal with acid. Only from the matrix of the activated
carbon strontium could not be washed. There is no need to determine the
concentration of strontium directly in the activated carbon.

It has been confirmed that by the reduction of the filtration rate of the solution
containing strontium ions through the adsorbent column, the strontium ion
adsorption value is increased. In the adsorbent process, under dynamic conditions,
the adsorption capacity is lower than under static conditions. In this case the
adsorbent layer is characterized by the dynamic activity (ad) which is always smaller
than the static activity (as). The degree of adsorption capacity of the adsorbent
(ad/as) is usually between 0.8-0.9.
It is obvious that the working time of column containing activated carbons depends
on the initial concentration of strontium ions in the solution to be filtered, as well as
on its filtration rate.
The contact time τ of the solution containing strontium ions with the adsorbent
granules depends on the size of the column and the filtration rate Vfilof the solution
filtered through it:
τ = Vads./Vfil. (1)
where Vads. is the adsorbent volume.
Figure 9. Dynamics of desorption of Sr2+ ions from the CAN-7 activated carbon.
The filtration rate of 0.36% hydrochloric acid solution is 0.85 m/hr. Length of the
adsorbent layer is 360mm.
The dimensions of the adsorption column: height of the column was 910mm, its
thickness was 18mm. By introducing these values in equation (1), for each filtering
rate (6.7, 5.75, 1.9, 0.95 m/hr), the contact time of the strontium ions with the
adsorbent granules is equal to 2.25, 2.6, 7.9 and 15.8 min respectively.
From the data obtained an increase in the contact time of the strontium ions with the
adsorbent granules with the reduction of the filtration rate of the solution through the
column was noticed. Obviously, the value of adsorption of strontium ions on the
adsorbent will be higher as the contact time of the solution with the adsorbent
granules increases.

Conclusions
The study of the process of adsorption of strontium ions from aqueous solutions on
the CAN-7 activated carbon under dynamic conditions has demonstrated the option
of removing this pollutant from deep waters.
It was found that at the filtering rate 0.85 m/hr of the solution, initially containing
100 mg/L of Sr2+, on the CAN-7 activated carbon, the length of working layer of the
column is 185 mm.
The activated carbon CAN-7 with adsorbed strontium ions was completely
regenerated with 0.36% hydrochloric acid.
Acknowledgements
The research leading to these results has received funding from the MSCA-RISE action;
project 734641 NanoMed, within the H2020 Marie Skłodowska-Curie Research and
Innovation Staff Exchange Programme.
References
Chegrouche, S, Mellah, A & Barkat, M 2009, 'Removal of strontium from aqueous
solutions by adsorption onto activated carbon: kinetic and thermodynamic
studies', Desalination, vol. 235, no. 1-3, pp. 306-318.
Ciobanu, M,Botan, V, Lupascu, T,Mitina, T &Rusu, M 2016, 'Adsorption of
strontium ions from water on modified activated carbons', Chemistry Journal
of Moldova, vol. 11, no. 2, pp. 26-33.
Hasany, SM & Chandhary, MH 1981, 'Adsorption studies of strontium on
manganese dioxide from aqueous solutions', International Journal of Applied
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'Determination of strontium ions in waters with a high content of sodium ions',
Chemistry Journal of Moldova, vol. 10, no. 1, pp. 20-24.
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Mohamed EK 2011, 'Thermodynamic and fixed bed studies for the removal of
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of Sr(II) ions in the gels based on polysaccharide derivates', Journal of
Hazardous Materials, vol. 171, no. 1-3, pp. 820-826.
Yavari, R, Huang, YD&Mostofizadeh, A 2010, 'Sorption of strontium ions from
aqueous solutions by oxidized multiwall carbon nanotubes', Journal of
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pp. 1-6.

Zhang, AY, Wei, YZ & Kumagai, M 2004, 'Synthesis of a novel macroporous

silica-based polymeric material containing 4, 4′, (5′)–di(tert-
butylcyclohexano)-18-crown-6 functional group and its adsorption mechanism
for strontium', Reactive and Functional Polymers, vol. 61, no. 2, pp. 191-202.

ANALYSING WOOD DENSITY AND BIOMASS: A CASE STUDY OF

FOREST PLANTATIONS FROM MOLODOVA NOUA WASTE HEAPS,
ROMANIA
Ilie-Cosmin Cantar1, Ion Chisalita 1,2, Lucian Dinca1

1
„Marin Dracea” National Institute for Research and Development for Forestry, 128 Eroilor
Boulevard, Voluntari, Ilfov, icas@icas.ro, Romania
2
Banat’s University of Agricultural Science and Veterinary Medicine “King Michael I of
Romania” from Timisoara, 119 Calea Aradului, Timisoara, Romania
Abstract
The present paper emphasizes the possibility of using wood from the plantations
installed on waste heaps by analysing the density of wood mass and establishing the
biomass of species planted on the waste heaps from Moldova Noua. In order to
determine wood biomass for the analysed species, wood samples were gathered
from a specific sample area. As such, their volume and mass were established both
before and after drying them in a stove at a temperature of 105 degrees Celsius for
24 hours. The plantations biomass was calculated by using wood density according
to the work method previously described as well as the wood mass volume per
hectare. The last element was determined after biometric measurements realized in
12 sample surfaces of 100 square meters each, arranged in four variants with three
recursions. In the specific case of Moldova Noua waste heaps, the values obtained
for wood density attest the high-quality wood of these plantations from the point of
view of their density, in comparison with the wood from similar species grown
under favourable vegetation conditions. Furthermore, analysing the productivity of
plantations installed on the waste heaps from Moldova Noua, attest the framing of
these plantations in an inferior production class from a productive point of view.
The papers conclusions discuss the obtained results in the context of data from
specialty literature concerning the productivity and wood density of forest
plantations from the waste heaps located in Moldova Noua.
Keywords: black locust, cooper ore, oleaster, tailing dumps, wood
Introduction
Created as an outcome of material storage resulted from the flotation process, waste
heaps, also known as cesspools, represent anthropic field surfaces in which the
growth and development of vegetation is difficult due to sterile instability. This
phenomenon is accentuated in Moldova Noua, Romania (Figure 1) by periods with
winds characteristic to this area.
Dust pollution from Moldova Noua is a result of these surfaces together with the
strong winds representative for this area. This type of pollution has displeasing
effects on the other side of Danube, namely in Serbia. In the year 1988, this
phenomenon has led to an international process won by the Yugoslavian Republic,
in which Romania was obliged to stop the dust pollution from Moldova Noua. That
juridical decision has contributed to motivating and accelerating the initiation of
works.
As such, in the following period, the embankment and part of its neighbouring
plateau were afforested, while the waste heaps plateau was grassed. The works were
realized by Moldova Noua Forest District and S.C. Pajistea S.R.L. Moldova Noua
based on a project elaborated by the Silvicultural Forest and Management Institute.
The successful used species were: black locust (Robinia pseudoacacia L.), a species
that usually does not vegetate well on very alkaline soils (Dinca 2017), oleaster
(Elaeagnus angustifolia L.) and sea buckthorn (Hippophae rhamnoides L.). Besides
its high content of vitamins and nutritive elements (Dinca et al 2018), this last
species has the capacity to fix degraded fields (Constandache et al 2016).
These stabilization works enterprises on Moldova Noua waste heaps, with the help
of vegetation, especially the forest one, have led nowadays to the presence of a
phytogeographical complex that presents both perspectives for reintegrating these
surfaces in the natural landscape, as well as results in this direction (Figure 1).
Figure 1. Waste heaps complex from Moldova Noua, Romania
The investigations detailed in the present paper have an important role in regard
with the aging of current plantations, the eventuality of harvesting wood mass and
the natural or artificial regeneration of surfaces that present waste heaps with the
same forest species. Future capitalization of the wood grown in this area is also
important for the present paper and demonstrates the possibility of using wood from
the plantations installed on waste heaps by analysing the density of wood mass and
establishing the biomass of species planted on the waste heaps from Moldova Noua.


In order to determine wood biomass for the analysed species, wood samples were
gathered from a specific sample area. As such, increment cores from the 30
exemplars belonging to the selected species were extracted as follows: increment
cores from 15 black locust exemplars and 15 oleaster exemplars. They were
extracted from the plantations situated on three waste heaps (waste heaps number
one and two from „Bosneag” group and waste heap number three from „Danube’s
Meadow”). Therefore, five locust increment cores and five oleaster increment cores
were extracted from each waste heap. Their volume was then determined by total
water immersion, by measuring the dislocated liquid volume.
After determining core volumes by using a 5 ml tube and the mass with the help of
an electronic scale (both in humid and dry state), followed by stove drying at a
temperature of 105° C for 24 hours, the apparent density was established for both dry
and humid wood by using the following formulas:
m (1)
ρ a0 = 0
Va0
where:
ρ a is the apparent density for almost dry wood;
0
m0 is the mass of totally dry core;

Va0 is the volume of totally dry core.
mu
ρa = (2)
u
Vu
where:
ρ a is the apparent density od dry wood;
u
mu is the core mass at a certain humidity of 0% < u < 30%;

Vu is the core volume at the same u humidity.
The locust and oleaster wood biomass was determined by taking into consideration
the above mentioned relationships, namely:
m= ρ ⋅ V (3)
The plantations biomass was calculated by using wood density according to the
work method previously described, as well as the wood mass volume per hectare.
The last element was determined after biometric measurements realized in 12
sample surfaces of 100 square meters each, arranged in four variants with three
recursions: V1 – plantations on the „Bosneag” group plateau, V2 – plantations on the
„Bosneag” group slope, V3 – plantations on „Lunca Dunarii” waste heap plateau, V4
– plantations on „Lunca Dunarii” waste heap slope. The disposal of repetitions from
within the three variants was used by Blada, with another number of variants and
repetitions. The current situation was adapted to the field arrangement of forest
plantations situated on the waste heaps from Moldova Noua (Blada et al 2013).

A number of six trees were gathered from the plantations belonging to the three
waste heaps, as follows: one locust tree and one oleaster from each waste heap.
Their diameters were situated in the average diameter category (4-6 cm for locust
and 2-4 cm for oleaster). The root was extracted for each of these trees in order to
determine the total volume. The volume calculation for the extracted exemplars was
realized through the xilometration and section method for the trees cone and only
through xilometration for roots and branches.
In accordance with the methodology previously described, the determination of the
plantations wood mass volume was realized based on the average trees volume. By
extrapolating this value to the number of trees per hectare, the plantations volume
per hectare was also obtained.

Locust and oleaster wood density
In the specific case of Moldova Noua waste heaps, the values obtained for wood
density attest to the high-quality wood of these plantations from the point of view of
their density, in comparison with the wood from similar species grown under
favourable vegetation conditions.
The following tables render data regarding volumetric, gravimetric and densiometric
characteristics for each sample, as well as the average density (expressed in kg/mc)
both before (Table 1) as well as after the samples were dried in stove (Table 2).
An important fact to mention is that the samples average density is calculated based
on the density of all samples and not based on the samples mass and total volume.
Table 1. The apparent locust and oleaster wood density for plantations situated on
Moldova Noua waste heaps
Waste Total mass of Total volume of Average density of
Species
heap samples (g) samples (ml) samples (kg/mc)
Locust 4.23 5.10 833.222
1
Oleaster 4.05 5.10 775.159
Locust 5.34 6.40 834.015
2
Oleaster 4.2 5.30 777.436
Locust 5.04 5.70 883.074
3
Oleaster 3.54 4.80 729.491
Apparent density of locust humid wood 850.104
Apparent density of oleaster humid wood 760.695

Table 2. The apparent density of completely dry locust and oleaster wood for
plantations situated on Moldova Noua waste heaps
Total mass of Total volume of Average wood
Waste heap Species
samples (g) samples (ml) density (kg/mc)
Locust 3.29 4.70 701.30
1
Oleaster 2.91 4.60 628.17
Locust 4.08 5.60 729.25
2
Oleaster 2.58 4.40 584.70
Locust 3.67 4.80 764.75
3
Oleaster 2.74 4.60 592.90
Apparent density of completely dry locust wood 731.77
Apparent density of completely dry oleaster wood 601.92
Therefore, the locust apparent wood density is of 850.1 kg/mc in a humid state and
731.8 kg/mc in a completely dry state. In the case of oleaster, density values of
760.7 kg/mc were obtained for humid wood and 601.9 kg/mc for completely dry
wood.
Locust and oleaster biomass
Locust and oleaster biomass represents almost in totality the plantations wood mass
volume. The biometrical characteristics of other species are much more inferior,
having very low diameters and heights. As such, the biomass was calculated as a
sum of locust wood biomass and oleaster wood biomass.
Table number 3 centralizes the results of calculating locust and oleaster biomass
from Moldova Noua waste heaps.
Table 3. Locust and oleaster wood biomass from forest plantations installed on the
waste heaps from Moldova Noua
Volume (mc/ha) Biomass (kg/ha)
Nr. Density
Species State Without Without
crt. (kg/mc) Total Total
root root
Humid 850.104 39.9 31.2 33919.1 26523.2
1 Locust
Absolutely dry 731.77 39.9 31.2 29197.6 22831.2
2 Humid 760.695 24.8 17.9 18865.2 13616.4
Oleaster
Absolutely dry 601.92 24.8 17.9 14927.6 10774.4
Total humid wood biomass /ha 52784.4 40139.7
Total absolutely dry wood biomass /ha 44125.2 33605.6
The results obtained by us and rendered above where then compared with similar
investigations as follow in the next paragraphs. A study concerning the locust
biomass production realized in Slovakia in optimal vegetation conditions highlights
certain similarities with the results obtained in the present paper. Bencat has studied
the production of locust biomass in South Slovakia in three experimental surfaces
with locust tree ages ranging from 8 and 27 to 49 (Bencat 1989). Interesting for us
are the results obtained by the above-mentioned author in the experimental surface
number 2, where the locust age at the research date was 27, with approximately 5
years older than the age of locusts from Moldova Noua waste heaps, at their
harvesting date. The results obtained by Bencat in Slovakia reveal a density of 875.4
kg/mc for the humid wood and 566.8 kg/mc for the completely dry wood.

In Romania, experimental investigations concerning the physical properties of locust

wood were realized by Porojan. She has studied locust wood harvested from two
different geographical areas from Romania, North (Carei area) and South (Arges
area). The locust wood from the North area presented a green wood humidity of
35.11 %, while the determined absolute density was of 664 kg/mc, meaning a humid
wood density of 897.13 kg/mc. Similar values, without significant differences, were
obtained for the locust wood from the South area, where the green wood humidity
was of 36.42 %, the absolute density was 651 kg/mc, meaning a humid wood
density of 888.1 kg/mc (Porojan 2009). Studies concerning oleaster, realized in
Uzbekistan, have emphasized a density of the completely dry wood of 530 kg/mc
(Khamzina et al 2006). However, the age of the studied oleaster was not mentioned.
In regard with the age and its influence on the woods density and caloric power, it is
known that the low calorific values of young wood may be due to a low wood
density, which corresponds to a soft wood texture of younger trees. The lower
caloric values of softwood are explained by its lower content of hemi-cellulose in
combination with higher content of lignin when compared with hardwood (Doat
1977).
Conclusions
For locusts with similar ages to the ones from Moldova Noua waste heap plantations
but grown in Slovakia in other vegetation conditions than waste heaps or degraded
fields, the humid wood density is of 875.4 kg/mc (Bencat 1989), a value close to the
one determined by us in the present paper. The same author has determined a value
of 567 kg/mc for the completely dry wood density, a value that is smaller than the
one determined by us.
In our country, the values identified by Porojan for the absolute locust wood density
are of 664 kg/mc (in North Romania) and 651 kg/mc (in South Romania), while the
humid wood has density values of 897.13 kg/mc in North and 888 kg/mc in South.
These values are similar with the ones obtained by us for humid wood (850 kg/mc)
and completely dry wood (731 kg/mc)
In regard with the oleaster that vegetates on Moldova Noua waste heaps, the
completely dry wood density is of 602 kg/mc, with over 70 kg/mc higher than the
values specified in the specialty literature for this species, values determined by
Lamers and Khamzinal in Kazakhstan (Lamers & Khamzina 2008).
By comparing these results with the ones obtained in the present paper, a similarity
between humid wood densities is observed, as well as significant differences
between absolutely dry wood densities. This fact is mostly due to growing
differences and implicitly to the formation of a denser wood but with lower
humidity in plantations situated on Moldova Noua waste heaps. The growths of
locusts from Moldova Noua waste heaps are smaller, a fact that leads to the
formation of a denser wood with a lower humidity content in comparison with the
exemplars grown in optimal stational conditions.
The locust wood humidity registers a value of 16.17 % compared with the oleaster
wood that reaches a humidity of 26.38 % with 19 % higher. These values were
obtained by determining wood humidity for exemplars grown on Moldova Noua
waste heaps, as a difference between wood densities determined after harvesting but
in the same conditions for both species and the one obtained in a completely dry
state. As such, we can recommend the wood of locusts grown on waste heaps as
having a higher absolute density and a better calorific power than the one of species
grown in benevolent vegetation conditions. We consider that this species can we
used successfully as fire wood in the case of exchanging or gradually replacing
species from forest plantations situated on Moldova Noua waste heaps.
Furthermore, the oleaster wood grown on waste heaps is not inferior to the locust
one in regard with its usage as fire wood. However, its arbustive appearance with a
lower wood productivity makes it inferior to locust and does not recommend it as a
sub stand for stimulating locust growths or as a prime intervention species for
afforesting degraded fields. However, in order to be used as firewood, additional
tests are required on the process of bioaccumulation of pollutants in plants and a
characterization of combustion emissions, too.
As such, the energetic potential of arborescent or arbustive species is recognized and
recommend them for planting on waste heaps in order to stabilize them (Dinca et al
2011, Dinca et al 2012).
References
Bencat, T 1989, ‘Black locust biomass production in souther Slovakia’, Veda.
Blada, I, Tanasie, S, Dinu, C & Bratu, I 2013, 'Experimental Plants with Pinus
cembra and P. mugo from Dumitrelu Dump situated in Calimani Mountains',
Revista de Silvicultura si Cinegetica, no. 32, pp.110–116. In Romanian.
Costandache, C, Peticila, A, Dinca, L & Vasile, D 2016, ‘The usage of Sea
Buckthorn (Hippophae rhamnoides L.) for improving Romania degraded
lands, AgroLife Scientific Journal, vol. 5, no. 2, pp. 50-58.
Dinca, L, Dinca, M, Serbanescu, A, Stanca, A, Darie, G, Prisecaru, T, Ciobanu, V &
Patrut, I 2011, ‘Reconstruction of tailings dumps by the use of potentially
energetic species’, Tehnica Silvica Publishing House, pp.179.
Dinca, L, Cantar, IC, Dinca, M & Adam, I 2012, ‘Cultivating the waste heaps from
Moldova Noua with forest species that have an energetic potential’, Scientific
Bulletin of the Polytechnic University of Bucharest, Series C Electrical
Engineering and Computer Science, vol. 74, no.1, pp. 39-48.
Dinca, L 2017, ‘Influence of calcium carbonate (CaCO3) on soil on acacia tree
productivity’, Forest Magazine, no. 2, pp. 7-10. In Romanian.
Dinca, L, Dinulica, F, Socaciu, C, Constandache, C, Blaga T & Peticila, A 2018,
‘Hipphophae Salicifolia D. Don - a miraculous species less known in Europe’,
Notulae Botanicae Horti Agrobotanici Cluj-Napoca, vol. 46, no. 2, pp. 474-
483.
Doat, J 1977, ‘Le pouvoir calorifique des bois tropicaux, Bois et Forêts des
tropiques’, no. 172, pp. 33-55.
Khamzina, A, Lamers, JPA, Botman E & Velk PLG 2006, ‘Assessing the potential
of tress for afforestation of degraded landscapes in the Aral Sea basin of
Uzbekistan’, Agroforestry Systems, no. 66, pp. 129-141.
Lamers, JPA & Khamzina, A 2008, ‘Fuelwood production in the degraded
agricultural area of the Aral Sea Basin’, Uzbekistan, Bois et forest des
tropiques, no 297, 3.
Porojan, M 2009, ‘Experimental research regarding the physical properties of acacia
wood (Robinia pseudacacia L.)’, Pro Ligno, vol. 5, no. 1.

GROWTH ACTIVATION OF SACCHAROMYCOPSIS (ENDOMYCOPSIS)

FIBULIGERA Y-436 STRAIN BY SQUALENE AND ANOLYTE WATER IN
LABORATORY EXPERIMENTS
Irina Senicovscaia, Tatiana Grozova, Georgiy Poleshchuk
“Moldova Verde Project” Association, 12 Meshterul Manole, MD 2044, Kishinev,

irina_sen@mail.ru , tanya.grozova87@gmail.com, Republic of Moldova
Abstract
The phenomenon of growth activation of the industrial strain of mycelial fungus S.
fibuligera Y-436 under the influence of squalene and anolyte water has been
investigated. Squalene had a stimulating effect on the growth of the strain on YEPD
Broth in all doses. The stimulating effect of squalene was maintained for 54 hours,
in a dose of 0.0005% - up to 78 hours of the strain cultivation under aerobic
conditions. The growth rate of the strain in the exponential phase between 4 and 6
hours on medium with a squalene of 0.0005 % is 0.30, 0.001 % - 0.44, 0.002 % -
0.41, on medium without squalene - 0.24. Squalene promotes faster adaptation of
the strain to the substrate and reduces the duration of its lag phase of growth by 2-4
hours. The number of cells increases by 2.2-2.3 times with the use of squalene in
doses of 0.0005-0.001 % after 24 hours and by 1.4 times after 48 hours of
incubation on the nutritional mixture based on wheat flour. The strain reached the
stationary phase after 24 hours of cultivation with the use of squalene, while in the
control variant - after 48 hours. This reduces the duration of cultivation by 2 times.
Anolyte water contributed to the rise of generative activity of the strain due to the
acid reaction by 34.3 % in comparison with the initial water. The most effective
method of activation of the strain is the combined use of anolyte water and squalene
in a dose of 0.0005-0.001 %.
Keywords: anolyte water, fodder protein, growths activation, S. fibuligera Y-436,

squalene
Introduction
The way to solve the problem of deficiency of fodder protein is its production by
microorganisms. The perspective group of microorganisms for obtaining the protein
feed is mycelial fungus Saccharomycopsis (Endomycopsis) fibuligera (Smirnov et al
1997); (Tsygankova et al 1997). S. fibuligera is found to actively accumulate
trehalose from starch. This yeast is also found to secrete a large amount of amylases,
acid protease, β-glucosidase and pectinases, which have highly potential
applications in fermentation industry (Chi et al 2009).
S. fibuligera is food-borne, dimorphic yeast, which has been considered, in the
realm of ascomycetous yeast species, as one of the best producers of amylolytic
enzymes (De Mot et al 1984). The capability of S. fibuligera to degrade starch
relates with the production of two types of amylases: endo-acting ɑ-amylase and
exo-acting glucoamylase. Some S. fibuligera strains synthesize both enzymes while
others produce only one type of amylase. The ability of amylases to digest raw
starch is a technologically interesting property. Such enzymes can be used for

energy saving in starch-processing (Saha & Ueda 1983). Raw starch degradation is
rare among yeast amylases, but one of the known yeast enzymes having this
capability is the glucoamylase produced by S. fibuligera IFO 0111 (Hostinová
2002).
It is known that additives of squalene as biochemically active substance, which has a
property to capture oxygen and saturate the microorganism cells with it during the
simple biochemical interaction with water, ensure the more complete use of the
substrate. According to some studies, squalene stimulates the aerobic
microorganisms’ multiplication, which can activate the aerobic stage of wastes
treatment and improve their preparation for the methanogenesis process.
Additionally, the adding of amaranth seeds to the methanogenic bioreactor
stimulates the process of methanogenesis also (Covaliov et al 2015).
Thus, it was assumed that biologically active additives obtained from the amaranth
and added in the nutrient medium for cultivation of S. fibuligera can be used as one
of the essential elements of the technology for producing fodder protein. In order to
simplify and reduce the cost of technology the further research has been planned to
conduct with natural sources of squalene - with amaranth oil.
The method of water activation by electric field is also interesting in terms of its
application on the technology of obtaining protein feed products. Electrochemically
activated water (catolyte, anolyte and mixed water) acquires new properties that
affect its biological characteristics, kinetics of the reactions and the solubility of
substances. It has been established that electrochemically activated water can
increase the yeast fermentation and their generative activity in comparison with the
initial water (Pankiv et al 2013). The authors explain this fact by increasing the
permeability of the membrane of the yeast cell by providing a potential difference
on its surface, which contributes to a better transport of nutrients into the cell. The
particular interest is the anolyte water, because it has an acidic reaction of medium
and a high redox potential.
The purpose of the research was to investigate the effect of squalene and
electrochemically activated water on the strain of S. fibuligera Y-436 in connection
with its application as a producer of fodder protein for animals.

Inoculum preparation of S. fibuligera Y-436. Industrial strain of mycelial fungus
Saccharomycopsis (Endomycopsis) fibuligera Y-436 was purchased from the
Russian National Collection of Industrial Microorganisms of the Federal Institution
"State Research Institute of Genetics and Selection of Industrial Microorganisms of
the National Research Center "Kurchatov Institute" (Moscow, Russian Federation).
The strain S. fibuligera Y-436 is not genetically modified.
The strain was maintained on Yeast Extract Peptone Dextrose (YEPD) Agar slant
consisted of 5 g l-1 yeast extract, 10 g l-1 peptone, and 20 g l-1 dextrose. Then
incubated at 28°C for 48 hours and stored at 5°C. The slant culture was transferred
to YEPD Broth. Cultivation conditions were 28°C with 100 rpm shaking for 48
hours. Next, 10% v/v submerged culture was used as the fodder protein producer.
Cultural-morphological characteristics of the strain. On a complete yeast medium it
forms white, smooth, matte colonies with pasty consistency, which with aging
begins to flutter and starts to turn into fungal colonies with a true mycelium. Cells
have an oval or elongated shape with sizes of 4.0-8.0 * 6.0-18.0 μm. S. fibuligera Y-
436 strain assimilates soluble starch, glucose, arabinose, galactose, sucrose, maltose,
lactose, raffinose, glycerol and mannitol. The strain uses organic and inorganic
nitrogen and forms sediment and films on liquid media. The rate of reproduction in
the YEPD Broth is 0.40 cells hour-1. The optimal growth temperature of the strain is
t=28°C, pH = 5.0-5.5.
Substrate preparation. The wheat flour was selected as substrate in the present study
to produce fodder protein. The hydro-module contained 12.5 % w/v wheat flour and
5.0 % (NH4)2SO4. The stages of preparation of the hydro-module consisted of
heating water to 50° C, adding wheat flour, heating the mixture to 60° C, steaming
40 minutes, heating to 95° C, steaming 60 minutes and cooling.
Water preparation. Electrolyzed water (catolyte, anolyte and anolyte+catolyte) for
experiments was obtained from the tap water with the aid of a device of “Ecovod-6”
(Ecovod LTD, Ucraine).
Experiments preparation. All experiments were conducted in shaken flasks using
1000 ml Erlenmeyer flasks with a working volume of 500 ml. Benchtop
thermostatic shaker-incubator ES-20/60 (Biosan, Latvia) has been used in studies for
controlled incubation.
Experiment 1. In this experiment, various doses of squalene contained in the
amaranth oil were tested with in relation to the strain of S. fibuligera Y-436
cultivated on the YEPD Broth. As the source of squalene was used oil of amaranth.
Amaranth oil contained 8 % of squalene. The following concentrations of squalene
have been selected for the research: 0.0005%, 0.001% and 0.002% which were
equivalent to the introduction in each shaking flask of 5.0, 10.0 and 20.0 mg of
active substance (squalene) per liter of the nutrient mixture. The introduction of
amaranth oil and mycelial fungus S. fibuligera Y-436 was carried out after cooling
the nutrient mixture to 28° C. The culture suspension was added to the medium once
at the start of incubation in a volume of 10 % v/v. Cultivations condition were 28°C
with 100 rpm for 78 hours.
Experiment 2. In this experiment, various doses of squalene contained in the
amaranth oil were tested with in relation to the strain Y-436 cultivated on a nutrient
medium with wheat flour.
The experimental procedure is the same as in experiment 1. Cultivations condition
were 28° C with 120 rpm for 48 hours.
Experiment 3. The experiment examined the effect of the electrolyzed water
(anolyte, catolyte and mixture of catolyte and anolyte) on the strain of mycelial
fungus S. fibuligera Y-436 cultivated on a nutrient medium with wheat flour.
Cultivations condition were 28° C with 120 rpm for 48 hours.
Experiment 4. The objective of this experiment was to investigate the combined
effect of anolyte water and various doses of squalene on the growth of the strain S.
fibuligera Y-436 cultivated on a nutrient medium with wheat flour. Cultivations
condition were 28° C with 120 rpm for 48 hours.
Methods. Cells of S. fibuligera Y-436 were counted using the Gorjaev's chamber at
least in five fields of vision. Dissolved oxygen, total dissolved solids (TDS) and pH
measurements were determined by use of multi-channel analysers “Consort C3010’’
(Belgium). The product mass was measured by a weight method after separation of
the solid and liquid phases by centrifugation. The biomass was determined by the
calculation method.

Effect of squalene on S. fibuligera Y-436 strain. Squalene had a stimulating effect in
all doses on the growth of the strain Y-436 on YEPD Broth (Figure 1).
Figure 1. Growth curves of the S. fibuligera Y-436 strain on YEPD Broth as a

function of squalene doses (experiment 1)
The stimulating effect of squalene was maintained for 54 hours, in a dose of

0.0005% - up to 78 hours of the strain cultivation under aerobic conditions.
Differences in the growth of the strain on a medium without squalene and with it
were manifested already after 4 hours of cultivation of the strain. The strain reached
the stationary phase after 54 hours of cultivation under use of squalene in a dose of
0.001% and after 28 hours of culture - in a dose of 0.002%. Activation of the growth
of the strain lasted up to 78 hours under conditions of application of 0.0005%
squalene. The dynamics of growth at this dose of squalene was similar to control.
However, the number of cells exceeded the control by 1.3-2.1 times throughout the
experiment. Apparently, the substrate consumption by culture was more gradual in
comparison with doses of squalene of 0.001% and 0.002%. The growth rate of the
strain in the exponential phase of growth between 4 and 6 hours on medium with a
squalene of 0.0005% is 0.30, 0.001% - 0.44, 0.002% - 0.41, while on medium
without squalene - 0.24. A similar regularity was observed up to 28 hours in the
growth of the culture. Squalene promotes faster adaptation of the strain to the
substrate and reduces the duration of its lag-phase of growth by 2-4 hours.
Squalene had a rather strong influence on the physicochemical parameters of the
nutritional mixture with wheat flour and the growth of the strain Y-436 on it. The pH
in all variants of the experiment decreased during the growth of the strain S.
fibuligera Y-436 on nutritional mixture as a result of carbohydrates use (Table 1).
However, in the nutritional mixture with squalene, the pH values decreased more
significantly than in the control. The strongest effect was observed with the growth
of the strain on the medium from 0.002% squalene, the pH value was 3.78, while on
the medium without squalene - 4.42. This indirectly indicates the faster use of
carbohydrates by the strain when 0.002% squalene was added to the medium.

A faster growth of the strain was also recorded in terms of the oxygen content in the
medium. Its amount in the medium with squalene supplements was 12.9-31.0 times
less than in the medium without squalene after 24 hours of strain cultivation. The
total dissolved solids (TDS) also decreased during the experiment that indicates their
use by the strain for cells growth and reproduction.
Table 1. The physicochemical characteristics of the nutritional mixture with

squalene during the growth of the strain S. fibuligera Y-436 (experiment 2)
Carbohydrates,
pH O2, ppm TDS, g l-1
Variant %
24 h 48 h 24 h 48 h 24 h 48 h 24 h 48 h
Control 5.00 4.42 1.55 0 3.95 3.79 8.0 7.2
Squalene 0,0005% 4.57 3.85 0.12 0 3.78 3.59 8.0 7.2
Squalene 0,001% 4.53 3.83 0.05 0.03 3.76 3.78 8.0 7.2
Squalene 0,002% 4.43 3.78 0.11 0.04 3.73 3.75 8.0 6.8
* Initial values: pH=6.09; O2 = 2.40 ppm; TDS = 0.408 g l-1; carbohydrates = 7.0 %.
The additive of squalene in the composition of amaranth oil in all doses has
increased the number of cells of the strain Y-436 after 24 and 48 hours of the
incubation (Table 2). The number of cells increases by 2.2-2.3 times with the use of
squalene in doses of 0.0005-0.001% after 24 hours of incubation and by 1.4 times
after 48 hours of incubation. It should be noted that with the use of squalene, the
strain reached the stationary phase after 24 hours of cultivation, while in the control
variant - after 48 hours. In other words, squalene contributes not only to a faster
growth of the strain, but also reduces the time of passage through the growth phase.
Table 2. The number of cells of S. fibuligera Y-436 and the sediment weight
(experiment 2)
Sediment weight, g l-1
Number of cells∙106 cc-1
Variant total biomass
24 h 48 h 48 h
Control 63.0 90.0 181.1 51.1
Squalene 0,0005% 138.0 123.8 210.5 80.5
Squalene 0,001% 141.5 124.3 225.5 95.5
Squalene 0,002% 113.3 129.3 244.3 114.3
* initial number of cells in the hydro-module is 34.5 ∙106 cc-1 .
This reduces the duration of cultivation by 2 times. As a result, the biomass of the
strain increased by 1.6-2.2 times, and the total weigh of the product - by 1.2-1.4
times, respectively.
Effect of electrolyzed water on S. fibuligera Y-436 strain. Parameters of electrolyzed
water are presented in the Table 3. The initial pH of the catolyte was 6.85; anolyte -
4.38; anolyte+catolyte water - 6.16, while the tap water taken for the experiment
(control) - 6.59. As a result of the growth of the strain and its consumption of
substrate, the pH of the nutrient medium was shifted to the acidic side, and with the
use of anolyte - up to 3.71. The strain sustained an acidic reaction of the medium.
This is mainly due to the contribution of plasma membrane ATPase activity which
seems to be implicated in internal pH regulation (Serrano 1984, Eraso & Gancedo
1987). For example, yeast cells are able to maintain their internal pH between 6 and
7.5 when the extracellular pH varies from 3.5 to 9 (Borst-Pauwels & Peters 1977).
During the growth of yeast on acid media was observed the activation of the plasma
membrane ATPase and that is a mechanism for regulating internal pH.
The oxygen content during the cultivation also decreased significantly due to its use
by the strain. TDS changed slightly.
Table 3. The physicochemical characteristics of the nutritional mixture on

electrolyzed water during the growth of the strain S. fibuligera Y-436 (experiment 3)
Carbohydrates,
Variant %
0 h 24 h 48 h 0h 24 h 48 h 0 h* 24 h 48 h 0 h 24 h 48 h
Control 6.59 4.71 4.00 2.92 0.12 0.12 0.404 6.91 6.67 7.5 8.0 7.8
Catolyte water 6.85 4.97 3.91 3.93 0.13 0.11 0.363 7.12 7.17 7.5 7.5 6.5
Anolyte water 4.38 3.98 3.71 2.35 0.15 0.43 0.553 8.63 8.60 7.5 7.8 7.0
Anolyte +
6.16 4.51 3.99 5.08 0.20 0.16 0.363 7.06 7.11 7.5 7.7 7.1
catolyte water
* (NH4)2SO4 was added after the measurement and before culturing.
The most effective for growth and reproduction of the strain was the use of anolyte.
The anolyte due to the acid reaction of the medium, contributed to the increase of
the generative activity of the strain S. fibuligera Y-436 by 28.5 % compared to the
initial water after 24 hours and by 34.3 % after 48 hours of growth (Table 4). The
number of cells, when catolyte was used remained at the control level. The use of a
mixture of catolyte and anolyte stimulated growth by 17.9% only after 24 hours.
Table 4. The dynamics of growth of the S. fibuligera Y-436 strain on the nutritional
mixture in the hydromodule prepared with electrolyzed water (experiment 3)
Variant
0h 24 h 48 h
Control 8.9 61.5 68.0
Catolyte water 8.9 52.0 70.0
Anolyte water 8.9 79.0 91.3
Anolyte + catolyte water 8.9 74.5 48.0
Growth activation of the S. fibuligera 436 strain in conditions of combined use of
squalene and anolyte. The dynamics of changes in the physicochemical parameters
of the nutrient mixture, prepared on the basis of anolyte was almost identical in the
control and in the variants with squalene (Table 5). The reaction of the medium
shifted to the acidic side, the content of oxygen, TDS and carbohydrates decreased.
Table 5. The physicochemical characteristics of the nutritional mixture on anolyte

water with squalene during the growth of the strain S. fibuligera 436 (experiment 4)
Carbohydrates,
Variant %
0 h 24 h 48 h 0 h 24 h 48 h 0 h* 24 h 48 h 0 h 24 h 48 h
Control 4.90 3.62 3.31 2.20 0.13 0.11 0.398 4.42 4.39 7.0 7.5 6.5
Squalene
4.90 3.60 3.31 2.20 0.13 0.11 0.398 4.28 4.24 7.0 7.4 6.4
0,0005%
Squalene
4.90 3.61 3.31 2.20 0.17 0.03 0.398 4.17 4.08 7.0 7.6 6.4
0,001%
* (NH4)2SO4 was added after the measurement and before culturing.
The use of squalene in doses of 0.0005-0.001% as an additive in a nutritional

mixture prepared on the basis of anolyte, promoted activation of the growth and
reproduction of the strain S. fibuligera Y-436 (Table 6). The number of cells
increases by 1.6-1.7 times with the use of squalene in doses of 0.0005-0.001% after
48 hours of incubation. The biomass of the strain increased by 23.3-34.9 %, and the
total weight of the product (sediment weight) – by 5.8-8.7 %.
Table 6. The number of cells of S. fibuligera Y-436 and sediment weight

(experiment 4)
Sediment weight, g l-1
Variant total biomass
24 h 48 h 48 h
Control 80.8 122.5 173.0 43.0
Squalene 0,0005% 76.0 195.0 188.0 58.0
Squalene 0,001% 77.8 212.5 183.0 53.0
* initial number of cells in the hydro-module is 8.0 ∙106 cc-1 .
Conclusions
The phenomenon of growth activation of the industrial strain of S. fibuligera Y-436
under the influence of squalene and anolyte water results from the faster adaptation
and use of substrate by the strain and acid reaction of the medium, optimal for
growth and reproduction mycelial fungus. Squalene had a stimulating effect on the
growth of the strain S. fibuligera Y-436 under aerobic conditions as on the YEPD
Broth and on the nutritional mixture based on wheat flour in all doses. The
stimulating effect of squalene was maintained on YEPD Broth for 54 hours, in a
dose of 0.0005 % - up to 78 hours of the strain cultivation. The growth rate of the
strain in the exponential phase of growth between 4 and 6 hours on medium with a
squalene of 0.0005 % is 0.30, 0.001 % - 0.44, 0.002 % - 0.41, while on medium
without squalene - 0.24. Squalene reduces the duration of its lag-phase of growth by
2-4 hours. The biomass of the strain and the total weigh of the product increased by
1.6-2.2 times and 1.2-1.4 times. Squalene had a rather strong influence on the
physicochemical parameters of the nutritional mixture based on wheat flour and the
growth of the strain S. fibuligera Y-436. Due to the shift in pH to the acid side, the
strain used substrates and absorbed oxygen more rapidly. The additive of squalene
increased the number of cells by 2.2-2.3 times with the use of squalene in doses of
0.0005-0.001 % after 24 hours and by 1.4 times after 48 hours. With the use of
squalene, the strain reached the stationary phase after 24 hours, while in the control
variant - after 48 hours, thereby reducing the time of passage through the growth
phase. This reduces the duration of cultivation by 2 times. This fact is important for
the decrease of energy consumption and the reduction of fodder protein production
cost. The most optimal electrolyzed water for the preparation of a nutritional
mixture based on the wheat flour for the strain of S. fibuligera Y-436 was anolyte.
Anolyte water contributed to the rise of generative activity of the strain due to the
acid reaction by 34.3 % in comparison with the initial water. The most effective
method of activation of the strain is the combined use of anolyte water and squalene
in a dose of 0.0005-0.001 %.

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INQUIRY INTO THE POTENTIAL USE OF IONIC LIQUIDS

INSTEAD OF INORGANIC ACIDS IN HYDROTHERMAL HYDROLYSIS
OF MACROALGAE
Konstantza Tonova, Madlena Lazarova
Institute of Chemical Engineering – Bulgarian Academy of Sciences, Acad. G. Bonchev Str.,

Bldg. 103, 1113–Sofia, konstantzatonova@yahoo.com, Bulgaria
Abstract
Macroalgae represent a worldwide spread renewable source of valuable
biopolymers, polysaccharides and proteins that after pretreatment constitute an
intermediate platform for microbial and chemical production. In the present study
the potential of some ionic liquids (ILs) to extract and hydrolyze the algal
carbohydrates derived from Ulva sp. is examined and compared to the conventional
inorganic acid catalysts, H2SO4 and HCl. The experimental results reveal that the IL,
1-butyl-3-methylimidazolium acetate, is superior to both acid auxiliaries in
extracting carbohydrates. The capacity of this IL for splitting reducing sugars under
the conditions of hydrothermal hydrolysis is comparable with the power of HCl, but
higher than HCl in terms of monosugar fraction and protein released. The highest
yields of reducing and monosugars and of protein are obtained by using the strong
dibasic acid, H2SO4. It could, however, produce dehydration by–products which
would incur inhibition of enzymatic and microbial processes fed by the algal liquor.
Keywords: alga, carbohydrate, hydrothermal hydrolysis, ionic liquid, Ulva sp.
Introduction
Ionic liquids (ILs) are molten salts assembled only by ions, usually a charge–
stabilized organic cation and an inorganic or organic anion. ILs display physical
properties unusual for common one–component molecular solvents, such as
negligible vapor pressure and high thermal stability. The chemical reactivity towards
the plant cellulose matrix, by stoihiometric H–bonding interactions between the
cellulose and the IL’s ions (Dong & Zhang 2012, Bogdanov & Svinyarov 2013),
makes the ILs exceptional solvents for cellulose dissolution. However, the effects of
the ILs on the plant material pretreatment aimed at biopolymers’ degradation have
been barely investigated so far.
The present study is a research for potential ILs that could simultaneously enhance
the extraction and catalyze the hydrolysis of natural biopolymers (polysaccharides
and proteins) so that valuable platform chemicals (simple sugars and amino acids) to
be derived from renewable biomass feedstocks. The subject of the study is a
widespread marine green macroalgal species, Enteromorpha linza (Guiry 2018).
Previously Park and Jeong 2013 studied the hydrothermal hydrolysis of Saccharina
japonica alga by ILs as catalysts. It was found that the hydrophilic ILs with acidic
– –
anions, [BF4] or [HSO4] , are able to split the polysaccharide chain and produce
–
reducing sugars to the same extent as the inorganic acid catalyst, H2SO4. The [BF4]

anion, however, is prone to undergo hydrolysis (Freire et al 2010) and not the IL
itself but the released hydrofluoridric acid is mostly responsible for the catalytic
action. Acidic conditions were also recommended for the extraction of the main
polysaccharide of the green algal species, ulvan (Robic et al 2009, Yaich et al 2014).
The ILs based on acetate anion have been recently proved effective in pre-treating
lignocellulosic material prior to enzymatic conversion to monosugars (Raj et al
2018, Husson et al 2018). In these studies the plant material has been immersed and
incubated in pure ILs. Here, minimizing the IL’s amount, we use dilute solutions for
hydrothermal hydrolysis of Ulva alga biomass. It has been recently reported that the
Ulva sp. has the highest potential for economic income among the photosynthetic
organisms, including macroalgae, microalgae and terrestrial plants, based on the
prices of extractable and purified monosaccharides (Robin et al 2018 a, b).

1-Butyl-3-methylimidazolium acetate, [C4C1im]Ac, of high purity (>99%) and
tetrabutylphosphonium chloride, [P4,4,4,4]Cl (>95%), were purchased from IoLiTec
(Heilbronn, Germany). The inorganic acids were puriss. p.a., H2SO4 was supplied by
Sigma–Aldrich, HCl was a domestic product (Bulgaria). The substances required for
the analyses, phenol, DNS, Folin–Ciocalteu’s reagent, Rochelle salt, Na2CO3, NaOH
were all of analytical grade.
The Enteromorpha linza alga was harvested on 27th of June 2017 from a rocky
shore at the Elenite, Bulgaria (lat. of 42° 42ʹ 3.66ʺ N; long. of 27° 48ʹ 28.43ʺ E). It
was rinsed with tap water, dried to the air and sun, and grinded until the particles
passed through a 70 mesh sieve.
The powdered alga was subjected to solid–liquid extraction–hydrolysis in a
laboratory autoclave at 121 °C for 40 min. The process was carried out at solid–to–
liquid ratio of 1:25 (w/v). The liquid phase was distilled water or an aqueous
solution of the catalyst, 0.06 mol dm-3 of the acid or the IL.
After autoclaving the solid phase was sunk by centrifugation at 10 000 rpm for 15
min. The liquid phase was subjected to quantitative analyses for total carbohydrates
(Dubois et al 1956), reducing sugars (Miller 1959), monosaccharides by HPLC
equipped with a RI detector (LC–25 Perkin Elmer) and Aminex HPX–87H column
(mobile phase 0.005 M H2SO4 at a flow rate of 0.6 ml/min, 65 °C), total protein
(Lowry et al 1951) and total phenolics (Waterhouse 2001).
The initial carbohydrate content of the dried Enteromorpha linza alga was also
assayed following the phenol–sulfuric acid protocol (Dubois et al 1956) and was
determined to be 23.4% (w/w).

Two ILs were selected to be studied and compared with the inorganic acids used in
extraction and hydrolysis of algal polysaccharides. The one was [C4C1im]Ac which
is exploited in lignocellulose pre-treatment, as it was discussed above. The other
was [P4,4,4,4]Cl, a cheap IL which was chosen because of the acidic pH of its aqueous
solution at the given concentration (pH = 2.09). The aqueous solution of
[C4C1im]Ac at the same concentration has pH = 5.56. These ILs solutions were
compared to the aqueous solutions of HCl (pH = 1.20) and H2SO4 (pH = 1.13) with
respect to the effect on the extraction extent and the efficiency of hydrolysis of the
polysaccharide derived from the autoclaved Enteromorpha linza alga.
Carbohydrate extraction
Enteromorpha linza alga contains ulvan as the main polysaccharide, which is a
sulphated rhamnoglucuronan (Rioux & Turgeon 2015). The total carbohydrate
content of the extracts is the primary indication for the polysaccharide recovery.
Figure 1 represents the percentage amount of the extracted carbohydrates regarding
the total carbohydrate content of the dried alga (23.4% w/w). First of all, the
supreme capacity of the IL, [C4C1im]Ac, to withdraw carbohydrates from the algal
matrix should be highlighted. The highest extraction degree of total carbohydrates
(TCH), 99.3%, was attained in the case of [C4C1im]Ac–treated alga.
Total carbohydrate (TCH) extraction
100%
(% of the dried alga content)
80%
TCH in the extract
60%
40%
20%
0%
Acid or IL solution, 0.06 mol dm-3
Figure 1. Effect of the acid or IL added on the extraction of algal carbohydrates
Lower contents of TCH were yielded in the liquor by treating the alga with acids
solutions, even when the dibasic H2SO4 was used. The TCH extraction in the
presence of HCl was substantially less effective (70.1%) and only the half of the
algal carbohydrate content was extracted in the case of the IL, [P4,4,4,4]Cl, similarly
to the reference case of distilled water. Despite the acidic pH of the aqueous solution
of [P4,4,4,4]Cl, the extraction was not positively affected.
Carbohydrate hydrolysis
Reducing sugar and monosugar contents
Further, the degree of polysaccharide hydrothermal hydrolysis in the presence of
acids and ILs was evaluated by measuring the fraction of reducing sugar content.
Results are displayed in Figure 2A. As it was expected, the dibasic acid, H2SO4
which is a donor of two reactive protons, exerted the most powerful hydrolytic
action on the polysaccharide chain. 81.1% of the extracted carbohydrates responded
to the analysis for reducing sugars. A smaller fraction of reducing sugars, 29.5%,
was obtained by using the monobasic acid catalyst, HCl. Based on the total
carbohydrate content of the dry alga, the fraction of reducing sugars yielded in the
extract with the aid of [C4C1im]Ac was ca. 20%, which was comparable to that one
hydrolyzed by HCl catalyst. This reveals the potential of the IL, [C4C1im]Ac, to play
a double function as an extractant for the polysaccharide and a catalyst for its
hydrolysis.
The share of the monosugars in the whole reducing sugar content was estimated
based on the HPLC analysis. Two peaks appeared on the chromatogram and they
were attributed to glucose and rhamnose monosugars. The sum of their
concentrations was used to calculate the monosugar fraction. Results are presented
in Figure 2B. More than the half of the reducing sugar content released by H2SO4
was estimated to be the fraction of monosugars. Interestingly, the hydrolysis by
[C4C1im]Ac also gave a substantial monosugar fraction which was even higher than
the one obtained by the acid, HCl. This unravels the potential of [C4C1im]Ac not
only to extract, but also to hydrolyze the algal carbohydrates directly to simple
sugars. The yield in the case of [C4C1im]Ac exceeded the maximal yield of reducing
sugars reported for Enteromorpha intestinalis alga (14.3% on the basis of TCH)
obtained under much more severe hydrothermal conditions which require a
temperature of 170 °C and a pressure of 7.94 bar (Kim et al. 2014). Here, with much
less energy input the algal polysaccharide was totally extracted and partially
converted to simple sugars. The hydrolysis could be accomplished either through
optimization of the IL’s concentration or by post–hydrothermal enzymatic
hydrolysis. As a whole, the treatment by H2SO4 resulted in the greatest production
of reducing and monosugars, but it was shown to be associated with the increase in
the formation of dehydration by–products, such as 5-HMF and levulinic acid
(Meinita et al 2012). These by–products, however, are known to inhibit both the
post–hydrothermal enzymatic hydrolysis (Kim et al 2014) and the microbial growth
and production (Larsson et al 1999).
Protein content
Besides the polysaccharides, the crude protein derived from macroalgae can
additionally enhance the nutritional value of the algal liquor. Proteins that occur in
the plant material are usually combined with polyphenolics in complexes.
Quantitation of protein has proved to be difficult because the majority of standard
methods (A280, Lowry assay, Bradford assay, bicinchoninic acid assay) are
susceptible to the functional phenolic groups both present in the polyphenols and in
the aromatic amino acids of the proteins (Hagerman 2012).

(A) - Reducing sugar (RS) fraction (B) - Monosugar (MS) fraction

100% 100%
% of the extracted TCH % of the extracted RS
% of the dry alga TCH % of the dry alga TCH
80% 80%
RS content in the extract
MS content in the extract

60% 60%
40% 40%
20% 20%
0% 0%
Acid or IL solution, 0.06 mol dm-3 Acid or IL solution, 0.06 mol dm-3
Figure 2 (A-B). Effect of the added acid or ILon the hydrolysis of the
polysaccharide. (A) – reducing sugar fraction; (B) – monosugar fraction
First the extracts from Enteromorpha linza alga were assayed for the presence of
polyphenols (Waterhouse 2001, Singleton et al 1999). Minor polyphenol amounts
were detected. The concentration of the H2SO4–extract was 0.128 g dm-3, while in
all the others it was ≤ 0.071 g dm-3. The low polyphenolics content gave us the
opportunity to obtain some rough results about the protein content by using Lowry
method which was shown to be more suitable for a similar case (Redmile–Gordon et
al 2013). The protein concentrations of the algal extracts are shown in Figure 3.
Protein extraction
0.5
Protein concentration of the extract [g dm-3]
0.4
0.3
0.2
0.1
Acid or IL solution, 0.06 mol dm-3
Figure 3. Effect of the acid or IL added on the extraction of proteins

Expectedly, the combination of a strong acid (H2SO4) and a high temperature

(during the autoclaving) caused a severe destruction of the algal tissue that resulted
in biopolymers’ release. Although the concentration of the total protein extracted
was low, it can be seen that the IL, [C4C1im]Ac, has the potential to withdraw the
proteins from the material. The amount extracted by this IL was almost double
compared to the water extraction and significantly greater than by the acid, HCl. As
it was already discussed, the Ac–anion is able to break any kind of H–bonds down,
including those of protein carboxyl groups, thus probably making the protein
extraction easier (Dang et al 2018).
Conclusions
The experimental results showed the supremacy of the IL, [C4C1im]Ac, over the
both acid auxiliaries (H2SO4 and HCl) in algal carbohydrate extraction. 99.3% of the
total carbohydrate content of the Enteromorpha linza alga was recovered in the
liquor. The capacity of [C4C1im]Ac for splitting reducing sugars under the
conditions of hydrothermal hydrolysis is comparable with those of HCl, but superior
to HCl in terms of monosugar release and protein yield. As it was expected, the
highest concentrations of reducing and monosugars were obtained by using the
strong dibasic acid, H2SO4. However, the formation of dehydration by–products,
such as 5-HMF and acids, in addition to the low pH (= 1.43), would inhibit the next
biological processes, the enzymatic hydrolysis to fulfill the monosugar composition
or the microbial production fed by the algal liquor. Contrary, the extract derived
from the alga pretreated by [C4C1im]Ac has a neutral pH (= 6.58) thus providing a
favorable condition for microbial processes. Moreover, the content of the total
protein released additionally increases the nutritional value of the must. These first
results reveal the potential of the ILs, specially [C4C1im]Ac, as pH neutral
extractants and catalysts for valorization of macroalgae as renewable sources for
microbial and chemical production. Future studies will be carried to investigate the
ILs effects on the selectivity of extraction from algal material and on its post–
hydrothermal enzymatic hydrolysis.
Acknowledgement
The authors thank Prof. Dr. Daniela Dzhonova-Atanasova heartily for providing the
Enteromorpha linza alga.
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KINETIC ANALYSIS OF MANGANESE REMOVAL FROM MINE WATER

- CONTINUOUS FLOW REACTION SYSTEM
Laurentiu Razvan Dinu1, Valeriu Robert Badescu1, Viorel Ion Patroescu1, Gabriela Geanina
Vasile1, Voicu Oncu2
1
National Research and Development Institute for Industrial Ecology-ECOIND, 71-73 Drumul
Podu Dambovitei, district 6, 060652, Bucharest, tehnologi@incdecoind.ro, Romania
2
SC CEPROMIN SA, Str. 22 Decembrie nr. 37A, Deva, office@cepromin.ro, Romania
Abstract
Manganese removal from mine water by oxidation-precipitation often requires
significant contact time and the use of a high pH-value for reaction stage. In order to
avoid reactor over sizing or under sizing, kinetic data for manganese oxidation using
mine water or very similar aqueous systems are needed. As the batch type tests can
be difficult to control (e.g. to set a certain pH value during the start-up), the
continuous flow reaction systems seem to be more reliable as the direct
determination of reaction rate is possible in this case.
Results obtained using manganese sulphate solution and real mine water are
presented here. A third order reaction rate law was obtained, taking into account
homogenous and heterogeneous mechanism.
Keywords: mine water, manganese, reaction rate
Introduction
Often manganese is present in mine water from few ppm to hundreds of ppm and is
associated with sulphate. Manganese is typically difficult to be removed from water
using the conventional treatment with calcium hydroxide and aeration. Sometimes
oxidizing agents are proposed. With aeration, raising the working pH above 10.0
will greatly improve the reaction rate and will also favor the precipitation
mechanism, but a pH adjustment step (e.g. with HCl or better with CO2) is to be
introduced (Dinu et al 2014, Hallberg & Johnson 2005, Janneck et al 2013).
Moderate pH values of 9.0 to 9.5 can be used instead, depressing the reaction rate.
The rate law is to be known as it is needed for a proper reactor design.
The rate of Mn oxidation and precipitation has been found to increase with
concentration of dissolved Mn and with the abundance of Mn-oxide and hydroxide
surface. At a given pH and abiotic, the reaction rate is described by equation
-d[Mn(II)]/dt = k1•[Mn(II)] + k2•[Mn(II)]• [MnOx] (1)
where [Mn(II)] is the concentration of dissolved Mn2+ species; [MnOx] is the surface
area of Mn oxide precipitate; t is time; k1 and k2 are rate constants.
The Mn oxidation is autocatalytic, because precipitated solids accelerate manganese
oxidation. Since the term [MnOx] depends on the reaction advance {[Mn]initial -
[Mn]final} the law is of second order in [Mn]. This type of equations are often
referred as Stumm & Morgan dependencies (Morgan & Stumm 2005, Stumm &
Morgan 1996, Means et al 2005, Von Langen et al 1997).

Batch tests can be used to obtain the kinetic law using differential or integral
methods (Levenspiel 1999), but, in this case, the time needed to set a constant pH
and also the time needed to filter the heterogeneous reaction mixture, comparable
with reaction time intervals between samples, will lead to inaccurate results.
By using continuous flow systems, such as continuous stirred reactors (CSTR,
known also as mixed flow reactors) it is possible to directly determine the apparent
reaction rate corresponding to the working condition and to the working reactant
concentration.
For an ideal stirred tank reactor operating at steady state the mass balance for
constant density is (Levenspiel 1999, Davis & Davis 2003).
(CA,0 - CA) = - τ • rA (CA,) (2)

where CA,0 is the inflow concentration and CA is the reactor concentration for the
component A, τ = V/Q is the space-time and rA(CA) is the reaction rate, which is a
function of CA.
So, knowing the inlet and outlet concentration and also the flow rate and volume,
the reaction rate corresponding to the outlet concentration (equal to any point in the
reactor concentration, for this type of circulation) can be calculated. This will be the
apparent reaction rate, as it depends on mass transfer intensity. Steady state regime
is mandatory and the time required to be achieved depends on the space-time, τ.
Evaluation of the overall reaction kinetics from flow-through tests is used by some
researchers (Dietz et al 2002). An experimental study has been carried out to assess
manganese oxidation-precipitation reaction using model solution (MnSO4) and real
mine water.

The water treatment system comprised a cascade of two continuous flow stirred
reactors (R1, V1 = 2.5 L and R2, V2 = 15 L). Each reactor reactor was equipped with
mechanical mixer, 3 blades pitch blade turbine (diameter to tank equivalent diameter
ratio = 0.3), variable speed n = 0-2000 rpm, medium bubble aeration difusers and
with individual pH control assembly (PID) with dosing pump for lime milk. Water
was pumped with a centrifugal pump Iwaki Direct Drive Pump RD-05-HCV 24-05
and the flow rate was measured by a rotameter (Figure 1).
In order to avoid non-ideality, measurements of residence time distribution were
done for various mixing speed values and flow rates, using the posive step
perturbation (NaCl step tracer addition) and with continuous recording of electrical
conductivity which further on allows the calculation of the concentration using
calibration data. This way the residence time distribution E(t) - exit age distribution
and the integral residence time distribution F(t) could be appraised.
Manganese sulphate solution and the mine water were subjected to treatment using
the laboratory continuous flow set-up described above.
When changing the parameters, e.g. pH, initial concentration, flow rate (to change
the space-time), the system was allowed to work for at least 6 times of total system
space-time to reach the new steady-state and samples were drawn from reactors,
immediately filtered (0.45μm) and preserved using HNO3. Manganese concentration
was determined using AAS (Solar M6 Dual Thermo Electron).

DAQ-
PC
P102 P103
V102
Ca(OH)2 A102
V103
A101 Ca(OH)2
V101
P101 Reactor Reactor

EIC R1 R2
201
Figure 1. Continuous flow laboratory set-up

Mine water was sampled from a Romanian manganese ore mining perimeter and
analyzed for the main specific chemical parameters (Table 1 and 2). This mine water
is characterized by a circum-neutral pH and a low content of iron and low iron to
manganese ratio (approx. 0.04 mg/mg in this case, typically 0.04 to 0.10 mg/mg
according to our long term records).
Table 1 -Mine water characterization
PARAMETER UNITS VALUES
PH pH units 6.5
ELECTRICAL
mS/cm 1.47
CONDUCTIVITY
CCO-MN mg O2/L 19.3
SO42- mg/L 989
CL- mg/L 5.2
NO3- mg/L 2.6
NA+ mg/L 8.7
CA2+ mg/L 153
MG2+ mg/L 78.5
Table 2. Mine water characterization regarding heavy metal content

Parameter Units Values Parameter Units Values
Mn, omg mg/L 170.5 Cr, total, omg mg/L 0.373
Fe, filtr. mg/L 0.074 Cr, total, filtr. mg/L 0.041
Fe, omg mg/L 6.10 Cu, filtr. mg/L 0.043
Al, filtr. mg/L < 0.05 Cu, omg mg/L 0.043
Al, omg mg/L 0.201 Ni, filtr. mg/L 0.646
As, filtr. mg/L <0.001 Ni, omg mg/L 0.754
As, omg mg/L <0.001 Pb, filtr. mg/L 0.007
Cd, filtr. mg/L < 0.001 Pb, omg mg/L 0.007
Cd, omg mg/L 0.0013 Zn, filtr. mg/L 0.316
Co, filtr. mg/L 11.917 Zn, omg mg/L 0.349
Co, omg mg/L 14.652
Note: omg = homogenous sample; filtr. = filtered sample (0.45 µm)


Following the residence time distribution tests, we could ascertain that the flow
characteristics are close to ideality for mixing speed values above 400 rpm for the
two CSTR model reactors (illustrated for R1, n = 100 rpm in Figure 2 and for n =
400 rpm in Figure 3).
Figure 2. Residence time distribution for R1 (function E for n =100 rpm, τ = 300s)
Figure 3. Residence time distribution for R1 (function E for n =400 rpm, τ = 300s)
The apparent reaction rate values were determined versus manganese exit
concentration using the mass balance equation (2) for temperature t = 21oC and
various pH values (8.5 to 10.0, with emphasis on pH = 9.5), while the oxygen
concentration was maintained at 7 mg/L.
The best correlation representing the experimental kinetic data was found to be a
third order polynomial mathematical model (equation 2),
-d[Mn(II)]/dt = k’1•[Mn] + k’2•[Mn]• (k3• [Mn] initial - [Mn])2 (3)
which coefficients account for:

k1 - the contribution of homogenous mechanism,

k2- heterogeneous mechanism catalyzed by the reaction products (manganese oxo-

hydroxide), which depends on the reaction advance ([Mn] initial - [Mn]final) and also a
correction coefficient k3 for the proportion of active solid manganese species versus
total manganese precipitate (non dimensional, subunit).
Equation (3) is equivalent with
-dX/dt = k’2 X3 - 2k’2k’3C0•X2 + (k’1 + k’2 k’32 C02)•X (4)

where X is the manganese concentration.
The results are shown in Figure 4 for the MnSO4 model solution (2mM) and in
Figure 5 for the mine water. Data were compared with kinetic data calculated using
Stumm & Morgan equations, results being similar to a limited extent for low
manganese concentration values.
35
y = 0.0019x3 - 0.0517x2 + 0.5187x

30
R2 = 0.9975
Reaction rate, mg Mn/L/min
25
20
15
10
0
0 5 10 15 20 25 30 35 40
c(Mn), mg/L
Stumm&Morgan Experimental Experimental-trend
Figure 4. Reaction rate for manganese precipitation using MnSO4 solution (c(O2) =
7 mg/L, pH =9.5, t = 21oC)
Reaction rate for manganese oxidation-precipitation is higher for the mine water
versus the manganese sulphate solution, most probably due to higher solids
formation, including manganese precipitates, but also iron oxohidroxides in the case
of the mine water.

35
y = 0.0094x3 - 0.2469x2 + 2.205x

30
R2 = 0.9912
Reaction rate, mg Mn/L/min

25
20
15
10
0
0 10 20 30 40
c(Mn), mg/L
Stumm&Morgan Experimental Experimental-trend
Figure 5. Reaction rate for manganese precipitation from mine water (c(O2) = 7
mg/L, pH =9.5, t = 21oC)
The rate law obtained herein is applicable for medium manganese concentration
values (tens of ppm), thus could be used to assess the volume requirements for
treatment if using a reaction system containing one reactor or two CSTR in series
and also plug-flow reactors, with very useful engineering results.
Conclusions
The mixed-flow reactor model was used to evaluate the kinetic rate of the
manganese precipitation for model solution and for mine water. The apparent
reaction rate values fit a third order polynomial mode. After further pilot level
kinetic investigations for the rate law validation, the model will be used for mine
water treatment reaction systems on higher level. It can be recommended to
establish rate laws using onsite continuous pilot level trials for any mine water
source, because of strong dependance on the reaction rate to specific factors,
including iron content, iron to manganese ratio and also because of the availability
of mine water with real temperature.
Acknowledgements
The publishing of this work was supported by the Competitiveness Operational Program 2014
– 2020, Action 1.2.3 "Partnerships for Knowledge Transfer", Project: ID P40_300; Contract
55/05.09.2016 ; SMIS 2014+ 105581, Sctr. 01530/2017.
References
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Edition. McGraw-Hill Higher Education, New York
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Using Recirculated Iron Oxides In A Complete Mix Reactor', Proceedings of
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Lexington, KY, pp 496-516.

Dinu, L, Stefanescu, M, Balaiu, I, Cosma, C, Cristea, I & Badescu, V 2014, 'Acid

Mine Water Treatment Using High Density Sludge Technology', Journal of
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in Natural Waters, Wiley Interscience, New York.

NANOSCALE IRON PARTICLES FOR WASTEWATER

DECONTAMINATION
Eugenia Panturu1, Razvan Ioan Panturu2, Gheorghita Jinescu3, Antoneta Filcenco – Olteanu1,
Aura Daniela Radu1
1
National Research & Development Institute for Metals and Radioactive Resources-ICPMRR,
70 Carol I Blvd., 0209917, Bucharest, ioanpanturu@yahoo.com, Romania
2
Honeywell, 169A CaleaFloreasca, 014459, Bucharest, Romania
3
University Politehnica of Bucharest, Chemical and Biochemical Engineering Department,
Polizu Street no.1-6, Bucharest, Romania
Abstract
This paper described the equilibrium and the kinetic of uranium adsorption from
waste water using activated carbon without/with nano-iron impregnated, applying
batch method. Adsorption isotherms of uranium equilibrium are analysed with
Freundlich isotherms which reveal high affinity to activated carbon impregnated
with nano-iron compared to nonimpregnate. Kinetic study showed that the decisive
step of the uranium adsorption process rate is the intraparticle diffusion.
Keywords: activated carbon, adsorption isotherms, diffusion, nano-iron, uranium
Introduction
A wide range of methods are available for removal of heavy metal ions from
aqueous solutions. These include ion exchange, solvent extraction, reverse osmosis,
precipitation, filtration, electrochemical treatment, adsorption etc. The most studied
and applied method was the adsorption process. A number of researchers have used
a variety of adsorbents to remove heavy metal ions from aqueous solutions such as
activated carbon, bentonites, zeolites, iron oxides, clays etc. (Akperov &
Maharramov 2010, Alic & Manea 2013, Bratkova & Angelov 2013, Erust & Sahin
2014, Mas Haris & Abdul Wahab 2011, Oprčkal & Mladenovič 2017, Hu & Wang
2011). Research on the radioactive pollutants removal from the wastewater by
adsorption processes using nano-iron or nano-iron impregnated solid support, gain a
more general interest. In the early 1990s, the reducing capabilities of metallic
substances, such as zero-valent iron, began to be examined for their ability to treat a
wide range of contaminants in hazardous waste water. The small particle size and
high surface area to mass ratio make iron nanoparticles highly reactive and
extremely versatile. The high surface area and surface reactivity compared with
granular forms enable the nanoparticles to remediate more material at a higher rate
and with a lower generation of hazardous by-products (Zhang 2003). The ability of
the nanoparticles to act as strong reducers also enables the remediation of an
extremely wide range of contaminants. It proved to be particularly suitable for the
decontamination of halogenated organic compounds, but subsequent studies have
confirmed the possibility of using zero-valent iron in aim to the reduction of: nitrate,
bromated, chlorate, nitro aromatics compounds, brominates pesticides. Zero-valent
iron proved to be effective in removing arsenic, lead, uranium and hexavalent
chromium (Alvarado & Rose 2010, Dickinson & Scott 2010, Gheju 2011,
MacFarlane & Payton 2014, Mamadou & Duncan 2013, Eglal & Ramamurthy 2015,
Panturu et al 2010, and Panturu et al 2011). In 1997 Wang and Zhang (Wang &
Zhang 1997) first produced the nanoscale iron particles in the laboratory using the
method of sodium borohydride reduction. This work aimed to study equilibrium and
kinetics of adsorption of uranium from wastewater, using as adsorbent material
simple activated carbon Purolite AG 20 G and impregnated with nano-iron.

Synthesis of activated carbon Purolite type AG 20 G (from Purolite Company,
Romania) impregnated with nano-iron was done by the method of reduction of iron
ions (III) by sodium borohydride in the presence of sodium hydroxide, resulting in a
coal with a nano-iron content of 5.99%. To study the equilibrium of the U (VI) ions
adsorption process, well-defined quantity of activated carbon Purolite type 20G AG
without/with impregnated nano-iron was put in contact with solutions, in the glass
bottles containing uranium with varying initial concentration, C (g U L-1), a solid:
liquid ratio of 1:10 (wt.). The solutions pH, determined with a pH meter InoLab was
adjusted to 8 ± 0.2 values. Samples were kept under stirring at constant temperature
25 ± 1 ºC in a thermostat type bath shaker to achieve balance. The two phases were
separated by filtration. Scanning Electron Microscopy method was made with an
electronic microscope Quanta Inspect F and particle size analysis was performed
with Zetasizer Nano ZS ZEN device 3600. The analyses have highlighted the
absence and presence of iron nano-particles (average size of 211.5 nm) on the
activated carbon (Figure 1-2).
Figure 1. Activated carbon – initial structure and composition
Figure 2. Nano-iron on activated carbon, structure and composition

Adsorption Isotherms
Freundlich isotherm (Khan 2012), which describes processes detention of U (VI)
ions on adsorbent materials, used for this study, is described by the Equation (1):
(1)
where qe (g U kg -1) is the amount of adsorbed material retained on adsorbent unit,
Ce(gUL-1) is the equilibrium concentration of the contaminant in aqueous solution
and Kf and n are Freundlich constants which correspond to adsorption capacity.
For interpretation of the balance (Figure 3) was used Freundlich isotherm in the
linear form Equation (2):

(2)
Figure 3. Isotherms for the uranium adsorption on activated carbon Purolite type
AC 20 G without/with nano-Fe° impregnated
The Figure 4 and Figure 5 show the Freundlich isotherms for uranium adsorption on
activated carbon Purolite AC 20 G without respectively with nano-Feº impregnated.
The slope (1/n) and Kf intercepts of the two isotherms (log qeversus log Ce) are
determined. After determining the constants Kf and n, Freundlich equations for the
two cases are given in Equation (3) and Equation (4):
Activated carbon non-impregnated with nano-Feº
(3)
Activated carbon impregnated with nano-Feº
(4)
Figure 4. Freundlich isotherm for the adsorption of uranium on activated carbon

Purolite AC 20 G non-impregnated with nano-Feº

Figure 5. Freundlich isotherm for the adsorption of uranium on activated carbon

Purolite AC 20 G impregnated with nano-Feº
R2 correlation coefficients of 0.9439 and respectively 0.9893 and constant values

show that both isothermal experimental data fit well.
The Gibb’s free energy (ΔG º) is calculated to evaluate the thermodynamic
feasibility of the process (Bhattacharya 2006). The standard free energy can by
calculated using Equation (5):
(5)
Where R (J mol-1 K-1) is the universal gas constant, T (K) is the absolut solution
temperature and Kd is the distribution coefficient, calculated by Equation (6):
(6)
The negative value of ΔGº (-7.734 kJmol-1 for non-impregnated activated carbon
with nano-Feº, respectively -8.294 Kjmol-1 for impregnated activated carbon with
nano-Feº) establish the feasibility of the sorption process and the spontaneous nature
of the adsorption with a high preference of uranium on the activated carbon
impregnated with nano-Feº.
Intraparticle diffusion
Experimental data obtained from kinetic studies for the two materials (Figure 6)
were processed by applying the Shell Progressive Model for establishing the rate
decisive step of the adsorption process.
Figure 6. Kinetic curves for the adsorption of uranium on activated carbon Purolite
AC 20 G without/with nano-Feº impregnated

According to the model, the process rate decisive steps are:

External diffusion - Equation (7) :
(7)
Internal diffusion - Equation (8) :
(8)
Chemical reaction - Equation (9) :
(9)
where t (s) is the time, to (s) is the time needed for the reaction to be complete and X
(%) is the conversion of activated carbon (progressive achievement of adsorption
equilibrium; ratio of adsorption capacity at time, t and maximum adsorption
capacity). In Figure 7 and Figure 8 are showed the kinetic equations test results for
the three rate decisive steps corresponding of the two types of materials.
In both cases, the chemical reaction and the diffusion through the outer liquid film
of the grain are excluded as process rate limiting steps, because their graphic
representation is not a straight line for any of the studied coal type.
Figure 7. Kinetics of adsorption of uranium and testing of model equations for Shell
progressive model for activated carbon Purolite AC 20 G non-impregnated with
nano-Feº
0,12
0,1
0,08
0,06
G(X)
0,04
0,02
0
0 20 40 60 80 100
time, minute
external diffusion chemical reaction internal diffusion
Figure 8. Kinetics of adsorption of uranium and testing of model equations for Shell
progressive model for activated carbon Purolite AC 20 G impregnated with nano-Feº
Linear regression results for the two cases are presented in Table 2 intersection
values, slope and linear correlation were determined by MathCAD program.
Table 2. Linear regression values for the batch experiment

Applied Criteria value
Experiment Intersection Slope
function Gauss,Ω
X 3.1×10 -2 1.176×10 - 3 3.716×10 - 4
AC 20G 1 – (1 – X) 1/3 10 – 2 4.089×10 - 4 4.294×10 - 5
2/3
1 – 3(1 – X) +
4.157×10 - 4 4.981×10 - 5 1.799×10 - 7
2(1 – X)
X 2.612×10 - 2 1.08079×10- 3 2.72023×10 - 4
AC 20G with
nano-Feº 1 – (1 – X) 1/3 8.805×10 - 3 3.74092×10- 4 3.11364×10 - 5
2/3
1 – 3(1 – X) +
2.797×10 - 4 4.10146×10- 5 7.28861×10-8
2(1 – X)
Linear regression results for internal diffusion, as the rate limiting step of the
process, shows a high correlation. Ω functions, adequate of each rate decisive
equations represent the standard deviation of experimental values toward the
calculated values. The equation for the minimum of the Ω function is the equation
which fit best with experimental data, so is the equation which describing kinetic of
process. Notice that for the external diffusion and chemical reaction, the deviations
are much higher (of order 10 - 4 and 10 - 5) towards the deviations for the internal
diffusion which are of order 10 -7 or 10 - 8. The slope values were used to calculate
diffusion coefficients using the equation for controlling intraparticle diffusion
process. The calculating values of diffusion coefficients are presented in Table 3.
These values have size grades in accordance with data presented by other authors
referring to cations retention on different supports (Allen & Mckay 1989, Weber &
Morris 1963).
Table 3. The calculated values of diffusion coefficients

Type activated carbon Diffusion coefficient, m 2s -1
Activated carbon Purolite AC 20 G non-

1.61 × 10 - 12
impregnated
Activated carbon Purolite AC 20 G
1.75 × 10 - 12
impregnated withnano-Feº
Conclusions
This paper described the equilibrium and the kinetic of uranium adsorption from
waste water (from the uranium industry), using activated carbon without/with nano-
Feº impregnated, applying batch method. For the interpretation of experimental
results was used Freundlich model. Calculated values of Freundlich isotherm
constants and correlation coefficients R2 0.9439 for activated carbon Purolite AC 20
G non- impregnated and respectively 0.9893 for activated carbon Purolite AC 20 G

impregnated with nano-Feº prove the favourable adsorption of uranium on the two
solid supports. The negative standard Gibbs energy calculated using distribution
coefficient of uranium and spontaneous adsorption establish that the impregnation of
iron increase the selectivity of activated carbon for uranium and therefore its
retention capacity. Kinetic study (applying the Shell progressive model) showed that
intraparticle diffusion is the rate decisive step for uranium adsorption process. The
diffusion coefficient value for activated carbon Purolite AC 20 G impregnated with
nano-Feº is greater than for activated carbon non-impregnate, so in the first case,
mass transfer resistance is lower and the adsorption process arise easier.
References
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cross-linked allyl propionate-maleic anhydride-styrene terpolymer’, Turkish
Journal of Chemistry, vol. 34, pp.99–108.
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of zero-valent iron’, Journal of Environmental Monitoring, vol. 12, pp.1524-
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different adsorbents’, Chemical Engineering Journal, vol. 123, pp. 43-51.
Bratkova, S & Angelov, A 2013,’Biotechnogical removal of heavy metals from
mining wastewaters by dissimilative sulphate reduction’, Revista Minelor, vol.
19, no. 3, pp. 22-28.
Dickinson, M & Scott, TB 2010,’The application of zero-valent iron nanoparticles
for the remediation of a uranium-contaminated waste effluent’, Journal of
Hazardous Materials, vol. 178, pp.171-179.
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Urban Mining’, Recycling Industry,vol.78, no.3, pp. 74-78.
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Aquatic Systems’, Water Air Soil Pollution, vol. 222, pp. 103-107.
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cross-linked magnetic chitosan resin: Isotherms, kinetics and
thermodynamics’, Journal of Hazardous Materials, vol. 185, pp. 306-314.
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equilibrium constant expression’, Turkish Journal of Chemistry, vol. 36, pp.
219-231.
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NEW LABORATORY TECHNIQUES ON SOIL DECONTAMINATION
Maria Popa, Loredana Irena Negoita
University of Petroleum – Gas of Ploiesti, Bd. Bucuresti, 39, 100680, Ploiesti,

mariapopa2007@gmail.com, irena.negoita@gmail.com, Romania
Abstract
The paper presents a study on the possibility of electrical decontamination of soils
contaminated with liquid petroleum products. The study involves the
characterization of a soil type by: capillary, permeability, retention and
granulometry. Electrically polluting is done with the help of stainless steel
electrodes arranged radially in a vessel. The pollutant-diesel oil product was
characterized by density and viscosity. The experiment had a duration of one week
and determined the degree of polluting and the influence of polluting soil on it.
Also, the germinating potential on such a depolarized soil was verified.
Keywords: diesel oil, electrode, soil
Introduction
The soil chosen for the study is a brown soil that has been characterized in the
laboratory. The pollutant used in the study, a liquid petroleum product, was
characterized by representative physical properties, which give information on
penetration into the soil structure.
Choosing the method of polluting contaminated soil with liquid petroleum products
should take into account several factors. Several types of soils and various methods
of polluting at the laboratory level have been studied (Popa & Negoita 2016, Popa &
Onutu 2016, Popa et al 2017). Among the methods of depollution applied at
laboratory level less studied is the electrical method (Han et al 2004, Li et al 2018,
Lycenko et al 2018, Ren et al 2014, Risco et al 2016a). Starting from literature data
(Streche et al 2014) a device has been designed which involves the existence of
electrodes mounted inside the soil sample polluted with a liquid petroleum product.

Soil preparation for analysis consisted in drying it, thus establishing the water
content. The physical properties were determined on the devices presented below
(Patrascu et al 2008). The soil capillary capacity was determined on the device in
Figure 1.
The soil permeability was determined on the device of Figure 2. At the same time
the soil retention capacity could be calculated.

Figure 1. Experimental assembling for capillary determination (Patrascu et al 2008)

1-tube glass; 2-layer earth; 3-front moisture; 4-liquid supply vessel; 5-clamp; 6-
vessel with constant liquid level; 7-nozzle overflow; 8- collector vessel.
Figure 2. Experimental installation for permeability determination (Patrascu et al

2008) 1-pot supply; 2-clamp; 3-tube Wolff; 4-spout jet; 5-layer soil; 6-cylinder
graduated; 7-collector vessel.
The device on which granulometric distribution was determined is shown in Figure

3.
Figure 3. Experimental assembling for granulometry determination (Patrascu et al

2008) 1-sieves; 2-elastic clamping struts; 3-vibrator system.
The electrical depollution was done on the experimental assembly shown in Figure
4.
a b
Figure 4. Experimental installation: a-electrodes arrangement; b-general assembly.
The method of depollution used was the electrical method. Laboratory-based

electrodeposition technique was carried out on an experimental assemblage
involving the use of stainless steel electrodes, a cathode and eight anodes inserted
into the soil polluted with the petroleum product according to a recommended model
in the literature (Risco et al 2016 b). The cathode was immersed in the center of the
soil surface and the anodes were submerged radially on the soil surface as in Figure
4a. Two supply voltages for electrodes, 5V and 12V, were chosen. The polluted
sample was periodically wetted and the vessel was provided with a bottom hole,
through which water and the petroleum product were collected.

Capillarity is the property of the soil to allow a pollutant to penetrate vertically, from
bottom to top, into the soil structure. The wet layer height was set for both water and
petroleum products – Diesel oil, measured from 10 to 10 minutes for one hour. The
results obtained are shown in Table 1.
Table 1. Measured values for soil capillarity

1. Soil type Brown soil
2. Liquid Water Diesel oil
3. Hu,10, mm 29 37
4. Hu,20, mm 36 56
5. Hu,30, mm 43 68
6. Hu,40, mm 52 85
7. Hu,50, mm 55 89
8. Hu,60, mm 60 99
Permeability is the property of the soil to allow the upstream pollutant to penetrate,
so the soil retention capacity can also be established. Also, determination was made

for both water and petroleum product. The permeability was calculated from 15 to
15 minutes and an average was determined, Pm.
Pτ= Vτ∙60/τ (1)
where Vτ - volume of liquid filtered through the layer during t = 15, 30, 45, 60
minutes, cm3. The results obtained are presented in Table 2. The retention capacity
was calculated with relation (2).
CR= (mf-mo)∙103/Vstrat (2)
where, mo - the mass of the dry soil sample, g and mf the soil sample mass at the
end, g, the volume of soil layer, cm3.
Table 2. Results obtained for permeability and retention capacity

Soil type Brown soil
Liquid Water Diesel oil
P15, cm3/h 1100 100
P30, cm3/h 1080 104
P45, cm3/h 1055 90
P60, cm3/h 876 89
Pm, cm3/h 1028 96
CR, kg/m3 450 325
Granulometry is the percentage distribution of soil particles, which is achieved by

the sieve method. The results are shown in Table 3.
Table 3. Granulometric distribution of soil

Sieve Sieve 2 Sieve Sieve 4 Sieve 5 Sieve 6
Soil type 1 0,49 3 0,12 0,088 0,06
1,5 mm 0,2 mm mm mm
mm mm
Brown mi, g 55 32 6 5,3 1,2 0,5
soil % 55 32 6 5,3 1,2 0,5
The physical properties of the pollutant that influence the penetration into the soil
structure are density and viscosity. They were determined at several temperatures,
20, 40 and 60 oC.
Table 4. The properties of petroleum product
Density Viscosity
Temperature, ºC
ρ, kg/m3 µ∙106, kg/ms
20 840 5,1
40 820 4,1
60 813 3,2
The physical properties of diesel oil have led to a complex definition of the soil-
polluting system, to conclusions on the penetration of the pollutant into the soil
structure. Controlled pollution of a soil with petroleum product has taken place.
Experimental results after electrical depollution are shown in Table 5.

Table 5. The results of electrical depollution

Electrical voltage, V
The day of 5V 12V
collection 5% pollutant 10% pollutant (200 ml)
Volume of Volume of Volume of Volume of
water, ml pollutant, ml water, ml pollutant, ml
1 0 - 0 0
2 15 - 180 5
3 70 - 260 12
4 140 - 335 22
5 160 - 420 28
6 180 - 480 36
7 220 - 560 40
Degree of
depollution, % - 20
Figure 5. The collected volumes of water and pollutants at 10% and 12 V
1. The polluted product with 5% diesel oil was watered with water for five days and
for another two days the sample was left under the action of electric current at 5V
without watering. After one week the collected water was measured. It was found
that at this concentration of pollutant and with the voltage of 5V was not collected
and petroleum product.
2. The sample was polluted with 10% diesel oil and the electrical voltage was
increased to 12V. He was also watered with water for five days and another two
days operated under electric current. Compared to the initial volume of 200 ml of
diesel, a volume of 40 ml of diesel was collected, together with water, which means
a degree of depollution of 20%.
For the verification of the germination potential, three samples, coded as in Figure 6,
were prepared, where 1 - pure soil sample, 2- electrically depolluted soil, 3 - soil
polluted with 10% pollutant.

Figure 6. Verification of germination potential
Conclusions
The electrically polluting method is the only method to recover the pollutant.
Increasing the voltage used (from 5V to 12V) and the concentration of petroleum
product (from 5% to 10%) leads to the idea of obtaining a higher degree of
depollution.
The electric method can be successfully applied to soils with low permeability and
high retention capacity and high capillary capacity.
Only 20% can be explained by the fact that the duration of action of the electrodes
on the soil sample was only one week.
As far as the germination potential verification is concerned, it can be restored only
in the presence of clean soil mixed with the one undergoing the electrical
depollution method.
As future research directions, the authors consider changes: concentrations and
thermal voltages, soil types, types of electrodes.
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NUMERICAL MODELING OF FLOW OVER AN OGEE SPILLWAY AND

INVESTIGATION OF EFFECT OF DOWNSTREAM INFLUENCES ON
DISCHARGE
Ali Yıldız1, Alpaslan Yarar1, Şerife Yurdagül Kumcu2
1
Selcuk University Civil Engineering Department, 369 Akademi Mah. Yeni Istanbul Cad.,
42130, Selcuklu-Konya, aliyildiz@sekcuk.edu.tr, ayarar@selcuk.edu.tr, Turkey
2
N. Erbakan University Civil Engineering Department, yudagulkumcu@gmail.com, Turkey
Abstract
The main aim of this study was to investigate flow over an ogee spillway and
simulating by numerical model. A commercially available computational fluid
dynamics (CFD) program, which solves the Reynolds-averaged Navier-Stokes
equations (RANS), was used to model the physical model setup. Flow over an ogee
spillway has free surface and turbulent flow so that in some cases calculating flow
rate and flow depths are difficult. Increasing in water level at downstream may
cause reduce in discharge because of suction forces and negative pressure. In this
study, different numerical turbulence models are used to predict discharge and
compared with experimental results. In experiments, discharge and flow depths of
physical model were recorded for 22 different total head over the crest. The results
show that there is reasonably good agreement between the physical and numerical
models for discharges.
Keywords: degree of submergence, downstream influence, numerical modeling,

Ogee spillway
Introduction
Dams are built for water storage, floods control and energy production. Generally a
dam construction consists of foundation, body, dam reservoir, spillway, bottom
outlet and water intake structures. Spillways are one of the most important dam
structures in terms of dam safety. Spillways transfer excess water, coming to the
dam reservoir, to the downstream safely without damaging dam and other structures.
Many failure of dams have been caused by improperly designed spillway are
insufficient spillway capacity (Bradley 1952). Hydraulic design of the spillways is
done with some graphical and analytical methods. In some cases design of the
spillways is made with physical models. At design stage of hydraulic structures, the
small-scaled physical models are constructed to observe the behavior of water and
determine the problems that may be encountered. However, preparing physical tests
models requires professional labor work. Moreover, experimental studies may be
more expensive, take longer time and have scale effect.
Although the main reason for the need for dams do not vary past today, significant
steps were achieved in dam construction by progressive engineering techniques and
computer technologies. Computational Fluid Dynamics (CFD) is a type of numerical
modeling technique developed to solve fluid mechanics problems. CFD investigates

fluid-fluid and fluid-solid interactions behavior. Applicability of CFD to spillway

design is great advantage of hydraulic engineering due to its features (Cederstorm
1998). Although solution of numerical models take a long time in the computer,
results such as free surface profile, velocity and discharge which cannot be obtained
from one and two dimensional models can be easily examined in 3-Dimensional
models. CFD can be used in many areas where fluid flow is present.

Ogee spillway design
The relationship of the ogee crest coefficient, Co, to various values of P/H, is shown
on Figure 1. These coefficients are valid only when the ogee is formed to the ideal
naple shape; that is, when He/Ho = 1 (Maynord 1985). Discharge coefficient ratio
C/Co continues to increase with He/Ho (as shown in Figure 1) up to maximum value
of head ratio (He/Ho). With a narrower crest shape, negative pressures along the
contact surface will occur, resulting in an increased discharge. Figure 1 shows the
variation of the coefficient as related to values of He/Ho, where Ho, is the actual head
being considered.
Figure 1. Determining discharge coefficient for flow over an ogee spillway
The general equation (1) for discharge over an ogee crested spillway is given as
(USBR 1987):
Q=Co*L*Ho1.5 (1)
where Q is the total discharge, L is the lateral crest width, Co it the crest coefficient
and Ho=total head upstream from crest.
In some cases, discharge coefficient, C decreases because of submergence.
Submergence can result excessive tail water depth. The effect of tail water
submergence on discharge coefficient changes depending on degree of submergence
defined by hd/He (shown in Figure 2).
Figure 2. Tail water submergence
Two different flow type can be occur after ogee spillway, depending on the position
of apron and downstream water surface. These situations are a submerged hydraulic
jump and no jump may occur. When the submerged hydraulic jump occurs, the

decrease in the discharge coefficient is caused by the back-pressure effect. Figure 3

shows the effect of downstream apron conditions on discharge coefficient.
Figure 3. Ratio of discharge coefficients caused by tail water effects.
Physical Modeling (Experimental Study)

A physical model of a typical ogee spillway was fabricated from plexiglas and
placed in open channel. Design head and crest height of ogee spillway are choose
H0=14,4 cm and P=28 cm respectively. General shape and dimensions of spillway
can be seen in Figure 4.
Figure 4. Ogee spillway used in experiments
The open channel which made of tempered glass is 6 m long, 0.6 m wide and 0.5 m
height with zero tangential slope. The open channel is contracted to 0.3 m in region,
to get higher heads over the ogee spillway. The open channel has a closed water
loop system and flow to the channel is supplied from reservoir by pump. Pumps
send water from reservoir-1 to reservoir-2 by pipes and water coming to reservoir-2
passes to channel. Discharges values are measured by Ultrasonic flow meter which
placed on pipe coming from pumps. Total heads over the ogee spillway is
determined with limnimetre. General view of the open channel system can be seen
on Figure 5.

Figure 5. General view of the open channel system
Numerical Modeling-Flow-3D
The flow over the spillway was modeled by Flow-3D VOF-based CFD program and
uses finite-volume approach to solve the Reynolds Averaged Navier Stokes (RANS)
equations (Flow Science 2002). The program evaluates the location of the flow
obstacles by implementing a cell porosity technique called as the fractional
area/volume obstacle representation of FAVOR method. The computational domain
is subdivided using Cartesian coordinates into a grid of variable-sized hexahedral
cells. The general governing RANS (3) and the continuity equations (2) for an
incompressible flow, including the FAVOR variables, are given by
where ui is the velocities in x-y-z direction, t is time, Ai is fractional areas open to

flow, VF is volume fraction of fluid in each cell, ρ is density of fluid, p is hydrostatic
pressure, gi is gravitational forces, fi represent the Reynolds stresses.
Boundary conditions are determined in accordance with real experiments to
represent physical model accurately in numerical model. There are six different (+X,
-X, +Y, -Y, +Z, -Z) boundaries on the main grid system because of flow domain is
defined as a hexahedron. The upstream boundary condition (-X), where water is
supplied to channel and behave as reservoir, is defined hydrostatic pressure. This
hydrostatic pressure is entered to Flow-3D as a height and it creates a total head over
the ogee spillway. Therefore, varying total heads over the ogee spillway is provided
by changing hydrostatic pressure value at (-X). Downstream boundary condition (-
X), in other words end of the channel is defined as output. On the top boundary (+Z)
defined as atmospheric pressure and the bottom boundary (-Z) defined as wall. Side
walls (-Y, +Y) is defined symmetric.
In the numerical analysis two different mesh plane system were used. Firstly a mesh
plane is generated to cover all system which have same dimensions with real
physical model and the cell size of the mesh is chosen as Δx=Δy=Δz=0,01 m. Total
number of the cells was calculated as 770000. Analysis duration of numerical model
takes too long time, when effect of the turbulence flow and total mesh number are
considered. In experimental study, measurements are conducted for 22 different
total heads and discharge values. One analysis takes 6 hour to complete and get
steady-state solution. Therefore, mesh plane is contracted to middle of channel to
make a solution with lower number of cells. However there are two questions arises
“Will side walls affect the flow characteristic?” and “Will contracted mesh plane
affect turbulent forces. To answer these questions, analyses conducted with two
different mesh plane on model as seen Figure 6.
a) Mesh solution-1 with 0.3 m same as channel width
b) Mesh solution-2 with 0.1 m smaller than channel width

Figure 6. Two different mesh solutions
Second mesh plane is generated as cover middle section of channel. With of the
second mesh plane is set 10 cm smaller than first mesh plane which has 30 cm
width. The total number of cells in second mesh plane was calculated as 170500.
However side walls conditions (-Y, +Y) is defined different from first mesh. Side
wall conditions defined as Symmetry to remove effect of wall frictions on fluid
flow.

The physical model carried out in the laboratory and the numerical model analyzed
by Flow-3D were compared and discussed in terms of total heads (He) over the ogee
spillway, tail water heights and corresponding discharges (Q) (Figure 7).

Figure 7. General schema of physical experiment and measurement points (He:

Total head over ogee, H1: Tail water height)
The main objective of the comparison of the physical model with the numerical
model was to determine how much numerical model is successful for predicting
flow rate under effect of tail water submergence. Firstly, performances of two
meshes systems are evaluated. According to results there is no significant difference
between mesh systems in terms of total head and discharge values. By using
contracted mesh planes, analysis time is shortened from 6 hours to 0.5 hours.
Table 1. Results obtained from models

PHYSICAL MODEL NUMERICAL MODEL
He(m) H1(m) Qexperimental (l/s) He(m) H1(m) Qmodel (l/s)
0.024 0.113 1.98 0.017 0.124 1.67
0.043 0.121 4.93 0.049 0.140 6.60
0.064 0.131 9.80 0.059 0.151 9.06
0.067 0.132 10.56 0.070 0.156 11.61
0.081 0.142 14.17 0.079 0.163 13.74
0.085 0.151 15.52 0.088 0.167 17.16
0.091 0.152 17.88 0.098 0.180 20.43
0.095 0.157 19.29 0.107 0.185 23.67
0.099 0.161 21.00 0.117 0.204 27.24
0.104 0.171 22.84 0.125 0.210 30.99
0.110 0.166 24.18 0.135 0.223 35.04
0.116 0.173 27.43 0.142 0.240 39.03
0.123 0.183 30.10 0.154 0.250 43.29
0.127 0.187 32.04
0.130 0.196 33.02
0.137 0.205 37.01
0.145 0.210 40.31
0.150 0.218 43.51
0.158 0.222 45.50

Table 1 shows total head over the ogee spillway and discharges values get from
numerical and physical model. To make a more objective comparison between
models results are showed on graph. Figure 8 shows comparison of total head vs.
discharge values for both model and Figure 9 shows comparison of tail water depths
vs. discharge values.
Figure 8. Comparison of total head results over ogee spillway get from numerical
and physical model
Figure 9. Comparison of tail water heights which causes submergence effect
Total head (He) results given by numerical and physical model are compatible with
each other. Flow-3D is very successful predicting total heads (He) and related
discharge values. Also contracted mesh system worked very good to analyze
physical model and provide time saving. However tail water results get from models
don’t show good agreement with each other as total heads show. Reason of these
differences is high turbulences effects at this region. Measuring tail water flow
depths in physical experiments are not correct one hundred percent because of
waving of water surface. Although waving of water surface, Flow-3D give
acceptable results and water surface profile (Figure 10).

Figure 10. Water surface profile get from Flow-3D
Conclusions
Results obtained experiments showed that the discharge values obtained by Flow-
3D were good agreement with physical model. This study showed that the numerical
tools using RANS equations are sufficiently advanced to simulate a flow over an
ogee spillway.
References
Bradley, JN 1952, Discharge Coefficients for Irregular Overfall Spillways, United
States Department of the Interior Bureau of Reclamation (USBR), Denver,
Colorado.
Cederstorm, M 1998, ‘CFD modeling of spillway capacity- A comparison between
hydraulic and mathematical models’, Dam Safety, Balkema, Rotterdam.
Flow Science 2002, Theory manual of Flow3-D, Flow Science, Los Alamos, NM.
Maynord, ST 1985, General Spillway Design, US Army Corps of Engineers
(USACE), Washington DC.
United States Department of the Interior Bureau of Reclamation (USBR) 1987,
Design of Small Dams, A Water Resources Technical Publication, Washington
DC.

OXIDATION OF SULPHUR SPECIES ON ACTIVE CARBONS:

THE SUGGESTED MECHANISM
Raisa Nastas, Vasile Rusu, Tudor Lupascu
Institute of Chemistry of Academy of Sciences of Moldova, 3 Academiei, MD-2028, Chisinau,

ichem@asm.md, nastasraisa@yahoo.com, Republic of Moldova
Abstract
The oxidation of sulphur (II) species with oxygen in the absence of catalysts is very
slow, due to the unfavourable symmetry of the spin state resulting from the different
electronic configurations of the reactants. Among the efficient catalysts for the
oxidation of sulphur (II) species the activated carbons are indicated, being able to
change the electronic configuration of the reactants (S(II) or O2).
The type of the products and intermediates formed during the oxidation process with
oxygen depends largely on pH, reagents concentrations (S(II), oxygen), and the type
of the activated carbon (as catalyst).
In this work the experimental results were corroborated with literature data, and
plausible mechanism or reaction scheme was suggested for each case of active
carbon used.
Keywords: active carbon, mechanism, oxidation, sulphide ion
Introduction
Oxidation of sulphur (II) species has a complex stoichiometry because of the broad
spectrum of products and meta-stable intermediates produced during the reaction,
including colloidal sulphur Sn, octarhombic elemental sulphur S8, thiosulphate ions
S2O32-, sulphite ions SO32-, poly-sulphides S42-, S52-, tetrathionate ions S4O62-,
sulphate ions SO42- (Alferova & Titova 1969, Chen & Morris 1972, Hoffman 1977,
O’Brien & Birkner 1977, Kotronarou & Hoffman 1991, Dalai et al 1999, Avrahami
& Golding 1968, Lefers et al 1978). The reaction mechanism of oxidation of sulphur
(II) species in water by oxygen and the nature of the products strongly depend on the
pH of the solution according to literature data (Alferova & Titova 1969, Chen &
Morris 1972, O’Brien & Birkner 1977, Kotronarou & Hoffman 1991, Dalai et al
1999, Avrahami & Golding 1968).
For the oxidation of sulphur (II) species in neutral, weakly alkaline and weakly acid
solutions the following reaction scheme has been proposed (Chen & Morris 1972):
2HS- + O2 → 2S + 2OH- (1a)
HS- + (x-1)S → H+ + Sx2- (1b)
where S denotes the colloidal sulphur.
The formed polysulphide (Sx2-) can react with oxygen to produce several products
(Chen and Morris 1972):

(2)
For pH>11 the following reaction scheme was proposed (Avrahami & Golding
1968):
2HS- + 3O2 → 2SO32- + 2H+ (3a)
2SO32- + O2 → 2SO42- (3b)
2SO32- + 2HS- + O2 → 2S2O32- + 2OH- (3c)
2S2O32- + O2 → 2SO42- + 2S (3d)
Thiosulphate ions are very stable at this pH value and oxidation to sulphate ions is
very slow (Avrahami & Golding 1968).
Overall, the oxidation of sulphur (II) species with oxygen in the absence of catalysts
is very slow, due to the unfavourable symmetry of the spin state resulting from the
different electronic configurations of the reactants (Alferova & Titova 1969, Chen &
Morris 1972, Hoffman 1977, O’Brien & Birkner 1977, Kotronarou & Hoffman
1991, Dalai et al 1999, Avrahami & Golding 1968, Lefers et al 1978).
Among the efficient catalysts for the oxidation of sulphur (II) species the activated
carbons are indicated, being able to change the electronic configuration of the
reactants (S(II) or O2) (Steijns & Mars 1974, Adib et al 1999, Mikhalovsky &
Zaitsev 1997, Primavera et al 1998, Klein & Henning 1984, Katoh et al 1995,
Cariaso & Walker 1975, Bagreev et al 2001, Lupascu & Cater 1997, Choi et al
2008, Li et al 2008, Bandosz, 2006).
The type of the products and intermediates formed during the oxidation process with
oxygen depends largely on pH, reagents concentrations (S(II), oxygen), and the type
of the activated carbon (as catalyst).
Generally, it is considered that on the surface of active carbon the hydrogen sulphide
can be oxidized to elemental sulphur and/or sulphur dioxide. In the presence of
activated carbons as catalysts, the sulphur is frequently shown as the major product,
especially when the pH of the active carbon surface is higher than the hydrogen
sulphide dissociation constant (pKa 7.3) (Alferova & Titova 1969, Dalai et al 1999,
Steijns & Mars 1974, Adib et al 1999, Mikhalovsky & Zaitsev 1997, Primavera et al
1998, Bagreev et al 2001, Lupascu & Cater 1997, Steijns et al 1976, Bagreev et al
2000, Adib et al 2000), while the sulphur species S4+ and S6+ are recorded in smaller
amounts (about 30%) (Adib et al. 1999, Mikhalovsky & Zaitsev 1997, Bagreev et al
2001, Adib et al 1999, Bagreev & Bandosz 2001).
The mechanism of formation of elemental sulphur and SOx species is determined
largely by the acid-base properties of activated carbon and their surface pH in

suspension (Adib et al 1999, Bandosz, 2006). It is considered that the first step is the
catalytic activation of oxygen on free active centres on the surface of active carbon
(Adib et al 1999).
The source of active oxygen on the active carbon surface is considered either the air
oxygen (Bagreev et al 2000, Lupascu et al 2014), the functional groups on the
surface (Lupascu et al 2014, Mikhalovsky & Zaitsev 1997) or the chemisorbed
oxygen (Adib et al 1999, Mikhalovsky & Zaitsev 1997).
The pH value influences the type and quantities of sulphur species formed during
oxidation with oxygen in aqueous media (Alferova & Titova 1969). In the pH range
7-14 the main oxidation product is thiosulphate, up to 45-60%. At low pH values
poly-thionic acids are formed in small quantities and their content decreases with
increasing pH, lacking in solution at pH 8.9. Sulphite ions are formed at pH higher
than 8. Overall, it appears that sulphite ions, thiosulphate and sulphate ions are
formed in significant quantities at pH>10-11 (Alferova & Titova 1969).
The aim of this work was to corroborate the experimental results with reported
literature data, and to suggest a plausible mechanism or reaction scheme for each
case of active carbon used.

A series of active carbons with different surface chemistry have been used for
oxidation of sulphur (II) species in water solutions (Table 1).
Table 1. Characterisation of active carbons

pH of
Sample characterization
suspension
CAP23, initial (R. Moldova) from peach stones 5.2
CAPO23, oxidized oxidized with nitric acid 4.6
CAPO23Cu (0.4 meq Cu2+/g) impregnated with copper ions -
CAPO23Fe (0.8 meq Fe3+/g) impregnated with iron ions -
CAP23-NiO (0.5 meq Ni2+/g) impregnated with nickel oxide -
BAU-A, commercial (Russia) from birch wood 10.0
The experiments were performed by using lab installation provided with an air
bubbler and recovery flask for aerated hydrogen sulphide at appropriate parameters,
i.e. solid/liquid ratio, aeration flow rate, pH of the medium, initial concentration of
sulphur (II) species (Nastas 2006). Elemental sulphur, thiosulphate, sulphite and
sulphate ions, and aerated hydrogen sulphide from recovery flask were determined
by standard methods (Standard methods for the examination of water and
wastewater 1999). All sulphur species were recalculated as H2S.

Studies show that as the oxygen content increases on the surface of the active
carbons, both by concentration in functional groups and by chemisorbed oxygen
(comparison of initial (CAP23) and oxidized (CAPO23) samples), the oxidation of
the hydrogen sulphide species is increased and is promoted to higher oxidation
degrees of sulphur (Table 1 and 2) (Lupascu et al 2014).

Table 2. Sulphur species formed in the process of oxidation of Sulphur (II) in the
presence of activated carbons (Experimental details were reported earlier by
Lupascu et al 2014)
Sulphur species formed in the process of oxidation, %
Sample
S0 colloidal S2O32- SO32- SO42-
CAP23 20.4 0 12.5 67.1
CAPO23 6.1 11.7 15.4 65.9
BAU-A 32.9 32.9 4.5 31.2
CAPO23Fe 0 16.1 17.7 66.2
CAPO23Cu 0 9.3 32.7 58.1
CAP23-NiO 95.5 4.8 0 0
To be noted the important role of acid-basic properties of active carbons, influencing

dissociation and oxidation of sulphur (II) species onto different species of sulphur
(Adib et al 1999). The more acidic is the carbon surface, the greater is the proportion
of sulphur oxidized to S4+ and S6+ species (Adib et al 1999). For CAP23 and
CAPO23 samples the surface pH is acidic, 5.2 and 4.6 respectively, while the
surface pH of BAU-A carbon is alkaline, reaching pH 10, which causes different
mechanisms of oxidation processes on their surfaces (Table 1). It appears that S(IV)
and S(VI) species prevail if the sulphide oxidation is carried out in the presence of
oxidized activated carbon (CAPO23) which contains significantly more carboxylic
groups on the surface as compared to their quantities on the surface of un-oxidized
sample (CAP23) (Table 2) (Lupascu et al 2014).
For acidic surface of active carbons (pH <pKa for H2S), the content of
hydrosulphide ions on the surface is low, i.e., the case of oxidized active carbon
CAPO23 (or active carbons obtained by chemical activation method with
phosphoric acid). In this case, it is supposed that sulphur is present in the form of
free radicals on the surface of active carbon, which are easily oxidized to sulphur
oxides (Steijns & Mars 1974, Adib et al 1999, Hoffman 1977), the suggested
mechanism being:
HS-(ads) + C(O) → C(S*) + OH- (4a)
C(S*) + O2 → SO2(ads) + Cf (4b)
SO2(ads) + ½O2 → SO3(ads) (4c)
SO3(ads) + H2O(ads) → H2SO4(ads) (4d)
H2SO4(ads) + H2S → SO2 + 2H2O. (4e)
For basic active carbons (pH> pKa for H2S), i.e., the case of commercially available
active carbon BAU-A, the concentration of the hydrosulphide ions on the surface is
higher, leading to formation of the stable ortho-rombic sulphur (colloidal sulphur,
Sx) (Adib et al 1999, Steijns et al 1976):
2HS-(ads) + C(O) → C(SSH) + OH- (5a)
C(SSH) + HS- → C(S2SH2) → C(Sx). (5b)
Impregnation of active carbons with transition metals modifies the catalytic
properties of samples (Andreev et al 1996, Lupascu et al 2014, Mikhalovsky &
Zaitsev 1997, Li et al 2008, Bouzaza et al 2004, Huang et al 2006). Oxidation rate of
sulphur species in the presence of CAP23-NiO active carbon is much higher, being
by 2-2.5 times higher than in the presence of other samples (Lupascu et al 2014).
However, the major product of the oxidation in the presence of CAP23-NiO is
colloidal sulphur (up to 95%, Table 2). In the presence of active carbons CAPO23Fe
or CAPO23Cu oxidation products are thiosulphates, sulphites and sulphates
(Table 2). To be mentioned that in the presence of these catalysts colloidal sulphur is
not formed during oxidation.
In the presence of molecular oxygen, metal ions catalyze the oxidation of hydrogen
sulphide in aqueous solutions through redox processes (Chen & Morris 1972,
Kotronarou & Hoffman 1991, Katoh et al 1995):
2Fe3+ + HS- → 2Fe2+ + S + H+ (6a)
4Fe2+ + O2 + 2H+ → 4Fe3+ + 2OH-. (6b)
There are reported two possible mechanisms for the catalytic oxidation of hydrogen
sulphide species by transition metal ions, (i) either through the formation of free
radicals by electron transfer, or (ii) by the formation of metal-sulphide complexes
and the precipitation of sulphur (Chen & Morris 1972, Kotronarou & Hoffman
1991). The oxidation process of the hydrogen sulphide species in the presence of
Cu(H2O)62+ or Ni(H2O)62+, is initiated by the transfer of electron from the HS- ion to
the hexaaqua metal ion, forming the HS• hydrosulphide radical, which is further
oxidized by oxygen through the chain reaction (Kotronarou & Hoffman 1991):
Cu2+ + HS- → Cu+ + HS• (7a)

HS• + O2 → HSO2• (7b)
HSO2• + O2 → HSO4• (7c)
HSO4• + HS- → HSO4- + HS• (7d)
2HS• → H2S2 (7e)
H2S2 ↔ 2H+ + S22-. (7f)
The state or the form of immobilized metals on the surface of activated carbon
influences significantly the selectivity of formation of sulphur species. The catalyst
obtained by impregnation with nickel oxide (CAP23-NiO) exhibits considerably
higher catalytic activity and the major oxidation product is colloidal sulphur.
It is considered that catalytic activity of the samples, obtained by modification of
active carbons with nickel oxide, is due to the presence of the nickel hydroxide
phase (Andreev et al 1996). The reaction mechanism includes activation of the
oxygen molecule in the heterogeneous redox transformation process Ni2+↔Ni3+ and
the formation of HO2•- radicals:
Ni2+(OH)2 + O2 → Ni3+OOH + HO2•- (8a)
Ni3+OOH + HS- → Ni2+(OH)2 + S (8b)
HS- + HO2•- → S + 2OH-. (8c)
Conclusions
Studies show that as the oxygen content increases on the surface of the active
carbons, both by concentration in functional groups and by chemisorbed oxygen

(case of oxidized sample CAPO23), the oxidation of the hydrogen sulphide species
is increased and is promoted to higher oxidation degrees of sulphur.
Is noted the important role of acid-basic properties of active carbons, influencing
dissociation and oxidation of hydrogen sulphide to different species of sulphur.
Oxidized active carbon, CAPO23, is rich in acidic functional groups on the surface
and has a higher catalytic activity, therefore is more efficient compared to
commercial activated carbon BAU-A, which is poor in acidic functional groups and
has a basic pH of surface.
Active carbons modified with iron(III) and copper(II) ions (samples CAPO23Fe and
CAPO23Cu) show higher catalytic activity in the oxidation of sulphur (II) species,
compared to CAPO23 sample. Oxidation products are thiosulphate, sulphite and
sulphate ions, without the formation of colloidal sulphur, suggesting the mechanism
of catalytic oxidation of sulphur (II) species by free radical formation. The process
is initiated by the transfer of electrons from the hydrosulphide ion to the metal ion,
forming HS• radicals, which are further oxidized with oxygen through chain
reactions.
The state or the form of immobilized metals on the surface of activated carbon
influences significantly the selectivity of formation of sulphur species. Impregnated
metals in the form of ions favour the formation of sulphur in high oxidation degrees
(S4+ and S6+) while impregnated metals as oxides favour the oxidation of sulphide
ions to elementary sulphur. The catalyst obtained by impregnation with nickel oxide
(CAP23-NiO) exhibits considerably higher catalytic activity and the major oxidation
product is colloidal sulphur, suggesting the reaction mechanism which includes the
activation of oxygen molecule in the heterogeneous redox transformation process
(Ni2+↔Ni3+) and the formation of HO2•- radicals that convert hydrosulphide ions to
colloidal sulphur.
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PHOSPHATE REMOVAL FROM WASTEWATER BY USING LOW-COST

ADSORBENT MATERIALS
Oanamari Daniela Orbulet, Cristina Modrogan, Cristina Orbeci, Dancila Madelene
University Politehnica of Bucharest, Faculty of Applied Chemistry and Materials Science,

Analytical Chemistry and Environmental Engineering Department, 1-7 Polizu, Bucharest,
c_modrogan@yahoo.com, Romania
Abstract
The need to develop new technologies for removing and recovering phosphates from
wastewater has derived from increasing the demand for these sustainable
compounds, setting stricter limits for discharges in order to prevent eutrophication
of natural water resources, as well as tightening sludge disposal restrictions derived
from wastewater plants. Removing phosphates from domestic and industrial
wastewater and rationalizing the use of fertilizers in agriculture lead to reducing the
main factors driving the proliferation of aquatic vegetation and hence, the secondary
pollution of surface water. The subject of this work is part of an environmental issue
and proposes a method for wastewater depollution by using adsorption processes,
taking into account the technical and economic aspects, by using low-cost
adsorbents namely pumice stone and autoclaved cellular concrete (BCA). The
objectives of the present study were mainly to model phosphorus adsorption
processes using Langmuir and Freundlich classical isotherms and to understand the
influence of pH on these processes. For a complete description of the process,
isotherms were determined at pH values of 3 and 9, and mathematical processing of
experimental data was attempted based on the above mentioned models. Based on
the experimental results obtained, it is observed that the removal of phosphate ions
from the wastewater by adsorption processes on pumice stone and BCA is more
efficient at a strongly acidic pH, and the Freundlich thermodynamic model offers
better process behavior.
Keywords: adsorption, autoclaved cellular concrete, phosphate, pumice stone,

wastewater
Introduction
Surface waters contain a certain level of phosphorus in various forms, which is an
important component of living organisms. Excess phosphorus contained in receiving
waters leads to excessive algal growth (eutrophication). The phenomenon of
eutrophication usually decreases the water quality and as a result, it can significantly
increases the cost of water treatment (Archna et al 2012, Thiruvenkatachari et al
2008).
As is well known, currently, the eutrophication is one of the main problems in the
monitoring of water sources in industrialized countries. Because a small amount of
phosphorus can cause water contamination and accelerates the growth of algae and
other aquatic plants, effluent standards for phosphorus concentration are becoming
stricter. This is why wastewater needs removal of phosphate before it is discharged
into emissaries. The biological treatment for phosphate removal is a popular and
important method mainly due to reduced costs, but usually the effluent does not
meet strict standards to be discharged and, as a consequence, it requires further
treatment. Chemical precipitation is another approach used for phosphate removal
and usually has a high removal efficiency, but produces large amounts of sludge and
leads to the problem of secondary pollution. The advantage of the adsorption
process towards the biological and chemical approach is that it does not present their
problems (Blowes et al 2000, Yan et al 2010). Thus, developing an extremely
efficient adsorbent can lead to a promising method for removing phosphate
(Huichaoa et al 2011, Oguz et al 2003).
The pumice stone and autoclaved cellular concrete (BCA) are porous materials with
a high specific surface area (the pore volume reaching up to 85% in the case of
pumice stone) and a high silicon content (generally 60-75% SiO2) which gives them
excellent adsorptive properties. Moreover, these are low-cost and locally available
materials (Ayoub & Semerjian 2006, Weijie et al 2016).
According to NTPA 001/2002 and NTPA 002/2002 (Table 1), wastewater must
meet certain conditions before it is discharged to the emissaries.
Table 1. Limit values for phosphorus loading of industrial and municipal

wastewater
Admissible limit values,
Quality indicator Analysis method
mg/dm3
Total phosphorus 1 (2) SR EN 1189:1999
SR ISO 7825/1:1996
Synthetic detergents 0.5
SR ISO 7825/2:1996
According to the Technical Standard for Water Protection NTPA 002/2002, the limit
values for the loading of pollutants (phosphorus) of industrial and municipal
wastewater discharged into the sewerage networks of the localities and directly in
the wastewater treatment plants are in accordance with Table 1.

A series of adsorption experiments were carried out in this work in order to establish
the influence of some parameters such as the pH and phosphate concentration of the
initial solution, as well as the chemical composition of the adsorbents on the
adsorption efficiency. The experiments were carried out on two types of adsorbent
materials namely pumice stone and BCA at two pH values of 3 and 9 and at a mass
ratio of 1:10. The granule size of the adsorbent materials was between 0.063 and 2
mm.
The adsorption experiments involve contacting the samples of adsorbent material for
1 hour with the phosphate solution of variable concentrations of 10, 20, 40, 60, 80,
100 mg / L, to achieve the equilibrium. After 1 hour the suspension was filtered
(size filter of 0.45 μm) and the resulting solution was measured for concentration.
The resulting aqueous extract was analyzed on the X-ray spectrometer (Blank &
Eksperiandova 1998, Marguil et al 2009). The chemical composition of the
adsorbent materials (Table 2) and subsequent analysis of samples was performed by
XRF analysis (X-ray fluorescence).

Table 2. Chemical composition for pumice stone and BCA, XRF analysis
Composition SiO2, % Al2O3,% Fe2O3, % CaO, % MnO,% Others,%
Pumice stone 51.26 14.84 3.16 28.08 0.099 2.54
BCA 61.01 13.05 2.93 21.73 0.078 1.2
The energy spectra for the two adsorbents are shown in Figure 1 and Figure 2.
Figure 1. The energy spectrum for pumice stone
Figure 2. The energy spectrum for BCA

The equilibrium curves derived from experimental results are used to determine the
degree of retention of phosphorus on the two types of adsorbent materials (pumice
stone and BCA) using the Langmuir and Freundlich isotherms at a mass ratio of the
adsorbent material: water of 1:10, at pH 3 and pH 9. With Langmuir and Freundlich
isotherms, the Langmuir and Freundlich isotherms were constructed using linear

model regression models. Using the model parameters, computed by linear

regression, the Langmuir and Freundlich isotherms were drawn (Dada et al 2012).
Based on the adsorption isotherms describing the relationship between the adsorbed
phosphorus and its concentration at equilibrium in the solutions, the Langmuir and
Freundlich isotherms were drawn and the maximum adsorption (amax) and the
constant (K) relative to the adsorption energy were calculated. The Langmuir model
considers that retention results from the adsorption of the solute on an energy-
homogeneous surface, and the Freundlich model starts from the hypothesis of
reaching the chemical equilibrium when there is a dynamic exchange between the
molecules of the adsorbed phase and the one left in the solution. The relevant
parameters obtained using the Langmuir and Freundlich models are shown in Tables
3 and 4.
Table 3. Thermodynamic parameters for pumice stone
Langmuir Freundlich
pH K amax
R2 K m R2
(mg-1·L) (mg/kg)
3 0.134 1006.69 0.9174 141.939 0.597 0.9755
9 0.042 924.14 0.9204 67.82 0.594 0.9540
Table 4. Thermodynamic parameters for BCA

Langmuir Freundlich
pH K amax 2
R K m R2
(mg-1·L) (mg/kg)
3 0.087 859.20 0.8271 88.66 0.6188 0.9304
9 0.058 630.50 0.8209 68.369 0.5153 0.9047
According to the quadratic value of correlation coefficients (R2) the adsorption of

phosphate was better evaluated by the Freundlich model (R2 = 0.90÷0.97) than the
Langmuir one (R2 = 0.82÷0.92) for both of adsorbents. These results reflect the
surface heterogeneity of these adsorbents in relation with the active sites and their
energies.
The various phosphate anions in the solution are attracted by the positively charged
areas at the surface of the adsorbent material particles in accordance with the anion
exchange capacity.
Using the model parameters, computed by linear regression, the Langmuir and
Freundlich isotherms were drawn (Figures 3 and 4).

a) pH = 3 b) pH = 9
Figure 3. Langmuir and Freundlich isotherms for pumice stone at pH 3 and pH 9
a) pH = 3 b) pH = 9
Figure 4. Langmuir and Freundlich isotherms for BCA at pH 3 and pH 9
The data of the adsorption isotherms shown in these figures were fitted based on
these isotherms using the smallest squares method (R2 = 0.82÷0.97). The isotherm
graph, for the Langmuir and Freundlich model, represents the loading (the amount
of phosphate adsorbed) depending on the concentration of the phosphates in the
solution. The shape of the Langmuir isotherm is characterized in this case by an
initial abrupt sector, practically linear, followed by a curved middle sector. The
absence of the horizontal sector demonstrates the high availability of the adsorbent
material for the adsorption process. This trend is specific to the chemosorption and
physical adsorption phenomena where the adsorption is carried out in the
monomolecular layer.
At high concentrations of the phosphate ions in the solution, the adsorbent sorption
capacity is exceeded, and the isotherm is flattened. At low concentrations, the
isothermal slope can become abrupt, resulting in the normal Langmuir isotherms. In
the present case we have isotherms indicating pronounced adsorption.
Figures 3 and 4 illustrate the adsorption f phosphorus on the pumice stone and BCA.
It can be seen that the phosphorus retention equilibrium on the two types of
adsorbent materials can be mathematically described by Langmuir and Freundlich
thermodynamic models.
The adsorption isotherms express the specific relationship between the sorbent
concentration and the amount adsorbed on its surface under the given experimental
conditions. The phosphorus adsorption on the surface of the adsorbent materials is
determined by both the surface load and the protonation state of the phosphorus in
the crude solution. Laboratory studies on pumice stone and BCA have shown that
phosphorus sorption varies with pH (Loganathan et al 2014). Adsorption occurs not
only through adsorbent interactions with phosphate ions, but also through the
physical interferences between AlPO4 and the adsorbent surface (Zhou et al 2005).
Conclusions
The results of this study show that BCA and pumice stone are effective adsorbents
for the removal of phosphate ions from aqueous solutions. It has been found that the
amount of the phosphate adsorbed depends on the pH of the solution. Thus, the
removal of phosphate ions from wastewater through adsorption processes on pumice
stone and BCA is more effective at a strongly acidic pH, and the Freundlich
thermodynamic model offers better process behavior.
The phosphate adsorbed on BCA and pumice stone can be used in agriculture as a
fertilizer. Thus, developing an extremely efficient adsorbent can lead to a promising
method for removing phosphates.
By effectively acting to remove phosphorus from domestic and industrial
wastewaters and rationalizing the use of fertilizers in agriculture, the main factors
driving the proliferation of aquatic vegetation can be reduced, so the secondary
pollution of surface water can be also reduced.
In conclusion, equilibrium equations, in particular their parameters, can be input
data for mathematical models that describe the phosphorus behavior more fully
while the phosphorus adsorption process presents a complicated mechanism and can
be influenced by various factors.
References
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2000, ‘Treatment of inorganic contaminants using permeable reactive
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and Dubinin–Radushkevich Isotherms Studies of Equilibrium Sorption of Zn2+
Unto Phosphoric Acid Modified Rice Husk’, IOSR Journal of Applied
Chemistry, vol. 3, no.1, pp 38-45.
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‘A study of phosphate adsorption by different temperature treated hydrous
cerium oxides’, Rare Metals, vol. 30, no. 1, pp. 58.
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Environmental Science and Technology, vol. 44, no. 8, pp. 847-907.
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Fluorescence Analysis’, Encyclopedia of Analytical Chemistry.
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by adsorption’, Water, Air and Soil Pollution, vol. 148, pp. 279-287.
Thiruvenkatachari, R, Vigneswaran, S & Naidu, R 2008, ‘Permeable reactive barrier
for groundwater remediation’, Journal of Industrial and Engineering
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waste, crashed autoclaved aerated concrete, as a crystalline nucleus for the
removal of low concentration of phosphate’, Desalination and Water
Treatment, vol. 57, no. 30, pp. 14169-14177.
Yan, L, Xu, Y, Yu, H, Xin, X, Wei, Q & Du, B 2010, ‘Adsorption of phosphate
from aqueous solution by hydroxyl-aluminum, hydroxyl-iron and hydroxyl-
iron-aluminium pillared bentonites’, Journal of Hazardous Materials, vol.
179, pp. 244-250.
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39, pp. 1245–1254.

PHOTODEGRADATION OF RHODAMINE 6G IN PRESENCE OF Ag/TiO2

PHOTOCATALYST
Maria Harja1, Amalia Maria Sescu1, Lidia Favier2, Doina Lutic3, Gabriela Ciobanu1
1
“Gheorghe Asachi” Technical University of Iasi-Romania, Faculty of Chemical Engineering
and Environmental Protection, 73 Mangeron Blvd., 700050, Iasi, Romania
2
Superior National School of Chemistry of Rennes, Department of Chemistry, Rennes, France
3
“Alexandru Ioan Cuza” University of Iasi, 11 Carol I Blvd., 700506, Iasi,
amalia.sescu@ch.tuiasi.ro, Romania
Abstract
In this work, the commercial titanium dioxide P25 was doped with silver ions via
wet impregnation method, in order to improve its catalytic activity. It is already well
established that Ag ions can improve the activity of a catalyst and diminish the
electron-holes recombination rate. The catalysts obtained by samples calcination at
450 and 600oC were tested as heterogeneous photocatalysts in the degradation of
Rhodamine 6G, a very stable fluorescent dye.
The obtained results confirm the improvement of the catalytic activity, compared to
TiO2 P25. Despite the degradation efficiency is not very high, it is worthy to note
that the Ag doped catalyst has a higher activity compared to commercial P25. Thus,
we can conclude that modifying the catalyst surface leads to an improvement of the
properties, probably by forming an intermediate energy level between the valence
and conduction bands of TiO2.
Keywords: Ag-doped catalyst, photocatalysis, rhodamine degradation, titanium

dioxide
Introduction
The occurrence of organic dyes in water represents an increasing environmental
problem due to their high toxicity and, therefore, their consequences on human
health (Ciobanu et al 2013, Ciobanu et al 2014, Harja et al 2011, Harja et al 2016,
Harja et al 2017, Harja & Ciobanu 2018, Rokesh et al 2018, Rusu et al 2014). The
heterogeneous photocatalysis, using metal oxide semi conductive nanoparticles,
proven to be one of the most effective “green” techniques for the degradation of
organic and inorganic micro-pollutants from wastewater (Favier et al 2016, Wen et
al 2015). The most popular semiconductors in this respect are: TiO2, ZnO, CuO,
Fe2O3, CeO2, (Nutescu Duduman et al 2016, 2018, Saleh et al 2016); the first being
from far the most promising, due to its high photocatalytic activity, chemical
stability, lack of toxicity, low cost, large availability (Wen et al 2015). The
performant photocatalysts can mineralize the organic compounds to carbon dioxide,
water and simple mineral acids. This mechanism is attributed to the semiconductor’s
ability to form electron-holes pairs and produce hydroxyl radicals by the reaction
occurring between charged carriers and water, under UV light irradiation. Despite
these advantages, efforts are still dedicated to TiO2 activity improvement, by its
doping with metal ions (Nakata et al 2012).

The objective of this work was to test the activity of Ag-doped photocatalyst in the
degradation of Rhodamine 6G (R_6G), a chemically stable organic dye widely used
as a textile dye, water flow tracer, biotechnological applications (various versions of
fluorescence microscopy) (Li et al 2018, Lutic et al 2012).
The activity of the doped catalyst was compared to that of the parent P25 (Degussa).

TiO2 P25 Degussa (P25) was used without further purification. Silver nitrate
(AgNO3) used for Ag doping was purchased from Sigma Co.
The Ag/TiO2 catalyst was prepared by the incipient impregnation method. The P25
powder was dried for 2 hours at 200oC, then the AgNO3 solution in water and
ethanol was added fast, in order to fill the empty pores from the solid structure and
allow the uniform Ag dispersion on the whole surface. The sample was cooled at
25oC and dried at 100oC for a few hours. One half of the powder was calcined at
450oC, the other half at 600 oC (1o/min) for 2 hours.
The P25 and synthesized materials were characterized by EDAX, SEM and XRD.
The photocatalytic activity of Ag/TiO2 was evaluated by the degradation of R_ 6G,
under UV light. The experiments were performed in a batch reactor, magnetically
stirred, with internal irradiation, using an Osram UV-A lamp (9W). The tests were
carried out at ambient temperature, without adjusting the native pH of the dye.
The working solutions of dye were obtained by diluting accordingly stock solutions
prepared in deionized water, by dissolving precisely weighted amount of of R_6G.
In order to achieve the adsorption-desorption equilibrium, the solution with the
photocatalyst powder was first stirred in dark for 30 min, and then the lamp was
turned on. The photocatalytic tests were run for 120 min and samples were taken at
specific times, filtered through 0.45 µm syringe filters to remove the catalyst and
measured. The dye concentration was determined by spectrophotometry, using a
Shimadzu UV-1700 spectrophotometer, on the basis of the characteristic R_6G peak
from 525nm.
The degradation efficiency was calculated with the following equation:
D % = (C0 – Ct)/C0 * 100 (1)
where C0, Ct – initial and respectively time t pollutant concentrations.

The samples were analyzed by EDAX analysis in order to determine their chemical
composition. The results are shown in Table 1.
Table 1. The EDAX measurement of Ag/TiO2 450 oC and 600 oC samples.

Element Ag, wt% Ti, wt%
Ag/TiO2 450 oC 9.91 52.17
Ag/TiO2 600 oC 6.79 55.6
From the results, it can be seen that at a higher calcination temperature, the Ag
percentage on the catalyst surface decreases and the Ti percentage increases
accordingly. This indicates that Ag particles could be removed at a higher
temperature.
The obtained catalyst was characterized by XRD to determine the crystalline
structure and phase purity. The XRD diffraction patterns reveals that the sample
calcined at 450oC mostly contains anatase phase, while the one calcined at 600oC is
composed only of rutile phase, Figure 1. At higher calcination temperature, the
anatase phase was almost entirely converted to rutile phase (Sangchay et al 2012).
Figure 1. XRD for the Ag/TiO2 samples uncalcined and calcined at 450 oC
The SEM for samples uncalcined and calcined at 450oC are presented in Figure 2.
uncalcined calcined
Figure 2. SEM for the Ag/TiO2 samples uncalcined and calcined at 450oC
The activity of the doped catalyst was investigated by heterogeneous photocatalysis

in the degradation of R_6G (chemical formula: C28H31N2O3Cl) and compared to that
of P25 Degussa.
Ag/TiO2 calcined at 600oC was totally inactive for the photodegradation of R_6G,
since the rutile phase is known to be unsuited for photocatalysis. Therefore, the
notation Ag/TiO2 used from now on refers to the sample calcined at 450oC.
In order to highlight the effect of catalyst loading, we ran tests at a catalyst loading
of 0.5 g/L and 1 g/L and a pollutant concentration of 40 mg/L, in the fore-mentioned
operatory conditions.
The activity of the catalysts is very low at a catalyst dose of 1g/L (data not shown).
This is due to an overload of catalyst which produces a “screening effect”; the
aqueous photocatalyst slurry is almost opaque, therefore the irradiation effectiveness
decreases (Yoon et al 2012). The other series of tests were carried out at a catalyst
loading of 0.5 g/L.
The data in Figure 3 indicate that a degradation of almost 35% was achieved when a
R_6G solution of 40 ppm was used. This is a quite high initial concentration for
R_6G, the optical density of the solution hinders in an important extent the radiation
to reach the active sites of the catalyst, which are in turn highly covered with
multilayers of pollutant molecules (Yang et al 2018).
Figure 3. Degradation efficiency of R_6G in presence of Ag/TiO2. Experimental

conditions: [R_6G] = 40 mg/L, [Ag/TiO2] = 0.5 g/L.
The use of pristine P25 in same photoreaction conditions led to a degradation

efficiency of only 23% (Figure 4). These results clearly show that the doping with
Ag improved the photocatalytic activity of P25.
Figure 4. Degradation efficiency of R_6G in presence of P25. Experimental

conditions: [R_6G] = 40 mg/L, [P25] = 0.5 g/L.
From the absorbance spectra (Figure 5) it can be seen that the main peak decreases
constantly during the photocatalytic reaction, likewise the peak from the UV region.
Thus, this indicates that during the reaction, the pollutant molecule is mineralized.
Figure 5. R_6G spectra during the photocatalytic assay. Experimental condition:

[R_6G] = 40 mg/L, [Ag/TiO2] = 0.5 g/L

Conclusions
The results shown that by doping TiO2 photocatalyst with Ag via wet impregnation
method is a promising approach to increase the photocatalytic activity of the
semiconductor.
Acknowledgements
The financial support was provided by “Gheorghe Asachi” Technical University Doctoral
School of Iasi.
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Ciobanu, G, Ilisei, S. Harja, M & Luca, C 2013, 'Removal of Reactive Blue 204 dye
from aqueous solutions by adsorption onto nanohydroxyapatite', Science of
Advanced Materials, vol. 5, pp. 1090-1096.
Favier, L, Harja, M, Simion, AI, Rusu, L, Kadmi, Y, Pacal, ML & Bouzaza, A 2016,
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based on power plant ash', Environmental Engineering and Management
Journal, vol. 10, no. 3, pp. 341-347.
Harja, M, Ciobanu, G, Favier, L, Bulgariu, L & Rusu, L 2016, 'Adsorption of crystal
violet dye onto modified ash', The Bulletin of the Polytechnic Institute from
Iaşi. Chemistry and Chemical Engineering Section, vol. 62, pp. 27-37.
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direct green 6 dye onto modified power plant ash', Agronomy Series of
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Lutic, D, Coromelci-Pastravanu, C, Cretescu, I, Poulios, I & Stan, CD 2012,
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ZnO', International Journal of Photoenergy, vol. 2012, article ID 475131,
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Palamarciuc, I & Gómez De Castro, C 2016, 'Obtained of nanocomposites:
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PHYSICAL MODELING OF FLOW OVER AN OGEE SPILLWAY AND

INVESTIGATION OF SCALE EFFECTS BY USING FROUDE
SIMILARITY
Ali Yıldız, Alpaslan Yarar
Selcuk University Civil Engineering Department, 369 Akademi Mah. Yeni Istanbul Cad., 42130,
Selcuklu-Konya, aliyildiz@sekcuk.edu.tr, ayarar@selcuk.edu.tr, Turkey
Abstract
Ogee spillways are used to control the discharges and water levels in reservoir. In
some cases, steps and baffle blocks are placed at the stilling basin to change flow
regime supercritical to subcritical and improve energy dissipation. Physical models
are built in the laboratories to represent its real-world prototype; however some
scale effects may arise between models. Two open channel setups, called as model
and prototype, are used in this study. The experiments of the study are performed on
these channels using identical Froude Numbers and geometric scaling ratio of 4:1.
The flow depths at four different points are measured from model and prototype for
28 total head. The results showed that there is 92% consistency between model and
prototype, whereas this consistency was not observed at turbulence existing regions
due to scale effects.
Keywords: dimensional analysis, Froude similarity, hydraulic simulate, ogee

spillway
Introduction
Dams are large obstacle structures and constructed from different materials in
different types for preventing, directing and delaying flow of water to create a lake
or reservoir. Water is an important natural resource of human, animals and plants
life therefore studies for water usage is begin with the existence of mankind. Dams
are built for many purposes such as drinking water, irrigation, energy production
and transportation. A dam’s body basically composed of reservoir, spillway, bottom
sluice, water intake structure and energy generation facilities.
Spillways transfer the excessive water coming to dam reservoir to downstream side
in safe and controller manner. Spillways have an important place in dams in terms of
operation and stabilization of dam. 22% of the dam damages are caused by
insufficient spillway capacity and their faulty operation (ICOLD 1995).
Physical models of dams are built, to project dams in the best way. A physical
model represent the actual prototype to be built in real life and model is used as a
tool to find the most technical and economical solution (Novak 1984). The
reliability of a physical model depends on correct construction. If the model is built
incorrectly, error in the data obtained from the model will increase (Yalin 1989).
There are some numerical ratios and scales that must be taken into account when
constructing the physical model. Scale ratio between physical model and prototype
is important. As the scale ratio is reduced, error caused by scale effect is increased
and the results obtained from model and prototype is getting away. Scale effect arise
due to coefficient of the associated force ratio between the model and prototype is
not kept constant (Huger 1993). Incorrect modelling of flow conditions, turbulence
intensity and fluid properties also causes scale effects.
In this study, physical modelling of hydraulic structures has been studied. In this
study, 2 experimental setups which are called model and prototype are used. The
scale ratio between model and prototype is 4. Froude similarity is applied to results
of model to predict experimental result of prototype.

Ogee spillway design and experimental study
The ogee spillway is a control weir having an ogee (S-shaped) overflow profile. It is
one of the most used spillway type in hydraulic structures because of its ability to
pass flood flow out of reservoir safely. Ogee spillway idea is first recommended by
(Muller 1908). A typical ogee spillway can be seen in Figure 1.
Figure 1. Flow over and ogee spillway.
The general equation for discharge over an ogee crested spillway is given as (USBR
1987):
Q=Co*L*Ho1.5 (1)
where Q=total discharge, L=lateral crest width, Co=crest coefficient and Ho=total
head upstream from crest.
The small open channel construction used as model is 400 cm long, 7.5 cm wide and
20 cm deep. The model experimental setup is a simple flume and made of smooth
transparent plastic. The slope of flume is set zero. Dimensions for ogee spillway
model used in model are (P)model=7 cm (crest height), Lmodel=7,5 cm (crest length)
and C0=2.17 (discharge coefficient). The general view of model setup and ogee
spillway can be seen Figure 2. The ogee spillway used in model is fabricated from
stainless steel. The water flow in the model setup is provided by a pump which gives
the Qmax=4 l/s.
The large open channel construction used as prototype is 650 cm long, 30 cm wide
and 50 cm deep. The slope of the channel is zero same as model setup. The
prototype open channel is made of tempered glass. The spillway model used in
prototype is made from plexiglas. Dimensions for ogee spillway used in prototype
are (P)prototype=28 cm, and Lprototype=30 cm and C0=2.17. Crest height and crest length
of spillway used in prototype is 4 times larger than the spillway used in model
because of scale ratio (Figure 2).

Figure 2. Spillway models used in model and prototype
Specifications of the ogee spillway which is used in the tests that downstream
portion profile of ogee is determined as constants given below for both model and
prototype (USACE 1985);
Y/Hd=-K*(X/Hd)n (2)
where (Hd)model=3.6 cm and (Hd)prototype=14.4 cm. K is chosen 0.5 and n is chosen
1.85 for both model.
Hydraulic similitude
A physical model represents its real-world prototype. Physical models are
commonly used design stage of prototype to optimize a structure and ensure safe
operation after constriction. A physical model is valid only if these three criteria is
satisfied; geometric similarity, kinematic similarity and dynamic similarity.
Geometric similarity is a geometric ratio between prototype and model. In this study
geometric ratio between models Lr=4 is taken.
Kinematic similarity is that similarity of motion between model and prototype
particles. In this study velocity ration Vr=2 and discharge ratio Qr=32 is taken.
Dynamic similarity means that all force ratio in the model and prototype are
identical. Froude similarity is used in experiments. It means that model and
prototype have identical Froude numbers. (Fr)model=(Fr)prototype
Dimensional analysis
Before building a physical model in the laboratory dimensional analysis is applied to
determine relationships between model and prototype. Dimensional analysis gives
dimensionless quantities appear in both models. Dimensional analysis shows that
Froude number is seen in both model so that Froude similarity is used (Buckingham
1914).

Results obtained from physical model and prototype were evaluated and compared
according to hydraulic similarity rules in terms of flow depths and water surface
profiles. The aim of the comparing flow depths is to determine how the flow profiles
of models and prototype are consistent with each other and hydraulic similarity
rules.
Firstly water surface profile of model and prototype is compared. The purpose of the
comparing the flow profiles is to determine how the flow profiles of the model and

prototype are consistent with each other and whether they are consistent with the
hydraulic homogeneity rules. When comparing the general flow profiles, it was also
investigated by observing whether there is a difference in the profiles due to the
scale effect. When general flow profiles are investigated, it is seen that the model
and the prototype show high consistency (Figures 3, 4).
Figure 3. Water surface profiles at model
Figure 4. Water surface profiles at prototype
Flow depths are measured at four different points (shown in Figure 5) and flow rates
are measured for both model and prototype. The ratio of flow rates between model
and prototype must be same with geometric ratio Lr=4. Therefore, 4 times larger
ogee spillway model is used in prototype.
Figure 5. General view of models and position of measurement points
The discharge ratio between model and prototype should be Qr=32. The results
obtained from model and prototype can be seen in Table 1 and Table 2 respectively.

Table 1. Flow depths get from model at 4 different points and discharge values
Flow depths and Discharge Measurement for Model Setup
H1(m) H2(m) H3(m) H4(m) Qmodel (l/s)
0.0165 0.0341 0.0450 0.0110 0.33
0.0225 0.0390 0.0507 0.0155 0.56
0.0260 0.0424 0.0557 0.0178 0.71
0.0290 0.0465 0.0592 0.0203 0.86
0.0307 0.0470 0.0610 0.0215 0.94
0.0341 0.0503 0.0652 0.0251 1.11
0.0365 0.0533 0.0675 0.0278 1.22
0.0384 0.0555 0.0703 0.0295 1.40
Table 2. Flow depths get from prototype at 4 different points and discharge values
Flow depths and Discharge Measurement for Prototype Setup
H1(m) H2(m) H3(m) H4(m) Qprototype (l/s)
0.067 0.132 0.176 0.046 10.56
0.091 0.152 0.211 0.062 17.88
0.104 0.171 0.225 0.071 22.84
0.116 0.173 0.240 0.087 27.43
0.123 0.183 0.247 0.091 30.10
0.136 0.200 0.269 0.101 35.63
0.145 0.210 0.279 0.118 40.31
0.150 0.218 0.282 0.121 43.51
When flow depths, discharges values obtained from model and prototype are
compared, there is a high consistency with the values of Lr=4 (geometric ratio) and
Qr=32 (discharge ratio) used in the Froude Smilarity law (Table 3).
Table 3. When Discharge Ratio (Qr=32) is provided, controlling the ratio of flow
depths (Lr=4)
(H1)p/(H1)m (H2)p/(H2)m (H3)p/(H3)m (H4)p/(H4)m Qprototype/Qmodel
4.06 3.87 3.91 4.18 32.17
4.02 3.90 4.16 4.00 31.93
4.01 4.03 4.04 3.99 31.99
4.01 3.27 3.56 3.05 32.01
3.99 3.89 4.05 4.23 31.97
3.99 3.98 4.13 4.02 32.02
3.97 3.94 4.13 4.24 32.93
3.91 3.93 4.01 4.10 30.98
Lr=4 Lr=4 Lr=4 Lr=4 Qr=32
In order for Hydraulic Similarty rules to be valid, Froude numbers should be same in
both system. Flow depths obtained from model and prototype at measure point-3 are
divided to Total Head (He=H1) to obtain dimensionless reletive flow depth. The
relative flow depths of two system and froude numbers at this point is shown in
Figure 6. Model and Prototype show good consistency with each other in terms of
Hydraulic Similarti rules.

Figure 6. Comparison of Froude Numbers
Conclusions
Model and prototype show 92% consistency with each other in terms of flow depths
and flow rate. However this consistency was not observed at turbulence existing
regions due to scale effects. In this study, hydraulic calculation of an uncontrolled
ogee spillway is estimated by a physical model and prototype which are constructed
in laboratory. Froude similarity model gives satisfactory results in cases where flow
continuous in one direction and without turbulence. When turbulence is high, there
are difference between the results of model and prototype. Turbulences have a
significant effect on the forces, and these ratio of these forces don’t appear to be
appropriate for hydraulic similarity rules. These force differences can lead to
observe some events that we cannot observe in the model.
References
Buckingham, E 1914, ‘On physical similar systems – Illustrations of the use of
dimensional equations’, Physical Review, vol. 4, pp. 345-376.
Hughes, SA 1993, ‘Advanced series on ocean engineering’, Physical Models and
Laboratory Techniques in Coastal Engineering, Londra, vol. 7, pp. 27-33.
International Commission of Large Dams 1995, Dam Failures and Statistical
Analysis, ICOLD bulletin 99, Paris, pp.75-80.
Muler, R 1908, ‘Development of Practical Type of Concrete Spillway Dam’,
Engineering Rec., vol.58, pp. 461.
Novak, P 1984, ‘Scaling factor and scale effects in modeling hydraulic structures’,
Scale Effects In Modelling Hydraulic Structures, Esslingen, pp.1-5.
U.S. Army Corp of Engineers 1985, General Spillway Investigation, USACE
Technical Report Hl-85-1, Washington DC, pp.5-10.
U.S. Department of the Interior Bureau of Reclamation 1987, Design of Small
Dams, USBR A Water Resources Technical Publication, Washington DC,
pp. 365-375.
Yalın, MS 1989, ‘Fundamentals of Hydraulic Physical Modelling’, Recent Advances
in Hydraulic Physical Modelling, vol. 165, pp.1-6.

REMOVAL OF HEXAVALENT CHROMIUM IONS FROM THE

SIMULATED WASTEWATER USING ELECTROCOAGULATION
PROCESS
Firas Hashim Kamar1, Karim Khalifa Esgair1, Baker M. Abod1, Aurelia Cristina Nechifor2
¹Institute of Technology-Baghdad, Middle Technical University, kamarfiras@yahoo.com,

karimkhalifa70@yahoo.com, baker_mu@yahoo.com, Iraq
²Department of Analytical Chemistry and Environmental Engineering, University Politehnica
of Bucharest, 1-7 Gheorghe Polizu, 011061, Bucharest, Romania
Abstract
The removal of hexavalent chromium (Cr+6) ions from simulated wastewater was
investigated by using batch electrocoagulation. The influence of several variables on
the removal process was studied such as a type of electrodes, initial pH, initial
concentration of Cr+6 ions, electrolysis time, sodium chloride concentration and
current density. The experimental results showed that the removal efficiency of Cr+6
ions was more effective when using iron electrode comparing with the aluminium
electrodes. The maximum removal of Cr+6 ions was 96.58% at pH 6.0, initial ion
concentration 40 mg/L, electrolysis time 15 min, sodium chloride concentration 2
g/L, and the current density 30 mA/cm2.
Keywords: Cr+6 ions, electrocoagulation, heavy metal removal, wastewater
Introduction
In the last years, the development in industrial led to producing of variant types and
a large amount of pollutants discharged directly or indirectly as industrial
wastewater. This has affected the surface and groundwater sources (Zhao et al
2018).
In general, the pollutants can be classified into three main groups: biological
particles, organic and inorganic. Inorganic pollutants are of interest because they
contain heavy metals (Vosoogh et al 2017).
The environmental pollution mainly depends on the presence of heavy metal in the
wastewater. Generally heavy metal has density more than 5 g per cubic centimetre.
The problem of these elements is the high solubility of their compounds in water, in
addition to being carcinogenic and highly toxic. The generality of heavy metal such
as chromium, lead cadmium, arsenic and mercury resort to cumulate in living
organisms producing different health issues (Azimi et al 2017, Kamar et al 2016).
The focus of this study will be on chromium. Hexavalent chromium ions is
employed in various industries such as leather tanning, electroplating, pigment,
chemical catalyst, printing inks and corrosion inhibitors, which also being present in
the wastewater from these industries (Gunatilake 2015, Rehman et al 2015).
Cr+6 ion is a highly poisonous, non-biodegradable and carcinogenic element for the
most living organism. Thence Cr+6 ions removal is very important to be done before
discharging the wastewater into water bodies (Dermentzis et al 2011).
Commonly, there are various methods employed to remove heavy metal from
wastewater such as chemical precipitation, adsorption, ionic exchange, electro-
dialysis, membrane system, bio-sorption, and electro-oxidation. These techniques

are employed for effective removal of heavy metal but have some disadvantages,
such as generation of other pollutants, operational cost, and being unsuitable for
small industries (Chandrasen et al 2013, Kamar et al 2016).
To get over the disadvantage of traditional treatment methods, electrocoagulation
technicality has been suggested as an alternative process. This technology has some
advantages, it is safe and easy in operation, low cost, with simple equipment installs,
reliable and effective, needs short reaction time, certain efficient, generate less
sludge, uses less chemicals, and is effective for a wide range of contaminants. The
only one disadvantage of this technology is the need of replacing the sacrificial
electrodes (Vlachou et al 2013, Beyazit et al 2014).
Electrocoagulation has been exhibit efficient results in various wastewater treatment
applications, such as textile wastewater, tannery wastewater, oil-water emulsions,
purification of drink water, and removal of heavy metal ions, dairy wastewater and
slaughterhouse wastewater (Khalaf et al 2016).
This work is aimed to study the effect of operating variables which include the type
of electrode, initial pH, initial Cr+6 concentration, contact time, wastewater
conductivity, current density on the removal efficiency of Cr+6 from simulated
wastewater to determine the best-operating conditions.

Electrocoagulation experiments
A glass electrocoagulation reactor was used to conduct the experiments. The volume
of the reactor was 500 mL. Each pair of iron and aluminium reactor electrodes plates
were used in parallel, vertically positioned, having a rectangular shape (dimensions
6.0 cm × 4.0 cm × 1 mm). The interspace between two electrodes was 10 mm. The
current supply to the process from a digital power source (PS-305D, Dazheng,
China) to attain required values of current densities applied in the experiments.
Electrolysis time was 5, 10, 15, 20, 25 and 30 minutes.
All electrodes were cleaned after each experiment, the precipitates of metal
hydroxide and other impurities being removed from electrodes by immersion in 0.01
M of hydrochloric acid for three minute, and abundantly wash by water, then
weighted after air drying. The electrodes must be replaced if loss about ten percent
from its weight.
Prepared wastewater
Dried potassium dichromate was employed to prepare synthetic wastewater with
Cr+6 ions concentration of 1000 mg/L by dissolved 2.82 g of dried potassium
dichromate in the one-litter deionized water. Electrical magnetic stirrer was used to
mix the potassium dichromate with deionized water. The initial concentration (Co)
varied between 20 and 100 mg/L.A 0.1 M H2SO4 or 0.1 M NaOH was used to adjust
pH value of simulated wastewater between 2.0 and 12.0 and concentration of NaCl
from 0 to 4.0 g/L was used to obtain a varied conductivity. To study the influence of
any one of above variable on the removal of Cr+6 ion, that variable has been varied
gradually while keeping the other variables constant to obtained the maximum
removal percent of chromium by electrocoagulation process.

Analytical methods
Ultraviolet visible spectrophotometer (Model 6310, Jenway Co., UK) was used to
measure the Cr+6 ions concentration in wastewater at 540 nm wavelength with
diphenyl carbazide.
In the end of each experiment, the concentration of Cr+6 ions in solution at
equilibrium was measured (filtered sample).
The removal efficiency of ions (R %) due to electrocoagulation process was
calculated according to the following equation:
(1)
where:
Co = is the Cr+6 ions concentration in the wastewater before experiment;
Ce = is the concentration of Cr+6 ions at equilibrium.
Digital multi range ammeter and voltmeter was used to measure the current and
voltage supply to the electrocoagulation reactor.
Results and Discussions

Effect of the electrode material
The influence of the various electrode material pairs on the removal efficiency of the
Cr+6 ions using electrocoagulation method was studied by making all variables
constant and changes the type of electrode material only (see Figure 1). The pairs of
electrodes were coordinated as anode/ cathode Al/Al, and Fe/Fe to carry out the
experiments. Laboratory experiments demonstrated that the pair of electrodes Fe/Fe
has given the highest percentage removal of Cr+6 ions, reaching 58%, while the pair
of electrodes Al/Al reaches 49% for the same conditions. The explanation for that is
the number of anions that are generated in the electrocoagulation with Fe/Fe is much
higher than the anions generated with Al/Al, according to Faraday’s first law for
electrolysis. Therefore, firstly that the amount of metal hydroxide generated, density
and concentration of hydroxide groups flocs in the electrocoagulation cell when
using Fe-Fe are higher than when using Al/Al, which leads to the removal of Cr+6
ions from wastewater through adsorption of Cr+6 ions by a complex reaction on the
surface with a hydroxyl group.
Secondly, the electrolysis of iron leads to the formation of Fe+2, which in turn
oxidize to Fe+3 due to the presence of oxygen dissolved in the electrocoagulation
cell, which helps to reduce hexavalent chromium to Cr+3 ions, which precipitates,
therefore the Cr+6 ions can be removed by surface reactions and precipitation
reactions.
For these reasons the pair of electrodes Fe/Fe was selected in all subsequent
experiments. Lu et al. study also the removal of Cr+6 ions from aqueous solution
using electrocoagulation and found that the best electrode material pairs are iron (Lu
et al 2016).

100
90
80
70
R%
60
50
40
30
20
10
0
Fe Al
Type of material electrode
Figure 1. The effect of type of electrode material on the removal efficiency of Cr+6
ions; t=30 min, current density=20 mA /cm2, NaCl=1 g/L, CO=40 mg, pH=4.
Effect of initial pH
Figure 2 illustrates the influence of the primary pH of simulated wastewater on the
removal efficiency of Cr+6 ions. This figure demonstrates the removal of this ions is
increased with increases the initial pH of the wastewater, reaching 78% as its
highest value at pH = 6. The Cr+6 ions removal percentage was decreases slightly
with an acidity of up to 74% at pH 8. After that, the removal efficiency of Cr+6 ions
was a fast decreased with the initial pH increase.
In general, there are two mechanisms for removal of the Cr+6 ions, the first is the
precipitation and co-precipitation and the second is the adsorption, but when the
mechanisms precipitation and co-precipitation are weak, that adsorption will be
dominant in this process. From the above, we will be chosen the initial pH 6 for
subsequent experiments. Arroyo et al 2009 found the maximum removal of Cr+6
ions from aqueous solution using electrocoagulation at pH 6.0.
100
50
R%
0
0 5 10 15
Intial pH
Figure 2. Effect of initial pH on the removal efficiency of Cr+6 ions; t=30 min,
current density=20 mA/cm2, NaCl=1 g/L, CO=40 mg.
Effect of initial concentration for Cr+6 ions

The influence of the initial concentration of Cr+6 ions between 20 and 100 mg/L on
the removal efficiency was studied. Experimental data denote that the removal
efficiency of Cr+6 ions was decreasing with increasing the initial concentration of it
as shown in figure 3. The removal efficiency gradually decreased from 78% to 49%
when initial concentration increased from 40 to 100 mg/L. This is due to the fact
when the Cr+6 ions concentration increase, the quantity of coagulant produced from

electrolysis of anodic electrode is constant when all variable are constant, so with
increasing the Cr+6 ions concentration, the quantity of coagulant turn into very low
compared with the Cr+6 ions, subsequently deceasing the removal efficiency.
100
80
60
R%
40
20
0
0 50 100 150
Initial Cr+6 concentration (mg/L)
Figure 3. Effect of initial concentration for Cr+6 ions on the removal efficiency of
Cr+6 ions; t=30 min, current density =20mA/cm2, NaCl=1g/L, pH=6.
Effect of electrocoagulation time

Removal of Cr+6 ions was investigated in electrocoagulation reactor at electrolysis
time between 5 and 30 min and figure 4 shows that. This figure shows that removal
of this ions increase with increasing of electrolysis time to reach 78% as a maximum
value at 15 min of electrolysis time and it rests approximately fixed with despite
increasing the electrolysis time. Therefore, we chose 15 min as the best electrolysis
time for all experiments (similar to Dubrawski et al 2015)
100
R%
50
0
0 10 20 30 40
Electolysis time (min)
Figure 4. Effect of electrolysis time on the removal efficiency of Cr+6 ions; pH=6,
current density =20 mA/cm2, NaCl=1 g/l, CO=40 mg.
Effect of conductivity
The influence of conductivity for simulated wastewater on the removal of Cr+6 ions
was studied by using NaCl concentration between 0 and 4 g/L as shown in figure 5.
Cr+6 removal increased quickly with increasing the conductivity of simulated
wastewater, reaching the highest value of 85.2% when that the NaCl concentration
was 2 g/L. Since we desired the highest removal efficiency and minimum salting of
the simulated solution after electrocoagulation, therefore we considered the best
conductivity of wastewater corresponding to 2 g/l of NaCl, which was used for the
subsequent experiments.

This experimental results may be interpreted as a follow: the conductivity of the

electrolyte increases when the concentration of NaCl increases and the passivation
removed by the anions Cl− were increases also, therefore increases the electrolysis
rate of a sacrificial anode by the participation of Cl− in the reaction of metal
electrolysis or by the incorporation of Cl− in the oxide film (El-Taweel et al 2015).
100
R%
50
0
0 2 4 6
S odium chloride concentration (mg/l)
Figure 5. Effect of wastewater conductivity on the removal efficiency of Cr+6 ions;

t=15 min, current density =20 mA/cm2, CO=40 mg, pH=6.
Effect of current density

One of the main parameters to control of electrocoagulation technique is the current
density. It is also an important variable for the economy of energy and consumption
of the electrode, because it is determining the coagulant production rate, as well as
the hydrogen production which influences on the growth rate and bulk of flocs.
150
100
R%
50
0
0 20 40 60
Current density (mA/cm2 )
Figure 6. Effect of current density on the removal efficiency of Cr+6 ions; t=15 min,
NaCl= 2 g/L, CO =40 mg, pH=6.
Figure 6 show effects of several current densities used between 10 and 50 mA/cm2
on the removal of Cr+6 ions by electrocoagulation. The results obtained from
experiments were explained by the increase of the current density from 10 to 20
mA/ cm2 was caused to increase the ions removal from 35.4% to 85.2%, whereas the
increase from 20 to 30 mA/cm2 was caused an in increase the Cr+6 ions removal
from 85.2% to 95.58 %. While the increasing of the current density from 30 to 40
mA/cm2 was given an insignificant increase in the ions removal (from 95.5% to
96.2%), accordingly, 30 mA/cm2 was selected as a best current density. The reason

for this is due to the electrical energy consumption was concerning with the square
rate of the current density (Lee & Gagnon 2016).
Conclusions
The present study shows that the electrocoagulation is an effective technique for
removal of Cr+6 ions from industrial wastewater. The efficiency of this process was
influenced major by the following variables: initial pH, initial concentration of Cr+6
ions, electrolysis time, simulated wastewater conductivity as well as current density.
The removal process efficiency was increased with increase of pH value up to 6.0;
also it's increased with increasing other variables such as electrolysis time,
wastewater conductivity, and current density, while it's decreased with increasing
the initial concentration of hexavalent chromium. The maximum removal efficiency
of Cr+6 ions, up to 96.58% was obtained for pH = 6.0, initial concentration of
chromium ions 40 mg/L, electrolysis time 15 min, salt content of simulated
wastewater 2 g NaCl/L, and current density 30 mA/cm2.
References
Azimi, A, Azari, A, Rezakazemi, M & Ansarpour, M 2017, ‘Removal of Heavy
Metals from Industrial Wastewaters: A Review’, ChemBioEng Reviews,
vol. 4, no. 1, pp. 37-59.
Arroyo, MG, Perez-Herranz, V, Montanes, MT, Garcia-Anton, J & Guinon, JL
2009, ‘Effect of pH and chloride concentration on the removal of Cr+6 in a
batchelectrocoagulation reactor’, Journal of Hazard Material, vol. 169,
pp. 1127-1133.
Beyazit, N, 2014, ‘Copper (II), Chromium (VI) and Nickel (II) Removal from
Metal Plating Effluent by Electrocoagulation’, International Journal of
Electrochemistry Science, vol. 9, pp. 4315-4330.
Chandrasen, F, Rajemahadik, SV, Kulkarni, H & Kulkarni, GS 2013, ‘Efficient
Removal of Heavy Metals from Electroplating Wastewater using
Electrocoagulation’, International Journal of Scientific and Research
Publications, vol. 3, no. 10, pp.1-5.
Dermentzis, K, Christoforidis, A & Valsamidou, E 2011, ‘Removal of nickel,
copper, zinc and chromium from synthetic and industrial wastewater by
electrocoagulation’, International Journal of Electrochemistry Science, vol. 1,
no 5, pp. 697-708.
Dubrawski, KL, van Genuchten, CM, Delaire, C, Amrose, SE, Gadgil, AJ &
Mohseni, M 2015, ‘Production and transformation of mixed-valent
nanoparticles generated by Fe(0)electrocoagulation’, Environmental Science
and Technology, vol. 49, pp. 2171-2179.
El-Taweel, YA, Nassef, Ehssan, MI & Doaa Sayed, E 2015, ‘Removal of Cr(VI)
ions from waste water by electrocoagulation using iron electrode’, Egyptian
Journal of Petroleum, vol. 24, pp.183-192.
Gunatilake, SK 2015, ‘Methods of Removing Heavy Metals from Industrial
Wastewater’, Journal of Multidisciplinary Engineering Science Studies, vol. 1,
no. 1, pp.1309-1318.
Khalaf, AM, Mubarak, AA & Nosier, SA 2016, ‘Removal of Cr (VI) by
Electrocoagulation Using Vertical and Horizontal Rough Cylinder Anodes’,
International Journal of Electrochemistry Science, vol. 11, pp. 1601-1610.
Kamar, FH, Mohammed, AA, Faisal, AAH, Nechifor, AC & Nechifor, G 2016,
‘Biosorption of Lead, Copper and Cadmium Ions from Industrial Wastewater
Using Fluidized Bed of Dry Cabbage Leaves’, Revista de Chimie, vol. 67,
no. 6, pp. 1039-1046.
Lu, J, Wang, ZR, Yu-Ling Liu, YL, Qing & Tang, Q 2016, ‘Removal of Cr ions
from aqueous solution using batch electrocoagulation: Cr removal mechanism
and utilization rate of in situ generated metal ions’, Process Safety and
Environmental Protection, vol. 104, pp. 436-443.
Lee, SY & Gagnon, GA 2016, ‘Growth and structure of flocs following
electrocoagulation’, Separation and Purification Technolology, vol. 163, pp.
162-168.
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Influence on Heavy Metal Removal from Metal Plating Wastewater by
Electrocoagulation Process’, Chemical Engineering Transactions, vol. 43, pp.
2251-2256.
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hardness from groundwater via electro-coagulation method’, Pollution, vol. 3,
no. 2, pp. 213-224
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Removing Cr and Ni From Model Wastewater by Using Electrocoagulation’,
Global NEST Journal, vol. 15, no. 4, pp. 494-503.
Zhao, Y, Kang, D, Chen, Z, Zhan, J & Wu, X 2018, ‘Removal of Chromium Using
Electrochemical Approaches: A Review’, International Journal of
Electrochemistry Science, vol. 13, pp. 1250-1259.

REMOVAL OF NITRITE IONS FROM WATER

IN DYNAMIC AND OXIC CONDITIONS
Tatiana Goreacioc1, 2, Raisa Nastas1, Maria Sandu2, Tudor Lupascu1, Anatolie Tarita2
1
Institute of Chemistry, 3 Academiei, MD-2028, Chisinau, ichem@asm.md,
araputatiana@yahoo.com, Republic of Moldova
2
Institute of Ecology and Geography, 1 Academiei, MD-2028, Chisinau,
ieg@asm.md, Republic of Moldova
Abstract
Active carbons have been found the most efficient and commonly used adsorbents
in water purification all over the world.
The purpose of this work was to investigate the possibility of applying active
carbons AG-5 and AG-5ox for the removal of nitrite ions from water in (i) dynamic
and (ii) oxic conditions.
Obtained results reveal that the sample AG-5 is more efficient for removal of nitrite
ions from water in the dynamic conditions but sample AG-5ox is more efficient in
oxic conditions.
The capacity of active carbon AG-5 for nitrite ions removal from water, expressed
in dynamic conditions as a ratio of the adsorbent volume to the solution volume
passed through column with adsorbent, is about 1:80.
Studies show that the application of the recommended method using the AG-5ox
carbonic adsorbent provides of 75% efficiency in the removal of nitrite ions from
natural water and 100% of the model solution.
Keywords: active carbon, dynamic condition, nitrite ions, oxic condition, removal
Introduction
The treatment processes of water contaminated with nitrate ions have been studied
much more widely than nitrite-contaminated water treatment processes. However,
several literature procedures describe the removal of nitrite ions from water. These
include: biological nitrification/denitrification (Kapoor & Viraraghavan 1997, Ng' &
Stenstrom 1987, Srinu & Pydi 2012, Zubair et al 2012); chemical denitrification
(Horold et al 1993, Kapoor & Viraraghavan 1997, Lemaignen et al 2002, Soares et
al 2008); adsorption (Afkhami 2003, Afkhami et al 2007, Mir 2010, Öztürk & Köse
2008).
Active carbons have been found the most efficient and commonly used adsorbents
in water purification all over the world (Kawamura 1991). The reason that active
carbon is such an effective adsorbent material is due to its high surface area, porous
structure, and high degree of surface activity. Active carbons are also highly inert,
thermally stable and can be used over a broad pH range (Kawamura 1991).
For the treatment of drinking water and wastewater, it is quite common to use
activated carbon in granular form.

The adsorption efficiency depends both on the type of contaminant that is adsorbed,
on the porous structure and on the surface chemistry of adsorbents (Kapoor &
Viraraghavan 1997, Kawamura 1991, Lupascu 2004).Therefore, chemical
modification of the active carbon surface is of great interest in obtaining adsorbent
materials with specific applications. More often, the surface of activated carbon is
modified by oxidative methods, producing a more hydrophilic structure with a large
number of oxygen-containing functional groups (Bandosz 2006, Rivera-Utrilla et al
2011).
The adsorption of ions does not depend only on the specific area of the adsorbent
but also on the presence of the surface groups. The oxidation of active carbons can
lead to the increase amount of the oxygen functional groups on the surface of the
adsorbent, and the result of this is an increase in polarity and hydroliphilicity of the
surface of the carbon adsorbent (Bandosz 2006, Rivera-Utrilla et al 2011).
In order to minimize operational problems during water treatment processes,
particular attention should be draw to the size of the active carbon particles. Large
particles have a small outer surface and large distances of the internal diffusion
trajectory (Choma 1998). This reduces the mass transfer rate, resulting in long
lasting processes of adsorption / removal of pollutants from water.
The purpose of this work was to investigate the possibility of applying active
carbons AG-5 and AG-5ox for the removal of nitrite ions from water in (i) dynamic
and (ii) oxic conditions.

In this work, were used two active carbon samples: (I) AG-5 commercially available
activated carbon, obtained from coal (Russia) and (II) oxidized sample with
concentrated nitric acid AG-5ox (Goreacioc 2015). The physico-chemical
characteristics of active carbons were evaluated by a series of general indices,
including humidity, ash content, and elemental analysis, pH of active carbon slurry,
granulation and bulk density (Table 1) (Goreacioc 2015).
The activated carbon samples are predominantly microporous, according to the
results obtained from nitrogen adsorption isotherms (Goreacioc 2015). Infrared
spectroscopy and Boehm titration method results revealed that AG-5 sample has a
basic surface and AG-5ox sample has acidic surface (Table 1); after oxidation
process the acidic functional group are formed on the surface of the activated carbon
AG-5ox; the concentration of acidic groups on the surface of AG-5ox follows the
series: strong carboxylic groups > weak carboxylic groups > phenolic groups
(Goreacioc 2015).
The process of nitrite ions removing from water under dynamic conditions has been
studied in a system with two parallel-mounted columns filled with AG-5 active
carbon and AG-5ox oxidized activated carbon (30 g, working fraction 0.8-2.0 mm)
on the installation shown in Figure 1.
The removal of nitrite ions from water in oxic conditions (by adsorption/oxidation
processes) was performed on the laboratory installation provided with an air bubbler
and recovery flask (Figure 2). Tests have been done on the model solutions as well
as on natural underground water from the village Isacova, district Orhei, Republic of
Moldova (Table 2).

Table 1. Description of active carbon samples

Bulk density, g/cm3 The character of surface
Sample (fraction 0.8-2.0 mm) pH of slurry groups, meq/g
Acidic Basic
AG-5 <0.578>±0.005 6.65 0.38 0.48
AG-5ox <0.553>±0.004 3.30 2.33 0.13
Figure 1. Scheme of the installation for removal of nitrite ions in dynamic

conditions. 1 - water tank containing nitrite ions, 2 - pump, 3 – columns with
activated carbon, 4 - taps, 5 - sample collection vessel, I – AG-5, II – AG – 5ox.
Figure 2. Scheme of the installation for removal of nitrite ions in oxic conditions.
1-Reactor; 2- recovery flask for nitrogen oxides; 3- flow meter; 4- air pomp;
5- sample port
Adsorption capacity (a) of active carbons has been determined by Eq. 1 and removal
efficiency (R) of nitrite ions from water by Eq. 2.

a=
(Co − Ce )⋅ V (1)
m
where C0 and Ce are the initial and equilibrium concentration of nitrite ions (mg/L),
V is the solution volume passed through the column (mL), m is the amount of
adsorbent (g).
C0 − Ce
R= ⋅100% (2)
C0
where C0 and Ce are the initial and equilibrium concentration of nitrite ions (mg/L).
Table 2. Quality indices of underground water from Isacova village (Orhei district)
No. Determined parameters* (selective) Values MAC**
1 Hardness, mol/m3, max. 0.9 7.0
2 Dry residue (110o C), mg/L 1309 1500
3 NH4+, mg/L 4.10 0.50
4 Nitrate ions (NO3-), mg/L 5.90 50
5 Iron (Fe) total, mg/L 0.38 0.3
6 Chloride ions (Cl -), mg/L 63.01 250
7 Sulphate ions (SO42-), mg/L 208.08 250
8 Fluoride ions (F-), mg/L 4.40 1.5
9 Sodium (Na+ ), mg /L 503.01 200
10 Potassium (K+), mg/L 9.10 -
11 Nitrite ions (NO2-), mg/L 7.35 0.5
12 pH value 8.3 ≥6.5 and ≤9.5
13 RedOx, mV 97-109 -
14 O2, mg O2/L 0.05 -
15 Conductivity, mS 2.28 -
16 Temperature, ºC 14.5 -
*Quality indices were determined by standard methods.
**Maximal allowable concentrations regulated by Government of Republic of
Moldova. Official Monitor No. 276-280 from 29.11.2013. Art. No. 1037.

The process of nitrite ions removing from water under dynamic conditions has been
studied in a system with 2 parallel-mounted columns filled with AG-5 active carbon
and AG-5ox oxidized activated carbon (Figure 1). The concentration of nitrite ions
in the initial solution varied between 1.5 and 10 mg/L and the flow rate was between
5.5 and 50 mL/min. In the eluates the concentration of nitrite ions, the pH value and
the conductivity of the solution were determined. Selective results are shown in
Figures 3 and 4. Since activated carbon AG-5 exhibited greater adsorption capacity
of nitrite ions under dynamic conditions, it was used for further researches. A
research team from Poland reported results regarding the dynamic adsorption of
nitrate, nitrite and ammonium ions on AG-5 active carbon AG-5 and oxidized
sample with hydrogen peroxide (Gierak & Lazarska 2017), but the purpose of their
work was to extract these ions from the mixture (the concentration of nitrite ions
was 1 mg/L and the flow rate of the solution was 3 mL/min). According to their
results, the efficiency of the removal/adsorption process of nitrate ions under
dynamic conditions does not depend on surface chemistry of active carbons.
The process of removing nitrite ions from water in dynamic conditions using initial
active carbon AG-5 was studied at the initial concentration of nitrite ions of 10 mg/L
and the flow rate of the 5.5 mL/min (Figures 5 and 6). The capacity of active carbon
AG-5 for nitrite ions removal from water, expressed in dynamic conditions as a ratio
of the adsorbent volume to the solution volume passed through column with
adsorbent, is about 1:80.
a, mg/g a, mg/g
0,8 1 1,2
[NO2-]0=1,53 mg/L 1
[NO2-]0=3,2 mg/L
1,0
0,6
0,8
0,4 0,6
2
0,4 2
0,2
0,2
0,0
0 1 2 3 4 5 0,0
Vi, (L) 0 1 2 3 4 5
Vi, (L)
Figure 3. Capacity of active carbons for Figure 4. Capacity of active carbons for
nitrite ions removal in dynamic nitrite ions removal in dynamic
conditions. C0 =1.53 mg/L, (1) column conditions. C0 =3.2 mg/L, (1) column
with AG-5, (2) column with AG-5ox with AG-5, (2) column with AG-5ox
Ce/Co a, mg/g
0,7 0,8
[NO2-]0=10 mg/L
0,6
0,6
0,5
0,4
0,4
0,3
0,2
0,2
0,1
0,0 0,0
0 1 2 3 4 5 0 1 2 3 4 5
Vel, L Vel, L
Figure 5. The variation of nitrite ions Figure 6. Capacity of AG-5 active

concentration in the eluates. carbon for nitrite ions removal in
Column with AG-5, C0=10mg/L, inflow dynamic conditions.
5.5 mL/min.
Active carbons AG-5 and AG-5ox have been tested in order to choose the most
efficient one for nitrite ions removal from water by adsorption/oxidation processes
(in oxic conditions) using laboratory installation provided with an air bubbler and
recovery flask (Figure 2). Tests have been done on the model solutions as well as on
natural underground water (Table 2) under same conditions: room temperature,
solid/liquid ratio equal to 1/200, air flow rate of 1.4 L/min, contact/treatment time of
water was of 5 hours. For comparison, experiments were performed at two pH
values, 8 and 6. Some researchers proposed an acidic environment for denitrification

of waters contaminated with nitrate/nitrite ions (Mir 2010). The efficiency of

adsorbents was estimated by studying the kinetics of the process, being monitored
the concentration of nitrite and nitrate ions, as well as pH value.
Depending on the pH of the medium, nitrogen oxides can be formed according to
the reactions (Burgot 2012):
pH < 3.3 3HNO2 → 2NO(g) + NO3- + H+ + H2O

3.3 < pH < 5 3NO2- + 2H+ → 2NO(g) + NO3- + H2O
pH ≥ 5 NO2- + ½O2 → NO3-.
The formed oxides are retained in the recovery flask (Figure 2). Comparative
analysis of research results demonstrates the need of acidulation of treated water in
order to optimize the nitrite ion removal process (Table 3). The studies proved that
the application of the recommended procedure using the AG-5ox active carbon
provides 75% efficiency in removing nitrite ions from natural water and 100% of the
model solution (Table 3).
Table 3. Experimental results of nitrite ions removal from water
NO2-aerated, %
NO2- residual,
active carbon
Adsorbed on
water/model
oxidated, %
pH (initial)
NO2- /NO3-
solution
Sample
Natural
mg/L
R, %
Model
AG-5ox 6.1 0.52 95.15 26.91 4.05 64.19
solution
Without
active Natural 5.7 7.20 2.04 0.85 0 1.19
carbon underground
water,
AG-5 7.35 - - - -
Isacova 8.3
AG-5ox 6.5 12.16 9.46 0 2.70
(Orhei)
AG-5ox 5.7 1.80 75.51 20.07 2.89 52.55
Conclusions
The capacity of active carbon AG-5 for nitrite ions removal from water, expressed
in dynamic conditions as a ratio of the adsorbent volume to the solution volume
passed through column with adsorbent, is about 1:80.
Comparative studies of efficiency of active carbons to remove nitrite ions in oxic
conditions highlight the adsorbent AG-5ox modified by oxidation with nitric acid.
The results showed that the recommended process, by using active carbon AG-5ox,
ensures 100% efficiency for the removal of nitrite ions from model solution and
75% from underground water.

References
Afkhami, A 2003, ‘Adsorption and electrosorption of nitrate and nitrite on high-area
carbon cloth: an approach to purification of water and wastewater samples’,
Letters to the Editor, Carbon, vol. 41, pp. 1309-1328.
Afkhami, A, Madrakian, T & Karimi, Z 2007, ‘The effect of acid treatment of
carbon cloth on the adsorption of nitrite and nitrate ions’, Journal of
Hazardous Materials, vol. 144, pp. 427–431.
Bandosz, T 2006, Activated Carbon Surfaces in Environmental Remediation,
Academic Press, New York.
Burgot, JL 2012, Ionic Equilibria in Analytical Chemistry, Springer, New York.
Choma, J, Jaroniec, M, Burakiewicz-Mortka, W, Klinik, J & Olejniczak K 1998,
‘Structural and surface properties of active carbons oxidized with nitric acid at
high temperature’, Polish Journal of Chemistry, vol. 72, no. 5, pp. 860-868.
Gierak, A & Lazarska, I 2017, ‘Adsorption of nitrate, nitrite, and ammonium ions on
carbon adsorbents’, Adsorption Science and Technology, vol. 35, no. 7, pp.
721-727.
Goreacioc, T 2015, ‘Oxidation and characterization of active carbon AG-5’,
Chemistry Journal of Moldova, vol. 10, no. 1, pp. 76-83.
Horold, S, Tacke, T & Vorlop, KD 1993, ‘Catalytical removal of nitrate and nitrite
from drinking water: I: Screening for hydrogenation catalysts and influence of
reaction conditions on activity and selectivity’, Environmental Technology,
vol. 14, pp. 931-939.
Kapoor, A & Viraraghavan, T 1997, ‘Nitrate removal from drinking water-Review’,
Journal of Environmental Engineering, vol. 123, no. 4, pp. 371-380.
Kawamura, S 1991, Integrated design of water treatment facilities, John Wiley &
Sons, Inc, New York, USA.
Lemaignen, L 2002, ‘Catalytic denitrification of water with palladium-based
catalysts supported on activated carbons’, Catalysis Today, vol. 75, pp. 43–48.
Lupascu, T 2004, Active carbons from vegetal raw materials, Stiinta, Chisinau.
Mir, SA 2010, ‘Effect of electrolytes on the adsorption of nitrite and nitrate from
aqueous solutions by activated carbon’, Journal of Applied Sciences and
Environmental Management, vol. 14, no. 3, pp. 5-11.
Ng, A & Stenstrom, MK 1987, ‘Nitrification in powdered-activated carbon-
activated sludge process’, Journal of Environmental Engineering, vol. 113, no.
6, pp. 1285-1301.
Öztürk, N & Köse, TE 2008, ‘A kinetic study of nitrite adsorption onto sepiolite and
powdered activated carbon’, Desalination, vol. 223, pp. 174-179.
Rivera-Utrilla, J, Sanchez-Polo, M, Gomez-Serraro, V, Alvarez, PM, Alvin-Ferraz,
PM & Diaz, JM 2011, ‘Activated carbon modifications to enhance its water
treatment applications. An overview’, Journal of Hazardous Materials, vol.
187, no. 1-3, pp.1-23.
Soares, OSGP, Orfao, JJM & Pereira, MFR 2008, ‘Activated carbon supported
metal catalysts for nitrate and nitrite reduction in water’, Catalysis Letters, vol.
126, pp. 253–260.
Srinu, NS & Pydi, SY 2012, ‘Biological denitrification of wastewater-A Mini
Review on Carbon Source’, International Conference on Chemical,
Environmental Science and Engineering (ICEEBS'2012), Planetary Scientific
Research Center, Pattaya (Thailand), pp. 47-51.
Zubair, A, Sung-Min, K, Kim, IS, Min-Soo, B, Chae, J-K, Joo, J-H, Ok, YS & Oh,
SE 2012, ‘Nitrification and denitrification using biofilters packed with sulfur
and limestone at a pilot-scale municipal wastewater treatment plant’,
Environmental Technology, vol. 33, no. 11, pp. 1271-1278.

SEEDLINGS PLANTING INNOVATIVE TECHNOLOGY DEDICATED

FOR SLOPE DEGRADED TERRAINS AND HARD ENVIRONMENTAL
CONDITIONS
Constantin Gabriel Bogdanof1, Alexandra Liana Visan1, Dumitru Milea1, Radu Ciuperca1,
Alexandru-Ionut Petrisor2
1
INMA Bucharest, 6 Ion Ionescu de la Brad Blvd., 013813, Bucharest, gbogdanof@gmail.com,
Romania
2
Ion Mincu University of Architecture and Urban Planning, 010014, 18-20 Academiei,
district 1, Bucharest, alexandru.petrisor@incd.ro, Romania
Abstract
This paper aims to present a seedling planting innovative technology developed to
achieve forestation and rehabilitation works of degraded slope lands. Form the
experimental data obtained from testing activity conducted to conclusion that the
designed equipment’s are adequate and comply with the specific works
requirements, namely in heavy environmental conditions (degraded soil processing,
levelling and terrace surface modelling, planting settlement, etc.). This technology
answers to the need to implement measures of environmental rehabilitation (namely
restoration/ establishment of green infrastructure) and enhancement of slope-
degraded forestlands. The innovation element consists in development of several
adaptable equipment’s to the real working conditions (land stability, terrace
dimensions, type of power source and seedlings planting variety) in order to achieve
the highest performances and to respect labour safety standards. This technology
raises the mechanization performance of forestry and pomiculture works with
impact on soil remediation, lowering the surface and depth erosion degree,
capitalization of rainwater, lowering the dust pollution and natural calamity risk and
the rehabilitation of inland flora. Appling this innovative technology within
environmental management process can conduct to a good cost-benefit analysis that
has a great impact on medium and long time by lowering the calamity risks and the
threads of entire populations and local species.
Keywords: degraded terrains, environment improvement, green infrastructure,

planting technology, soil remediation
Introduction
Attempting to reconcile man and environment, the concept of sustainable
development, was defined by Brundtland and involves a balanced integration of
three traditional pillars: economy, society and environment. Due to their
interconnectivity the sustainable development requires three actions: environmental
policies design to internalize the environmental costs based on assessing the
potential impact of human activities; natural areas conservation as protected areas
and ecological restoration of degraded systems. Nowadays the restoration of
degraded ecosystems is provided by the” ecosystem services”, this concept
represents the benefits offered by ecosystems to the human society (Zakri & Watson
2003, Watson & Zakri 2005, Young 2010). Ecosystem services have economic,
social, cultural, and insurance value, in addition to the environmental include air
purification, noise reduction, urban cooling, and runoff mitigation (La Greca et al
2011, Gómez-Baggethun & Barton 2013). The importance of forests lies in the
multitude of ecosystem services provide: an improvement of microclimate (habitat,
low pollination, or protection against floods and landslides), air quality and water, as
well as cultural and supporting services (Jim & Chen 2009, Petrisor 2015). Despite
their ecological value, worldwide forests disappear at increasing rates due to the
deforestation (Andronache et al 2016). The latest Romania studies has indicated that
deforestation represent a threat to forest ecosystems during the transition period
(Popovici et al 2013, Petrisor 2015, Petrisor & Petrisor 2017). This issue is common
to transition countries and constitutes a consequence of land restitution (Kuemmerle
et al 2007, Müller & Munroe 2008, Knorn et al 2012, Kupková et al 2013). The
international experience indicates, that the only way to mitigate the forest loss is to
restore the forests on degraded lands, fact that lead to ecosystem restoration
(Chazdon 2008). The forests restoration can be achieved by two processes,
afforestation and reforestation, (afforestation is conversion of other land-uses into
forest, while reforestation is re-establishment of forest formations), and in these
cases the canopy covers more than 10% through plantations/natural regeneration and
less than 10% due to human-induced or natural perturbations (Dutca & Abrudan
2010).
In order to accomplish a proper green infrastructure on slope degraded lends, first of
all it must be established the trees specialists and panting density. Using the
appropriate planting methods must be achieved appropriate landscaping works to
establish adequate vegetation in accordance with site specific flora and fauna and
also to reduce erosion processes (Pop 2012). From the technological point of view,
the most suitable landscaping works are the terracing works, because the
meteorological precipitations are drained and directed towards established plants
root system, whose role is to absorb the excessive moisture and assure the
appropriate conditions to develop them. Fact that will improve the microclimate by,
stabilizing the soil; preventing ravines and landslide generation and stopping the
wind erosion.
In practice, was proven, that the most efficiently terraces are those with counter-
slope platform of 150 and 0.6÷1.5 m width, alternated with shredded strips,
especially for humidity deficit mountain slopes. In this case, the precipitations are
absorbed by the shredded strips and assures the water necessary for forestry
seedlings. In accordance with rainfall quantity is chosen the strip with; the number
of seedlings planted and also the terrace counter-slope. Also, was proven that the
water quantity that can be retained is of 17 l/m-2 (for a counter-slope of 10 %) and
25 l/m-2 (for a counter-slope of 15 %). If it is taken in to consideration also the water
infiltrations from the terrace surface it can be archived a total rainfall retention of
approx. 20÷40 l/m-2, especially if the terraces counter-slopes are periodically
maintained (Untaru 2010).

The innovative technology developed by INMA institute, is sustainable because can
be easily used and adapted to establish a wide range of green infrastructure (forestry
seedling requirements), with terrain geographical type (terrace dimensions and
structure, climatic and soil factors) and afforestation scheme, Figure 1. For degraded
lands the infrastructure must be composed mainly form trees altered with arboretum
and this species, must be chosen so that: to be resistant to severe weather conditions
(especially drought); less demanding from the ground; to have a vigorous growth; a
well distribution on the ground; to not have common diseases; to produce rich litter;
to regenerate easily and naturally; to produce valuable wood, etc. Normally, the
work process begins from upstream to downstream, respectably from the confluence
area to the main collector.
Figure 1. Technologic process of seedlings planting innovative technology
The innovation consists in using a small gauge power source, namely 318 Bertolini
motocultivator of 19 HP, that will be equipped with a succession of equipment’s
designed to work in difficult soil conditions (unstable or compacted soils; reduced
working space, high inclination, etc.), as: a horizontal milling equipment for soil
processing – FM; a soil modelling equipment with levelling blade - LM and also an
innovative drilling equipment that generate seedling dwelling – BM.
From technological point of view the FM is used to loosen and grinding the soil, fact
that will allow to be easily modeled the terrace surface using the LM (designed to
generate the counter-slope inclination). In cases when the counter-slope is more then
150, it is required to be used the FM again, in order to improve the soil permeability.
The BM equipment has been designed to generate vertical holes indifferent of
terrace counter slope inclination (≤300), fact that will improve seedlings
development rate (orientation of root system and seedling crown) and for this reason
its considerate most demanding and important operation. The BM requires a
powerful power-source, low weight, small gauge and high maneuverability, also its
PTO has a grate advantage because has two driving shafts and the driving direction
can be easily change in accordance with equipment requirements, only by rotating
the steering wheel.
The experimental methodology was made to validate the constructive and working
parameters for every equipment incorporated, to assess the energetic parameters and
also its productivity.
The first step was to evaluate the physic-mechanical terrace soil (compaction and
humidity measurements at different depths). The data were taken for two land strips:
on cultivated and grounded strips and are presented in Table 1.

Table 1. Physical-mechanical soil properties of experimental field

Experimental
Grounded land Cultivated land
parameters/
Depth [cm] 5 10 15 20 5 10 15 20
Average
compaction 175.5 772.7 1299.5 1580 140 578.5 604 789.5
grade [MPa]
Average
35.2 35.2 35.4 35.5 23.3 27.0 30.6 33.2
humidity [%]
The FM equipment it was powered by 600 rot min-1 PTO shaft and the working
speed on cultivated and also the grounded strips, are evaluated at every working
cycle, so to obtain average values. The semi-trailed LM equipment has a leveling
blade of 74x10x1000 mm, that weights 42 kg and it was coupled to its towing
system using a detachable fastening and removable stiffening system. This
equipment is provided with: a double-edged knife to increase reliability; two
adjustable transport wheels that can be adapted to road conditions and easily
dismantled prior to the soil modelling commencement; the working depth adjust
system (-140; -70; 0; +70; + 140 mm) – Figure 2a; an blade inclination system
left/right towards the direction of advancement (0, 10, 15, 25 0) – Figure 2b and an
active blade width system (1; 0,98; 0,94; 0,88 m) – Figure 2c. The number of LM
passes, depends of the counter-slope inclination.
a. b. c.
Figure 2. LM working parameters adjusting systems
During the levelling process it is necessary to equilibrate the blade using additional
weights of 30 kg in order to maintain constant the working depth. If the terrace
width is larger than 1 m, the levelling operation it is necessary to be done on at least
two passes, if we take in to consideration the blade loading level.
The BM equipment weights max. 112 kg and is provided with two earth augers of Ø
300 and Ø 400 mm, that can work at 300 mm and 400 mm depth. The augers are
guided by the adjusting position system (designed for max. 300 left and right
inclination), this technical solution is patent at OSIM no. A/00705 at 05.10.2016.
The auger working speed is controlled by the human operator, using the acceleration
handle and the maximum rotation speed is 135 rot. min-1. In Figure 3 and Figure 4,
are presented the working parameters adjusting systems.

1 - positioning system, 2 – screw, 3 - nut 4 – position stopper, 5 - assembly elements

Figure 3. Adjusting the drill inclination Figure 4. Adjusting the drilling depth
For normal working conditions (terrace counter-slope less the 150) the technological
process does not raise any outstanding problems, but for a counter-slope higher, the
soil modelling process can be made from several passes so to dislocate a greater soil
volume.

The experimental models of FM, LM and BM equipment’s worked well in
aggregate with 19 HP motocultivator, in stationary and exploitation conditions
(during approx. 120 hours), the experimental data obtained are presented in Table 2.
Table 2. FM, LM and BM operating parameters.

Soil type Grounded land - GL Cultivated land - CL
Type of equipment FM LM BM (Ø FM LM BM (Ø
300/400) 300/400)
Average working 800 310/ 805 312/
parameters
Processing
width/diameter [mm] 408 410

*Average working 100 285/ 150 298/
depth/angle [mm]/[0] 375 395
*Grinding percentage 80 - - 90÷ - -
[%] ÷90 95
*Average working speed 2.3 2.2 28.8/ 3.14 15/45
2.8
Energetic parameters in
[km/h] 75.4
Average driven power 14.5 1345
12.5 6 10 4.7
exploitation
[HP]
*Average fuel 3.42/1.9 2.9/1.7
1.05 0.95 0.9 0.9
consumption [l/h]
*Hour average work 90/ 110/
0.06 0.05 0.08 0.06
capacity [ha/h] 47** 62**
*Shift average work 720/ 880/
0.48 0.4 0.64 0.48
capacity [ha/sch.] 376** 496**
*Depends on the soil type and processing state; **The economic parameters for BM
equipment’s are evaluated in accordance with number holes.
At high working speeds the FM is working at a low depth and the grinding is higher,
but for low speeds the depth is higher and the grinding value is lower. For this
reason, the motocultivator power must be adapted to the soil type and work depth, in
this way the energetic and exploitation parameters can be improved.

The BM equipment it is in line with the specific technological requirements of

forestry and pomiculture equipment’s. Also, the operational parameters tested had
verified one technical solutions that was patented (A0075/05.10.2016) and will be
provided in the future developments with other two innovative solutions
(A01001/12.12.2016 - System for rapid mounting and damping the axial shocks of
the drill for making the planting holes and A0056/11.08.2017 - Deviations
compensation device during the drilling process using a guided auger by
parallelogram mechanism). Appling the mathematical algorithms for drilling
equipment’s, were determine the qualitative indices: the power consumed during the
working process that is influenced by auger rotation moment (rep. the max. gear
motor speed of output shaft) and by the transmission mechanical efficiency (that in
our case it has the value of 0.8); average depth and drilling period. These indices are
presented in Table 3.
Table 3. BM equipment qualitative indices for cultivated land.

Soi Terrace counter-slope
Qualitative indices l 00 15 0 20 0 00 15 0 20 0
typ
Auger diameter [mm] e 300 400
Gear motor speed [rot/min] - 135 135
CL 29.8 30.6 31.2 39.5 40.5 40.9
*Average depth [cm]
GL 28.5 30.26 31.66 37.5 38.1 39.6
CL 15 26 32 45 49.3 52.3
*Drilling period [s]
GL 28.8 38 40 75.4 76.8 81.6
CL 0.88 0.52 0.43 0.39 0.37 0.35
*Auger advancement [cm]
GL 0.44 0.35 0.35 0.22 0.22 0.22
1247.6 739.1 612.3 979.9 917.1 873.0
CL
Auger rotation moment [kgf 3 1 0 9 6 9
cm] 1087.5 875.1 869.8 971.7 969.2 948.1
GL
5 5 6 1 6 6
CL 866.34 923.41
Average [kgf cm]
GL 944.19 963.04
CL 2.94 1.74 1.44 2.31 2.16 2.06
Power consumed [HP]
GL 2.56 2.06 2.05 2.29 2.28 2.23
CL 2.04 2.17
Average [HP]
GL 2.22 2.27
*Estimations obtained from experimental data.
The auger rotation moment depends by soil physical-mechanical properties: the

global specific resistance coefficient for drilling is 2 kgf. cm-2 (cultivated land- CL)
and of 3.5 kgf. cm-2 (grounded land- GL).
The testing results of this aggregates conducted to the innovative afforestation
technology homologation, the success of green infrastructure establishment of fruit
trees seedling (seedling with root bale earth) that were planted in the first year of
production, in this way the establishment period is shorten and the soil remediation
process is shorter, fact that will lead to a medium time management environmental
management and improvement of the slope degraded terrains. The equipment
qualitative and energetic parameters can oscillate in the acceptable limits, especially
when the equipment is used in hard working conditions. All the values presented can

be influenced by the human factor, respectively by the physical force and the
experience of the operator.
Conclusions
This research has described the technical details of a concrete solution for the
afforestation of degraded lands. In a broader sense, the forestation of degraded lands
contributes to the restoration of their ecological services, and, through the ecological
services, to the overall sustainability. Future research should analyze whether the
project was able to restore the ecosystem services of the area, including the impact
on the activities carried out in the adjacent areas (agriculture etc.).
The potential beneficiaries can be: companies which carry out land reclamation,
landscaping and green spaces; trading companies that carry out works in forestry,
fruit growing and viticulture; forest fund management and maintenance associations,
and so one.
Acknowledgements
This paper is the product of the project “Researches on substantiating an innovative technology
for the afforestation of degraded slope lands”, financed by The Romanian Nucleu Programme,
contract no. 8N from 09.03.2016.
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SLUDGE DRYING IN TUNNELS USING PHOTOVOLTAIC PANELS
Cornel Sava1, Marius-Daniel Roman2, Elena Maria Pica1

1
Faculty of Engineering Materials and the Environment, Technical University of Cluj-Napoca,
28 Memorandumului, 400114, Cluj-Napoca, sava.cornel47@yahoo.com, Romania
2
Building Services Engineering Department, Technical University of Cluj-Napoca, 128-130
December 21 Blvd., 400604, Cluj-Napoca, Romania
Abstract
The objective of this work is to give the fundamental information that should be
known about sludge drying methods. The purpose of all types of sludge processing
is to reduce the volume, stabilise the sludge, remove water and kill pathogenic
organisms. It is processed in stages that contain a sequence of treatments such as
thickening, dewatering and drying.
Sludge drying in tunnels using photovoltaic panels is a continuous operation from
the sludge treatment which reduces the water content of sludge by heating it for
short periods. Dried product not only reaches granular formation with 92 - 95% DS
but also gets stabilized. This is a complicated process with contemporary heat and
mass transfer attended by physical-chemical transformations. Drying occurs as a
result of vaporization of liquid by supplying heat to wet feedstock.
Keywords: dehydration, drying process, tunnel dryer, sludge
Introduction
Sewage sludge is formed during mechanical, biological and chemical treatment of
wastewater. This causes the generation of large amounts of sewage sludge and its
management becomes a growing problem.
Raw sludge obtained from wastewater treatment consists of 95 to 99% water.
Remaining part is the solid sludge with different compositions depending on the
type and characteristics of influent, treatment technology applied and operational
conditions (Houdková et al 2008). Typical raw sludge consists of 60.27% carbon,
6.51% hydrogen, 24.89% oxygen, 8.35% nitrogen, and 0% sulphur (Houdková et al
2008). After digestion, the values change to 62.70% carbon, 8.27% hydrogen,
19.45% oxygen, 7.38% nitrogen, and 2.22% sulphur, respectively (Houdková et al
2008). The contents of dried sludge from municipal wastewater treatment plants
(WWTPs) are similar to the composition of brown coal, which has 21 MJ/kg of
calorific value (Stasta et al 2006). Sludge also includes phosphorus and potassium
compounds. Typical values for stabilized wastewater sludge are 3.3% nitrogen,
2.3% phosphorus, and 0.3% potassium (Tchobanoglous et al 2003, Gljzen 2002).
Although these values are lower compared to fertilizers for typical agricultural use
(5% nitrogen, 10% phosphorus, and 10% potassium), sludge provides sufficient
nutrients for good plant growth (Tchobanoglous et al 2003). In order to benefit from
the solid particles of sludge the obstacle of high water content should be reduced.
Dewatering, drying and thickening are three techniques to remove water from
sludge. These techniques can remove water by up to 32%, 6% and respectively 63%
(Flaga 2007). Drying has a number of advantages compared to dewatering and
thickening. It can remove more water than dewatering and thickening, which results
in volume of sludge to be minimal Reducing sludge volume decreases transportation
cost. Also, dried sludge with thermal drying does not need any stabilization or
pathogen removal Dry sludge can be stored easily and safely (Flaga 2007).
Moreover, dry sludge is preferable than the wet one because it can be used as an
alternative fuel source in a combustion facility or as a soil conditioner in agriculture
(Stasta et al 2005).
Sludge Thickening
Thickening is a process, which reduces the water content in sewage sludge; thereby
not only solid content of sludge increases but also overall sludge volume decreases.
Thickening process can enrich 0.8% of DS content of sludge to 4%. This process is
desirable because it reduces both the capital and operational cost of subsequent
sludge-processing steps. Even though sludge thickening process leads to high
volume reduction ratio (almost 80%), physical characteristic of sludge is still fluid.
Settling thickening, gravity thickening, flotation thickening, centrifugal thickening,
gravity-belt thickening, rotary-drum thickening are some thickening processes
(Tchobanoglous et al 2003, McFarland 2000).
Sludge Dewatering
Dewatering is the water removal technique to reduce the water content and total
volume of sludge. Typically dewatering comes after thickening and after
dewatering, sludge is no longer a fluid. Dewatered sludge can be carried with a belt
conveyer easily or transported by trucks. Since after dewatering sludge becomes a
solid, the transportation and sludge handling costs are reduced, incineration
efficiency is increased and leachate production potential during landfilling is
reduced. Typical dewatering processes are centrifugation and belt filter press
(Tchobanoglous et al 2003, McFarland 2000).
Centrifugation uses the centrifugal force developed by a rotating cylindrical drum or
bowl to achieve liquid-solids separation. The centrifuge is essentially a high-energy
settling unit. By this technique, it is possible to reach 25-35% dry solid content
(DSC) (McFarland 2000, Chen et al 2012).
Belt Filter Press dewaters sludge by forcing the water out from sludge under
squeezing shear forces. Product sludge achieves 15-25% DS content while raw
sludge solid concentration is 2-5% DS (Tchobanoglous et al 2003, Chen et al 2012).
Sludge Drying
Drying is the process, which can remove high amount of water from sludge. While
thickening and dewatering can remove 7% and 35% of the total amount of water,
respectively, drying can remove up to 62% additional water content after applying
these two systems (Flaga 2007). Sludge drying is an energy intensive process. This
system not only reduces volume but also stabilizes sewage sludge. Transportation,
storage, packaging and retailing are easy and cost efficient for dried sludge. Drying
increases calorific value of sludge. Thereby, sludge can be incinerated without
auxiliary fuel. Moreover, its potential as an alternative fuel in cement factories
improves. Dried sludge is also beneficial for agricultural purposes. Drying makes
sludge hygienic (without pathogenic organism), improves sludge structure and
increases its market value (Flaga 2007, Chen et al 2012).

The purpose of this study is to investigate the use of dry tunnels using photovoltaic
panels to dry sludge to 90% DS.
In order to design the drying tunnel, it is necessary for laboratory experiments to the
working temperature and the sludge keeping time inside the drying tunnel.
Laboratory experiments performed will reveal how much the drying space
influences the tunnel construction with controlled air movement and without air
movement.
Samples are dried to constant mass in an oven at different temperatures. The
difference in mass before and after the drying process is used to determine the dry
substance and the water content.
The procedure consists in:
• Place an evaporating dish or crucible in the drying oven set at different
temperatures for a minimum of 30 minutes and then cool to ambient
temperature in a desiccator, with the lid closed. After cooling, weighs the
dish or crucible to the nearest 1 mg, (ma).
• Depending on the expected water content, weigh into the evaporating dish
or crucible a suitable amount of sludge, (mb), so that the dry matter
obtained has a mass of not less than 0.5 g.
• Place the evaporating dish or crucible containing the sample in the drying
oven set at different temperatures until the residue appears dry, typically
overnight.
• After cooling in the desiccator, weigh the evaporating dish or crucible and
contents for the first time, (mc).
• The mass (mc – ma) shall be regarded as constant if the mass obtained after
another hour of drying does not differ by more than 0.5% of the previous
value or 2 mg, whichever is the greater. Otherwise, repeat drying until
constant mass is reached.
• Calculate the dry substance (wds) or the water content (ww) expressed as a
percentage of mass or grams per kilogram using the following equations:
mc − ma
w ds = ⋅f (1)
mb − ma
m − mc
w wc = b ⋅f (2)
mb − ma
where:
wds is the dry substance of the sample, in percentages or grams per kilogram;
wwc is the water content of the sample, in percentages or grams per kilogram;
ma is the mass of the empty dish or crucible in grams;
mb is the mass of the dish or crucible containing the sample in grams;
mc is the mass of the dish or crucible containing the dry matter in grams;
f is a conversion factor, f = 100 for expression of results as a percentage and factor
f = 1 000 for expression in grams per kilogram.
Values should be rounded to the nearest 0.1% (w/w) or alternatively to the nearest 1
g/kg.

a) b)
Figure 1. Dry substance without air movement (a) and with controlled air
movement (b).
Figure 2. Mass of the dish containing the sample in grams.
There is a risk of a cake surface forming. The formation of such cake surface
impedes even drying. To avoid this, a glass rod can be weighed along with the
crucible. If cake formation occurs during drying, the glass rod is used to stir the
sludge to break up the cake and bring the liquid surface into contact with hot air.

For dry substance without air movement were obtained 3 samples that are
introduced into the drying space at the same time at a temperature of 50 °C and
extracted after 30, 60, respectively 100 minutes.
Table 1. Experimental values for dry matter without air movement at 50°C
The mass of the dish
The mass of the
The mass of the or crucible The dry
dish or crucible
empty dish or containing the dry substance of the
Samples containing the
crucible substance after sample
sample
30,60,100 min.
g G g %
1 16.15 54.48 53.25 7.62
2 17.42 62.95 61.16 10.27
3 14.83 48.04 44.76 22.11

Figure 3. Results for dry substance without air movement at 50°C
Also another 3 samples are introduced into the drying space at the same time at a
temperature of 100°C and extracted after 30, 60, respectively 100 minutes.
Table 2. Experimental values for dry substance without air movement at 100°C
The mass of the
The mass of the or crucible
dish or crucible The dry substance
Samples empty dish or containing the dry
containing the of the sample
crucible substance after
sample
30,60,100 min.
g G g %
1 11.73 50.08 46.82 27.79
2 15.90 61.47 55.16 39.69
3 10.31 43.53 35.66 76.33
Figure 4. Results for dry substance without air movement at 100°C

Figure 5. Graphical representation of the results without air movement
Drying area without air movement ensures that the sludge is dried without
introducing heat into the entire sludge mass to be dried.
The lack of space ventilation makes the water vapour released by drying to
precipitate back into the dry sludge. The drying solution without air movement is a
low-productivity solution.
For dry substance with controlled air movement were obtained 3 samples that are
introduced into the drying space at the same time at a temperature of 50 °C and
extracted after 30, 60, respectively 100 minutes.
Table 3. Experimental values for dry matter with controlled air movement at 50°C
The mass of the
dish or crucible
Samples empty dish or containing the dry substance of the
containing the
sample
30,60,100 min.
g G g %
1 12.38 48.25 45.61 21.32
2 13.43 47.21 41.75 40.66
3 13.19 46.99 38.56 63.91

Figure 6. Results for dry matter with controlled air movement at 50°C
Also another 3 samples are introduced into the drying space at the same time at a
temperature of 100°C and extracted after 30, 60, respectively 100 minutes.
Table 4. Experimental values for dry substance with controlled air movement at
100°C
The mass of the
dish or crucible
Samples empty dish or containing the dry substance of the
containing the
sample
30,60,100 min.
g G g %
1 15.23 51.1 43.36 50.82
2 15.69 49.47 38.84 67.75
3 24.60 58.4 37.83 83.62
Figure 7. Results for dry substance with controlled air movement at 100°C

Figure 8. Graphical representation of the results with controlled air movement
Laboratory experiments results from data obtained in the samples for dry substance
with controlled air movement at 50°C and 100°C can vary widely from day to day
even for the same constant mass, this being also very difficult to determinate. But
the results for dry substance with controlled air movement at 100°C allow the user
to make a good prediction of how much the drying space influences the drying
process, knowing the dry substance and the water content.
Dry tunnels using photovoltaic panels

The drying performance of a dry tunnel, cannot go beyond 70% DS on average.
Therefore, dry tunnels should be supported with auxiliary heat to reach 90% DS.
This can be achieved through photovoltaic panels.
Figure 9. An illustration of the suggested tunnel dryer supported with photovoltaic

panels (Kurt 2014).

The system was evaluated based on the area required for photovoltaic panels and
tunnel dryer. Water removal rate in tunnel dryer is an indicative parameter for the
total cost and area requirement.
Kurt (2014) obtained in the case studies, that the amount of water that should be
evaporated to reach at most 70% DS impacts the area of the tunnel dryer itself while
the amount of water that should further be evaporated to reach 90% DS impacts the
additional energy requirement and therefore the area of photovoltaic panels.
An optimization model used in order to determine the costs of sludge drying with a
tunnel dryer supported with photovoltaic panels in which the relative energies
supplied (and therefore the costs) by the tunnel dryer and photovoltaic panels are a
function of an intermediate dry solids. Optimization helps to find the best solution
among all the feasible solutions (Kurt 2014).
Seginer and Bux (2005) have used several models for evaporation rates from tunnel
dryers. In general, they describe the evaporation rate as a function of weather, “state
of the sludge” (dry solids content, sludge temperature) and control within the
ventilation rate, mixing rat. Seginer and Bux used the vapor balance method in their
initial modeling efforts, which consists of measuring the humidity ratio, “w”, of the
ventilating air at the inlet and outlet of the unit; multiplying the difference, wo-win,
by the density of air and the discharge of the ventilation fans. Based on experimental
data, they also proposed a linear equation, for evaporation rate as follows:
E = 0.000461R₀ + 0.001010Qv + 0.00744T₀ - 0.220σ + 0.000114Qm (3)
where:
E is the evaporation rate (mm/h);
R₀ is the outdoor solar radiation (W/m2);
Qv is the ventilation rate (m3/m2-h);
T₀ is the air temperature (°C);
σ is the dry solids content of the sludge (kg solids/kg sludge);
Qm is the air mixing (m3/m2-h).
Conclusions
This study concludes after laboratory experiments for dry substance with controlled
air movement at 100°C can obtained 83.62% DS, also in a tunnel dryer, and
combined with photovoltaic panels, drying of the sludge is more efficient in removal
of moisture and enhances volume reduction up to 90% DS. Tunnel dryer is also
efficient in removal of bound water content that is not removed using mechanical
dewatering systems.
The photovoltaic panels are highly dependent on weather parameters like solar
radiations, wind velocity and relative humidity. The combination of tunnel dryer
with photovoltaic panels shows from studies that can save more in energy costs.
Acknowledgment
The authors would like to express appreciation for the support of the Doctoral School within
the Technical University of Cluj-Napoca, Romania.
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SYNTHESIS OF ZnO/CuO NANOCOMPOSITES WITH CNF AND Ag BY

GEL SOL
Catalina Nutescu Duduman 1, María Gómez De Salazar Y Caso De Los Cobos José 2,
Consuelo Gómez De Castro 2, Marius Niculaua 3, Gabriela Ciobanu 1, Maria Harja 1
1
Gheorghe Asachi Technical University of Iasi, Department of Chemical Engineering, 73
Mangeron Blvd., 700050, Iasi, mharja@tuiasi.ro, Romania
2
Complutense University of Madrid, Department of Materials Science and Metallurgical
Engineering, Av. Séneca 2, 28040, Madrid, Spain
³Romanian Academy Iasi Branch, Research Centre for Oenology, 18 Carol Blvd., 700505, Iasi,
Romania
Abstract
The synthesis of ZnO/CuO with Carbon Nanofiber (CNF) and Ag nanocomposites
have been conducted. Nanocomposites were synthesized using sol-gel method. The
nanocomposite products were characterized by SEM, TEM, XRD and DSC. The
results of the XRD analysis showed that the CuO-ZnO composite has a nanometer
size with the average of 10 nanometer. The SEM-EDX analysis showed that the
ZnO has a hexagonal structure whereas the CuO has a monoclinic structure. The
importance of impregnating the nanofibers with the precursors has been
demonstrated. The hydrazine is a better reducing agent than tannic acid. In this study
was synthesized polycrystalline silver as evidenced by XRD. SEM-EDAX analysis
indicate presence of oxides, nanofibers and silver.
Keywords: carbon nanofibers, characterization, sol gel method, nanocomposites,

silver
Introduction
In the recent years, the uses of nanoparticles become very important, in
interdisciplinary with chemistry, physics, biology, medicine, material science, etc.
(Shchemelinina et al 2017). The most application of the oxidic nanomaterials are
catalysis, biomedicine, coatings, semiconductors etc. (Harja et al 2016, Harja et al
2017, Kotova et al 2018, Noli et al 2015). Semiconductor materials are attractive due
to their properties reported different potential applications (Mousavi-Kamazani et al
2015, Li et al 2016).
ZnO is recognized as photocatalytic material, it can be activated by UV and visible
light to form the electron-hole pairs. The ZnO materials can produce radical
compounds and can be used as an antibacterial agent. However, the ZnO material
has large band gap of 3.3 eV (Widiarti et al 2017). The addition of CuO to ZnO
could form the CuO-ZnO composite that increased particle size and decrease the
band gap energy (Sathishkumar et al 2011). The increase of CuO content determines
decreasing of band gap energy. It increased the stability can be used CNF, addition
of Ag ions conducted to high antibacterial activity (Nutescu Duduman et al 2018).
The metal oxides ZnO/CuO have been widely used as adsorbents, conductive
materials, photo catalysts etc (Chatkaewsueb et al 2017).

There are various methods reported in literature for preparation of nanocomposite

materials such as sol gel, impregnation (El-Shobaky et al 1999, Harja & Ciobanu
2004) co-precipitation in aqueous or organic solutions (Shen et al 1997, Agrell et al
2003) and co-precipitation in an inorganic solvents (Zhang et al 1997, Ning et al
2001). Sol-gel is a simple method for nanomaterial synthesis, which consist in two
stages: sol and gel formation. In the sol-gel many parameters could be modified:
initial precursor, time of gel formation, type of activator, pH, gel formation
conditions etc (Habibi & Karimi 2014).
In this study nanostructure CuO/ZnO oxide mixture was prepared using the sol-gel
method using zinc and copper sulphates as precursors under thermal decomposition.
Were synthesized 4 samples that were characterized by SEM, TEM, XRD and DSC.
Materials and methods

For synthesis were used: Zinc Sulphate Heptahydrate (ZnSO4•7H2O) by Panreac,
Copper (II) Sulphate Pentahydrate (CuSO4•5H2O) by Panreac, hydrazine (N2 H4)
Sigma-Aldrich, tannic acid (C76H52 O46) Sigma-Aldrich, CNF Grupo Antolín
Ingeniería S.A, Silver nitrate (AgNO3) Panreac, deionized water (H2O) and sodium
hydroxide pearl 98-100% (NaOH) Panreac.
The nanocomposite was obtained by the sol-gel method (Nutescu Duduman et al
2016); (Nutescu Duduman et al 2018). The first step was dissolution of
ZnSO4•7H2O and CuSO4•5H2O, for obtaining 200 mL from each solution with
0.5M, respectively 0.2 M. After this were added 1.5 g of CNF and stirred 2.5 h, for
CNF impregnation. For obtained nanocomposite with silver AgNO3 is added after
impregnation. The next step is to add the required amount of NaOH to reach a pH
over 12. All of the samples were decanted, filtered, washed for removal reactant
excess and dry to constant mass. Sample drying was carried out in the oven at a
temperature of 110°C for 24 hours.

In the case of obtaining the nanocomposite, samples were synthetized, comparing
the results to highlight the route that leads to the obtaining of nanocomposites under
optimal conditions. For this purpose, two experiments are equally quantitative,
roughly the same conditions differ that the first experiment did not occur without
CNF impregnation and in the second experiment it was done. In the SEM and TEM
analysis very fine particles are observed, there are copper oxides and zinc oxide
leaving the free carbon nanofiber. This is due to the lack of impregnation before
CNF (Figure 1).
In the EDX spectrum of this nanocomposite, the formation of ZnO and CuO is
verified. If precursors, deionized water and CNF are added and the mixture was
allowed to stir for 2.5 hours to impregnate the CNF, analysis SEM can see spheres
form of CuO, ZnO is laminated and carbon nanofibers are coated with oxides. The
nanocomposite has a compact structure (Figure 2).

Figure 1. SEM and SEM-EDX analysis for sample 1 that did not impregnate CNF.
Figure2. SEM analysis for sample 1 with CNF impregnation.
In the TEM analysis of sample 1, agglomerates containing copper and zinc oxides
can be observed. Carbon nanofibers are free without being integrated into the
structure (Figure 3), as they did not have time to impregnate CNF.
Figure 3. TEM images of the sample 1.
In the TEM analysis (Figure 4) it can be seen that the areas belonging to the
agglomerated phases are in the form of nanoparticles and oxides and CNF.

Figure 4. TEM analysis of the sample 2.
Nanofibers are coated with oxides because in this analysis the CNF precursors were
impregnated forming a compact structured nanocomposite. EDS analysis confirms
the presence of oxides as well as CNF. Therefore, it can be concluded that there is a
difference between the two samples, the role of CNF impregnation can be clearly
seen. The morphology and structure of the 2 differs, we can see in sample 2 how
nanofibers are coated with copper and zinc oxides.
In Figure 5 shows peak X-ray corresponding to the different crystallographic planes
of the sample. The crystallinity of the synthesized nanocomposites composed of
copper and zinc oxides and CNF is confirmed. JPCDS card files for the CuO
monocyclic structure were used through the file JCPDS number 80-1268 and the
structure obtained is zinc-shaped with hexagonal structure indexed with JCPDS-36-
1451 files.
ZnO CuOCu5Zn8
Figure 5. XRD Diffractograms of samples 1 and 2.
A complex of copper and zinc seem to be intermetallic compounds Cu5Zn8 showing

the degree of reactivity during the process. For samples 3 and 4 the reduction
AgNO3 was done with tannic acid and hydrazine. Because the CNF impregnation
yielded good results, the two experiments were impregnated.
SEM analysis (Figure 6) shows a morphology consisting of oxides and CNF
agglomerates. SEM-EDX analysis shows the presence of Ag, Cu, Zn constituents.

Figure 6. SEM and SEM-EDX analysis of sample 3 using tannic acid.
Figure 7. SEM and SEM-EDX analysis of sample 4 using hydrazine.
When hydrazine was used as reducing agent, SEM morphologic analysis shows a
larger quantity of irregularity-sized oxides (Figure 7). Ag is observed in SEM-EDX
but in SEM images it is not likely to be observed in the matrix of the
nanocomposite. In the image obtained by TEM, agglomerates are observed, in the
red contour the Ag particle is bounded (Figure 8) which was identified by TEM-
EDS analysis. The diffractogram corresponding to the silver crystal is attributed to
the Burgers vector. Hydrazine is a stronger reducer than tannic acid and a change in
morphology is observed. Separated Electron Diffraction (SEAD) is compared to
known structures and we can state the Ag crystal.
Figure 8. TEM analysis of sample 4.
By the X-ray diffractogram analysis, cubic and orthorhombic crystalline structures

are confirmed (Figure 9). There are also peaks attributed to the cubic crystalline
structure of Ag read with card files.

Figure 9. XRD Diffractograms of samples 3 and 4.
In DSC analysis in which tannic acid was used, one exothermically process was
observed at 350 ℃, which refers to the elimination of tannic acid, another
exothermically process appears around 250℃, refers to the transformation of AgNO3
that did not completely react and the last one around 500 °C, refers to combustion of
carbon nanofibers, Figure 10.
Figure 10. DSC analysis of samples 3 and 4.
DSC analysis (sample 4) of the reduced hydrazine sample the endothermic peak
occurring at 140 ℃ corresponds to transforming AgOH into Ag2O.

Conclusions
The nanocomposite ZnO-CuO-CNF-Ag was obtained by the sol-gel method. To
ensure good results, the pH should be over 12. The importance of impregnating the
nanofibers with the precursors has been demonstrated and stirred for 2.5 hours. By
using the hydrazine, good results are obtained being a better reducing agent than
tannic acid. In this study was synthesized polycrystalline silver as evidenced by
XRD. SEM-EDAX analysis of samples indicate agglomerate containing oxides,
nanofibers and silver.
Acknowledgements
This work was supported by Ministry of Economy and Competitiveness. Reference:
MAT2013-46755-R.
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THE INFLUENCE OF TEMPERATURE ON SO2 RETENTION FROM

RESIDUAL GASES BY ABSORPTION INTO DILUTE BASIC SOLUTIONS
Annette Madelene Dancila, Cristina Modrogan, Cristian Onose, Oanamari Orbulet, Cristina
Orbeci
Politehnica University of Bucharest, Faculty of Applied Chemistry and Material Science, 1-7
Gheorghe Polizu, Bucharest, dancila.madelene@yahoo.com, Romania
Abstract
The work is part of current concerns regarding the reduction of SO2 emissions in the
atmosphere. The study aimed the SO2 retaining by absorption in dilute NaOH
solutions at different temperatures in the range of 20-60oC.
The analysed parameters were: the pressure variation of SO2 in the gaseous phase
depending on the SO2 volume injected, the degree of loading of the solution, the
pressure variation according to the degree of loading, the amount of SO2 absorbed
depending on the volume of SO2 injected and the absorption efficiency of the
solution depending on the volume of SO2 injected.
Keywords: absorption, diluted solutions of NaOH, SO2
Introduction
In latest years, particular attention has been paid to the removal of SO2 from various
industrial sources (Zhu et al 2005, Gómez et al 2007, Jannelli & Minutillo 2007).
Numerous industrial gases have a high content of sulphur, as for example, the gas
from coke ovens and thermal power plants, especially those that use fuels with high
sulphur content. Certain plants, such as chemical plants producing sulphuric acid,
emit gases containing sulphur dioxide, which is considered one of the most
dangerous air pollutants. Recourse to the use of natural fuels with low sulphur is
limited to availability and high price. There have been developed technologies for
flue gas desulfurization system for fuels with high sulphur content (Yan et al 2014).
Current studies emphasize the high cost of these operations; besides this, it was not
proved on a satisfying manner the possibility of sulphur extension in a desired
proportion by the methods of hydrodesulphurisation of coal, oil or residual oil with a
high content of residual sulphur (Dupart et al 1993, Spörl et al 2013, Cheng et al
2017, Ladwig & Blythe 2017).
Other methods of solving the pollution problem with sulfur oxides refers to their
removal from the exhaust gases and establishing the concentrations limits for
harmful gases which may be disposed of into the atmosphere (Kilicarslana & Qatu
2017, Wei et al 2011).
Normally the concentration of sulfur dioxide emission gas from existing sulphuric
acid plants is 2,000-3,000 ppm and sometimes reach up to 5,000 ppm. The value of
2,000 ppm is equivalent to the cca. 12.5 kg to 1 tone of H2SO4 produced, and the
maximum limit is 2.7 kg/t of H2SO4 produced.
Emissions of sulphur dioxide have decreased by 66% between 1990 and 2005. In
2005, the most significant source of SO2 emissions was the energy industries sector

(41%), followed by emissions occurring from industrial processes (35%) and

industrial energy use (13%) (www.eea.europa.eu).
According to the European Directive, CAFE 2008/50/EC, the emission limit values
for SO2 in the atmosphere are comprised between 20 µg/m3 air per year, 125 µg/m3
air/24 hours and 350 µg/m3 air/1 hour. (www.europarl.europa.eu). Absorption of
SO2 is performed in order to obtain a gas sulphate of high concentration (SO2) to
enrich the poor gas, which cannot be used directly to obtain sulfuric acid and
purification of flue gases with a low content of SO2. As an absorbent are used:
water, solutions of inorganic and organic compounds or their solutions.
The process of SO2 retention in various liquid fumes is mostly a physical absorption
process, accompanied by a chemical reaction, so it is a process of chemosorbtion.
The most widely used methods are: chemosorbtion-based processes on metallic
oxides (MgO, CuO, MnO2 and especially CaO) (Przepiórski et al 2012, Gaudin et al
2016, Osaka et al 2015, Czyzewski et al 2013); absorbents in suspensions-based
processes (e.g. LIME process that uses a suspension consisting of CaO or process
water and LIMESTONE, a suspension of CaCO3 and process water or LIME-
LIMESTONE a suspension of CaCO3∙CaO, and water) (Srivastava 2000, Kohl &
Riesenfeld 1985, Dagaonkar et al 2001a, 2001b) sodium citrate (Bekassy-Molnar et
al 2005). Other methods used so far are absorbents in ammoniacal solution, process
solutions, Wellman-Lord (which uses NaOH as absorbent and Na2CO3); a
disadvantage of this procedure is that in time we obtain Na2SO4 that is inactive
against SO2. A modified version of this procedure (the ionic process Stone Webster)
partially removes these disadvantages by introducing a secondary processing of the
solution of Na2SO4 through electrolysis, when recovering NaOH and get H2SO4
(Irabein et al 1992, Wang et al 2011).

The study aimed to determine the quantity of SO2 absorbed depending on the
volume of SO2 and apprehension SO2 injected into the NaOH solutions of different
concentrations, temperatures and degrees of loading. Solutions of NaOH
concentrations used in this study were 2, 5 and 10 %, and temperatures of 20, 40 and
60 °C. The plant used to perform the study is shown in Figure 1 and consists of a 1-
thermostat absorption vessel in which it was introduced a volume of NaOH solution
of different concentrations, 2-airtight device for injecting volumes of SO2 to the
upper side, 3-magnetic stirrer and 4-differential manometer with mercury.
The thermostat vessel is mounted on a magnetic stirrer and has an airtight device for
injecting volumes of SO2 to the upper side. The pressure difference is read on
differential manometer with mercury.

Figure 1. Work installation (1-thermostat absorption vessel; 2-airtight device for

injecting volumes of SO2; 3-magnetic stirrer; 4-differential manometer). Reaction
mechanism of absorption of SO2 in NaOH solutions.
Version A
NaOH + SO2 → NaHSO3 ΔH=361.26 kJ/mole
Version B
2NaOH + SO2 → Na2SO3 + H2O ΔH=-155.68 kJ/mole
Na2SO3 + SO2 +H2O → 2NaHSO3 ΔH=-566.84 kJ/mole
NaOH + SO2 → NaHSO3 ΔH=-361.26 kJ/mole
Version C
NaOH + NaHSO3 → Na2SO3 + H2O ΔH=205.58 kJ/mole
2NaHSO3 → Na2SO3 + H2SO3 ΔH=534.94 kJ/mole
In order to determine which mechanism is more useful for SO2 retention by

absorption, the study tracked several parameters: pressure variation according to the
volume of SO2 injected, the loading degree of the solution, pressure variation
according to the loading degree, the amount of SO2 absorbed depending on the
volume of SO2 injected and the absorption efficiency depending on the volume of
SO2 injected.
Calculation of the load of the solution with SO2 were made on the basis of formulas:
moles SO2
β=
moles NaOH (1)
where: VSO2 corrected

moles SO2 =
22400 (2)
VSO2 corrected = the volume of SO2 injected, brought under normal circumstances
VNaOH ⋅ ρ NaOH ⋅ C NaOH 1

moles NaOH = ⋅
100 M NaOH (3)


Pressure variation depending on the volume of SO2 injection
Figure 2. SO2 absorption in various solutions of NaOH at 20, 40 and 60 °C.
Comparative analysis of curves, coordinate ΔP= f(VSO₂) where ΔP is the partially

pressure variation of the SO2 in the gas phase, lead to the conclusion that as
increases SO2 injected amount, increases the SO2 pressure in the gaseous phase,
which highlights the fact that SO2 absorption in solutions of NaOH is not total
Increasing the temperature of the NaOH solution favours retaining of a larger SO2
volume.
NaOH solution 10% concentrated can retain more SO2, which is observed by lower
SO2 pressure values in the gaseous phase than at 2% and 5% NaOH solutions.
The low temperature of 20 °C favours the dissolution (physical absorption) of SO2
in solutions, regardless of the concentrations. At 40 oC temperature, NaOH solutions
of 2% and 5% the physical absorption is shorter, SO2 being retained by chemical
absorption, the reaction mechanism to this temperature resulting from version A to
obtain NaHSO3.
The temperature of 60 °C leads to SO2 retention in the case of 2% solutions only by
chemical reaction, and in the case of 5 and 10% solutions the SO2 absorption takes
place first in the form of physical absorption and then as chemical absorption made
after the reaction Version B.
Pressure variation depending on the degree of loading solutions of NaOH
Figure 3. The loading degree of NaOH solutions at 20, 40 and 60 oC temperature.
Figure 3 illustrates the loading degree of NaOH solutions according to temperature.

At 20 oC temperature, loading of solutions is low compared to solutions that retain
SO2 at temperatures of 40 or 60 oC. The 2% solution saturates much faster
regardless of the temperature of the solutions. Solutions of 5% and 10%,
respectively, can retain higher volumes of SO2.
Initially, SO2 retention occurs by physically absorption at temperature of 40 °C up to

a β = 0.3 load. For the solution at 60 oC temperature the physical absorption of SO2
takes place up to a load of β = 0.5, then the retention is done by chemical reaction
with obtaining of sodium sulphite acid. The fact that all graphs have ascending
curves leads to the conclusion that the process is not complete, the solutions are not
saturated.
In case of retention at 40 and 60 degrees, the absorption process is a two-stage
process: first, a slow increase in pressure, which can be interpreted by a physical
SO2 absorption process in the solution and the second stage, evidenced by
accentuated pressure increase caused by beginning chemical absorption
characterized by a lower speed than dissolution rate.
The variance quantity of SO2 absorbed depending on the volume of SO2 injection
The amount of SO2 absorbed was calculated according to the relations:
VSO2 absorbed
mSO2 = ⋅ 64
22400 (4)
Where:
VSO2 absorbed = the volume of SO2 absorbed into solution of NaOH
VSO2 absorbed = Vgas − Vprecinct
(5)
Vgas= the volume of the mixture of air and SO2 which lies above the liquid phase
Vprecinct = the volume of the vessel after the injection of SO2 and absorption in
solution
Vgas = (273 + t ) ⋅
(V precinct )
+ VSO2 corrected ⋅ 756
293 ⋅ (756 + ∆P ) (6)
0.1256 ⋅ ∆P
V precinct = Vvessel + − VNaOH
VSO2 inj (7)
where:
VSO2 inj = the constant volume of SO2 injection
VNaOH = the volume of NaOH solution introduced in the absorption vessel
Vvessel = the volume absorption vessel was determined experimentally and it is
147.35 cm3
The graphs are in the form mSO absorbit = f (VSO corrected )
2 2

Figure 4. The variance of SO2 quantity absorbed at 20, 40 and 60 oC.
At constant temperature solutions with a higher NaOH concentration retain a higher

quantity of SO2 as shown in Figure 4.
Thus, in the case of 10% NaOH solution at 40 °C temperature, the amount of SO2
absorbed increases up to a volume of about 250 cm3 of SO2 injected, instead at
60 °C temperature, the amount of SO2 absorbed is slightly lower for the same
volume of SO2 injected, then it reaches a level characteristic to the saturated
solution.
In case of reaction at 40 oC temperature the process is a two stages process, both
through dissolution and chemical reaction; while at 60 °C temperature the process
flows only through chemical reaction, the amount of SO2 physically restrained being
much smaller due to the decrease of SO2 solubility into solution.
In the case of NaOH 5 % solution the rise of temperature leads to an increase of the
SO2 amount absorbed into solution. The explanation of what we have observed is
that gas is first physically restrained and then is retained by the chemical reaction;
the last process occurs with a lower speed and a greater time for reaction is needed.
Effectiveness of SO2 retentions in NaOH solutions of different concentrations at

different temperatures
Conversion level of SO2 retention in solutions of NaOH is calculated on the basis of
formulas:
V
η SO2 abs = SO2 abs ⋅ 100
Vgas
(8)
Figure 5. Effectiveness of SO2 restraint in the NaOH solution at 20, 40 and 60 oC.

From the three graphs it is noted that the absorption process is identical up to a
point, up to a certain volume of SO2 injected, about 40-50 cm3, regardless of the
reaction environment temperature, meaning the reaction goes first by physically
absorption followed by chemical reaction of SO2 retention into solutions, process
that occurs with a different speed. The shape of curves plotted at constant
temperature is similar to various concentrations of the solution.
It is noticed that the concentration increasement of the absorptive environment
conduct to increases the SO2 volume that is retained. For temperatures of 40 and 60
degrees there is a „ jump” of the restraint effectiveness, according to the beginning
of the chemical absorption.
Conclusions
Absorption is much better at high temperatures; in this case the sulphite conversion
level is much higher.
At 20 °C temperature, SO2 is physically absorbed, and SO2 may be desorbed when
removing the absorbent solution.
Temperatures of 40 and 60 °C lead to the chemical absorption of SO2 with
formation of sodium sulphite as for Version A if the solutions have concentrations
of 5%. The chemical absorption reaction can follow Version B if the solutions are of
10% concentration, requiring a higher amount of NaOH to fix also the physically
absorbed SO2.
The chemical absorption Version C with formation of Na2SO3 and H2SO3 can only
occur in the case of solutions with 10% concentration at 40 °C temperature, the
reactions being exothermic.
Acknowledgment
This work has been funded by University Politehnica of Bucharest, through the “Excellence
Research Grants” Program, UPB – GEX 2017. Identifier: UPB- GEX 2017, Ctr. No. 78/2017
Cod 136”.
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THE SOLUTION CHEMISTRY OF THE COPPER (II) - AMMONIA -

THIOSULFATE AQUEOUS SYSTEM
Igor Povar1, Stefano Ubaldini2, Tudor Lupascu1, Oxana Spinu1, Boris Pintilie1
1
Institute of Chemistry, 3 Academiei, MD2028, Chisinau, ipovar@yahoo.ca, Republic of
Moldova
2
The Institute of Environmental Geology and Geoengineering of the Italian National Research
Council, stefano.ubaldini@igag.cnr.it, Italy
Abstract
The paper presents a new thermodynamic approach to studying mixed ligand
complex formation reactions in multicomponent two-phase systems “solid phase -
saturated aqueous solution” under real conditions.
The quintessence of developed approach consists in the thermodynamic analysis of
concurrent reactions in the system Cu (II)-NH3-S2O32--H2O under real conditions on
the basis of the introduced notion of the generalized reaction equation. The
formation of mixed ligand complex species Cu (OH ) i ( NH 3 ) j ( S 2 O3 ) k is
characterized by certain peculiarities in the behavior of studied two-phase
heterogeneous systems. The new feature is to focus on the chemical description of
the overall process of complex formation consisting of a series of concurrent
reactions, where the nature and ratio of the concentrations of chemical species,
formed in such reactions, depend on the ratio of the concentrations of the metal Cu2+
and ligands, temperature and other factors (thermodynamic parameters).
Keywords: ammonia, copper (II), leaching, thermodynamics, thiosulfate
Introduction
The use of cyanide CNˉ was the dominant method used to extract gold from its ores
for many years. However, cyanide is extremely toxic to organic environments and
biological creature (Xu et al 2017, Zhang & Senanayake 2016). Significant efforts
candidate. This is mainly due to the fact that thiosulfate is nontoxic, inexpensive,
has a good selectivity to gold with limited interference from foreign cations and high
gold recoveries from a wide range of gold minerals such as ores copper, carbon
blacks and sulfide ores (Abbruzzeseet al 1995, Aylmore & Muir 2001a, Grosse et al
2003, Liu et al 2017). Additionally, thiosulfate has been used as a fertilizer for many
years due to its relatively low impact on the environment. Various oxidants for the
thiosulfate system, including oxygen, amine complexes of Cu (II), Co (III) amine
complexes and several Fe (III) complexes (Aylmore & Muir 2001b, Liu et al 2018,
Muir & Aylmore 2005, Senanayake & Zhang 2012) have been recommended. But
the Cu (II) amine complexes have been studied most intensely, potentially leading to
enhancement of copper concentrations in solution. Additionally, as the leach
solutions should be alkaline in order to avoid thiosulfate decomposition, the addition
of ammonia is required to stabilise the copper (II) as a copper (II) – ammine
complex (Breuer & Jeffrey 2003).

The overall reaction of gold leaching is Au + Cu (II) = Au(I) + Cu(I). Oxidation of

metallic gold in Au+ in ammonium thiosulfate solution in the presence of Cu(II)
takes place at the potential of ~ 0 V (relative to the standard hydrogen potential) and
can be represented by the following equations (Wan 1997):
2 Au + 10 S 2O32− + 2Cu ( NH 3 ) 24+ → 2 Au ( S 2O3 ) 32− + 8 NH 3 + 2Cu ( S 2O3 ) 53−
(1)
4Cu ( S 2O3 ) 53− + 16 NH 3 + O2 + H 2O → 4Cu ( NH 3 ) 24+ + 4OH − + 12S 2O32−
(2)
However, the mechanism of reduction of Cu(II) in Cu(I) illustrated in equations (3),
(4), (5) and (6) is much more complex and involves the formation of mixed
compounds in the Cu(II)-NH3-S2O32-, Cu(I)-NH3-S2O32- and Au(I)-NH3-S2O32-
systems and their adsorption on the surface of gold with the simultaneous oxidation
of gold and thiosulfate (Senanayake 2004, Senanayake 2005, Choo & Jeffrey 2004).
It has been shown recently that the presence of Cu (II) in the thiosulfate leach
solution does not only act as an oxidant, but in addition considerably enhances the
gold oxidation reaction (Breuer & Jeffrey 2003). Despite considerable research in
the thiosulfate –copper – ammonia leaching system, the lack of important formal
chemical thermodynamics has delayed the use of the thiosulfate process as an
alternative to cyanidation. The paper presents a developed thermodynamic approach
to studying mixed ligand complex formation reactions in multicomponent two-phase
systems “solid phase - saturated aqueous solution” under real conditions.
Its quintessence consists in the thermodynamic analysis of concurrent reactions in
the system Cu (II)-NH3-S2O32--H2O under real conditions on the basis of the
introduced notion of the generalized reaction equation (GRE). The formation of
mixed ligand complex species Cu (OH ) i ( NH 3 ) j ( S 2 O3 ) k is characterized by certain
peculiarities in the behavior of studied two-phase heterogeneous systems. The new
feature is to focus on the chemical description of the overall process of mixed
complex formation consisting of a series of concurrent reactions, where the nature
and ratio of the concentrations of chemical species, formed in such reactions,
depend on the ratio of the concentrations of the metal Cu2+ and ligands, temperature
and other factors (thermodynamic parameters).

The overall process, e.g. possible homogeneous chemical equilibria, considering all
potential Cu(II) species (parent and mixed hydroxo complexes of readily
hydrolysable copper ions, tris complexes in the case of large ligand excesses,
precipitation etc.), can be described by the following GRE equation (the quantity fijk
denotes the partial molar fraction of the respective species) (Povar et al 2018):
 
Cu 2+ + ∑ ∑ ∑ if ijk H 2 O + ∑ ∑ ∑ jf ijk  f NH 3 + f +  NH 3 +
i =0 j =0 k =0 i =0 j =0 k =0  NH 4

 
 ∑ f l H l S 2 O3  = ∑ ∑ ∑ f ijk Cu (OH ) i ( NH 3 ) j ( S 2 O3 ) k +
 ∑ ∑ ∑ kf ijk
(3)
 i =0 j =0 k =0  l =0 
 i =0 j =0 k =0
 
+
∑ ∑ ∑ if ijk H ,
i =0 j =0 k =0
where ∑ ∑ ∑ f ijk = 1 , f NH + f = 1 and ∑ f l H l S 2 O3 = 1 .

i =0 j =0 k =0
3 NH 4+ l =0

GRE is the generalization of a set of common chemical equations, taking into

account the simultaneous formation of several different chemical species.
The mass balance equations for the investigated system are as follows:
C0 = ∑ ∑ ∑ [Cu (OH ) i [ NH 3 ] j [ S 2O3 ]k = [Cu 2 + ]α Cu 2+

Cu 2+ i =0 j =0 k =0 (4)
0
C NH 3
= [ NH 3 ] + [ NH 4+ ] + ∑ ∑ ∑ j[Cu (OH )i [ NH 3 ] j [ S 2O3 ]k
i =0 j =0 k =0
(5)
C 0 2− = [ S 2O32− ] + [ HS 2O3− ] + [ H 2 S 2O3 ] + ∑ ∑ ∑ k[Cu (OH ) i [ NH 3 ] j [ S 2 O3 ]k (6)
S 2O3 i =0 j =0 k =0
where the alpha coefficient is calculated with the deduced expression:
α Cu 2+ = 1 + ∑ ∑ ∑ β ijk [ H + ]−i [ NH 3 ] j [ S 2O32 − ]k (7)

i =0 j =0 k =0
On the other hand, the precipitation-dissolution heterogeneous process of the

slightly soluble CuO(S) oxide in the thiosulfate – copper – ammonia leaching system
can be described with the following GRE:
( )
CuO( S ) + ∑ ∑ ∑ 2 − if ijk H + + ∑ ∑ ∑ jf ijk f NH 3 + f NH + NH 3 +
i =0 j =0 k =0 i =0 j =0 k =0
( 4
)
 
 ∑ ∑ ∑ kf ijk  ∑ f l H l S 2 O3  = ∑ ∑ ∑ f ijk Cu (OH ) i ( NH 3 ) j ( S 2 O3 ) k + (8)
 i =0 j =0 k =0  l =0 
 i =0 j =0 k =0
 
(
∑ ∑ ∑ 1 − if ijk H 2 O, )
i =0 j =0 k =0
The variation in Gibbs energy of the heterogeneous process (8) was calculated by
means of the expression (Povar & Rusu 2012); (Povar & Spinu 2014); (Spinu 2014):
∆G = − RT ln K S α Cu 2 + + RT ln C 0 [ H + ] −2 (9)
Cu 2 +
where KS is the equilibrium constant of the reaction:
CuO( S ) + 2 H + = Cu 2+ + H 2 O, K S = [Cu 2+ ] /[ H + ] 2

Based on the equations (1)-(9), a thermodynamic study was carried out to determine
the copper (II) species during gold extraction and recovery of the copper -
thiosulfate - ammonia systems. The equilibrium constants of all the possible
reactions in the investigated system are summarized in Table 1. The distribution of
soluble and insoluble copper species in the system Cu(II)-NH3-S2O32- was
investigated as a function of pH, copper, ammonia and thiosulfate concentrations
using the thermodynamic analysis and the repartition diagrams for heterogeneous
system (Povar & Rusu 2012). The area of thermodynamic stability of the solid phase
CuO(S) and relative amounts of each species depend on the [NH3]: [S2O32-] ratio in
solution. Figure 1 shows that CuO(S) is precipitated at pH = 12.64 at high
concentrations of ligands NH3 and S2O32- (curve 1). Our calculations showed that the
domain of stability of solid cupric oxide is expanding to lower and higher pH values
with increasing Cu (II) concentrationin the manner predicted by thermodynamic
modelling. The area of thermodynamic stability of cupric oxide substantially
extends also with decreasing the concentrations of both ligands NH3 and S2O32- at
the same initial concentration of Cu2+ (curves 2 and 3). The thermodynamic
speciation of copper species shown as a function of pH in figure 2 and figure 3 was
calculated based on the thermodynamic method and diagrams of heterogeneous
equilibria developed by (Povar & Rusu 2012, Spinu 2014). The cupric oxide
becomes the dominant species up to pH 8 at lower concentration of NH3 and high
concentration of S2O32-, prevailing over the mixed species Cu (NH3)2(S2O3)22-
(Figure 3).
The thermodynamic analysis has proved that the mixed-ligand complexes
Cu(NH3)2(S2O3)22- and Cu(NH3)3(S2O3)20 are more stable and dominant than other
species Cu(S2O3)k2-2k, Cu(NH3)j2+ at high concentrations of ammonia and/or
thiosulfate (Figure 2 and Figure 3). These results should be mandatorily taken into
account at studying the redox processes of the ammoniacal thiosulfate leaching of
gold.
1. C0(Cu2+) = 0.1 mol/L; C0(NH3) = 4 mol/L; C0(S2O32-) = 2 mol/L

2. C0(Cu2+) = 0.1 mol/L; C0(NH3) = 0.1 mol/L; C0(S2O32-) = 2 mol/L
3. C0(Cu2+) = 0.1 mol/L; C0(NH3) = 0.1 mol/L; C0(S2O32-) = 0.1 mol/L
6
4 3
2
2
1
∆G/2.3RT
-2
-4
-6
4 5 6 7 8 9 10 11 12 13 14
pH
Figure 1. The variation of Gibbs energy versus pH in the heterogeneous system

Cu(II)-NH3-S2O32--H2O.

Table 1. The equilibrium constants of all the possible reactions in the investigated
system
Species log K Source

Cu ( NH 3 )(OH ) + 0.9 Senanayake 2004a
Cu ( NH 3 ) 2 (OH ) 2 -12.3 Senanayake 2004a
Cu ( NH 3 )(OH ) 3− -25.7 Senanayake 2004a
Cu (NH 3 ) 2+ 4.2 Vazquez-Arenas et al 2007
Cu (NH 3 ) 22+ 7.75 Vazquez-Arenas et al 2007
Cu (NH 3 )32+ 10.6 Vazquez-Arenas et al 2007
Cu (NH 3 ) 24 +
12.9 Vazquez-Arenas et al 2007
Cu (NH 3 )52 +
12.43 Vazquez-Arenas et al 2007
Cu ( NH 3 ) 2 ( S 2 O3 ) 13.17 Senanayake & Zhang 2012
Cu ( NH 3 ) 3 ( S 2 O3 ) 13.65 Senanayake & Zhang 2012
Cu ( NH 3 ) 2 ( S 2 O3 ) 22− 15.06 Senanayake & Zhang 2012
Cu ( S 2 O3 ) 2.4 Senanayake & Zhang 2012
Cu ( S 2 O3 ) 22− 5.2 Senanayake & Zhang 2012
NH 4+ 9.4 Vazquez-Arenas et al 2007
HS 2 O3− 1.68a Aylmore & Muir 2001b

a
H 2 S2O3 1.98 Aylmore & Muir 2001b
CuOH +
-7.7 Smith &Martell 1976c
Cu (OH ) 2( aq ) -15.2 Smith &Martell 1976c
Smith &Martell 1976c

Cu (OH )3−
-27.5
Cu (OH ) 42− -40.4 Smith &Martell 1976
CuO(s ) 8.49 Plyasunova et al 1997
Cu (OH ) 2( s ) 9.1 Plyasunova et al 1997

2+
aRecalculated for the reaction: Cu + iNH 3 + jH 2 O = Cu ( NH 3 ) i (OH ) j + jH +
bRecalculated from the ∆G 0f (i ) values from CODATA recommendations.
cRecalculated for the reactions of hydrolysis.

1.0
Cu(NH3)2(S2O3)22-
0.8
fijk 0.6
0.4
0.2
Cu(NH3)3(S2O3)
Cu(NH3)52+
0.0
6 7 8 9 10 11 12 13
pH
Figure 2. Thermodynamic speciation diagram of Cu(II) species as a function of pH

in the homogeneous system Cu(II)-NH3-S2O32--H2O. Concentrations,
0 0
mol/L: C 2 + = 0.1 ; C NH = 4 ; C 0 2 − = 2
Cu 3 S 2O3
CuO
1.0
0.8
0.6
fijk
0.4 Cu(NH3)2(S2O3)22-
0.2 Cu(S2O3)22-
0.0
6 7 8 9 10 11 12 13 14
pH
Figure 3. Thermodynamic speciation diagram of Cu (II) species as a function of pH

in the heterogeneous system Cu (II)-NH3-S2O32--H2O. Concentrations,
0
mol/L: C 0 2 + = 0.1 ; C NH = 0.1 ; C 0 2 − = 2
Cu 3 S 2O3
Conclusions
An original thermodynamic approach to complex chemical equilibrium analysis was
used, taking into account complex reactions in multicomponent heterogeneous
systems under real conditions. Its principle consists in the thermodynamic analysis
of the conditions of realization of different processes based on the global
thermodynamic characteristics. The reciprocal relations of thermodynamic
characteristics for technological processes with different physicochemical properties
constitute the basis of the systematization of the experimental material, the
fundamental search for the optimal conditions of technological processes or the
suppression of unwanted processes.
The generalized equations of the soluble and insoluble species involved in the
complex homogeneous and heterogeneous process and the equation for calculating
the Gibbs energy variation of the precipitation-dissolving process of the less soluble
CuO(S) oxide were deduced.
A thermodynamic study was accomplished to determine the copper (II) species
during gold extraction and recovery with the copper - thiosulfate - ammonia
systems. It has been shown that mixed complexes containing two ligands
Cu(NH3)2(S2O3)22- and Cu(NH3)3(S2O3) are more stable than other species as
Cu(S2O3)i2-2i and Cu(NH3)j2+ at high concentrations of ammonia and/or thiosulfate.
The relative quantities of each species depend on the ratio [NH3]:[S2O32-]in the
solution.
The thermodynamic stability of the solid phase CuO(S) depends greatly on the pH
and concentrations of ammonia and thiosulfate.
The obtained results are useful for optimization of the overall scheme of thiosulfate
leaching for gold hydrometallurgy. The speciation of copper in such complex
system can have a detrimental effect on the environment as well as in the industrial
processes. The precipitation of cupric oxide above a critical pH can be used in the
treatment of Cu2+-containing wastewater.
Acknowledgement
Co-authors Igor Povar, Stefano Ubaldini, Tudor Lupascu and Oxana Spinu are thankful for the
financial support given by the National Research Council of Italy and Academy of Sciences of
Moldova of their project “Thermodynamic optimization of innovative processes developed to
valorize industrial wastes containing valuable metals” during the years of 2018-2019.
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USING THE LECHATE TREATMENT TECHNOLOGIES FOR

FERTILIZERS
Casen Panaitescu1, Cristinel Constandache2

1
Petroleum-Gas University of Ploiesti, 39 Bucuresti-Ploiesti Blvd., cpanaitescu@upg-
ploiesti.ro, Romania
²National Institute for Research and Development in Silviculture "Marin Dracea”, 7 Republicii,
Focşani, icasvn2006@yahoo.com, Romania
Abstract
Sludge’s from leachate treatment are liquid waste. Order 757/2004 regulates the
storage of sludge obtained in the process of treatment in the ecological deposit in a
proportion of 1:10. Since the sludge usually obtained has a moisture content of over
85%, it is necessary to store it in order to dry it. The new waste legislation in
Romania sets an objective for 50% reduction of waste disposal in landfills by 2020,
which will have an impact on the cost of landfilling sludge in landfills. The paper
draws attention to the reuse of the leachate from the ecological deposits in order to
fertilize the poor land in Romania.
Keywords: fertilizers, leachate, treatment
Introduction
Legislation on EC waste is hierarchical. The general framework for waste
management, including definitions and general principles, is established as the upper
level, called "horizontal" legislation. WFD, Council Directive 75/442 / EEC has
been revised twice since 1975, firstly in 1991 and then again in 1996. Directive
1999/31 / EC on the landfill of waste has as main objectives the establishment of
measures, procedures and guidelines to prevent or reduce adverse effects on the
environment and, in particular, pollution of surface water, groundwater, soil, air and
the environment in general, including greenhouse effect, and any other subsequent
risks for the human health that waste disposal activities may have throughout their
life cycle (O’Malley & Dupre 2005). Current legislation has imposed leachate
collection and treatment on all new deposits (Ottawa et al 2007).
The paper proposes the reuse of the leachate from the ecological deposits following
it with the help of a mobile wastewater treatment plant (SEM). The resulting product
is applied to the soil in order to increase the amount of nutrients.

For leachate cleaning, the following procedure is proposed: leachate is sucked
through a special device with side slots fixed at the end of the suction hose in the
tank number one or second tank of the SEM (depending on its composition - data
from the monitoring system of the Mobile Purification Station). The capacity of the
two tanks is adjustable from 4 mc to 4 mc, making it possible to set them as needed.
After the treatment is finished, the sludge will be sucked into the sludge tank.
The measurement of the final parameters of the purified water will be done with the
monitoring system of the SEM. It should be noted that from the data recorded up to
now on the quality of the leachate, the presence of heavy metals over the limits of
the two landfills was not signaled. The quality of the leachate treated with the
mobile wastewater treatment plant is assessed by monitoring the following
parameters: pH, conductivity, COD (chemical oxygen demand), BOD5 (biochemical
oxygen demand), total nitrogen. For metals Fe, Al, Cu, Mn no determinations were
necessary because both the treated leachate and the soil complied with the plant
development requirements. The values were measured using the monitoring system
with which the mobile station was equipped. Subsequently, these values were
verified in the laboratory by standardized methods of analysis in force
(www.anpm.ro).
Another important test that was made (ISO 11269-2:1995). Phytotoxicity was
assessed by germination of tomato seeds. 12 seeds were planted at a depth of 0.5 m.
The GI - germination index (Tiquia & Tam 1998), was calculated by counting the
number of germinated seeds and analysing the development of the roots for three
species of plants in comparison to samples developed on a reference soil:
(1)
where: G % - (number of seeds germinated in a sample / number of seeds

germinated in the reference soil) * 100; RRG % - ( the length of the root in a sample
/ the length of the reference root ) × 100; VI – Germination % * (root length+ shoot
length).
In the experiment, the seeds were germinated normally twice in order to determine
the energy at the end of the germination period to determine the germination
capacity. Normal germs were the most developed. The primary root of the normal
germs must be at least equal to the length or diameter of the seed and the germ at
least equal to the length of the seed (Tiquia & Tam 1998, ISO 11269-2:1995,
www.usamvcluj.ro).
The next phase after the laboratory tests were finished was the implementation of
the obtained results. The soil on which the leachate was applied was a poor soil. The
perimeter chosen was based on a pedological mapping process. Thus, there were
isolated three perimeters of 1 km length and 1 km width on which the scrapping and
milling works were carried out for three months during the period the spring, when
the land is ready for agricultural crops (Figure 1). The qualities of the soil were
analysed before and after the addition of leachate. The application technique was to
spread and subsequently incorporate into the soil.
For soil was analysed the humus content (STAS 7184/21- 82) and organic matter
content.
The application of the soil quality improvement solution was evaluated periodically
by monitoring the physical parameters. The most important physical parameters of
the soil (organic matter content, soil type, water retention capacity, nutrient content,
soil erosion etc.) subsequently provided the basis for studies for the choice
appropriate culture for the treated soil.

Figure 1. Test area.
Results and discussion

The medium value for characteristics of the treated leachate are shown in Table 1.
Table 1. The medium values recorded for treated leachate parameters monitored
with SEM
pH COD BOD5 Total nitrogen
Parameter Organic matter, %
units pH mg/l mg/l mg/l
1. 7.1 118 21 31 11.8
2. 7.2 111 18 22 14.5
3. 7.6 115 20 28 18.1
4. 7.4 127 21 26 22.2
5. 7.8 108 23 30 16.1
6. 7.8 92 18 28 16.8
7. 7.6 120 19 29 28.4
8. 7.9 113 21 26 21.9
9. 7.6 112 21 21 26.5
10. 7.4 99 22 27 22.9
The experimental information was used to train neural networks in order to estimate
some soil parameters following the leachate application. The program used was
MATLAB® R2012b. The network drive algorithm was the Levenberg-Marquardt
algorithm (ISO 10390:2005). The data entered into the program resulted in values
close to 𝑅𝑅 = 1, indicating that there is a good correlation between output data and
target data.

Training: R=0.98869 Validation: R=0.96182

120
120
Data Data
Fit Fit
100
100
Y=T Y=T
Output ~= 0.96*Target + 2.8
Output ~= 1*Target + 0.46

80 80
60 60
40 40
20 20
0 0
0 50 100 0 50 100
Target Target
Test: R=0.43146 All: R=0.98069

120
120
Data Data
Fit Fit
100 100
Y=T Y=T
80 80
60 60
40 40
20 20
0 0
0 50 100 0 50 100
Target Target
Figure 2. Train of neural networks with Levenberg-Marquardt algorithm.
It can be noticed that the pH of the treate leachate varied between 8.0-8.3 (pH units)
and the measured values for the soil were below 8.0 (pH units). The soil was alcalin.
Conductivity ranged between 30-40 mS/cm for the treated leachate. For the soil the
conductivity had a minimum value of 20 mS/cm.
The COD value for the treated leachate applied to the soil ranged between 158 mg/l
and 336 mg/l.
The BOD5 value for the treated leachate applied to the soil was of minimum 110
mg/l and maximum 324 mg/l. The total nitrogen value for the leachate applied to the
soil ranged between 11.8 mg/l and 28.4 mg/l. For the soil, the maximum recorded
value of total nitrogen was of 10.9 mg/l.
The results have shown that there are no significant changes in pH for the analysed
soil. The nitrification process took place, the ammonia being converted first into
nitrites and then nitrates. The degradation of organic matter in the soil has ensured
the need for ammonia.

The low amount of nitrogen in the soil is correlated with a small amount of organic
matter. The increase of the organic matter content to 0.2% shows that there are
conditions fulfilled for assessing the land quality and establishing its use.
The mean value obtained for GI was 81.24%, higher than 80%, indicating an
optimal development environment for tomatoes.
Conclusions
The results of the research are reflected in the development of a leachate treatment
technology based on modern concepts, namely: high purification rates and reduced
amounts of generated mud. A successful criterion is the reduction of the amount of
waste generated, the share and level of training of the personnel employed in the
research activities, the high technical and technological level (Buzoianu et al 2016).
In the process of identification of the strengths the following were taken into
account: the advantages of a proposal that improves the management of sludge and
waste; the advantages of partners that store waste against competition in the field -
the ecological landfills of partner waste in the project are renowned in the field; the
resources and the equipment that were used in the project show a vast experience in
the field of waste water treatment / leachate treatment research, nanotechnologies,
the use of modern technologies in soil fertilization in forestry and the treatment and
disposal of waste. The financial resources used, the location that was chosen
previously, the experience in the implementation of European projects and not only,
alongside all the partners involved, have led to the improvement of the leachate
management at national level.
The strengths capture positive internal aspects and add value to competitors,
monitoring major economic agents with a high risk of pollution (Panaitescu &
Bucuroiu 2014). Due to the monitoring of the leachate treatment process, the degree
of pollution that exists in household waste deposits will always be known. The
opportunities evaluate the external attractive factors that represent elements of
which the project team can take advantage.
Treated leachate leads to improved enzyme activity in the soil as well as microbial
activity due to superior organic matter and nutrients.
References
Buzoianu, DA, Panaitescu, C, Bombos, M & Stoica, ME 2016, ‘Study on efficiency
increasing of biological stage by sequential operating of aeration reactors’,
Revista de Chimie, vol. 67, no. 5, pp. 962-966.
ISO 11269-2:1995 Soil Quality, ‘Determination of the effects of pollutants on soil
flora - Effects of chemicals on the emergence and growth of higher plants’.
ISO 11269-2:1995 Soil Quality, ‘Establishment of the effects of pollutants on soil
flora - Effects of chemicals on the emergence and growth of higher plants’.
ISO 10390: 2005, 'Determination of soil pH in aqueous and saline suspensions and
in saturation paste, Romania'.
STAS 7184/21- 82, 'Determination of humus content in soil, Romania'.
O’Malley, MA & Dupre, J 2005, ‘Fundamental issues in systems biology’,
BioEssays, no. 27, pp. 1270-1276.
Otawa, K, Lee, SH, Yamazoe, A, Onuki, M, Satoh, H & Mino, T 2007, ‘Abundance,
diversity and dynamics of viruses on microorganisms in activated sludge
processes’, Microbial Ecology, no. 53, pp. 143-152.
Panaitescu, C & Bucuroiu, R 2014, ‘Study on the composition of municipal waste in

urban areas of Prahova county’, Environmental Engineering and Management
Journal, vol. 13, no.7, pp. 1567-1571.
Tiquia, SM & Tam, NFY 1998, ‘Elimination of phytotoxitcity during co-composting
of spent pig manure, sawdust litter and sludge’, Bioresource Technology, vol.
65, pp. 43-49.
www.anpm.ro
www.usamvcluj.ro/files/teze/gotea.pdf

POLLUTION ASSESSMENT & MANAGEMENT SYSTEMS
Section Pollution Assessment & Management Systems 176

APPROACHES TO PREDICT THE IMPACT OF AIR ATMOSPHERIC

COMPONENT IN ENVIRONMENTAL IMPACT ASSESSMENT REPORTS
IN ASSESSING EXTENSIONS TO ACTIVE INDUSTRIAL OBJECTS
Antoaneta Stefanova, Margarita Filipova
Ruse University, 7017, 8 Studentska, Ruse, astefanova@uni-ruse.bg, mphilipova@uni-ruse.bg,

Bulgaria
Abstract
The article deals with the approaches for predicting the impact on the Atmospheric
Air component in the approved reports (Environmental Impact Assessment Reports
EIAR) for the expansion of active industrial sites on the territory of the Republic of
Bulgaria for the period 2013-2016. Different approaches used by independent
environment experts have been identified as incoming forecasting data - using
approved Inventory Methodologies, established emission limit values for the
respective production under regulatory acts etc.
The purpose of the study is to compare the different approaches for predicting the
impacts on the component Ambient air for a particular site and to draw a conclusion
on the approach with the least variance. The need for a single methodology for
assessing the Atmospheric Air component in the EIAR is reflecting the planned
investment - an extension of an existing site. This need is studied and commented in
the paper.
Keywords: atmospheric air, environmental impact assessment, forecasting,

pollutants
Introduction
The main objective of the present paper is to study the applied methods for assessing
the impact on the atmospheric air for the extensions and reconstructions of existing
sites subject to a mandatory procedure for assessment of their impact on the
environment.
The research objectives are:
Studying of the sites subject to expansion documentation of completed
Environmental Impact Assessment (EIA) procedures on the territory of the regions
Razgrad, Ruse and Silistra, Republic of Bulgaria for the period 2013 – 2016.
Establishing the methodology used to assess the impact on the Atmospheric Air
component in the approved EIAR for the identified sites for the same period 2013-
2016.
Studying of possible deviations in the conclusions of impact on the Atmospheric Air
component using different methodologies for a selected specific site.

In order to provide sufficient information on the methodologies used, the EIAR of

the sites subject to the extension of the activity have examined all the agreed
reporting tasks and the environmental impact assessment reports themselves for the
period 2013-2016 concerning sites subject to expansion of the activity, which will
be realized on the territory of the three regions of the Republic of Bulgaria.

The necessary information for the analysis is providing through:
Use of publicly available information from the official site of the competent
Bulgarian regional authority for the approval of environmental assessment reports
for the three areas - Ruse, Razgrad and Silistra - Regional Inspectorate for
Environment and Water - Ruse (EIAR 2014, EIAR 2015b, EIA 2015, EIA 2016).
Use of publicly available information from the official website of the Bulgarian
Ministry of Environment and Water (EIAR 2013b, EIAR 2015a, EIAR 2017).
Information provided by the Regional Inspectorate of Environment and Water -
Ruse under the Access to Public Information Act - for the procedures with missing
data in the public registers (EIAR 2013a).

Investigation of the documentation of completed EIA procedures on the territory of
Ruse, Razgrad and Silistra Districts for the period 2013-2016 for sites subject to
expansion. From the survey of all approved sites for the period 2013-2016, which
will be realized on the territory of the Bulgarian districts of Ruse, Razgrad and
Silistra we have choosen the following sites subject to extensions.
Intensive breeding of poultry or pigs. Objects for intensive rearing of poultry - 4
sites (EIAR 2013a, EIAR 2013b, EIAR 2014, EIA 2016) and 2 sites for intensive
rearing of pigs (EIAR 2015b, EIA 2015).
Non-ferrous alloying / alloying of non-ferrous metals and surface treatment of
metals - 1 object (EIAR 2017).
Manufacture of gutron and bitumen - 1 site (EIAR 2015a).
Six of this sites are regulated by the Sixth Chapter of the Law for the Protection of
the Environment, which means that 75% (or 6 sites) are active in intensive breeding
of poultry and pigs. A major part of approved sites in the three areas under
consideration is in the frame of the Intensive Livestock Sector.
Establishing the methodologies used to assess the impact on the Atmospheric Air
component in approved environmental impact assessment reports from the period
under review for the identified sites. The in-depth study of the approaches for
assessment of the impact on the Atmospheric Air component in the EIAR shows that
we can group the applied methodologies into three main groups:
Group no. 1. Use of validated inventory methodologies for the pollutants expected
to be emitted from the objects in the ambient air. This group also includes
inventories with emission factors, corrected by taking into account the applied
pollutant reduction measures in the specific site;

Group no. 2. Use of established emission limit values in ambient air according to
normative documents. A study conducted in the Environmental Impact Assessment
Guidelines also found the availability of a third group of methods, namely
Group no. 3. Actual measurements of emissions from the existing part of the sites
subject to expansion carried out by accredited laboratories.
In tabular form - Table 1- data are presented on the methods used to estimate the
emissions of air in the areas subject to the expansion of the activity.
Table 1. Data on the methodologies used to estimate the emissions in the

atmospheric air from the sites to be expanded
Group no. 1 Group no. 2 Group no. 3
Inventory
(MOEW 2013);
(EMEA / EEA Еmission limit
Activity 2009); (EMEA / values ( Own Periodic
EEA 2013); (EPA ORDINANCE No. 1 Measurements
AP-42 2004); 2005).
(IPPC Directive and
the IED 2010).
Х
(EIAR 2013a);
Intensive breeding of
(EIAR 2013b);
poultry and pigs, --- ---
(EIAR 2014);
pollutant NH3
(EIAR 2015b); (EIA
2015); (EIA 2016).
X
Intensive breeding of
( EIAR 2013a);
poultry and pigs,
(EIAR 2013b);
РМ10 (from ---
(EIAR 2014);
combustion or
(EIAR 2015b); (EIA
industrial sources)
2016).
Melting / alloying of
non-ferrous metals
--- X ( EIAR 2017) ---
and surface
treatment of metals
Production of
vacuum Residue and --- X ( EIAR 2015a) ---
bitumen
The data presented shows different methods to provide inbound data for planned
extensions of objects to assess the impact on the Atmospheric Air component.
The practice in Environmental Impact Assessment procedures has imposed emission
factors from established inventory methodologies for sites in the Intensive Livestock
Sector (poultry and pigs) (MOEW 2013, EMEA / EEA 2009, EMEA / EEA 2013,
EPA, AP-42 2004, IPPC Directive and the IED 2010).
The reason for the imposed practice is the specificity of the ventilation systems of
the production halls (the displaced discharge of pollutants) and the lack of legal
provision for conducting own periodic measurements. These types of objects are not
of interest for this study.
Study of possible deviations in the application of the identified methodologies for a
selected specific site. The study is carried out in the sequence presented on the block
diagram of Figure 1.
For the purpose of the survey, an object of the Non-Ferrous Metals / Alloying Sector
has been selected for which we have:
Data from own periodic measurements reported with annual environmental reports
(Environmental Protection Act) and design data (Group no. 3);
Statutory Emission Limits on its Activities - (Group no. 2);
Emission factors according to inventory methodology (MOEW 2013) (Group no. 1).
The selected site performs casting of non-ferrous metals, falling under item 2.5 of
Annex 4 of the EPA (Environmental Protection Act), in which three melting
furnaces with one discharge device (Table 1) are available. It is planned to install
new furnaces to the plant, resulting in two new discharge devices (Table 1). The
pollutant studied is a powder with a particle size of 5 ÷ 10 μm.
Determination of
incoming data
for the assessment by a
Group 1 method
Determination of
Compare the results
incoming data Simulation modeling Obtaining predicted ground
Certain emissions from and form a final
for the assessment by a with PLUME software concentrations of the
point sources impact assessment on
Group 2 method pollutant tested the component
Determination of
incoming data
for the assessment by
a Group 3 method
Figure 1. Block diagram of the study process
Task 1: Identify incoming data

Group no. 1. Up-to-date Unified Methodology for the Inventory of Air Pollutant
Emissions (MOEW 2013) SNAP CODE 030310, was used to determine inputs for
the assessment. Production of Aluminium from Secondary Raw Materials. The
values obtained in ton / year for the pollutant are recalculated in grams per second
under the 3 shift mode of the plant, 360 days / year.

Group no. 2. To determine the input data for the assessment, the normative emission
limit values for this type of activity are used (Ordinance no. 1 2005).
Group no. 3. To determine the input data for the assessment, averaged data from its
own periodic measurements for the 2014-2016 period for the existing exhaust
system and for the new chimneys data from the investment projects (Annual reports
No 480) were used.
The results obtained are presented in tabular form - Table 2.
Table 2. Determination of incoming evaluation data

Source Group no. 1 Group no. 2 Group no. 3
Е dust, [g/s]
Emitter 1 0.102 0.061 0.014
Emitter 3 0.163 0.053 0.026
Emitter 4 0.326 0.097 0.049
Emitter 1 0.102 0.061 0.014
*Е dust – dust emissions from a emitter
Task 2: Simulation modeling with PLUME software

With the help of the established software program at national level (Methodology
for. 1998) a computer simulation was conducted to determine the mean annual
concentration of dust before and after the installation expansion. The coordinate
network (x, y) is being worked out, with the survey area of the air pool measuring
4000 x 4000 meters or 20 steps * 200 meters. The model is designed with a type of
sub-surface area ‘extra-urban area’. The site is located outside the regulation
boundaries of the settlement.
An annual wind rose for the closest meteorological station - Razgrad (Climate Guide
1982), is used as an incoming data regarding the weather conditions. The spread of
dust from the site before and after the expansion is presented in figures 2 to 7.
The figures obtained through mathematical modeling represent the predicted value
of the maximum annual average concentration for the pollutant and the distance
from the last source that is expected to spread it. Isolations of lower ground
concentrations from the determined maximum are plotted and their distribution in
the created coordinate network.
Task 3: Comparison of the results and formation of a final impact assessment on the
Atmospheric Air component
Table 2 presents the results of the average annual concentrations of pollutant dust
obtained by applying a method of the three groups. An estimate of the impact on the
Atmospheric Air Component was also calculated.
The estimated force of impact (EFI):
(1)
where
СAAC are the calculated ground concentrations of the pollutant, µg/m3
PHHAA is the annual average for the protection of human health – 40 µg/m3.
Table 3. Values of maximum average annual ground dust concentrations calculated

using different methods
Group no. 1 Group no. 2 Group no. 3
ААС Distance ААС Distance ААС Distance
mg/m3 m mg/m3 m mg/m3 m
Current
state
0.00051 848.53 0.0003 848.53 0.00007 1131.37
(before the
expansion)
Forecast
(after the 0.00233 930.17 0.00086 930.17 0.00035 930.17
expansion)
EFI before
the
1.27% --- 0.75% --- 0.17% ---
expansion,
%
EFI after
the
5.8% --- 2.15% --- 0.87% ---
expansion,
%
Impact
assessment Insignificant impact, Insignificant impact, Insignificant impact,
after the characterized by non- characterized by non- characterized by non-
expansion essential sensitivity essential sensitivity essential sensitivity
Current (<20% of PHHAA) and (<20% of PHHAA) and (<20% of PHHAA) and
state low impact power 5÷15 non-essential impact non-essential impact
(before the % power < 5% power < 5%
expansion)
*ААС – average annual concentration of dust
Figure 2. Isoliness of the average annual Figure 3. Isoliness of the average annual
concentrations of the plant dust before its concentrations of the plant dust after its
expansion using input data from Group 1 expansion using input data from Group 1
method method

Figure 4. Isolines of the average annual Figure 5. Isolines of the average annual
method method
Figure 6. Isolines of the average annual Figure 7. Isolines of the average annual
method method
Conclusions
The survey is about the production of site subject of expansion, with the following
restrictions being imposed:
The site is considered without a cumulative assessment of the component as a result
of the operation of existing industrial activities in the area;
Verification of predicted maximum single concentrations of the pollutant has not
been performed;
Only one pollutant - a powder considered as PM10 - has been investigated.
Despite the above limitations for the particular site, we can draw the following
conclusions:
It is not important which method for obtaining of incoming data is used. When
applying the three scenarios described above, the result is the same - the impact
assessment after the site expansion is of negligible impact. However, using the
inventory method, a low impact is reported, unlike the other two applied methods,
where the impact strength is considered insignificant. This necessitates the extension
of the study with the formation of sufficiently concrete conclusions.
There is a need for an in-depth study of the approved environmental impact

assessment reports at national level, covering more pollutants, as well as estimating
cumulative impacts in the application of methods by the three groups examined.
On the basis of the detailed study, the use of the most relevant methodology for the
relevant sector should be prioritized to provide input data when assessing impact on
the Atmospheric Air component.
Acknowledgements
The authors express their thanks to the employees of RIEW-Ruse for providing comprehensive
information on the procedures under Chapter Six of the Environmental Protection Act.
References
Annual reports on the implementation of the activities covered by CoR No 480 -
2014/2014, 2015 and 2016. Available from: http://eea.government.bg/bg/r-r/r-
kpkz/godishni-dokladi-14/index. [01 August 2018].
AP-42, EPA Compilation of Air Pollutant Emission Factors - U.S.Environmental
Protection Agency. Available from: https://www3.epa.gov/ttnchie1/ap42.
[01 August 2018].
Best Available Techniques Reference Document (BREFs) developed under the
IPPC Directive and the IED. Available from:
http://eippcb.jrc.ec.europa.eu/reference. [01 August 2018].
Climate Guide for Bulgaria, vol. IV, Institute of Hydrology and Meteorology, Sofia
1982 .
EIAR for the site ‘Farm for Intensive Growing of 102,850 Broilers with Sites
Location III, Reg. IV, Reg. V, Reg. X and Reg. XI, District 180 of the Plan of
the Town of Vetovo, Ruse District‘ RU 1-1 / 2013a of the Director of RIEW-
Ruse.
EIAR for the project ‘Increasing the capacity of a plant for intensive breeding of
birds (growing broilers for broilers and broilers for broilers) from 625 174 to 1
058 010 places for birds with location properties with numbers 000175 and
000227 in the land of the village of Chervena voda, Ruse‘, which was
concluded with Decision No. РУ 3-4 / 2013b of the Director of RIEW-Ruse.
EIAR for the site ‘Repair, expansion and equipment of a plant for intensive broiler
breeding and reaching a total capacity of 314 570 places for birds with
location: property number 050036 in the land of Shumentsi village, Tutrakan‘,
which was concluded with Decision No. РУ 2-2 / 2014 of the Director of
RIEW – Ruse.
EIAR for site ‘Increase of the capacity of an existing gudron and bitumen plant from
10 000 t / year to 200 000 t / year by raw material, located in UPI XX and
UPV XXVI on the plan of TM Ruse and construction of a new hydrocracking
complex within the territory of UPI XXII on the plan of TM AD - Ruse for the
production of petrol and diesel fuel from heavy oil fractions with a capacity of
250 000 tons / year on raw material‘, concluded with Decision No. РУ 2-2 /
2015a of the Director of RIEW-Ruse for partial approval of the investment.
EIAR for site ‘Combining two existing holdings in one, reconstruction of existing
and building of new buildings in order to increase the capacity of the holding -
pig farm with location: the land of the village of Popina, Silistra municipality’,
concluded with Decision No RU 3-3 / 2015b of the Director of RIEW-Ruse.
EIA report for the site ‘Reunification of five existing holdings / pigs / in one and
increase of the capacity of the farm with location properties 056001, 053002,
053003, 053004, 053005, 053006, 053007 in the village of Vetren, Silistra
municipality’ , which was concluded with Decision No РУ-5-7 / 2015 of the
Director of RIEW-Ruse.
EIA report for the site: ‘Increase the capacity of an existing poultry house, repair,
reconstruction and commissioning of two existing poultry buildings in order to
reach the total capacity of the poultry farm 122 724 birds, property № 000058
in the land of village of Kichenitsa, Razgrad‘, which ended with Decision No
РУ-1-1 / 2016 of the Director of RIEW-Rousse.
EIAR for the site ‘Installation of two aluminum recycling plants, aluminum chips
and other waste containing aluminum for the production of standard aluminum
alloys in ingots in a property with identifier 61710.506.30 according to the
plan of Razgrad, Razgrad municipality‘, Which ended with Decision No РУ-
1-2 / 2017 of the Director of RIEW-Ruse.
EMEA / EEA air pollutant emission inventory guidebook, 2009. Available from:
http://www.eea.europa.eu/publications/emep-eea-emission-inventory-
guidebook-2009. [01 August 2018].
EMEA / EEA EEA Air Pollutant Emission Guidelines Guide, 2013. Available from:
http://www.eea.europa.eu/publications/emep-eea-guidebook-2013. [01 August
2018].
Environmental Protection Act Available from:
http://www.lex.bg/bg/laws/ldoc/2135458102. [01 August 2018].
Methodology for calculation of leak height, dispersion and expected concentrations
of pollutants in the ground layer of 25 February 1998 adopted by the Ministry
of Environment and Waters, the Ministry of Regional Development and Public
Works and the Ministry of Health. Available from:
http://www5.moew.government.bg/. [01 August 2018].
Ordinance no. 1 of 27.06.2005 on emission limit values of pollutants emitted into
the atmosphere from sites and activities with fixed emission sources.
Available from: http://www5.moew.government.bg/?page_id=24089. [01
August 2018].
Updated unified methodology for inventory of emissions of harmful substances in
air (Order No РД-165 / 20.02.2013 of MOEW). Available from:
http://eea.government.bg/bg/legislation/air/methodology. [01 August 2018].

ASSESSMENT TERMS FOR LOCAL SUSTAINABILITY MANAGEMENT
Ildiko Tulbure1,2
1
University "1 December 1918", 11-13 Nicolae Iorga, 510009, Alba Iulia, Romania
2
Clausthal University of Technology, Adolph-Roemer-Str. 2A, D-38678, Clausthal-Zellerfeld,
ildiko.tulbure@tu-clausthal.de, Germany
Abstract
After the Conference for Environment in Stockholm in 1972 and after the release in
the same year of the first report to the Club of Rome, „The Limits to Growth“, was
understood that the wish of increasing our life quality by using new technological
applications could have beside desired effects, also undesired ones. Worldwide
began debates on scientific, political and social levels in order to find solutions for
these problems. The concept of sustainable development, defined for the first time
1987 in the Brundtland Report, largely discussed 1992 during the so-called “Rio”-
Conference as well as 2012 during the “Rio+20”- Conference, was worldwide
accepted as a possible solution for the global complex ecological, economic and
social problems. On a local level best strategies have to be found for developing
sustainable cities as well as most appropriate assessment terms. Newly debated
strategies for sustainable urban development have at their base the concept of
"Decoupling” firstly developed 2013 in the Club of Rome. Using new transportation
possibilities, other than cars as well as rehabilitating residential urban buildings and
constructing green buildings are as well in the discussions. These aspects are related
to mindset changes and to a new type of education of the young generation, a so-
called Holistic Education for Sustainable Development. Presently it is still not very
clear what a sustainable city should be and what components should be included,
getting a ”general methodology” for sustainable cities represents a big progress in
this field.
Keywords: Decoupling, Dynamic assessment methods, General methodology, Local

sustainability, Mindset changes
Introduction
In the context of the desire to rise the human quality of life especially after the
Second World War, tremendous technological developments have started to take
place on a global level. The positive effects of the significant technological
applications on the population quality of life were remarked due to their support in
carrying out day by day activities. On the other side, the world began to
simultaneously recognize the dangers and undesired effects of some human
activities, not only of industrial ones, activities which have been carried out in order
to develop many technological applications. At latest after the Conference for
Environment in Stockholm in 1972 and after publication in the same year of the first
report to the Club of Rome „The Limits to Growth“ was obviously understood that
besides wanted and positive impacts of the technological progress, undesired and
negative consequences can also occur (Meadows & Meadows 1972). Considering
these evolutions it was clear already at that time that the arisen regional and global
environmental problems are severe and need to be tackled, debated and solved.
Humanity is currently confronting itself with several global problems, named by the
Club of Rome as “World Problematique” (Meadows & Meadows 1972). This notion
is containing several issues, most important among them being the following three
ones, increase of natural resources and energy consumption, environmental pollution
and increase of world population (Jischa 2014) (Figure 1).
Economic Ecological Social

Sustainability Sustainability Sustainability
Applying Sustainable
Sustainable Strategy Urban
Development Development
Sustainable
Assessment Development
Terms Indicators
Global (Environ-
mental) Problems
Increase of Environmental Increase of world

resource/energy
consumption pollution population
Figure 1. Sustainable Development applying strategy by Assessment Terms as a

response to global (environmental) problems.
After recognising the complexity of the problems shown above with the goal of
finding solutions which could be applicable in the same way to the developed as
well as to the developing countries with respect to regional differences, worldwide
began discussions some time ago on political, scientific and social levels (Tulbure
2003).
The Brundtland Report of the World Council on Environment and Development,
published 1987, represented a result of these worldwide socio-political discussions,
where for the first time the concept of sustainable development was defined (Hauff
1987). This concept has been nevertheless soon accepted as a possible solution for
the much debated global complex ecological, economic, and social problems (Jischa
2014). The concept of sustainable development was very much discussed thereafter,
as for instance in 1992 on the Conference for Environment and Development in Rio
de Janeiro, being strongly emphasized in the conference closing document Agenda
21, as well as 2002 in the follow-up Conference Rio+10 in Johannesburg, Southern
Africa and 2012 during the Conference Rio+20 in Rio de Janeiro (Tulbure &
Prunariu 2017). Many actions after this time have emphasized that the evolution of
the pretty complex technical, social and environmental systems has to be analysed in
synergetic relation (Jischa 2014).

Concretely applying sustainable development on a local level, i.e. its
operationalisation means the translation of its goals into political measures and
controlling instruments (Jischa 2014, Lengsfeld et al 2003). In this regard, by
applying the sustainability systemic analysis on a local level, the general
methodology for sustainable urbanisation can be obtained, which is materialised in
the following steps (Tulbure 2016):
• defining the sustainability problem on a local level;
• establishing specific space and time scales;
• systemic approach of the analysed city by modelling the interactions;
• establishing concrete aims for the studied case by establishing priorities;
• developing assessment terms and controlling instruments;
• verifying possible results, which could be obtained after introducing the
proposed measures by developing scenarios for sustainable urbanisation;
• applying into practice the developed concept.
The operationalisation is only possible, when for an individual problem-case
concrete aims are established and from these aims concepts to achieve them are
developed. Sustainability is to be newly defined for each different case, where space
and time scales are to be established (Banse et al 2011).
As a possible solution for the challenges concerning sustainability, as environmental
pollution and recognized rebound-effects, the term of Decoupling has been
emphasised first time by the Club of Rome during its conference in Zürich,
Switzerland, in the time 15-16.10.2015 (Tulbure 2016). It is actually a response to
the multitude of global problems recognised and debated already 1972 in the first
report to the Club of Rome, ”Limits to Growth” and is meaning to break the long
held causal relationship between economic growth and growth in the consumption
of natural resources. The goal is to maintain the same life quality by decreasing
resource consumption, to have less environmental impact, and to avoid rebound-
effects by mindset changes. Improving the rate of resource productivity (“doing
more with less”) faster than the economic growth rate is the key notion behind
Decoupling. This means that in order to materialise Decoupling there is a need of
innovations in technical field, but in the same time a need of changes in social field,
i.e. changes in human behavior as well as mindset changes (Jischa 2014). In this
regard the holistic education receives an important role, beside other inter-related
aspects as economic development, appropriate local infrastructure, environmental
protection, cultural life, in the context of getting local sustainability (Banse et al
2011, Tulbure 2013). On the other side the field of developing future energy systems
is nowadays very much debated on different levels. The present discussions
regarding existing strategies on regional level for gaining best future energy systems
are led with the main goal of avoiding climate change (Parodi et al 2010).
From the made presentation it is obvious that for Managing Local Sustainability in a
proper way, there is a need for defining specific Sustainability Assessment Terms.
Part of what engineers do is to assess developments in technology. Their evaluation
has up to now almost without exception been focused on technical aspects, like
functionality and safety, and on economic aspects following legal and financial
boundary conditions (Jischa 2014). With respect to local sustainability management
specific assessment terms have to consider more criteria like: environmental quality,
social and human values, quality of life (Tulbure 2016). This assessment way needs
interdisciplinary cooperation (Parodi et al 2010, Tulbure 2016). In order to support
engineer activities when evaluating technologies a new discipline has been
developed, appeared firstly in the USA, i.e. Technology Assessment (TA)
(Grunwald 2010, Tulbure 2013, Jischa 2014).
On the global level the operationalisation of sustainable development means to
define general goals for the whole world, things which happened more or less 1992
with the ”Rio”- Conferences, 1997 with the well-known ”Kyoto”-Protocol and much
debated 2012 during the ”Rio+20”- Conference. On a national level this means to
define goals and to elaborate strategies by paying attention to the specific conditions
of a country, as usually national conditions are very specific and different from one
country to another one (Tulbure 2016). This aspect is especially to be remarked for
the social and cultural field, where national particularities can be very specific
(Banse et al 2011). On a local level concrete measures are representing the content
of Local Agendas 21 (City Council 2011).
Regarding the methodological side concerning urban sustainability the field of
applying sustainable development on a local level does represent a pretty young
direction for some countries in South Eastern Europe (Banse et al 2011, Tulbure &
Prunariu 2017). An appropriate way for developing strategies for urban
sustainability could be represented by using analytical instruments of Technology
Assessment, because very often the questions are regarding the possibilities to best
integrate new technologies on a local level into environment and society (Tulbure
2013). These questions are in the present conditions of Eastern European countries
from dominant importance, in the process of modernisation of old technologies and
implementation of new ones. From this reason Technology Assessment should play
a central role in the next technological, economic, environmental and social
development of these countries (Grunwald 2010, Tulbure 2013). Going into details,
the vision of getting sustainable cities, by taking into account regional differences, is

worldwide a pretty discussed topic, but has started to be debated also in some
Eastern European countries (Banse et al 2011, Tulbure & Prunariu 2017).
In order to get in the future sustainable cities in Romania debates on scientific level
have already started, regarding establishing a general methodology for developing
sustainable cities, in accordance to the already applied methodologies in other Euro-
pean countries by taking into consideration specific regional differences especially
on social and cultural level (Banse et al 2011, City Council 2011).
When analysing the above presented methodology for sustainable urbanisation one
can recognise that the urban sustainability means actually a transformation process
under changeable frame conditions (City Council 2011, Tulbure 2016). The so-
called Local Sustainability Management, as presented in Figure 2, means actually to
emphasise the development direction on a local level. This is possible to be done by
simultaneously considering economic, environmental and social aspects and by
representing them on the axis, as shown in Figure 2, by using relevant indicators for
each considered aspect. The evaluation of the development path is possible, if
desired (D) and undesired (U) ranges are defined for each considered aspect. If the
development is situated in the so-called „sustainable action range”, this means that
Local Sustainability will be assured. If the development is situated in the so-called
„unsustainable range”, the vision is to make corrections of development by
introducing some measures. It follows that Local Sustainability Management means
developing and applying local strategies, not only in technological or economic
fields, but also in environmental and social ones. Such sustainability strategies have
to be evaluated by considering specific sustainability requirements, which are more
or less dynamic ones (Tulbure 2016).
Figure 2. Local Sustainability Management

This means that Sustainability Assessment on a local level is a pretty difficult issue,
because comprehensive evaluation criteria cannot be defined for each field, as for
instance for the social field, because it is not possible to define „limit values“ in this
field. And in the field of Sustainable Development all three fields of Sustainable
Development have to be taken into account, economic, environmental and social
one. And for some fields there are no strict numbers, which could be interpreted as
“sustainability reference numbers” and used as reference values, in order to make
comparisons. In this case development tendencies are to be evaluated by using so-
called Dynamic Assessment Methods, DAM for Local Sustainability Management.
In this way it is possible to highlight if a certain developing path is in accordance
with the sustainable path on a local level (Tulbure 2013). The presented
methodology is generally to be applied on a local level, but special attention is to be
paid to following difficulties (Jischa 2014):
• Considered processes can be complex and uncertain;
• There is a need to handle quantitative as well as qualitative aspects, that
should be integrated into the analysis;
• There is a need to design indicators for urban sustainability, in order to
succeed evaluating the development direction at a certain time.

After joining the European Union in 2007, the word “sustainability” started to be
heard more frequently in Romania. Since then small steps have been taken,
sometimes because of bureaucracy, sometimes because of other priorities, and
sometimes because of lack of knowledge. Nevertheless it has to be mentioned that in
the last years some progress has been registered in the field of sustainable urban
development and local sustainability management (City Council 2011).
In order to emphasise this development, beside Sibiu, selected 2007 to become the
European Cultural City, the five biggest cities in Romania will be considered:
Bucharest, Cluj-Napoca, Timisoara, Iasi and Constanta. In order to become
sustainable cities, they all share some things in common (City Council 2011):
• need for urban regeneration;
• need to reduce energy consumption;
• use of new transportation possibilities, other than cars.
On the other side, the Romanian Government approved in the year 2009 a program
for the rehabilitation of residential urban buildings constructed from 1950–1990.
Also the idea of constructing green buildings has very much come into discussions,
as for instance in the city of Cluj-Napoca. This city has had first in Romania a
”Green School”, built-up in 2012. In this context, starting with 2013, the
construction of green buildings has been encouraged by Romanian local authorities,
for instance by reducing local taxes for them by 50% (City Council 2011).
Nowadays there are discussions also in the field of assuring alternative
transportation possibilities. The population in several cities did agree that bicycles
will need to be used more frequently. The largest bike-sharing project in the country
was launched 2010 in Bucharest, followed 2011 by Cluj-Napoca and Constanta as
well as 2012 by Timisoara. Each city is hoping that this initiative will help reducing
their carbon footprint and sustain the development of an adequate infrastructure for
cyclists (City Council 2011). Another newly discussed strategy is based on the usage
of bio-energies and biotechnologies, in order to establish future sustainable energy
strategies for sustainable urban development (Jischa 2014, Tulbure 2016).
By aapplying Dynamic Assessment Methods it is possible to evaluate the degree of
assuring urban sustainability in the analysed region. For this goal postulates started
recently to be defined, after FFRC, Finland Futures Research Centre, so-called
Sustainability-Postulates should be considered. For instance it can be postulated that
Sustainability cannot be achieved without respecting following assessment terms
(Jischa 2014):
• Postulate P1: A decrease of Environmental Pollution (EP): D(EP) < 0
• Postulate P2: A decrease of (at least keeping constant) the Energy Consumption
(EC): D(EC) ≤ 0
• Postulate P3: An increase of the Life Quality (LQ): D(LQ) > 0
In order to exemplify a case for local sustainability management in Romania the
Alba Iulia Association for Intercommunity Development, AIDA will be considered.
This association of 11 local administrative units (3 urban and 8 rural communities)
represents the interests of more than 120000 inhabitants and has the goal to get the
desired socio-economic development, based on specific actions (City Council 2011).
The most important city of the association is Alba Iulia, having about 66000
inhabitants, a city which constitutes a hystorical symbol for Romania. The city Alba
Iulia has a Development Strategy that aims to acknowledge urban mechanisms as a
positive force in improving housing standards, equity and sustainability standards.
The Strategic Development Plan is to address issues related to improving the quality
of pedestrian areas and of all public space areas and also to improve the accessibility
in the historical part of the city, this is the Fortress Area, which is pretty relevant for
the History of Romania. The environmental policy of Alba Iulia is also targeting
transport issues, as the tourism activities are pretty developed in this city. The
Association AIDA has several Strategic Objectives, as emphasized below, with the
vision of improving all human life aspects in this region (City Council 2011):
1. Developing the local and regional infrastructure;
2. Economic progress by developing new jobs;
3. Promotion of the so-called “green energies”;
4. Promotion of the local cultural values as well as of traditions;
5. Improving the educational, social and health infrastructure;
6. Building partnerships, as well as national or international cooperation’s.
Going into details, these Strategic Objectives are in the same line with the debated
Sustainability-Postulates P1, P2, P3, by using the Dynamic Assessment Methods
(Tulbure 2016).
In the mentioned strategy of the association AIDA several aspects are pointed out,
as being necessary for the future sustainability of this region (City Council 2011), as

the need of Transnational Cooperation, of Holistic Education for Urban Sustainabili-

ty, and establishing requirements for Sustainable Urban Development of Alba Iulia.
Conclusions
Nowadays there is no agreement regarding general requirements for local
sustainability management or there is no complete agreement regarding what
components should be included. Generally there is agreement that a sustainable city
should meet the needs of the present without compromising the ability of future
generations to meet their own needs. The ambiguity within this idea leads to
variations in terms of how cities carry out their attempts to become sustainable.
However, a sustainable city should be able to feed itself with minimal reliance on
surrounding countryside, and to power itself with renewable energy sources. The
goal is to generally promote sustainable urban development, by taking into account
all aspects related to this issue such as technical-economic, social and environmental
aspects in the field of adequate living conditions and housing space, proper resource
use, mobility, governance as well as of social life. This means that there is a real
need for interdisciplinary work among economists, engineers with social scientists.
Developing a kind of a ”general methodology” to be applied into the practice for
real concrete situations by taking into consideration regional differences is
representing a major progress in this field, just to come from the vision to the reality.
To achieve this main goal in the field of asuring a sustainable urban development it
is useful that Romanian cities become partners in European networks of sustainable
cities in order to successfully cooperate in this field. On the other side the desire is to
find appropriate ways to establish best strategies for local sustainability in Romania,
as proposed in the paper by the methodology for local sustasinability management.
References
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Technology, Clausthal-Zellerfeld, Germany. In Deutsch.
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M, Banse, G, Lindeman, K, C, Quint, A (Eds.) 'Designing Sustainable Urban
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International Multidisciplinary Scientific Geoconference, SGEM2017,
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Future”, no. 62, Section “Green Design and Sustainable Architecture”,
Albena, Bulgaria, pp. 779-786.

CHARACTERIZATION OF MINERAL SPRINGS FROM THE BUILA-

VANTURARITA NATURAL PARK AREA
Ovidiu Teodor Matica, Luisa Roxana Popescu
National Research and Development Institute for Industrial Ecology – ECOIND – Ramnicu Valcea
Subsidiary, 1 Uzinei, 240050, Ramnicu Valcea, valcea@incdecoind.ro, Romania
Abstract
This study present the results of the physico-chemical, microbiological and
hydrochemical characterization obtained for the mineral water samples taken from
14 mineral springs located in the Buila-Vinturarita National Park area.
For this study, has been conducted three sampling campaigns, in November 2017,
March 2018 and June 2018, for each mineral spring.
The physico-chemical quality indicators analyzed for each source were: pH,
chlorides, sulfates, bicarbonates, sodium, potassium, calcium, magnesium, total
silica and sulfides and hydrogen sulfide. In parallel with the physico-chemical
indicators, microbiological indicators were also determined, namely: total number of
bacteria at 22˚C, total number of bacteria at 37˚C, total coliform bacteria,
Escherichia coli, enterococci and Pseudomona aeruginosa.
The results of the physico-chemical and microbiological analyzes obtained for the
studied mineral springs were compared with the provisions of the Romanian
legislation in force GD 1020/2005, which transposes into the national legislation the
European Directive 2009/54 / EC.
Also in the present study, along with the physico-chemical and microbiological
characterization of the mineral water samples, studies were carried out on the
hydrochemical characterization of these springs.
These hydrochemical characterization studies were done by plotting the "Piper
Diagrams". With the help of the Piper Diagrams, we could have a more detailed
view of the mineral springs studied, from the analytical point of view and from the
point of view of the typology of these springs.
Keywords: hydrochemical typology, mineral water, Piper diagram, spring water
Introduction
The chemical content of mineral waters depends mainly on the geological structure
of the subsoil, especially its structure and lithology. The chemical composition of
water provides important information on the operation of the hydromineral system.
The classification of mineral water is very important for the assessment of its

characteristics. Various classification systems have developed, sometimes to the

point that, there are more authors of classification schemes than users (Eggenkamp
et al 2013). One of the methods widely used in the assessment of surface and
underground waters is the determination of hydrochemical typologies. This method
is capable of providing sufficient information on the chemical quality of water,
especially its origin. However, over the years, the methods have undergone
substantial changes without changing too much the theory on which they are based.
The first attempt in this direction was made by Hill (Hill RA 1940), then it was
modified by Piper (Piper AM 1944). Also, other authors (Sajil Kumar 2013, Teng et
al 2016) used the Piper Diagram for various applications and bringing improvements.
From the literature studies (Stanescu et al 2017, Catianis et al 2017, Dede et al 2017,
Radulescu 2017, Angheluta & Radulescu 2017), we can note to the interest of the
researchers regarding the knowledge of the physicochemical and microbiological
quality of the water as environmental factor. In the last years, from the large number
of bibliographic sources (Valjarević et al 2018, Hichem, et al 2018, Zhao et al
2018), we can observe the interest of researchers and research institutes to have an
overview of the water as environment factor.
The hydrogeochemical characterization of mineral water sources in different regions
of the world, the presentation of how they were influenced by natural and artificial
phenomena, shows the evolution of their quality over time. Due to its importance,
mineral water sources have been characterized and classified by a number of authors
around the world (Walraevens et al 2018, Zereg et al 2018). In Portugal
(Eggenkamp et al 2013) and in Slovakia (Bodiš et al 2010) have carried out a
classification of mineral waters using chemical analysis in the literature and the
latest water quality monitoring analyzes. The Muğla (Avsar et al 2016) and Kozakli
areas (Pasvanoğlu & Chandrasekharam 2010) in Turkey and the Jingyu region of
China (Zhang et al 2017) were hydrogeochemically described. In Romania, the area
located between the Harghita Mountains and the Transylvanian Basin, well known
for the abundance and diversity of the mineral water springs was characterized by
the quantification of the chemical content and correlations between the structure
geological subsoil and chemical composition of water (Kis et al 2012).
The first chemical studies on mineral waters in the Buila-Vanturarita Natural Park
area were conducted in 1829-1830 by Dr. Karl Friedrich Siller (Dumitrescu 1978).
In 1910, Dr. Ion Puturianu (Puturuianu 1910) grouped the mineral springs in several
categories, after the chemical composition and after their action on the body. The
complex studies carried out by various researchers on mineral waters, especially by
M. Feru between 1969 and 1985 (Feru 1972, Feru 1978a, Feru 1978b) showed that
the chemical elements (anions, cations) in these waters present variations (especially
in the case of large precipitations or earthquakes), but not in large proportions,
which demonstrates their chemical stability.
This study illustrates the results obtained by analyzing samples of mineral water
taken from 14 mineral springs located in the Buila-Vinturarita National Park area.
The obtained results were compared with the provisions of the Romanian legislation

in force. At the same time, Piper Diagrams were also drawn to follow the
hydrochemical evolution of the mineral waters studied.

All chemicals used to prepare reagent solutions, were analytical grade, according to
the standards of dermination methods in use.
The equipment used to determine the quality indicators analyzed was: pH
determined by multiparameter Thermo Scientific Orion Star A 215; sulfates and
sulphides and hydrogen sulphide determined by a Spectrophotometer Analytic Jena
UV-VIS-SPECORD 210 Plus; total silica determined by a Spectrophotometer
UV-VIS-WTW PHOTO LAG S12; sodium and potassium determined by Flame
photometer Analytic Jena FLAFO 4/766695. To determine the volumetric indicators
(chloride, bicarbonate, calcium and magnesium) were used calibrated burette with
volume 10 ml, 25 ml and 50 ml.
For the determination of microbiological parameters (total number of bacteria at
22˚C, total number of bacteria at 37˚C, total coliform bacteria, Escherichia coli,
enterococci, Pseudomona aeruginosa) were used the following equipment: oven
(incubator with cooling), Laboratory Binder Type FD115, Analytical Balance
Mettler Toledo Type XS205DU / M, SYSTEC Autoclave Type VE 120, Series
2600, Vertical Autoclave Type 5050 ELV Series 2409682.
The quality indicators analyzed were determined using standardized methods, also
the water samples were taken using standardized methods.

In this study, 14 samples were collected from springs located near the Buila-
Vinturarita (Figure 1). For each spring, three sampling campaigns were carried out
in November 2017, March 2018 and June 2018.
Figure 1. Location area for mineral water springs.

The studied qualities were: pH, chlorides, sulfates, bicarbonates, sodium, Potassium,
calcium, magnesium, total silica, sulphides and hydrogen sulphide, total number of
bacteria at 22˚C, total number of bacteria at 37° C, total coliform bacteria,
Escherichia coli, enterococci and Pseudomona aeruginosa.
The results obtained, after analyzing the quality indicators studied, were compared
with the legislation in force.
For a better characterization of studied mineral waters, Piper Diagrams were drawn
using Diagarammes (Laboratoire d'Hydrogéochimie d'Avignon, 2018). With these,
the hydrochemical evolution of studied mineral waters was followed.
Physico-chemical characterization of the springs studied

The values of the physical-chemical quality indicators analyzed for the studied
mineral waters are illustrated in Table 1. After comparison with the legislation in
force was observed that these indicators are within the limits imposed by law, it was
"according to the specific characteristics of mineral water analyzed".
Values of quality indicators physicochemical analysis does not vary uniformly for
all sources studied.
The value of the bicarbonate quality indicator for the samples taken in June 2018
from all the studied springs reached the highest values. Similarly, for the quality
indicator, total silica, higher values were observed for all mineral water samples
taken in March and June 2018. These increases in indicator values, total silica and
bicarbonate, can be explained by the accumulation of these indicators in spring
water samples due to the discontinuous flow of springs during this period.
Microbiological characterization of the springs studied

Evolution of microbiological parameters for the studied springs can be seen in
Table 1 and Figure 2.
In the water from all the studied springs, during the entire study period, the
microbiological quality indicator Escherichia coli was not met.
The values determined for the microbiological quality indicators, enterococci, the
total number of coliform bacteria and Pseudomonas aeruginosa, generally fall
within the values allowed by the legislation in force, with the exception of samples
taken in June 2018 from spring IZ 8 for the qualitative indicators enterococi and
Pseudomonas aeruginosa and from spring IZ 9 for the quality indicator the total
number of coliform bacteria.
For the microbiological quality indicators, the total number of bacteria at 22oC and
the total number of bacteria at 37oC, the values determined for the samples taken in
November 2017 are generally in the values allowed by the legislation in force, but
for the samples taken in March and June 2018 do not fall within the values allowed
by the legislation in force (Table 1, Figure 2). During this period, when the values of
the microbiological quality indicators exceeded the values allowed by the legislation
in force, the springs had a discontinuous flow, which could have favored the
development of microbiological bacteria.
Figure 2. The evolution of microbiological quality indicators for the mineral springs
studied.
Hydrochemical characterization of mineral waters using Piper diagrams
For better observation of the variation of hydrochemical parameters and
classification of water sources studied were built Piper Diagrams for each set of
samples of water taken (Figure 3). Generally, as can be seen from Figure 3 (A), (B)
and (C), the hydrochemical typologies of the mineral springs studied do not change
from one sampling campaign to the other. Exceptions are the waters of the springs
IZ 2; IZ 7; IZ 9 and IZ 14.
In the case of mineral water from the spring IZ 2, the hydrochemical typologies
change from alkaline earths, salts of strong acids, types of calcium chloride,
calcium, chlorides in November 2017 and March 2018 to alkaline earths salts, weak
acid salts, bicarbonate magnesium type, magnesium, bicarbonate in June 2018. It is
noted the change of calcium-dominated cation in November 2017 and March 2018
to magnesium June 2018. The dominant anion changed from chloride in November
2017 to bicarbonate in June 2018.
In the case of the mineral waters from the spring IZ 7, their hydrochemical typology
does not change to a very large extent, they change from chlorides as the dominant
anion in November 2017 and March 2018 to a type of water in which we do not
have a major anion in June 2018.
In the case of the mineral waters of the spring IZ9, they change the hydrochemical
typology from alkaline waters, salts of strong acids, sodium chloride type, dominant
sodium and potassium cations, no dominant anions in November and March 2018 to
alkaline earths, weak acid salts, bicarbonate magnesium type, non-cationic
dominant, bicarbonate salts in June 2018.

Table 1. The results of physical-chemical and microbiological quality indicators analyzed,

obtained for studied springs
Parameter U.M. Sample Parameter value determined
determined IZ 1 IZ 2 IZ 3 IZ 4 IZ 5 IZ 6 IZ 7
November 7.7 7.6 8 7.6 8 8 7.9
pH Unit pH March 2018 8 7.9 7.9 7.6 8.4 7.9 8
June 2018 7.8 7.6 8.2 7.8 8 8 8.1
November 2017 5531 425 3120 4113 2553 2694 319
Chloride mg/L March 2018 5928 236 2964 4042 2290 2425 269
June 2018 5793 7 3200 3772 2223 2290 283
November 2017 4 158 7 2 7 1 114
Sulfates mg/L March 2018 5 158 25 2 4 4 78
June 2018 7 144 26 4 21 2 70
November 2017 244 403 293 281 378 329 342
Bicarbonate mg/L March 2018 281 354 305 256 293 354 317
June 2018 329 525 464 415 500 512 537
November 2017 2589 7 1737 1416 1324 1324 236
Sodium mg/L March 2018 3107 9 1829 2391 3769 3769 217
June 2018 2004 5 1921 2391 3750 2600 180
November 2017 86 8 43 46 32 31 9
Potassium mg/L March 2018 81 9 44 74 32 33 11
June 2018 81 7 41 43 28 31 9
November 2017 262 160 160 180 84 204 88
Calcium mg/L March 2018 281 104 136 180 80 79 58
June 2018 281 88 140 172 92 82 59
November 2017 141 10 41 71 51 39 63
Magnesium mg/L March 2018 122 58 73 68 49 35 32
June 2018 119 109 66 73 41 40 31
November 2017 3 2 2 3 2 2 2
Total silica mg/L March 2018 17 16 17 16 16 16 15
June 2018 15 14 15 14 14 14 13
Sulphides and November 2017 120 0.1 15 102 76 106 67
mg/L March 2018 158 0.1 74 116 109 108 66
hydrogen sulphide
June 2018 155 0.1 33 112 106 129 70
UFC/ November 2017 0 0 0 0 0 0 0
Escherichia coli March 2018 0 0 0 0 0 0 0
100 cm3 June 2018 0 0 0 0 0 0 0
UFC/ November 2017 0 0 0 0 0 0 0
Enterococi March 2018 0 0 0 0 0 0 0
100 cm3
June 2018 0 0 0 0 0 0 0
Total number of UFC/ November 2017 0 1764 0 0 0 0 1
March 2018 36 27 26 31 42 26 32
bacteria at 22˚C cm3 June 2018 72 1382 12200 15 24 35 2427
Total number of UFC/ November 2017 0 0 0 0 0 0 0
March 2018 12 17 18 11 12 13 17
bacteria at 37˚C cm3
June 2018 41 7200 8400 0 5 2 123
Total coliform UFC/ November 2017 0 0 0 0 0 0 0
March 2018 0 0 0 0 0 0 0
bacteria 100 cm3 June 2018 0 0 0 0 0 0 0
Pseudomona UFC/ November 2017 0 0 0 0 0 0 0
March 2018 0 0 0 0 0 0 0
aeruginosa 100 cm3
June 2018 0 0 0 0 0 0 0

Parameter U.M. Sample Parameter value determined

determined IZ 8 IZ 9 IZ 10 IZ 11 IZ 12 IZ 13 IZ 14
November 7.7 7.7 8.4 8.2 7.7 7.8 8
pH Unit pH March 2018 7.8 7.9 8.4 8.4 8 7.8 8.1
June 2018 7.8 7.8 8.3 8.5 7.5 7.7 8.3
November 155 175 2 922 3971 2836 45
Chloride mg/L March 2018 147 182 20 916 4581 3099 47
June 2018 122 128 23 943 3974 2829 58
November 155 175 2 26 19 21 87
Sulfates mg/L March 2018 147 182 20 7 3 6 107
June 2018 122 128 23 12 4 26 137
November 305 342 293 427 268 427 325
Bicarbonate mg/L March 2018 232 305 281 281 293 439 305
June 2018 500 464 512 525 378 622 427
November 70 162 674 713 2485 1913 125
Sodium mg/L March 2018 81 144 695 787 2505 1913 90
June 2018 67 89 530 28 4000 3600 109
November 7 7 13 13 46 46 6
Potassium mg/L March 2018 7 9 14 13 68 44 6
June 2018 7 6 11 10 45 46 5
November 56 68 28 24 180 128 56
Calcium mg/L March 2018 53 72 16 14 168 116 40
June 2018 56 69 21 22 184 124 43
November 51 46 15 12 75 73 53
Magnesium mg/L March 2018 36 29 10 10 80 44 44
June 2018 40 31 11 6 68 70 9
November 1 1 2 1 4 3 3
Total silica mg/L March 2018 15 15 14 14 14 18 16
June 2018 13 14 14 14 15 18 16
Sulphides and November <0.01 <0.01 149 108 85 422 3
mg/L March 2018 0.1 0.1 158 119 99 390 22
hydrogen sulphide
June 2018 0.1 0.1 188 153 120 459 21
UFC/ November 0 0 0 0 0 0 0
Escherichia coli March 2018 0 0 0 0 0 0 0
100 cm3
June 2018 0 0 0 0 0 0 0
UFC/ November 0 0 0 0 0 0 0
Enterococi March 2018 0 0 0 0 0 0 0
100 cm3 June 2018 20 0 0 0 0 0 0
Total number of UFC/ November 1473 1627 0 0 0 0 0
March 2018 41 17 19 0 24 31 52
bacteria at 22˚C cm3
June 2018 24600 152 146 0 0 14 75
Total number of UFC/ November 0 150 0 0 0 0 0
March 2018 19 9 6 12 16 15 13
bacteria at 37˚C cm3 June 2018 11300 115 0 0 0 9 12
Total coliform UFC/ November 0 0 0 0 0 0 0
March 2018 0 0 0 0 0 0 0
bacteria 100 cm3
June 2018 0 73 0 0 0 0 0
Pseudomona UFC/ November 0 0 0 0 0 0 0
March 2018 0 0 0 0 0 0 0
aeruginosa 100 cm3 June 2018 44 0 0 0 0 0 0

In the case of mineral water from spring IZ 14, it changes its hydrochemical
typology, from alkaline-earth, weak acid salts, bicarbonate magnesium type, non-
cationic dominant, bicarbonate in November 2017 and March 2018 to in alkaline
waters, salts of weak acids, mixed type, sodium and potassium dominant cationic,
bicarbonate in June 2018.
The modification of the hydrochemical typologies of the water sources of the
springs IZ 2, IZ 7, IZ 9 and IZ 14 lead us to the conclusion that they are influenced
by external factors (precipitation, drought, water infiltration, etc.).
(A) (B)
(C)
Figure 3. Piper diagrams for all springs studied in the three sampling campaigns:
A - samples taken in November 2017, B - samples taken in March 2018 and
C - samples taken in June 2018.

Conclusions
The results of the physical and chemical analyzes obtained for the studied mineral
springs, by comparison with the legislation in force, show that the physico-chemical
parameters analyzed fall within the limits imposed by the law, being "in accordance
with the specific characteristics of the analyzed mineral waters".
From the microbiological point of view, the results obtained for all springs studied
in the three sampling campaigns, the following aspects can be observed: the
analyzed quality indicators, total coliform bacteria, Escherichia coli, enterococci
and Pseudomona aeruginosa, compared to the legislation in force, fall generally
within the limits provided by the legislation; unlike the quality indicators, the total
number of bacteria at 22˚C and the total number of bacteria at 37˚C, which generally
do not fall within the limits provided by the legislation in force.
The cause of the development of microbiological bacteria may be the discontinuous
flow of springs, in the period when in the water from these springs were recorded
exceedances of the microbiological parameters studied.
By drawing the Piper Diagrams, for all springs studied in the three sampling
campaigns, it is observed that most of the studied mineral springs fall into types of
alkaline mineral waters, hard acid salts, sodium chloride type, sodium and potassium
cations, anions mostly chlorine. Also, using these diagrams we can see that in
general the mineral springs studied keep their hydrochemical typology, except for
four springs.
Acknowledgements
The authors are grateful for the financial support from National Research and Development
Institute for Industrial Ecology Bucharest, where all the experimental studies were done.
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END OF WASTE CRITERIA FOR OIL WASTES
Georgeta Madalina Arama, Lidia Kim, Adriana Cuciureanu, Agnes Serbanescu, Ileana
Nicolescu, Mona Barbu, Bogdan Stanescu, Gina Traistaru
National Research and Development Institute for Industrial Ecology-ECOIND, 71-73 Drumul Podul
Dambovitei, district 6, 060652, Bucharest, madalina.arama@incdeconind.ro, Romania
Abstract
In the context of sustainable development, harmonized good management practices
should ensure the recovery of valuable components from wastes applying the
principle of waste hierarchy in order to comply with Waste Frame Directive
requirements. The article presents a scheme of a circular economic model applied to
the oil waste. Those oil wastes are of the particular interest because they can
positively respond to the End of Waste Criteria. Those criteria are referring to the
compliance of the waste derived products with the legal and regulatory applicable
specifications for their intended use, the existence of a market demand for this type
of products and with the fact that their production and use is safe for the
environmental and human health. After fulfilling those conditions the waste
producer can declare the end of waste status of the generated waste and proceed to
the recovery of valuables entities including the energy recovery. The article presents
the economic, ecologic and social implications of applying End of Waste Criteria to
the oil waste within such a circular economic model in order to respond to European
and Romanian strategy of increasing the recyclable degree of those types of wastes.
Keywords: circular economy, end of waste, oil waste
Introduction
In the context of sustainable development, harmonized good management practices
(Arama et al 2017) should ensure the recovery of valuable components from wastes
applying the principle of waste hierarchy in order to comply with Waste Frame
Directive requirements (EU Directive 2008). “The established EU guidance for
recovering resources from waste mandates – via the “waste hierarchy” of the Waste
Framework Directive (EU Directive 2008) – that in principle reuse is better for the
environment than materials recycling, recycling is better than energy recovery, and
energy recovery is better than disposal” (Iacovidou et al 2017) . In this paper, a
scheme of managing oil wastes within a circular economic model type is presented.
Those oil wastes are of the particular interest because they can positively respond to
the End of Waste Criteria. Those criteria are referring to the compliance of the
wastes derived products with the legal and regulatory applicable specifications for
their intended use, the existence of a market demand for them and with the fact that
their production and use is safe for the environmental and human health. After

fulfilling those conditions the waste producer can declare the end of waste status of
the generated waste and proceeds to the recovery of valuables entities including the
energy recovery. The article presents the economic, ecologic and social implications
of applying End of Waste Criteria to the oil waste within a circular economic type of
model in order to respond to the European and Romanian strategy of increasing the
recyclable degree of those types of wastes. In a circular economy idealistic model,
each human activity along “the life cycle of product/service” should either a) not to
generate negative environmental impacts or b) to transform them into positive inputs
for other activities to which the same rules should be applied trying to be as close as
possible to the zero wastes target. In this context, the producers of goods and
services, started to become aware about concepts like eco-design – referring to
products conceived from the very beginning as eco-friendly products - and eco-
efficiency – referring to sustainable re-thinking of the operational production flows
of goods and services so that the overall generated wastes to be minimum or even
zero - decoupling this way the economic growth from the consumption of natural
resources. In this idea, a new field of research evolved, namely the industrial
ecology that has a holistic approach recognizing that solving the current new
ecological issues involves actually understanding the connections existing between
societal, technical, economical, and environmental systems because small changes
in a part of the system can induce sometimes important changes in another part of it.
For example, changing the price of virgin raw materials on the market can determine
either the reduction of their availability or their abundance which can determine a
change in the market demand for the reprocessed materials from the virgin ones.
Accepting that global industrial economy can be modelled as a network of industrial
processes that use resources to transform them in merchandises that can be bought
and sold in the market, industrial ecology as a new emerging field of research tries
to quantify the material fluxes and to document them. It has in its field of activity
the assessment of the environmental impacts that the industrial activities have or can
have on the environment, the way in which natural resources are supplied and used
and the way in which the resulted wastes are eliminated. In the context of global
industrial economy, the industrial ecology is concerned specifically with the
dynamic of industrial processes, namely with the study of how present linear
economic systems based on a sequence of steps like: extraction, production,
consumption and eliminate waste, can make a transition to circular economic
systems in which wastes can become entries for new processes. In this respect the
eco-innovation is the basis for such an endeavour. The new European vision
consider eco-innovation as any innovation that can reduce the use of natural
resources especially the non-renewable or hard renewable ones and decrease the
pollutants discharge into the environment along the life cycle of the products and
services (EU Report 2011).


“The circular economy (CE) concept is gaining momentum among industry, politics
and academia, putting forward a number of claims about environmental and climate-
related benefits. Recently, the European Union has enacted a policy package calling
for a transition from linear - towards circular production cycles across its Member
States by 2050. The majority of research so far has focused on the micro- and meso-
level, investigating circular economy implications on the product and firm level. On
the national level however, a circular economy monitoring framework has yet to be
developed” (Jacobi et al 2018). In the British Standard 8001: 2017 Framework for
implementing the principles of the circular economy in organizations – Guide
(Standard UK 2017). that is a voluntary guidance standard to support organization in
implementing sustainable circular practices in their businesses is defining circular
economy as “an economy that is restorative and regenerative by design and which
aims to keep products, components and materials at their highest utility and value at
all times, distinguishing between technical and biological cycles” (Niero & Schmidt
Rivera 2018).Technical cycles is referring to the endeavour to keep as much as
possible the produced products and services as functional in the economy for their
initial designed utility or for another one preserving the natural resource to be
transformed into wastes to be discarded in the environment and to pollute it.
Biological cycle is referring to the possibility of the affected environment to restore
to its initial functionality that it had before the impact of the anthropogenic
activities. So circular economy is not about making a sort of “perpetum mobile” but
trying to keep the consumption of natural non-renewable or hard renewable
resources as it is for example a forest as low as possible, continuing the economic
development but with much more care and good innovative management practices
to allow decupling the economic progress from the expense of environmental
degradation. In this respect, concerted efforts also should be made by each
organization in order to find innovative solutions so that: everything that can be used
in common such as buildings, equipments etc., everything that can be used for a
longer period of time to increase the life cycle of an item such as different types of
lubricating oils, and also everything that can be reused through
reprocessing/regeneration such as waste oils, should to be used. Having waste oils as
materials of choice to implement such a circular economic model and to sustain its
performance it is necessary to use some methodological instruments in order to
reach this goal First instrument is referring to the existing of a harmonized
legislation for waste management at the European Community level. That has been
realized in the last three decades so that, at the level of 2015, that legislation was
already in place and functional also at the national levels where had been
transposed. However, for reaching the goal of transition to a circular economic
model some combined financial common institutional instruments and
organizational management instruments should be made functional in order to reach
the high degree of industrial symbiosis required for its implementation and
performance. This industrial symbiosis should be reached between all those who are
using oils and produce waste oils on a well defined horizon of time within European
common market space. Common efforts should be directed towards investments in

infrastructures for recycling or energetic recovery as well as towards eco-innovation
so that the products to be eco-friendly and the oil waste necessitating the disposal to
be kept at minimum. In the same time, the individual and businesses consumer’s
attitude towards the use of reprocessed oils should be changed. This change can be
done by having enough products’ information and economic incentives directed
towards good organizational management practices that use those types of re-
processed oils instead of similar grade oils from virgin materials. This is necessary
in order participants to be able to find about each other needs/necessities so the
overall recovery process of the valuable entities from the produced oil wastes to
show the expected benefits.“Thus, it is increasingly recognized that in the endeavour
to craft a meaningful monitoring framework to inform CE policies and provide links
to resource and climate policies, resource inflow and outflow data, as well as waste
and emissions data, need to be integrated and conceptualized together (Elia et al
cited in Jacobi et al 2018).
“The market penetration of recycled materials is highly dependent on their physical
and chemical characteristics, which will determine their price. However, not all the
existing recycling technologies enable a fair competition between virgin and
secondary materials, because their quality might differ”(Cobo et al 2018).The
consumers’ attitude can be changed by recognizing that the oils that are managed in
an inappropriate manner will represent a loss for the organization. So organization
that produce the oils should understand that any oil wastes not well managed
represent a loss for them and the consumers of the oils should understand that
paying taxes for the differences between the amount of used virgin oils and the
amount of waste recovered either by recycling or by incineration is also a loss and
the more they recover the less will be the loss. As the literature mentions (GEIR
cited in Zimmerman & Jepsen 2018) “waste oil is the largest liquid hazardous waste
stream in Europe (...) and the end-of-life treatment of waste oils is regulated by the
Waste Framework Directive 2008/98/EC (EU Directive 2008). That directive states
that waste oils should be collected separately where this is technically feasible,
should be treated in accordance with article 4 - i.e. applying waste hierarchy
principle - and article 13 - i.e. allowing protection of the environment and human
health. Because oil is a valuable resource, waste oil should be managed so that
waste oils of different characteristics and waste oils and other kinds of waste or
substances should not be mixed, if such mixed impedes their treatment for recovery,
fulfilling the EU targets (GEIR cited in Zimmerman & Jepsen 2018) which are by
2020: a collection rate of 95 % of collectable waste oil and a recycling rate of 60 %
of collectable waste oil, and by 2025 a collection rate of 100 % of collectable waste
oil and a recycling rate of 85 % of collectable waste oil. The literature (Zimmerman
& Jepsen 2018) recognizes also that until now” there is no consistent method for the
evaluation of the efficacy of the legal framework on waste oil treatment which can
be adapted by the single states”, each EU country has its own algorithm of
computing the figures in order to document this efficacy with data having different
national or European sources. One European source is for example the Union of
European Lubricants Industry that can assist in such cases by providing country
specific approximations using proprietary algorithms. When it comes to the
implementation of a circular economic model for oil industry the necessity of good
reliable data is a very important prerequisite because it represents the starting point
for building infrastructure for treatment waste oil in order to recycle them or for
energy recovery. Although this is a very important issue, it is generally recognized
by the professionals working in the field that it is time consuming and involving
waste oil flows analysis and complex national specificities. “The European waste oil
recycling industry is constituted of about 28 plants. Between 1,000 and 1,200 people
are employed in re-fining and 2,000 to 2,500 in collection of waste oil (excluding
waste oil from the food industry)” (EU Report 2009). There are significant
differences between EU countries regarding the topic of circularity of materials in
the oil extraction and processing industry field. If for example Germany, France,
Spain and Italy are well ahead documenting those oil wastes fluxes, because based
on those data and calculation they have already built re-refineries capacities, for
other countries like Austria, Czech Republic, Hungary, Romania and the Baltic
States there is not such infrastructure built. Motivations for such differences should
be found in the fact that recycling industry is facing adaptation issues that are not
easy to be solved. As Reh mentions (Reh 2013) when it comes to the big plants such
are the processing capacities, they need usually longer planning and also
implementation periods of time. For those big plants, and re-processing capacities
that are in this category being built with the intention to serve a significant
geographical region, having “high capital investments during the development,
planning and construction stages, by economical reasons have to be operated for
long periods, up to 10 fold of a political election period or two life generations.
During the first 2-5 years, depending on type and capacity of the plant under
planning, only costs accumulate. During about the same length of period of
operation then al revenues of the successfully started and operating plant are
recovering the costs of the construction period. Having reached returned on
investment (ROI) point of time, undisturbed marketing of its products and stability
of operational costs provided, the plant earns steadily money above the coverage of
its investment and operational costs. Toward the end of lifetime, repair and other
operational burdens as well as market competition or emission legislation make
operation unprofitable. With extra costs, the plant has to be dismantled in an
ecologically friendly way, with itself becoming an object of recycling or modified
reuse. (...) In normal operation, typical life times of plant and building projects
extend to more than 40 years. If plant life were shortened by unexpected or force
majeure events, huge losses of capital for future projects would occur. This capital
will be lacking for the urgently needed future investments. So even risk – taking
entrepreneurs take their time in preparing new plant projects properly. Legislative
and political stability will ease their actions and decisions! ” In an oil extraction
market were fluctuations of price and productions are high enough a market demand
for recycled oils although it is tempting enough when regarding circular economies
in different geographical regions should be carefully analyzed when it comes to the
global market in order to have a relative stable coverage of the investment costs of
the re-processing plants . In the scanned literature in the field we found an example
of an attempt to conceive a method to show the economic synchronicity for the
behaviour of a set of different oil and gas exploitations as a prerequisite of
implementation of a circular economic model in this field by relevant monitoring
and evaluation through a set of relevant and specific chosen indexes. Those indexes
have been designed to indicate different possible status-quo that considered pilot
projects in the example are going through their current operations within a defined
period of time in a certain region using an early warning method with fuzzy
ISODATA cluster analysis. Signalling no changes or relevant changes in the
operations status-quo should be an important help reference for the optimal
functioning of a circular economy. The authors (Jian & Kun 2011) show that to
determine warning references for a functional circular economic model is not about
only considering the convenience of data calculation, but also “the patterns of
economic exploitation complied with the principle of circular economy when
choosing criterion-referenced indexes” Analyzing the industrial waste is also a
matter of harmonizing the used analytical methods in order to have good reliable
results to be analysed (Kim et al 2017).
Results and discussion

In this paper a general scheme for wastes management based on product lifecycle
assessment within a circular economic type of model is presented in Figure 1.
Figure 1. General scheme for lubrication oil waste management based on

Product/Services LCA within circular economic model

In the scheme from Figure 1, an example for a lubricating oil type is taken. This
product is considered along its life cycle namely from the extraction, transportation
of raw materials needed for the manufacturing of the base oil and purchasing /supply
of additive necessary for its formulation and continuing through, production of base
oil necessary for lubricating oil product type and its bench formulation, lubricating
oil packaging, distribution, trading, use, recovery and disposal In each of those steps
corresponding to the phases through which this product is followed, in an ideal
circular economy at the level of each organization there is the need to have in place
good waste management practices in order to avoid or to minimize waste generation.
Whenever based on technological applied process involving those mentioned
phases, it is possible to apply local treatment for generated waste to end the status of
waste and to apply recovery techniques including the incineration for energy
recovery as a suboptimal option of recovery, all those techniques should be applied.
The resulted recovered waste oil can become input for other economic activity
within the local organization or within other ones within national/regional economy.
Regarding the presented scheme it looks on the paper simply enough. In reality as
presented in the former section such an endeavour requires a high degree of
synchronicity with reference to the two types of raw materials namely the virgin raw
material which is crude oil in the case of lubricating oil and recycled materials
which may form the raw materials for recycled products. The products involving a
high degree of circularity should have a quality similar to that from virgin raw
materials when it comes for examples for lubricating oils obtained from re-refined
used oils and be as we have mentioned earlier competitive as price i.e. the process of
re-refining should be adjusted all the time in certain limits to the price of the crude
oil on the market. This is a complicated endeavour on the unregulated, free market
which trading products (stocks) should be in good agreement and synchronicity with
the collection, transport and processing activity of the waste oils at least at the
national and regional levels ensuring in the same time the high protection of
environment and human health through evaluation of the hazards associated with
waste and products that use waste as secondary materials (Guta et al 2017). Very
good accounts about input-outputs levels with reference to the national production
of such a product in correlation with to the import-export of such goods where it is
the case should be kept to assure the industrial symbiosis. However, economic and
social implication of such a circular economy means actually a good deal of control
and national/regional intervention in order to have a functional economy.
Consequently, strict monitoring in order to signal alert level for supply of virgin and
secondary materials is necessary for assuring the level of planned outputs. From all
these steps certain amounts of waste derived and linked to the lubrication oil product
type result for the final disposal that also should be minimize in order to reach
sustainability.
Conclusions
Because circular economy is an emerging concept its application from the practical
point of view is supporting yet improvements so that challenges related to its
implementation to be solved in the most efficient way. The presented scheme helps
to give a general view about this very complex endeavour and is meant to be
supported in future with different specific management scheme applied for the oil
and oil waste field
Acknowledgments: The concept and work presented in this paper helped to enforce the
application of good waste management principles in practice considering the current updated
waste environmental legislation. The work has been achieved through funding support offered
by Romanian Nucleu Programme developed by the Romanian Ministry of Research and
Innovation within research and development, Project PN 18 05 04 01.
References
Arama, GM, Kim, L & Guta, D 2017, 'General scheme to evaluate the
dangerousness of wastes in order to manage them by producer/holder
organizations', 20th International Symposium “The environment and The
industry”, SIMI 2017, National Research and Development Institute for
Industrial Ecology ECOIND, Buucharest, pp. 151-158.
Cobo, S, Dominguez-Ramos A & Irabien, A 2018, 'From linear to circular
integrated waste management systems: A review of methodological
approaches', Resources, Conservation & Recycling, 135, pp. 279-295.
EC Directive 2008, Directive 2008/98/EC of the European Parliament and of the
Council of 19 November 2008 on waste and repealing certain Directives,
Official Journal of European Communities, L. 312 of 22.112008, Brussels.
EU Report 2009, 'Study on the selection of waste streams for End of Waste
assessment', Joint Research Centre, Final Report Annex I – Waste Stream
Profiles –Waste Oil, p. 304. Available from:
http://susproc.jrc.ec.europa.eu/documents/SelectionofwastestreamsforEoW-
FinalReport13_02_2009.pdf
EU Report 2011, 'Closing the eco-innovation gap, Eco Innovation Observatory
Annual Report'. Available from: http://www.eco-
innovation.eu/index.php/reports/annual-reports
Guta, D, Cuciureanu, A, Kim, L & Arama, M 2017, 'The Assessment of
dangerousness of waste, case study: waste originating from drilling muds'. 20th
International Symposium “The environment and The industry”, SIMI 2017,
National Research and Development Institute for Industrial Ecology ECOIND,
Jacobi, N, Haas, W, Wiedenhofer, D & Mayer, A 2018, 'Providing an economy –
wide monitoring framework for the circular economy in Austria: Status quo
and challenges', Resources, Conservation & Recycling, 137, pp. 156-166.
Iacovidou, E, Velis, AC, Purnell, P, Zwirner, O, Brown, A, Hahladakis, J, Millward
– Hopkins, J & Williams, TP 2017, 'Metrics for optimising the multi-
dimensional value of resources recovered from waste in a circular economy: A
critical review', Journal of Cleaner Production, 166, pp. 910-938.

Jian, Z & Kun, H 2011, 'Research on Early-Warning Method and its Application of
Complex System of Circular Economy for Oil and Gas Exploitation', Energy
Procedia, 5, pp. 2040-2047.
Kim, L, Muresan, AM, Cuciureanu, A, Guta, D, Arama, GM, Cristea, NI & Dediu,
V 2017, 'Experimental models of characterization and analysis of industrial
waste', 20th International Symposium “The environment and The industry”,
SIMI 2017, National Research and Development Institute for Industrial
Ecology ECOIND, Bucharest, pp.142-150.
Niero, M & Schmidt Rivera, XC 2018, 'The Role of Life Cycle Sustainability
Assessment in the Implementation of Circular Economy Principles in
Organizations', Procedia CIRP, 69, pp. 793 -798.
Reh, L 2013, 'Process engineering in circular economy', Particuology, 11, pp.119-
133.
Standards U.K. 2017, British Standard 8001: 2017 Framework for implementing the
principles of the circular economy in organizations – Guide. Standards U.K.
Zimmermann, T & Jepsen, D 2018, 'A framework for calculating waste oil flows in
the EU and beyond - the cases of Germany and Belgium 2015', Resources,
Conservation & Recycling, 134, pp. 315-328.

ENVIRONMENTAL ISSUES RESULTING FROM THE EXCAVATION OF

ALLUVIAL SOIL IN PROTECTED AREAS, CASE STUDY IN ROSCI 0103
LUNCA BUZAULUI
Giuliano Tevi1, Alexandra Stoica2
1
Ecological University of Bucharest, 1G Vasile Milea Blvd., Bucharest, giuliano.tevi@ueb.ro,
Romania
2
University of Bucharest, 6 Traian Vuia, Bucharest, nicoleta.alexandra.stoica@gmail.com,
Romania
Abstract
The current study tackles the issue of excavating alluvial deposits in protected areas
included in the Natura 2000 network, which was expanded in 2016 to 23% of
Romania’s territory. A significant percent of the Natura 2000 areas in Romania
directly target or are connected to fluvial elements where machinery for alluvial
deposits is used. The Natura 2000 ROSCI 0103 Lunca Buzaului following along the
Buzau River had an initial length of 110 km and a surface of 6987 ha; subsequent to
the 2016 expansion it now has a length of 140 km and a surface of 9575 ha. In the
studied area there are 62 perimeters leased for exploitation with a total area of
594.39 ha (6.2% of the site surface). For data analysis and management both GIS
techniques and specific methods for interpreting remote sensing data were used.
For this study, the following resources are used: Pleiades panchromatic and
multispectral images at 0.5 and 2 m spatial resolution, orthophotos at 2.5 m spatial
resolution, Digital Terrain Model (DTM) based on a 20m network. Thematic
vectors: ROSCI 0103 limits, road network, geology. Data is processed and
interpreted using specific software – ENVI EX for remote sensing data processing
and QGIS for the development of the GIS database.
Following the assessment, maps were drawn up highlighting the details of
exploitations, the risk elements associated with the spatial-temporal evolution.
These are key elements in the process of assessing the environmental impact and the
risk for the population in affected areas.
Keywords: environmental impact, GIS, Natura 2000, NDVI, remote sensing
Introduction
The Natura 2000 network was established in Romania in 2007 when 273 sites of
community importance (SCI) and 108 special protection areas (SPA) were
designated by MO no. 1964/2007 and GD no. 1284/2007, covering 17.84% of
Romania’s territory. In 2011 and 2016 the Natura 2000 network was expanded to
23% of Romania’s territory.
A significant percent of the Natura 2000 areas in Romania directly target or are
connected to fluvial elements where machinery for alluvial deposits is used. The
process of gravel pit excavation expanded over time, as population increased and the
need of aggregates (usually comprising sand and gravel) had to meet up with the
development of the infrastructure construction. Gravel pit is a term used in civil
engineering that refers to small scale quarries or excavations, usually close to water
streams and roads. Aggregate extraction is becoming an environmental issue as the
demand of construction materials follows a rising trend. Improper extraction and
restoration practices affect wide areas and can lead to vegetation clearing, soil
erosion, landslides, modification of the natural drainage, displacement of species
and habitats etc.
The Natura 2000 ROSCI 0103 Lunca Buzaului following along the Buzau River had
an initial length of 110 km and a surface of 6987 ha; subsequent to the 2016
expansion it now has a length of 140 km and a surface of 9575 ha. The protected
area is located in two counties, Buzau and Braila (Figure 1), crossing three
biogeographical regions – Alpine 0.54%, Continental 24.20%, and Steppe 75.27%.
Figure 1. Position of the ROSCI 0103 Lunca Buzaului protected area
The conservation objectives considered for the designation of the ROSCI 0103
Lunca Buzaului are the following: (Natura 2000, 2016):
Habitats - 1530 Pannonic salt steppes and salt marshes; 3130 Oligotrophic to
mesotrophic standing waters with vegetation of the Littorelletea uniflorae and/or of
the Isoëto-Nanojuncetea; 3240 Alpine rivers and their ligneous vegetation with Salix
elaeagnos; 62C0 Ponto-Sarmatic steppes; 6430 Hydrophilous tall herb fringe

communities of plains and of the montane to alpine levels; 91E0 Alluvial forests
with Alnus glutinosa and Fraxinus excelsior (Alno-Padion, Alnion incanae, Salicion
albae); 91F0 Riparian mixed forests of Quercus robur, Ulmus laevis and Ulmus
minor, Fraxinus excelsior or Fraxinus angustifolia, along the great rivers (Ulmenion
minoris); 92A0 Salix alba and Populus alba galleries; 92D0 Southern riparian
galleries and thickets (Nerio-Tamaricetea and Securinegion tinctoriae) and species -
Lutra lutra, Spermophilus citellus, Bombina bombina, Bombina variegata, Emys
orbicularis, Triturus dobrogicus, Barbus meridionalis, Cobitis taenia, Gobio
kessleri, Gobio uranoscopus, Callimorpha quadripunctaria, Cerambyx cerdo,
Lycaena dispar, Agrimonia pilosa and Eleocharis carniolica.
The protected area was designated for the conservation of aquatic and riparian
habitats, as well as of some plant species, invertebrates, amphibians, reptiles and
mammals. The life conditions for all these species are characterized by the presence
and quality of water.
In the studied area there are 62 perimeters leased for aggregate extraction (Figure 2)
with a total area of 594.39 ha (6.2% of the site surface).
Figure 2. Locations of perimeters leased for aggregate extraction
The application of an effective management in protected areas requires a strict

assessment as basis for the decision-making process regarding the permitting of any
economic activity. The large number of effects generated by the works executed in
the meadow area or directly in the river bed determines the use of some spatial
analysis instruments for assessing the river flow processes, the sediment accretion
rate and the management of infrastructure logistics components.

The impact assessment of the extraction and mining of useful minerals sometimes
requires complex analyses of the mining perimeter location and access roads,

correlated to the spatial distribution of protected elements, for which the protected
status was granted.
These assessments of extended areas which are characterized by geological,
pedological, topographic and even climatic variables require the storage and
processing of large data volumes. The best solution is to use the GIS environment
and remote sensing data. The accurate interpretation of these data sets requires
several stages of field calibration and validation so as to ensure that results are
representative under inevitable extrapolations.
For this study, the following software was used: QGIS 3.2 as GIS and ENVIEX
instrument for processing remote sensing data. As base map layers data for the
remote sensing data, images taken by the Pleiades satellite at 0.5 m (panchromatic)
and 2 m (4 layers multispectral – RGB-Ir) spatial resolution were used, as well as 3
layers - RGB orthophotos with 2.5 m spatial resolutions. The different moments of
the two data sets allow analyses of the processes’ dynamics from a temporal
perspective.
For the interpretation of the relief conditions and river area morphology on
distinctive sectors, the Digital Terrain Model (DTM) based on a 20 m network was
used.
The vector data used or developed throughout the study are: the limits of the ROSCI
0103 Lunca Buzaului protected area and those of perimeters leased for exploitation,
provided by the environmental authorities, as well as infrastructure elements
obtained by analyzing available OpenStreetMap data sets (http://
www.openstreetmap.org).
A common characteristic of the remote sensing data recorded for this type of
landscape - river environment located in a hilly area, with an extended development
of the water meadow area and terraces, and an increased density of localities and
infrastructure elements, is represented by the high degree of spectral heterogeneity.
In addition, there are also many natural or semi-natural habitats, characterized by
various plant associations. This is why it was required to use an index allowing for a
differentiated analysis and effective interpretation of available data. Due to the
importance and spread of the vegetation elements inside the protected area, the
authors chose to use the normalized difference vegetation index (NDVI), as this also
allows for extended assessments of the nature of the substrate, exceeding the
presence and consistency of the plant tissue and chlorophyll (Yengoh et al 2015).
The normalized difference vegetation index (NDVI) was initially designed and
introduced for the interpretation of satellite imagery for various evaluations of the
plant layer, the natural vegetation and various types of agricultural crops. This index
is determined based on an empirical formula (1), representing the ratio of the
difference between the near-infrared reflectance (NIR) and red and their sum.
NDVI = NIR-R/NIR+R (1)

NDVI values vary depending on the absorption of the radiation by chlorophyll in the
red spectral region and its reflectance in the near infrared spectral region. The values
may range from -1 to +1, the positive values corresponding to plant coverings. The
higher the chlorophyll content is, the higher the NDVI values, trending to 1.
In specialized studies substantiating the use of NDVI, its values are determined in
relation to various land uses, such as Omran, EE using Landsat 5 imagery from 1984
and Landsat 7 imagery from 2011 (Omran 2012) to calculate NDVI values for
several classes of land use (Table 1).
Table 1. NDVI by land-use type (Omran 2012)

Land-Use Classes NDVI 1984 Image NDVI 2011 Image
Water -0.3764 -0.4357
Waterlogged 1 -0.1089 -0.0813
Waterlogged 2 -0.3691 -0.5697
Vegetation 0.5276 0.6546
Barren Land -0.0945 -0.0864
Build-up Land -0.0291 -0.0465
In order to classify the land use from the ROSCI 0103 Lunca Buzaului protected
area so as to assess the impact generated by the exploitation of alluvial material, the
NDVI used was determined based on Pleiades multi-spectral 4-band satellite
imagery (RGB-Ir), with a 2 m resolution. The data was recorded in July, during the
maximum vegetation period.
By considering the taken imagery and the spatial distribution of the exploitation
perimeters (Figure 2), region of interest (ROI) were set (Figure 3).
Figure 3. NDVI for ROI
After NDVI was determined for these regions, an assisted classification algorithm of
obtained values was set and calibrated by correlating satellite imagery with field
observations (Figure 4).

Figure 4. ROI with land use classes based on NDVI
Table 2 presents Land-Use classes in the study area based on Pleiades imagery.
Table 2. NDVI by land-use type in study area, based on Pleiades imagery

Land-Use Classes NDVI min NDVI max
Water (River) -0.30 -0.20
Alluvial deposit -0.19 0.15
Vegetation 0.40 0.80
Following the land use analysis and its correlation with the spatial distribution of
perimeters leased for exploitation, two distinctive situations were identified, as
regards the potential impact on habitats. A first class was defined for surfaces with
low potential impact and another class includes surfaces with medium potential
impact. The first class includes surfaces located close to the river bed and occupying
areas of the natural deposition of alluvial material from the meanders of the minor
bed; the second class corresponds to perimeters containing vegetation; it was
concluded that the exploitation in this area generates an impact on the protected
habitats. This classification also considered the risk of erosion associated with the
exploitation of alluvial material in certain areas specific to the river bed. In the first
class were also included perimeters located outside the limits of the protected area
(Figure 5).
Figure 5. Potential impact rating classification

Another objective of the analysis was to assess the pressure applied on the
protection elements by the use of access roads servicing these perimeters. Based on
the vector layer representing access roads and extracted from processing
OpenStreetMap data, their total surface was identified, representing 0.43% from the
surface of the protected area. The impact of these access roads which in most cases
are improperly kept, is not generated by their surface, but because in many cases
they are near or crossing forest areas (Figure 6).
Considering that the analysis was carried out on leased perimeters where the
exploitation surfaces are constantly changing, we are of the opinion that as this
activity continues, the share of access roads may significantly increase.
Figure 6. Access ways to gravel pits

The data processing in the framework of this study highlights how effective is the
use of NDVI as a tool for assessing activities involving types of land management
connected to the spatial distribution and the necessity to protect certain vegetation
types. Besides the NDVI selectivity to the chlorophyll content and as a result for the
analysis of various categories of vegetal associations or of their health, from the
field calibration stage also resulted the index’ sensitivity to highlighting other
substrate types – alluvial sediments with variable humidity, water bodies or
agricultural land with no vegetation (soil).

The infrastructure elements generated by OpenStreetMaps data sets were very useful
in analyzing the impact generated by the exploitation of alluvial material. These data
allow for an accurate evaluation of the pressure applied by this economic activity on
species and habitats of community interest.
By considering how the vegetal associations are impacted and the risk for
accentuating the erosion processes, it resulted that around 30% from the leased
surfaces located inside the protected area, were included in the second class,
corresponding to areas with significant potential impact.
Conclusions
Following the assessment, maps were drawn up highlighting the details of
exploitations, the risk elements associated with the spatial-temporal evolution.
These are the key elements in the process of assessing the environmental impact and
the risk for the population in affected areas.
It is not possible to approach the issue of protected areas management, correlated
with the impact generated by the economic activities carried out in these perimeters,
without the use of appropriate tools to manage environmental data, spatial analysis
and development scenarios.
Although the Romanian legal framework clearly addresses these potential risks,
abandoned borrow pits are still a major environmental problem, fact that indicates a
lack of proper technical expertise, unsustainable engineering practice and
insufficient law enforcement.
Acknowledgements
Sectoral Operational Program Environment 2007-2013, Priority Axis 4 Implementation of
Adequate Management System for Nature Protection.
References
Formularul standard Natura 2000, Available from: Ministry of Environment,
http://www.mmediu.ro/app/webroot/uploads/files/2016_02_26_SDF_Natura%
202000_SPA_022016.pdf, pp. 790-797. [26 February 2016].
Omran, EE 2012, ‘Detection of Land-Use and Surface Temperature Change at
Different Resolutions’, Journal of Geographic Information System, vol. 4, no.
3, pp. 199.
Online maps: https://www.openstreetmap.org/#map=12/45.4247/27.7827
[02 August 2018]
Yengoh, GT, Olsson, DDL, Tengberg, Anna E &Tucker III, CJ 2015, Use of the
Normalized Difference Vegetation Index (NDVI) to Assess Land Degradation
at Multiple Scales, Springer, London, pp. 17-18.

EXPLORING THE POSSIBILITIES OF AIR PURIFICATION IN URBAN

ENVIRONMENTS USING GREEN ROOFING
Irina Tsvetanova, Ivanka Zhelev
Ruse University, Department Thermo engineering, Hydraulics, Ecology, 8 Studentska, 7017,

Ruse, irinaic@abv.bg, vzh@abv.bg, Bulgaria
Abstract
According to European Commission studies, poor quality air causes the premature
death of more people than the road accidents each year. Fine particulate matter
(PM10) is mainly a result of human activities - transport, industry and domestic
heating and causes respiratory problems, asthma, lung cancer and premature death.
At present in Bulgaria, sources of pollution are mainly old cars and solid fuel stoves
used for domestic heating. The environmental situation can be improved by building
more green areas. In cities it is difficult to separate areas where green areas are to be
built. This problem can be solved by using the roofs of buildings. Many plant
species are resistant to pollutants and have the property of purifying the air from
them. Properly designed roof gardens and the appropriate choice of plant species
could significantly improve urban conditions.
The purpose of this article is to explore the possibilities for purification and
improvement of air quality in urban zones using roofing landscaping. A study of
literature on this problem has been made and presented in the paper. Also how to
solve the problem with PM air pollution using green roofs in Bulgaria was
commented. In the paper we estimate two simulations done by the software PLUME
for annual average dust concentrations before and after construction of green roofs
in the Industrial zone of the city of Ruse, Bulgaria. The maximum annual average
concentration of dust after the building of green roofs is more than two times less
than the one without green roofs.
Keywords: air pollution, dust retention, fine particulate matter (PM), green roofs
Introduction
Sprawl of cities, growth of population and traffic deepen, and complicate the
problem of increasing air pollution in urban environments. Population growth and
concentration in large cities leads to increased traffic, while construction and
pollution at the same time reduce green areas. The combination of these factors
leads to a worsening of the ecological situation. Deteriorated environmental
conditions, high levels of air pollution cause serious damage to human health. The
environmental situation can be improved by building green areas, thus reducing air
pollution in the urban environment and creating a pleasant urban environment and
better living conditions of the population. Landscaping of buildings has been a
common building practice in advanced countries for several decades. Its popularity
around the world has become even greater in recent years in connection with the
concept of greening construction (Koleva 2011). In the cities it is difficult to
separate spaces in which to build new green areas. The available green areas are not
enough and they cannot cope with high levels of air pollution. Rooftop landscaping
in many places in large cities can replace and complement traditional gardens and
parks. In the large cities, it is very difficult to separate free terrains to build green
areas, especially in the central areas. The reason for this is the lack of free terrains,
as well as their high prices. In the cities there is often a lot of dense construction,
crowding and intense trafficking. The combination of all these factors requires
different solutions to the air pollution problem for the urban areas. One possible
solution is the use of roofs for building of gardens. In today's urban environment,
flat-roofed buildings are very well suited to building gardens. In this way, instead of
a "forest" of concrete and gray and boring roofs people can enjoy beautiful views
and lots of greenery (VEDAG GmbH 2007).
Garages, underground parking lots, public, commercial, warehouse, production etc.
buildings can be used for the construction of green roofs. Another advantage of
roofing landscaping is the improvement of thermal insulation during all seasons and
improved energy efficiency, which, although indirectly contributes to the reduction
of pollution. In this way, people can use less energy to heat or cool their homes, and
this would reduce the electricity and heat generation needs, whose production also
seriously pollutes the environment. In addition, green roofs help to restore the
disrupted ecological balance in cities. Plants have a favourable role in lowering the
maximum daily temperatures by several degrees in summer, increasing air humidity,
enriching it with oxygen, accumulating toxic gases, retaining heavy metals,
releasing substances that reduce disease-causing organisms (phytoncides). Enriching
the air with oxygen is due to the ability of plants to absorb carbon dioxide from the
air and release oxygen. As a result of the physiological and biochemical processes in
the plants, the contaminated air is diluted with oxygen-enriched air, their ratio
changes and the composition of the air as a whole is improved. This phenomenon,
known as oxidation, contributes to the healing of the air (VEDAG GmbH 2007).
What will be the degree of efficiency of roof gardens depends on their size, area and
species composition, as well as the degree of pollution and the type of pollutants.
Not all types of trees, shrubs and grasses digest carbon dioxide and emit oxygen at
one and the same degree. For example studies have been carried out to prove that
common spruce produces 4.5 times less oxygen than summer oak and the pyramidal
poplar separates 7 times more oxygen than ordinary spruce (Koleva 2011,
Doncheva-Boneva 1987). Overall, the study found that broad-leaved trees emit
larger amounts of oxygen than coniferous trees (Koleva 2011). This does not give
the benefits of deciduous species, because the climate and the fact that the deciduous
species remain without leaves and do not photosynthesize during the autumn-winter
period. Plants have good dusting properties: the leaves, branches and stems of the
trees, hedges (which can be included in the roof gardening) and bushes are a good
dust accumulator from the air. Many plant species are resistant to atmospheric
pollutants and have the ability to purify the air from them. Properly designed roof
gardens and the right choice of plant species, depending on climatic conditions and
main pollutants, can significantly improve urban conditions. Roof gardens are
beautiful and very suitable for increasing green areas in the urbanized environment
without being linked to the demand for free space. For this purpose, free space can
be used to increase green areas. This greatly reduces air pollution levels. Experience
can be traced back to ancient times. The green roofs are one of the oldest models of
roofs, traces of which are found even in stone-age dwelling. Information about roof
gardens was discovered during the Babylonian Empire. The ancient Romans used
their terraces and roofs to grow plants, and the roofs of the larger buildings were
turned into gardens. In the antiquity, they were rather cult, and in the modern way of
life they were mainly practical in their direction (Dobreva 2016). People living in
densely populated regions use every free space, including the land.
Roof landscaping has two main types - extensive and intensive. However, they are
not strictly defined and there are many intermediate solutions such as semi-intensive
and semi-extensive ones etc. (Evstatiev 2012, Sustainable Eastside project 2004,
Wark 2003, VEDAG GmbH 2007).
Intensive roof gardening uses flat roofs, it is rich and is provided for walking and
recreation. The soil layer is between 20 and 60 cm thick. A major disadvantage is
the higher load on the roof structure, which should be anticipated at the design level
of the building. Such roof gardens require system maintenance including watering,
mowing, cutting, etc. In the case of roofs of an intensive type, the standard layers
are: vapor insulation, waterproofing, protective layer, drainage layer, root insulation,
soil substrate and plant layer (Evstatiev 2012).
In extensive landscaping, roof gardens can be extremely simple in the form of
roofing boards with low bushes and tree plants, wild herbs and grasses (one-, two-
and perennials). In these cases, dry and resistant to periodic over-wetting low plants,
which have the ability to regenerate and do not require special care, are used
(Evstatiev 2012). The soil layer is less thick than intensive roofing. The load on the
construction of the building is not so great that it allows such kind of gardens to be
built at any one time. For this type of landscaping, sustainable and unpretentious
plants are used. These are predominantly different types of drought-resistant species
of succulent plants, sedums, mosses and grasses and flowers. The choice of just such
plants is made because they are resistant to drought and freezing of the soil, they
have a very shallow and horizontal root system and need a poor soil layer with a
depth of 7-10 cm. At the same time they form a beautiful color carpet.
In the extensive landscaping the layers are: steam insulation, heat insulation,
waterproofing, drainage layer, root insulation, soil substrate and plant layer. Due to
the comparatively small mass of the extensive configurations, there are virtually no
restrictions on the material used on the roof slab (Evstatiev 2012).
In the case of intensive roofs, there are virtually no restrictions on the type of plants,
which can be limited only by the thickness of the soil substrate, the local climate and
the planned budget (Evstatiev 2012, Sustainable Eastside project 2004, Wark 2003,
VEDAG GmbH 2007). Airborne dust is found to drop by 42% below the trees and
this is observed throughout the growing season (that is, when the trees have leaves)
compared to places where there are no trees and prevailing open areas (Koleva
2011, Doncheva-Boneva 1987). During the autumn-winter period, there was a
significant difference between tree vegetation sites and open areas, although there
was a certain decline in vegetation. In the areas where there are tree species, the dust
content is 37.5% less than in the open areas where there are no trees and shrubs
(Koleva 2011). Even during the period when the bushes and trees are without leaf
cover, they are able to reduce the dust content twice. Not all plant species have the
same ability to purify air from dust. Dust-retaining properties depend on several
factors, such as the area of the plant, the construction of the leaves and their surface.
Rough and sticky leaves hold more dust, and this is true for the leaves covered with
hairs.
Table 1. Data from measurements in Sofia, Bulgaria (Borisova garden and

nearboulevards) (Koleva 2011)
Plant type Quantity of retained dust, g/m2/ 24h
summer oak 3.25
mountain ash 3.25
small poplar 2.80
birch 1.9
Measurements have been made in other parts of the country, which show that elm
and beech retain 6 and 5 times respectively more dust than the balsamic poplar and
the birch - 2.5 times as much as the aspen. Very efficient dust extractors are the
odorous willow, the French grapes, the chalice and the bird's grapes. Coniferous
species are not very effective in dealing with dust pollution and their efficiency is 30
times less than that of broad-leaved species (Koleva 2011). Green vegetation has the
property not only of retaining dust, it has the ability to purify the air from toxic
gases such as sulphur, nitrogen and carbon oxides. This process takes place as the
harmful substances are trapped and neutralized in the tissues of the plants. Different
plant species have different gas accumulation properties. To what extent will the air
be purified and the levels of pollution will be reduced depends on several factors -
plant species, degree and concentration of the pollutant, size of the green areas.
Table 2 lists some basic types with high gas absorption capacity.
Table 2. Data from studies on the sulphur dioxide uptake capacity in Sofia's green
areas (Koleva 2011)
Plant type Amount of pooled and accumulated sulphur as a result of sulphur dioxide
taken up by air
small-linden lime 7.8 (g/kg dry leaf matter)
mountain ash 6.45 (g/kg dry leaf matter)
summer oak 5.75 (g/kg dry leaf matter)
birch 5.75 (g/kg dry leaf matter)

These data are indicative for the abilities of these species to purify the air. Data from
studies on the ability of tree and shrub plant species to retain sulphur, which are
made in other countries and are listed in Table 3 (Koleva 2011).
For urban landscaping, it is advisable to use species that are highly resistant to air
contamination. For areas with high levels of pollution as Sofia, suitable species are:
white dogwood, usually bird's grapes, narrow-leaved willow, sixth, sumac, tattooed
claw. In case of moderate or reduced air contamination suitable species are white
willow, white acacia, summer oak, sophora, white mulberry, mosquito, mountain
ash, philatelus, and calinolist subduct. It is not recommended to use small-linden
lime, caraway wood, and common lilac.
Table 3. Data from studies conducted in areas with low pollution for the sulphur
dioxide uptake capacity of green areas (Koleva 2011)
Amount of pooled and accumulated sulphur as a
Plant type
result of sulphur dioxide taken up from the air
white dogwood usually poultry grapes,
black currants, tartar claw, narrow-leaved 4.16 – 7.36 g/kg dry matter
willow, white willow
a simple birch, a simple lilac, a shiny
1.24 – 1.92 g/kg dry matter
cotoneaster
a canine-lipped sub-plant and some apple
species
Table 4. Data from studies conducted in areas with intensive pollution for the
sulphur dioxide uptake capacity of green areas (Koleva 2011)
Amount of pooled and accumulated sulphur as a
Plant type
result of sulphur dioxide taken up from the air
white dogwood usually poultry grapes,
black currants, tartar claw, narrow-leaved 4.16 – 7.36 g/kg dry matter
willow, white willow
a simple birch, a simple lilac, a shiny
cotoneaster
a canine-lipped sub-plant and some apple
species
In areas where pollution is not high it is recommended to use plant species that are
highly gas-absorbing. Here you can use the above-mentioned gas-resistant species
and some other plant species such as black currant and some apples. Succulent
plants can also be used that have the ability to accumulate sulphur, but they still
have to show a high enough gas resistance. Appropriate for this purpose are silver
spruce, shiny bird's grapes, white acacia, mountain ash, cornflakes. In areas with low
levels of pollution, some plant species that are not suitable for areas with high levels
of contamination may also be used. These are species that have increased sensitivity
to harmful gases (in fact, they can be used as an indicator of the air condition in the

area). Such are the lime-grass, the tree-beetle, the common lilac, the birch, the
Turkstone oak, the thistle.
The roof gardens presented in Figures 1,2,3,4, and 5 are examples of contemporary
solutions to the problems of air purification and increasing the amount of green
areas in cities. Still such types of gardens are mainly built on roofs of hotels and
public buildings, and residential buildings are rare. They are also a wonderful
ecological and aesthetic solution.
The idea of building roof gardens is applicable worldwide. We will also hope to see
more and more of these beautiful, spectacular and environmentally-friendly
solutions for industrial, administrative, public and private buildings, which are still
the privilege of the rich. Roof landscaping can be built even in areas with less
favorable climatic conditions (http://www.highviewart.com/eko/pokrivnite-gradini-
ot-ptichi-pogled-481.html). Figures 8, 9, 10 and 11 are examples of beautiful
gardens in places with harsh climatic conditions than those in moderate latitudes.
Figure 1. Roof landscaping on the terrace of Figure 2. Roof landscaping of a building in

DSK Bank building in Lyulin – Sofia, Sofia, Bulgaria - greening company Green
Bulgaria project
Figure 3. Sofia, Bulgaria - intensive roof Figure 4. Roof in Ruse, Bulgaria

garden: 120m2

Figure 5. Roof in Ruse, Bulgaria
Figure 6. Foster & Partners is also behind Figure 7. Toronto, Canada

another green project in the Middle East - a
solar-powered international airport in
Kuwait
Figure 8. Malmo, Sweden Figure 9. Osaka, Japan

Protection Partnership Department, the Environmental Protection Agency
Environmental Protection Agency (EEA), provides data that 93 m2 of green roof
space can reduce dust emissions in the air by 18.14 kg/year, while producing oxygen
and removing carbon dioxide (CO2) from the atmosphere.
Using the data released by the US Environmental Agency, a study has been carried
out on the possibility of reducing dust emissions from the territory of the industrial
zone of the city of Ruse, located on the bank of the river Danube. With the help of
the software product PLUME approved at national level for Bulgaria, a computer
simulation was carried out to determine the mean annual concentration of dust from
industrial sources on the territory of Industrial zone of city of Ruse, Bulgaria
without the presence of green roof spaces and after the realization of the green roof
of two of the production buildings and an administrative building in the area.
The total area of the green roof areas for the area under consideration is 6,198
square meters, with projections that roofing systems contribute to reducing dust
emissions from industrial sources by 1,222 kg / year.
Current situation in the region of Industrial zone of Ruse, Bulgaria is shown in the
figure10: PLUME software works with a coordinate grid (x, y), with the studied area
of the air pool having parameters 16000x16000m or 32 steps*500 m. The model is
made with the type of underlying surface "urban area" as the industrial zone is
located in the regulation boundaries of the town of Ruse.
The wind rose and the average annual temperature for the city of Ruse is from the
Climate Guide of the Republic of Bulgaria, volume 3: Air temperature, soil
temperature, frost and volume 4: Wind. They are used as inputs in terms of
meteorological conditions for PLUME software.
Figure 10 presents the isolines of the average annual dust concentrations from the
Industrial Zone of Ruse. The estimated maximum dust concentration in the area
under investigation is 1.79 μg/m3, spreading in the Northeast direction. This value
represents 4.5% of the annual human health protection standard (40 μg/m3).
Simulation after the realization of green roof spaces in the region of Industrial zone
of city of Ruse, Bulgaria is also made and presented.
In figure 11 the isolines of the average annual dust concentrations are presented. The
estimated maximum annual average concentration of dust in the area under
investigation is 0.79 μg/m3, propagating in the Northeast direction. The value
represents 2% of the annual human health protection standard (40 μg/m3). This
means that the maximum annual average concentration of dust after the building of
green roofs is more than two times less than the one without green roofs.
Figure 10. Average annual concentrations Figure 11. Average annual concentrations of
of dust from the territory of the Industrial dust from the territory of the Industrial zone
zone Ruse, Bulgaria Ruse, Bulgaria after green roofs building

Conclusions
The construction of mini-ecosystems in the urban environment is a guideline in
architecture, design and ecology, which is related to the improvement of the urban
environment. It is gaining increasing popularity and is growing ever more intensely.
It is increasingly involved in the realization of projects related to building more
green areas in urban environments and the use of free urban spaces to increase
greenery. Serious investments are needed for research and studies on how roof
gardening has an impact on city air purification. There is still insufficient reliable
information gathered to testify these facts. It is obvious that research,
experimentation and work in this field are needed. It is necessary to collect more
data as ours from this paper on the air condition, the levels of pollution before and
after the construction of the gardens. Only then it will be ascertained to what extent
roofing landscaping deals with the problem and how its efficiency can be improved.
More time is needed to gather information on the most appropriate type of roofing
that will best deal with the specific air contamination in a given area. Roof gardens
are part of future technologies that will lead to a better environment, cleaner air, and
people's health improvement. They have to become a priority and have to be
promoted at national level by the state.
References
Dobreva, I 2016, ‘Dragostanova AB of sustainable design’, Ed. New Bulgarian
University.
Doncheva - Boneva, M 1987, ‘Protective functions of woody vegetation against dust
and gas pollution’, dissertation thesis, Sofia University, Bulgaria.
Evstatiev, BI 2012, ‘Application of modeling and simulation of physical processes in
sizing and operation of buildings with green roofs’, monograph Ruse
University "Angel Kanchev", Ruse.
Koleva, P 2011, ‘Geometric plant compositions’, Matcom. Sofia, pp. 318.
Sustainable East side project, 2004, ‘Livingroofs.org. Green roofs. Benefits and
coast implications’, London.
VEDAG GmbH, 2007, ‘Green roof gardens; creating a natural environment’.
Wark, C & Wark, W 2003, ‘Green Roofs Specifications and Standards: Establishing
emerging technology’, The Construction Specifier, vol. 65, no. 8, pp. 12-23.
http://www.blog.imotidoverie.bg/2015/11/raiska-gradina-na-pokriva/.
[02 July 2018]. In Bulgarian.
http://citybuild.bg/news/krasivi-zeleni-sgradi-blizkiia/21662. [02 July 2018]. In
Bulgarian.
http://fiora.eu/. [02 July 2018]. In Bulgarian.
https://greenprobg.com/2016/12/09. [02 July 2018]. In Bulgarian.
http://www.highviewart.com/eko/pokrivnite-gradini-ot-ptichi-pogled-481.html.
[02 July 2018]. In Bulgarian.
http://unigarden-bg.com/ozeleniavane/pokrivno/. [02 July 2018]. In Bulgarian.

IDENTIFYING AND DESCRIBING THE MAIN CLIMATIC AND STRESS

FACTORS THAT ARE AFFECTING FOREST AND VITICULTURAL
ECOSYSTEMS
Diana Elena Vizitiu1, Lucian Dinca2, Viorica Enache3, Alina Donici3, Lucretia Popa4, Danut
Cociorva5, Gabriel Murariu6
1
National Research and Development Institute for Biotechnology in Horticulture Stefanesti
Arges, Stefanesti City, 37 Bucharest – Pitesti Avenue, Arges, 117715, office@incdbh-
stefanesti.ro, Romania
2
National Research and Development Institute in Forestry”Marin Dracea”, 128 Eroilor Blvd.,
Voluntari, Ilfov, 13 Closca, Brasov 500035, icas@icas.ro, Romania
3
Research and Development Station for Vine and Winemaking Bujoru, Tg. Bujor City, 65 G-
ral Eremia Grigorescu, Galati District, 805200, scdvvbujoru@gmail,com, Romania
4
National Institute of Research-Development for Machines and Installations Designed to
Agriculture and Food Industry, 6 Ion Ionescu de la Brad Blvd., district 1, Bucharest, 71592,
icsit@inma.ro, Romania
5
National Institute for Research and Development in Environmental Protection, 294 Splaiul
Independentei, district 6, 060031, Bucharest, incdpm@incdpm.ro, Romania
6
Faculty of Sciences and Environment, Department of Physics, Chemistry and Environment,
„Dunarea de Jos” University of Galati, 47 Domneasca, 800080, Galati,
decanat.stiinte@ugal.ro, Romania
Abstract
Climatic changes represent one of the main preoccupations of our century - a
complex domain in which the knowledge must be continuously improved and
understood in order to efficiently approach the challenges from this field. Climatic
changes determined by a multitude of natural and anthropic causes (for example:
atmospheric pollution, soil erosion, afforestation and field degradation) lead to an
intensification of negative processes. Amongst these, we mention the intensification
of climatic changes, the increase of afforestation surfaces, reducing biodiversity,
degrading soils and the apparition of desertification processes, as well as population
migration, depletion of resources and the occurrence of social conflicts. On their
own end, climatic changes induce an aggravation of abiotic and biotic threats posed
on forests such as: fires, droughts, storms, atmospheric pollution, forest
fragmentation as consequence of transport and infrastructure constructions etc.
During the last couple of years, Romanian forests and fields destined for
afforestation were negatively affected by: torrential phenomenon, landslides and
river breaches, surface erosions, surface rocks, depth erosion, floods or freezing
rain. Climate represents one of the main natural factors both in ensuring viticultural
growth and development conditions, as well as in establishing and scaling
management works for peaks and irrigations. The main climatic and stress factors
that have affected the viticultural ecosystem in the last period of time are:

temperature, precipitations, atmospheric humidity, average global, active and useful

temperatures, night humidity index and the Huglin index.
Keywords: grapevine, precipitation, soil, temperature, trees
Introduction
Climatic changes represent one of the main challenges and the biggest social
dilemma that humanity has to face. These changes can have significant effects on
forests (changing the distribution of tree species by translating phytoclimatic levels
at other latitudes and altitudes) and agriculture. The viticultural production is
especially influenced because these cultures are extremely sensible towards the
environment, while seasonal variations of grape productions are much larger than
other common cultures, such as cereals. On a long term, climatic changes can cause
major geographic changes in traditional viticultural production areas, threatening
traditional wine areas such as France and Italy.
Climatic conditions (solar radiation, heat accumulation, extreme precipitations, frost
intensity and duration, diurnal temperatures, humidity etc.) have a strong impact on
grapevine cultures, impacting the grapevines growth and development, the
apparition of certain diseases or the wine’s chemical and organoleptic
characteristics. In low afforested and hill areas, a considerable decrease of forest
productivity is estimated after the year 2040 due to the increase of temperatures and
the decrease of precipitation volume.

Climatic changes are determined both by internal factors (changes that appear inside
the climatic system or caused by the interactions between its components), as well
as external natural factors (solar energy variation, volcanic eruptions, Earth’s
orbital parameters variation) or external anthropogenic factors resulted from human
activities (changing the atmospheric composition as a result of increasing the
concentration of greenhouse gases).
The present study has analysed the changing tendencies of temperature and
atmospheric precipitations in Romania. As such, the following aspects were studied:
the impact of climatic changes over forest ecosystems and their regulation options
based on the areas geographic location, the main factors that affect forests, the
damage percentage of trees on biogeographical regions from Romania. Furthermore,
pathogen agents that bring damages in grapevine plantations from Stefanesti
viticultural centre and Dealul Bujorului vineyards were also identified, while their
climate was also analysed in the period 1980-2016.

Forest and viticultural ecosystems are facing nowadays more harmful ambiental
tendencies, among which the most important ones are: obvious climatic changes
represented especially by the growth of temperatures with profound ecological

effects (drought, heat waves etc.); harmful agents bioinvasion (diseases, harmful
agents, weeds) adapted to the new habitat conditions; production decreases.
Climatic changes produced by different causes and processes such as atmospheric
pollution, soil erosion, clearance and field degradation cause massive forest
productivity loses with major implications on the economy. Statistical data show
that the forest surface from Romania affected by abiotic and biotic factors has
evolved during the last 50 years from 4 % (in 1954) to 28 % (in 1998).
The last years have shown an increase in the frequency of extreme temperatures
(heats) that are amplifying the stress caused by drought. Some species are more
sensible towards this climatic parameter. Drought has affected annually an average
of 56.809 ha and especially young cultures from Dobrogea, the south and east of
Romania, with maximum values between 2002-2003 and 2007. The drought from
these periods has also favoured the mass multiplication of some harmful insects
(looper moths, bark insects).
Statistical data show that our country’s forest surface affected by abiotic and biotic
factors has evolved during the last 50 years as follows (Nitescu et al 1992,
Simionescu et al 2001, Simionescu et al 2012):
1954 - 4% (from which approximately 99% are harmful biotic factors);
1965 - 12,5 % (from which approximately 75% are harmful biotic factors);
1975 - 14,7% (from which 61% are biotic factors and 39% are abiotic factors);
1985 - 14% (from which approximately 82% are biotic factors and 18% are
abiotic);
1998 - 28% (from which approximately 79% are biotic factors and 21% are
abiotic).
Forest ecosystems from the plain area were strongly affected by drought, based on
some structural changes, anthropogenic in their origin. After the droughts from
1945-1947 and 1955-1961, the tree drying process has amplified, being identified on
approximately 40000 ha. After a stagnation period, drought intensifies after 1971,
affecting larger and larger surfaces both for pedunculate oak as well as for greyish
oak, pubescent oak and holm (Chira & Chira 1998).
Mountain ecosystems where predominantly affected by strong storms. During the
last years, the number of surfaces with fallen or ruptured trees has increased by ten
and even hundred thousand hectares (Nitescu et al 1992, Simionescu et al 2001).
During 1960-1961, wind has caused the fall of 3.534.000 m3 Norway spruces,
1.214.000m3 common beech and 305.000 m3 oaks. These calamities were located
both in the Oriental Carpathians as well as in the West Carpathians.
Freezing rain
As a consequence of a rare encountered meteorological phenomenon, namely
freezing rain (Figure 1), associated with strong wind towards the end of the 2015
vegetation season (October) while trees were not yet foliated, crown and stem
raptures were registered as well as falls/uproots in common beech and mixture
common beech stands. This phenomenon was registered at over 550 m altitude,
especially in Magura Odobesti area, on superior slopes, with an estimated 1000 ha
surfaces affected (Constandache et al 2018). Furthermore, a correlation between
altitude and harmful intensity was observed, namely that the harmful intensity
decreases as the altitude also decreases.
Figure 1. Stand affected by freezing rain Vidra forest district, Vrancea County
Drought has affected on average 56.809 ha (19,1% of the surface affected by

abiotic factors). This phenomenon has mainly affected young plantations especially
from Dobrogea, South and East Romania, with maximum values in the years 2002-
2003 and 2007 (Simionescu et al 2012). The last years have been characterized by
an increase of extreme temperatures (scorches) which amplify the stress caused by
drought as some species are more sensitive towards this climatic parameter. On the
general drought background, unfavourable phenomenon for biocenosis can also
appear such as the drying of forests and forest fires.
The drying of stands is the result of a complex abiotic and biotic factors. However,
statistical data emphasize a significant general decrease of drying stands. In
comparison with last 15 years (1986-2000), when this phenomenon has affected
over 234.400 hectares, in the period 2001-2010 this number is significantly reduced
to 45.400 hectares. The most affected areas affected in the period 2001-2010 were
oak forests (67%) and resinous forests (14%). Annual oak dryings on a surface of
over 30.000 hectares represents a low percentage in comparison with the previous
period, both as surface as well as intensity (Chira & Chira 1998, Simionescu et al
2001, 2012, Danescu et al 2015, Constandache et al 2016, Simonca et al 2017). This
area is also characterized by the presence of natural and artificial shrubby
associations composed of whitesea buckthorn (Constandache et al 2016), red sea
buckthorn, small locust etc. The phenomenon causes, amongst other, decreases of
tree growths (Silvestru-Grigore et al 2018). For resinous species, this phenomenon
still affects fir species (75%), in comparison with 13% for Norway spruce or 12%
for pine (Barbu 2017).
Forest fires were especially manifest in excessive drought periods, predominantly
affecting young cultures. The largest surfaces affected by forest fires were registered
in Caras Severin County (23%). Most of them happened in 2007 and 2013 in more
dry sites, usually as a consequence of cleaning pastures by fire (Adam 2007).

Damages caused by forest fires are usually not significant, mainly due to forest
compositions comprised of broad-leaved species. On average, approximately 88
fires are caused annually, while the affected forest area is of 276 hectares. Compared
with the total country’s forest fund area, the annually fired surface represents 0.15%.
Torrential phenomenon
In some Romanian hill and mountain areas, torrential phenomenon are strongly
connected with uncontrolled human interventions. Besides the anthropic factor, an
important role is also played by climatic factors as a result of climatic changes
caused by global heating (Clinciu et al 2012). The most part of our country’s forests
are situated in areas with hill and mountain relief, high slopes and lithological
sedimentary substratum, all contributing to the fields’ vulnerability towards erosion,
landslides or clogging (Dinca et al 2014, Sparchez et al 2013, Tarziu et al 2004).
Floods have caused damages on average surfaces of 11892 ha/year (four times
higher than the average of 2800 ha/year recorded in the previous timeframe), from
which 58% had a strong intensity. This phenomenon was dramatic in years with rich
precipitations, for example 2005-2006 and 2010 (Danescu et al 2011, Simionescu et
al 2012).
Landslides and bank ruptures are strictly local phenomenon (but which have
increased 10 times in the last decade). This phenomenon has affected the banks of
rivers with high debit that come from the mountain area. These fields represent
segments from the most strongly altered environment: they favour and amplify
ecological derangements, are the main focal point of alluvial alimentation during
floods and are strongly affecting the biological and habitat diversities.
The proliferation of the main pathogen and harmful agents from vinicultural
plantations is an important ecological phenomenon that is influenced by the zonal
ecological factors and ecological plasticity. The main pathogen and harmful agents
of grapes from the analysed vineyards are: Plasmopara viticola, Uncinula necator,
Botrytis cinerea, Lobesia botrana, Tetranychus urticae, Calepitrimerus vitis and
Eriophyes vitis. The main climatic factors that are affecting the viticultural
ecosystems are: temperature, precipitations, atmospheric humidity, the sum of
global, active and useful temperatures, the cool night index, and the Huglin index.
Romanian grapevine plantations located in Muntenia (Stefanesti viticultural centre)
and Moldova (Dealul Bujorului vineyards) are more and more affected by climatic
changes manifested in the last decades. The main factors that have influenced the
studied vineyard plantations were: high temperatures, precipitations, hailstone,
storms and rime.
Changing environment conditions have determined shifts in metabolism, growth and
development processes, with negative influences over the plants quality and vitality
(Figure 2A). Hailstone, through its mechanical (hitting) effect, has caused
significant damages to grapevine plantations. In many cases the grape production
was even irremediably compromised (Figure 2B).

A B
Figure 2. The effect of high temperatures and excessive drought (A) sand the effect
of hailstone over sprouting and grapes (B)
Air temperature is a decisive factor in the development of grapevine plantations and

in triggering the grapes phenophases. The most important inferior biological
threshold is the 10˚C temperature level that demarcates the length of the air’s
bioactive period (180-220 days in the temperate continental climate).
The evolution of temperatures in the two studied viticultural areas (Figures 3A and
B) has not recorded significant differences: the multiannual temperature was of
10.9°C in Stefanesti and 11.4°C in Bujoru, the multiannual minimal temperature
was of 6.4°C in Stefanesti and 5.8 in Bujoru, while the multiannual maximum
temperature was of 16.2°C in Stefanesti and 16°C in Bujoru.
A B
Figure 3. Temperature evolution in Stefanesti vinicultural centre (A) and
Dealul Bujorului vineyards (B)
Grapevine culture is possible at an annual precipitation regime ranging between

400-700 mm, from which 250 mm during the vegetation period, uniformly
distributed under the shape of useful rains (>10mm). Average 691 mm were
registered in Stefanesti viticultural areas, but the last 37 years have encountered an
uneven distribution for them (Figure 4A). The precipitation’s evolution in Dealu
Bujorului vineyard (Figure 4B) marks a cyclical tendency of approximately 7-8
years, in which the rain interval alternates with the drought one. During the last
period of time, a tendency for increased annual precipitations was observed with an
uneven distribution of them over the entire year, with drought periods framed by
short periods with abundant rains and usually with a torrential character.
The grapevine’s requirements for the relative air humidity depend on the vegetation
phenophase and range between 50-80%. In both viticultural areas, the atmospheric
humidity from the last 37 years has corresponded with the grapevine requirements
(Figure 4A and B).
A B
Figure 4. The evolution of precipitation and atmospheric humidity in Stefanesti
vinicultural centre and in Dealul Bujorului vineyards
In Stefanesti viticultural area, the sum of global, active and useful temperatures was
similar with multiannual averages. In comparison, Bujoru vineyard area records an
increase of these value up to the year 2008, followed by a slight decrease until 2014
and then an increase until 2016 (Figure 5).
Figure 5. The evolution of multiannual sum of global, active and useful

temperatures in Stefanesti vinicultural centre and in Dealul Bujorului vineyards
Huglin index (Figure 6) has values gathered between 1885 and 2667. During the last
37 years, only six years have a smaller than 2100 Huglin index, while all the other
years have higher values. This aspect situates the territory as warm with cultivation
possibilities for even late varieties situated in the 2100 < HI ≤ 2400 classification.

oC
3500 16
3300 14
3100 12
2900
10
2700
8
2500
6
2300
2100 4
1900 2
1700 0
1980
1982
1984
1986
1988
1990
1992
1994
1996
1998
2000
2002
2004
2006
2008
2010
2012
2014
2016
Huglin index Night cooler index
Linear (Night cooler index) Linear (Huglin index)
Figure 6. Huglin index and the night chill index in the period 1980-2016 in Dealul
Bujorului vineyards
Conclusions
During the last couple of years, Romanian forests and fields destined for
afforestation were negatively affected by: torrential phenomenon, landslides and
river breaches, surface erosions, surface rocks, depth erosion, floods or freezing
rain.
Drought and hailstone have negatively influenced the quality and vitality of
grapevine plants, causing significant damages in grapevine plantations. Air
temperature is a decisive factor in the development of grapevine plants, including
triggering the grapevine’s phenophase. The most important inferior biological
threshold is the 10˚C temperature level that demarcates the length of the air’s
bioactive period.
The culture of grapevines is possible in Stefanesti viticultural centre and in Dealul
Bujorului vineyards even though the recorded precipitations were uneven. In
Stefanesti viticultural area, the sum of global, active and useful temperatures was
similar with the multiannual averages recoded in Bujoru vinicultural area.
Acknowledgements
This research was supported through the project 3PS „Investigations in support of evaluating
and attenuating the influence of climatic changes and other stress factors over the health of
forest ecosystems and vinicultural cultures”. This project is funded by the Ministry of Research
and Innovation.
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LOW HEATING VALUE PREDICTION FROM PROXIMATE ANALYSIS

FOR SEWAGE SLUDGE SAMPLES
Agnes Serbanescu, Mona Barbu, Ileana Nicolescu, Georgeta Madalina Arama
National Research and Development Institute for Industrial Ecology – ECOIND, 71-73
Drumul Podu Dambovitei, district 6, 060652, Bucharest, agnes.serbanescu@incdecoind.ro,
Romania
Abstract
As global renewable energy demand grows, sludge from urban waste water
treatment plants could be one of the available renewable energy resources. Thermal
treatment of sludge is becoming more and more attractive due to the destruction of
dangerous constituents and the reduction of their volume.
The article presents a correlation equation based on the volatile matter content,
which allows calculating the low heating value of sludge samples from a city
wastewater treatment plant. The equation was developed by evaluating the
characteristics of more than 40 sludge samples analysed in the laboratory.
Validation of the equation revealed that the heating value deviation from the
experimental one was below 3.5%.
The estimation of the low heating value of sludge samples based on the
determination of volatile matter content is important where the experimental
determination of the low heating value involves time and the use of high-tech
laboratory equipment.
Keywords: correlation equation, low heating value, sewage sludge, volatile matter
Introduction
As a result of the increase of the population connection rate to the sewage system
and the modernization of the wastewater treatment plants, the statistical data show a
134% increase in the amount of sludge generated in 2014 compared to 2010
(192,000 t in 2014) (PNGD 2017).
According to the National Institute of Statistics data, from the total amount of sludge
treated in 2014, about 5% were used in agriculture and about 75% were stored on
their own platforms.
The use of sewage sludge as a fertilizer for agricultural lands can cause health risks
by infesting the soil and groundwater with heavy metals, pathogens and viruses.
These issues have generated a particular interest in other disposal alternatives, one
of which is the combustion of sludge.
Waste energy recovery in the EU comes to support the achievement of the
objectives of the Circular Economy Action Plan and is firmly guided by the EU
hierarchy of waste (EC 2017).
On the other hand, the combustion of sewage sludge is becoming more attractive as
a removal option, due to the destroying of hazardous constituents and considerable
volume reduction.
The use of sewage sludge as a source of renewable energy is an ecologically and
economically efficient option, both in the EU and in the Romanian sludge
management strategy.
Thermal processes involve removing the organic part of the sludge, leaving only the
ash component for final disposal Sewage sludge is a type of biomass fuel, its heating
value is similar to lignite (Fytili et al 2008). The main purpose of the thermal
treatment of sewage sludge is to use the stored energy in the sludge and to minimize
the impact on the environment at the same time, in order to meet the stricter
standards.
The article presents a correlation equation for calculating the low heating value of
the sludge resulting from a municipal wastewater treatment plant based on the
volatile matter content.
Heating value is an important characteristic of sludge used in combustion plants.
The higher heating value is determined experimentally by the complete burning of a
known amount of sludge in the calorimetric bomb. The heat released by the
combustion is transmitted to the calorimetric system comprising a known quantity of
water which temperature is recorded.
The characteristic of the interest in combustion plants is the low heating value. The
low heating value represents the number of heat units emitted by the complete
combustion of a unit fuel mass under standard conditions, in which the water
vapours formed during the combustion remains in the gaseous form, and
consequently does not give up its latent heat of vaporization.
The low heating value may be calculated by subtracting the latent heat of water
evaporation from the high heating value.
The experimental determination of the high heating value, and the calculation of the
low heating value for a material, requires the use of performance laboratory
equipment (calorimetric bomb, elemental analyser).
Another method for evaluate the heating value is the use of estimation equations
assuming that the heating value of a hydrocarbon is given by the heat of combustion
of carbon and hydrogen.
There are several types of equations for estimating heating value, such as those
based on elemental composition. Dulong's formula is one of the famous equations
that use elemental analysis results. This equation is often used to estimate the
heating value of coals (anthracite, bituminous coal) with 1.5% error, compared to
the values obtained experimentally.
Values calculated using the Dulong formula show deviations from the value
determined experimentally for lignite and subbituminous coal due to their high
oxygen content (Hosokai et al 2016).


Laboratory experiments were performed on a number of approximately 40
mechanically dehydrated sludge samples from a municipal waste water treatment
plant for a period of approx. 4 years.
The sludge samples were fully characterized using standardized methods. For
characterization, the sludge samples were prepared in the laboratory by air drying at
ambient temperature and milled using the Retsch Vibratory Disc Mill RS 200 in
order to obtain a laboratory sample with a grain size less than 200 μm (Serbanescu
et al 2017, Kim et al 2017) .
Determination of moisture content and volatile matter (5500C) was performed by
gravimetric methods (ASRO 2002, 2007).
The higher heating value was determined by calorimetric method (ASRO 2009)
using PARR 6200 calorimetric bomb. The low heating value was calculated (ASRO
2009) using the high heating value and the hydrogen content.
The elemental analysis, namely the determination of the carbon, nitrogen and
hydrogen content, was performed by a chromatographic method using the Thermo
Scientific FlashEA 1112 Elemental Analyzer (ASRO 2011). The FlashEA 1112
Elemental Analyzer is based on the well-known Flash Dynamic Combustion
method, which produces complete combustion of the sample within a high
temperature reactor, followed by an accurate and precise determination of the
elemental gases produced (N2, CO2, H2O and SO2), using a TCD thermal
conductivity detector. The sample combustion temperature was 9500C.
The sulfur content was determined by gravimetric method using the washing waters
from the calorimetric bomb (ASRO 2017).

In the laboratory research it was considered that the heating value of a sewage
sludge would depend on the organic substance content and the technology used for
waste water treatment and for residual sludge elimination.
Using the results obtained in the laboratory (Table 1), a correlation equation
between the low heating value and the content of volatile matter is established,
expressed on dry basis, for sludge samples from a municipal waste water treatment
plant. The coefficients of the interpolation formula were established by the least
squares method after the elimination of extreme values by mathematical statistical
methods.
Figure 1 shows the interdependence between the low heating value and the content
of volatile matter, in dry basis for the analysed sludge samples. The linear regression
equation expressing the dependence of the two variables is: y = 37,895 x + 605, 2

Table 1 Main physical-chemical characteristics of analysed sludge samples

Volatile LHV
Moisture C, H, N, S,
Sample matter, [kcal/
[%] [% d.b.] [% d.b.] [% d.b.] [% d.b.]
[% d.b.] kg d.b.]
1 61,2 29.41 1700 16.79 3.10 2.45 0.64
2 63,7 37.00 2159 20.70 3.62 2.98 0.63
3 66,3 40.31 2194 21.23 3.06 3.44 1.01
4 64,6 42.37 2098 20.36 3.35 3.06 0.70
5 67,8 43.79 2326 24.79 3.52 3.34 0.84
6 64,8 44.02 2253 23.94 2.92 3.98 0.63
7 68,6 44.23 2416 24.49 3.05 3.54 0.78
8 57,5 44.42 2221 21.68 3.50 3.07 0.42
9 64,5 44.77 2266 24.96 3.52 3.52 0.80
10 70,1 44.82 2145 24.67 1.88 4.35 1.11
11 68,3 46.07 2322 25.31 3.24 3.93 0.79
12 70,4 46.75 2401 25.22 2.88 3.28 1.18
13 66,7 46.97 2236 21.84 4.01 3.69 0.66
14 67,2 47.25 2387 26.39 3.44 3.55 0.65
15 66,5 48.78 2291 23.71 3.26 3.25 1.10
16 69,8 50.35 2666 27.21 3.41 3.94 0.96
17 73,4 51.29 2530 26.51 3.00 4.51 1.16
18 61,8 51.59 2675 27.59 3.44 3.81 0.72
19 71,6 52.07 2630 25.99 4.11 4.40 0.75
20 71,0 53.79 2709 27.10 4.09 4.58 0.81
21 72,1 54.68 2775 27.21 4.30 5.30 0.79
22 71,2 54.82 2686 26.68 4.12 4.43 0.83
23 68,5 54.98 2581 25.60 3.97 3.61 0.84
24 69,0 59.57 2835 28.90 4.73 3.71 0.85
where:
d.b.-dry basis
LHV-low heating value
Figure 1. Interdependence between low heating value and volatile matter content of
the analysed sludge samples
For two Gaussian distributed data series, the most synthetic correlation indicator is
the Pearson correlation coefficient r. The correlation coefficient is a quantitative
value describing the relationship between two or more variables, representing the
relationship between the covariance of the series and the product of their standard
deviations, and shows values between -1 and 1. The sign of the correlation
coefficient indicates the direction of the association (inversely proportional to the
sign - and directly proportional to the + sign) of the investigated variables ("Iuliu
Hatieganu" University of Medicine and Pharmacy Cluj-Napoca, 2017).
The value for the correlation coefficient r for the curve presented is 0.933.
According to Colton's empirical rules, a correlation coefficient greater than 0.75 (or
less than -0.75) indicates a very good association or correlation of the variables.
The coefficient of determination R² is the square of the correlation coefficient r.
The value of the determination coefficient expresses an intensity of the linear
relation between the two variables (low heating value and volatile matter content) or
answers the question: how much of the variation of Y can be explained by the linear
relationship with X.
The value of the calculated coefficient for the presented curve is 0.8713, suggesting
a very good performance.
To determine whether the correlation coefficient is significant, so the two
parameters (low heating value and volatile matter content) are correlated, the
parameter t, considering 22 degrees of freedom was calculated. The value obtained
by calculating parameter t is 12, 2. According to Student distribution, the value for t
of 12, 2 is converted to a probability error value: p, this being <0,001 leading to a
relatively significant statistic between parameters (University of Medicine and
Pharmacy-Craiova, 2018).
To validate the correlation equation between low heating value and volatile matter
content, sludge samples from the same municipal wastewater treatment plant other
than those used to establish the equation, were analysed. Table 2 shows the results
obtained, which demonstrates that the use of the proposed equation represents a fast
and relatively simple way to obtain a good estimation of the low heating value
knowing the value of the volatile matter content. The differences between the
calculated low heating values and those obtained by experimental determinations are
below 3.5%.
Figure 2 shows the applicability of the proposed equation for determining the low
heating value for several sludge samples. The continuous line represents the
equation describing the dependence between the low heating value and the volatile
matter content.
The predicted low heating value for sludge samples, compared to those determined
experimentally (Figure 3), indicates a good accuracy of the results.

Table 2. Characteristics used for the correlation equation validation

Volatile LHV LHV
Difference Difference
Sample matter, (kcal/kg, d.b.) (kcal/kg, d.b.)
(kcal/kg, d.b.) (%)
(% d.b.) experimental predicted
1 40.81 2137 2152 -15 -0.69
2 40.87 2105 2154 -49 -2.33
3 42.26 2140 2207 -67 -3.11
4 41.41 2128 2174 -46 2,16
5 44.14 2298 2278 20 0,88
6 53.04 2610 2615 -5 0,19
7 53.2 2662 2621 41 1,54
8 54.29 2717 2663 54 1,99
9 54.48 2651 2670 -19 0,72
10 55.28 2643 2700 -57 2,16
11 57.56 2823 2786 37 1,31
12 53.48 2677 2632 45 1.69
Figure 2. Application of the equation for low heating value for sludge samples
Figure 3. Experimental vs. predicted low heating value

Conclusions
Laboratory experiments has highlighted the interdependence between the net heating
values and volatile matter of sludge samples for a municipal waste water treatment
plant. This interdependence is presented as a correlation equation wich allows to
predict the low heating value of sludge samples using the volatile matter content,
both at dry basis. The equation allows the calculation of an important indicator for
combustion processes without using high-tech laboratory equipment.
The predicted low heating value for sludge samples, compared to those determined
experimentally, indicates a good accuracy of the results.
Acknowledgements
This work was supported by Romanian Nucleu Programme, Project PN 18 05 04 01
„Innovative researches to support the achievement of national targets aligned with EU policy
on waste management in the context of circular economy concept" being funded by Ministry of
Research and Innovation.
References
ASRO 2002, SR EN 12880: 2002, Characterisation of sludge’s-Determination of
dry residue and water content.
ASRO 2007, SR EN 15169: 2007, Characterisation of waste-Determination of loss
on ignition in waste, sludge and sediments.
ASRO 2009, SR EN 15170: 2009, Characterisation of sludge’s-Determination of
calorific value.
ASRO 2011, SR EN 15407:2011, Solid recovered fuels. Methods for the
determination of carbon (C), hydrogen (H) and nitrogen (N) content.
ASRO 2017, SR EN 14582:2017, Characterization of waste. Halogen and sulphur
content. Oxygen combustion in closed systems and determination methods.
EC 2017 - EUROPEAN COMMISSION, The role of waste-to-energy in the circular
economy, Brussels, 26.1.2017.
Fytili, D & Zabaniotou, A 2008, ‘Utilization of sewage sludge in EU application of
old and new methods’, Renewable and Sustainable Energy Reviews, vol. 12,
no. 1, pp. 116-140.
Hosokai, S, Matsuoka, K, Kuramoto, K & Suzuki, Y 2016, ‘Modification of
Dulong`s formula to estimate heating value of gas, liquid and solid fuels’, Fuel
Processing Technology, vol.152, pp. 399-405.
Kim, L, Muresan, AM, Cuciureanu, A, Guta, D, Arama, M, Cristea, NI, & Dediu, V
2017, ‘Experimental models of characterization and analysis of industrial
waste’, 20th International Symposium “The Environment and The Industry”,
Ecology ECOIND, Bucharest, pp. 142-150.
PNGD 2017- National Waste Management Plan, Romanian Official Monitor no. 11
bis from 5th January, 2018. In Romanian.

Serbanescu, A, Barbu, M, Nicolescu & Bucur, I 2017, ‘Interdependence between

total organic carbon content and heating value of sewage sludge samples’, 20th
University of Medicine and Pharmacy Iuliu Hatieganu Cluj-Napoca 2017,
Correlations and regressions, Available from:
https://www.info.umfcluj.ro/ro/did-ro/biostat ro/mg1ro-ro/item/1050-curs-12-
corelatii-si-regresii. [10 July 2017]. In Romanian.
University of Medicine and Pharmacy from Craiova 2018, Course 5, Statistical
Correlation, Available from: https://www.umfcv.ro/medicina-dentara,
studenti- disciplina-informatica-medicala.shtml. [04 July 2018]. In Romanian.

NEW APPROCHES REGARDING BAT CONCLUSION

IMPLEMENTATION
Valeriu Danciulescu, Andreea Cozea, Mihaela Petrescu, Raluca Diodiu, Gheorghita Tanase,
Andrei Vasile
National Research and Development Institute for Industrial Ecology - ECOIND, 71-73 Drumul
Podul Dambovite, district 6, 060652, Bucharest, poluare.aer@incdecoind.ro, Romania
Abstract
This paper presents some synthetic information regarding preliminary data obtained
along a multiple objective research project in which the principal objective was new
approaches regarding the implementation of pollutant air emissions -Directive
2010/75/UE, with the necessity coming to adopt the European Commission's
decisions on BAT Conclusions. In that study are presented the novelty elements
becoming from both important National Economy domains, such as Large
Combustion Plants and Intensive pig and chicken farming; beside these theoretical
aspects are presented in the paper also the first air emissions results such as HCl, HF
and Hg resulting from charcoal combustion related with an experimental model that
could be used in the Smell Management Plan development in the field of Intensive
Animal farming, required by the BAT conclusions.
Keywords: air polution, BAT-AELs, BAT conclusions, large combustion plants
Introduction
The air pollution and implicitly, the emissions reduction from anthropogenic sources
is a constant concern of the authorities, the scientific environment and of the
population due to the important health impact it can have it on the people (Bucur &
Danet 2016) and the influence on the other environmental factors with which they
are in direct interdependence. Maintaining air quality requires first and foremost is
the use of the best manufacturing techniques and technologies coupled with the most
efficient methods/techniques to reduce pollutant emissions from the environment.
BAT (BATC) conclusions as are defined (Directive 2010/75/EU), are the key
element of BAT reference documents and establish the conclusions of the best
available techniques, their description and also the information to assess their
applicability, emission levels associated with the best available techniques,
associated monitoring, consumption levels and where appropriate relevant site
remedial measures. Till present, based on European Commission Decisions have
been adopted the BAT Conclusions for 12 activity sectors (Table 1), but the process
is ongoing to perform all the IPPC Directive areas. In the Table 1 are also indicated
the implementing deadlines for the provided measures from the Directive
(Implementing Decision 2017/302/EU), (Implementing Decision 2017/1442/EU).
In addition to a brief information presentation compared with the BREF/BAT
documents, the BAT Conclusions also specify the most important techniques to
reduce these emissions - the techniques are presented in the table format without
insisting on their detailed description as well as the techniques/methods indicated for
air and water pollutants emissions from monitoring process.
Table 1. Activity domains for which they were adopted the BAT Conclusions
Activity domains Date of Implementation
adoption deadline
Cast, iron and steel production 28. 02.2012 2016
Glass manufacture 28.02.2012
Chloralkali production 9.12.2013 2017
Cement, lime and magnesium oxide production 26.03.2013
Hides tanning 11.02.2013
Mineral oil and gas refining 9.10.2014 2018
Cellulose, paper and cardboard production 26.09.2014
Wood based panels production 20.11.2015 2019
Common systems for the treatment / management of 30.05.2016 2020
waste water and waste gases in the chemical sector
Nonferrous metal industry 13.06.2016
Intensive chicken and pig farming 15.02.2017 2021
Large combustion Plants 31.07.2017
In this paper approaches are discussed the novelties in the field of large combustion
plants based on charcoal and the odour evaluation in the intensive pigs and chicken
farming;
Large combustion plants are plants with a total rated thermal input bigger or equal to
50 MW, irrespective of the type of fuel, solid, liquid or gaseous used for generating
electricity and/or heat. One of the major environmental problems generated by the
operation is the air emissions of SOx, NOx, CO, dust and also greenhouse gases
such as N2O and CO2 (Barbu et al 2015, Danciulescu et al 2017) and small
quantities of heavy metals (Petrescu et al 2017), halogenated compounds and
dioxins, furans, depending on the chemical composition of the fuel used, the
operating regime and applied emission reduction technologies (Nicolescu et al 2017,
Serbanescu et al 2017).
Taking into account the specific requirements of the BAT Conclusions, the first
results obtained in the process of assessing the emission of HCl, HF and mercury in
case of large combustion plants based on charcoal are also presented.


In order to determine the concentration of HCl, HF and mercury from the fixed
source emissions resulting from large combustion installations based on charcoal,
where respected the provisions of the standard method recommended by the BAT
Conclusions (Table 2), which require isokinetic sampling of air, with the retention
of pollutants on filter and absorbent solutions specific to each compound, followed
by analysis by atomic absorption spectrometry with cold vapour for mercury,
electrochemical method for HF and spectrophotometrical method for HCl
Table 2. HCl, HF and Hg determination methods for the fixed sources emissions
Polutant Determination Method
HCl SR EN 1911:2011 fixed sources emissions. Determination of the mass
concentration of gaseous chlorine, expressed as HCl. Standard reference
method
HF SR ISO 15713: 2008 fixed sources emissions. Sampling and determination of
fluorine gaseous form content.
Hg SR EN 13211: 2003 Air quality. Emissions from fixed sources. Manual
method for total mercury concentration determination.

By carefully reviewing the BAT Conclusions, same novelty elements with general
applicability have been identified such as: 1) Increasing the continuous monitoring
measurements versus periodic measurements; 2) Usually are recommend daily
measurements for continuous monitoring and during minimum 30 minutes for
periodical measurements; 3) the tendency to lower emission limit values; important
reductions are observed in large combustion plants; but also in the other analyzed
areas; 4) the possibility of using, under certain conditions, indirect methods of
monitoring the air emission pollutants, which have the advantage of simplicity and
reduced costs, and specific novelties with applicability only in certain areas: a) the
NH3 air emissions into in the field of intensive pigs and chiken farming, dosed in kg
of NH3/animal/year space, which implies the development of distinct measurement
and evaluation methodologies, b) the elaboration of the Smell Management Plans
for the case of complaints, with applicability in the field of intensive pig and chiken
farming and for the production of wood-based panels. The paper approches with
novelty issues regarding large combustion plants.
Large combustion plants

Regarding the Large Combustion Plant field, the lower limits were compared to
those of the current legislation and were introduced (Table 3), values which raises a
number of problems regarding how these requirements can be met. The experience
of the other states in solving similar situations indicates three type of approachs: i)
the optimization of existing processes, ii) partial change of existing technological
processes, iii) essential or total change of the initial process, depending on the
specificity of the process and the costs of the investment. Generally, air emissions
for these compounds are continuously monitored knowing exactly the current
existing level.
Table 3. Limit values for coal and lignite air emissions
SO2, mg/Nm3 NOx, mg/Nm3 Dust, mg/Nm3
New Existing New Existing New Existing
Capacity
instalation instalation instalation instalation instalation instalation
(MWt )
s s s s s s
Annual average
50-100 150-200 150-360 100—150 100–270 2-5 2-18
100-300 80-150 95-200 50-100 100–180 2-5 2-14
>300 10-75 10-130 50 - 85 < 85 - 150 2-5 2-10
Average daily
50-100 170-220 170-400 155–200 165–330 4-16 4-22
100-300 135-200 135-220 80–130 155–210 3-15 4-22
>300 25-110 25 - 165 80 -125 140 - 165 3-10 3-11
Law
278/201 400/250/200 300/450/200 30/25/20
3
It was also notes the introduction of new requirements for the monitoring of the
HCl, HF and mercury emissions, which were not regulated until now in
environmental legislation. In Table 4 are presented the limit values for these
pollutants emission and for each, annual limit values it have been set.
Table 4 Annual limit values for coal and lignite air emissions
Capaci CO, HCl, HF, Hg,
ty mg/Nm3 mg/Nm3 mg/Nm3 µg/Nm3
(MWt Existing New Existing New Existing New New
) instalatio instalatio instalatio instalatio instalatio instalatio instalatio
ns ns ns ns ns ns ns
< 30–
<300 - - - - 1-5 1-10
140
≥300 5-100 - - - - 1-4 1-7
<100 - 1-6 2-10 <1-3 <1-6 - -
≥100 - 1-3 1-5 <1-2 <1-3 - -
The compliance with these requirements raises special issues for plant process
operators from Romania, in order to reduce pollutant emissions for which the limits
it have been reduced (NOx, SO2 and dust) and measures to quantify the level of
current HCl, HF and Hg emissions in view of compliance.
For a punctual estimation of HCl, HF and Hg emissions in July 2018, a series of
momentary measurements were performed on four Large Combustion Plant LCPs
based on carchoal installations which, for the regulated indicators (Law 278/2013),
are within the required limits. The results of these determinations are described in
Table 5.
Table 5 Preliminary results for HCl, HF and Hg exposed in mg, µg/Nm3, based on
momentary measurements
HF, HCl, Hg,
Installation Observations
mg/Nm3 mg/Nm3 µg/Nm3
1 1.03 1.19 3.7 the values are in the admitted limits
the limit of HF is over the admitted
2 18.6 1.28 2.3
limit
the limit of HF is over the admitted
3 22.6 2.02 3.8
limit
4 1.81 1.91 4.9 the values are in the admitted limits
the values are in the annual average
BAT-AEL 1-3 1-5 1-10
admitted limits
Analising the obtained results we can observe that for Hg and HCl the momenaty
concentration measurements levels for all 4 LCPs, are situated into the admitted
emission limits for BAT for that kind of pollutants. For the HF determinations, two
measurements out of the four performed, we find values that exceed the limits
imposed by the BAT Conclusions; taking into account that the values obtained are
momentary values and the emission level varies over time, for an more exact
estimation, it is necessary to carry out a larger number of measurements covering a 1
year period, at least for the sources and indicators to which exceedances have been
identified. Interesting would be also the verification of the fluorine content of the
burned fuel at the sampling time.
Intensive pigs and chiken farming

According to the BAT Conclusions on Intensive Pig and Chiken farming, some
novelty elements are identified regarding the monitored pollutants, reporting units,
frequency and the mediation period, but the most important provision relates to
odour level and the Smell Management Conditions. In order to prevent or, where
this is not possible, to reduce the odour emissions by farming of produced, BAT
consists in the design, implementation and periodic review of an Odor Management
Plan. Starting from the provisions of the BATC regarding measures aimed at
reducing the level of odor generated by some activities, we propose an experimental
model comprising the steps and activities needed to elaborate the Smell
Management Plan presented in Figure 1:

Figure 1. Diagram of the Experimental Model for the Smell Management Plan elaboration.
The first four stages are dedicated to identifying and quantifying, as far as possible,
starting from the existing dates, the technological steps that can influence the air
quality, sensitive areas, emission sources, and fit the demand according to the
proposed objectives: the concern of economical agent to reduce emissions,
obligations imposed by environmental authorities, complaints coming from
residential areas. If will be necessary, the next step involves measuring/estimating
by direct measurements or by mathematical modeling of the odour concentration
and identification of the most affected areas, and the last stage is intended to assess
the impact and achieve an Action Plan designed to reduce the pollution smell level
within the desired limits.
For the odour concentration determination, for the conducted emission sources, the
dynamic olfactometry method is applied, SR EN 13725: 2003 (Vasile et al 2017).
For sources whose emissions can not be quantified by direct measurements,
emission factors or assessments by indirect methods may be used to estimate odour
emissions.
Conclusions
As it results from the BAT Conclusions adopted, the emission limits in the new
imposed areas, for the concentration of chemical pollutants, lower than in current
regulations, require, at least in the case of Large Combustion Plants based on
charcoal, measures aimed at optimizing, partially modifying or changing current
technology processes or improving the efficiency of reduction systems. For newly
introduced indicators in the regulations, the first step is to establish the current
emission level, depending on, if will or not be applied the reduction measures.
The results of the preliminary tests conducted on four emission sources
corresponding to four LCPs based on charcoal, it have revealed both concentrations

within limits and values that are above the annual limit, which requires further
testing to achieve an appropriate mediation.
Concerning the intensive pigs and chikens farming, the smell and its evaluation
represent the novelty element imposed for manageing, in order to reduce the levels,
but without assign limiting values. The experimental model exposed in the paper
represents a first step in the smell process assessing and also for implementing the
Smell Management Plan requested by BAT Conclusions.
Acknowledgements
This study was accomplished through the Romanian Nucleu Programme with the MCI support;
the authors would like to thank all those who contributed to this study.
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Impact Assessment of Odours from Solid Waste Landfills Located in Highly
Urbanized Areas’, Revista de Chimie, vol. 68, no. 8, pp. 1749-1752.

NEW ECOLOGICAL SOLUTION TO COMBAT THE VEGETATION IN

EXCESS IN NATURAL AND HYDROPOWER LAKES
Victorita Radulescu
University Politehnica of Bucharest, Faculty of Energy, Department of Hydraulics, Hydraulic

machinery and Environmental engineering, 313 Splaiul Independentei, district 6, Bucharest,
vradul4@gmail.com, Romania
Abstract
In Romania on Bistrita and Siret Rivers were realized between 1960-1970, 15
hydropower plants, some of them being today Natural Reservations. Due to
improper management of the water quantity, the capacity of the lakes was reduced,
mostly due to excessive, invasive development of vegetation. A specific problem
appears in the Vaduri Lake, which is Natural Reservation. Part of the water is used
for human necessities for more than 200 localities, and part for electric energy. The
lake represents an ecologic environmental for more than 30 species of birds which
nest here and for another 78 species who are passing during migration. For them is
necessary a clean surface of the lake and a good quality of the water. It was realized
a prototype using renewable resources, as to collect and partially dry the collected
vegetation for future utilization in a biomass power plant. This new solution
activated by solar panels is efficient, optimal, and ecologic, being tested in the lake
in the last two years. First are briefly analyzed the local conditions responsible for
the ecological changes, affecting the entire environment. First are mentioned the
previously tested solutions, without any effect. Some bird species decreased as a
number, and some of them disappeared, due to the improper conditions for nesting.
This new solution is realized on a mobile pontoon, which moves constantly with a
small velocity, without perturbing the ecosystem. It has the possibility of
displacement into the affected area, without noise, which could perturb the bird life.
Finally, some conclusions and references are presented.
Keywords: environmental engineering, natural reservation, prototype, renewable

resources, water conservation
Introduction
In the Romanian Energetic System, on Bistrita and Siret Rivers the hydropower
lakes are realized around 50 years ago. New and permanent problems appear,
needed constantly to be solved (Shumway 1990). One of them is represented by the
massive decrease of the lake’s volume capacity, partially due to sedimentation, and
partially due to the eutrophication. In present, more than 8 such hydropower lakes
have the capacity reduced by more than 60% since their commissioning. The
hydropower development of the River Bistrita is formed by 11 hydropower plants
and was accomplished during 1960-1970. The Lake Vaduri, finished in 1964, was
declared in 2004 Natural Reservation, has a surface of 1500 ha, offering favorable
conditions, necessary food and shelter for many species of wintering and migratory
birds as summer swan, high duck, rattle duck, Little Grebe, northern pintail, duck
with redhead, Common Pochard. Here is the largest population of the wintering
whooper swan from Romania besides the Danube Delta.
Nowadays the lake confronts with a massive development of the aquatic vegetation,
due to the eutrophication (Rodhe 1979) produced mainly by the new woodworking
factories and paper manufacturing. Consequently, the nitrites and the nitrates added
into water have led to an explosion of the aquatic vegetation growth (Smith 1999).
In the past were tried different solutions. Part of them is not recommended in
Natural Reservations or for lakes with water supply for population, as it is the Lake
Vaduri. The presented solution is totally ecologic, using renewable resources, well
adapted to the wild bird’s life.

Under natural conditions, the phosphor is the main nutrient, which provides the
synthesis of new tissue, being categorized before the nitrogen and carbon, (Seteanu
& Radulescu 1997, Martin 1994) in vegetation development. Therefore, the
phosphor represents a "limiting factor" influencing the increase or decrease of the
algal proliferations (Cole 1993, Lawton 1991). The human activities, domestic,
industrial, or agricultural, induce a nitrogen deficiency that stimulates the
proliferation of cyanobacteria capable of binding the molecular nitrogen. Table 1
presents the measured parameters during the campaigns of 2010-2015.
Table 1. Values of the hydro-chemical supply

Vegetal consumption Water Supply Consumption / Supply
Element Symbol
% % (approx).
Oxygen O 80.5 89 1
Hydrogen H 9.7 11 1
Carbon C 6.5 0.0012 5,000
Silicon Si 1.3 0.00065 2,000
Azoth N 0.7 0.000023 30,000
Calcium Ca 0.4 0.0015 <1,000
Potassium K 0.3 0.00023 1,300
Phosphor P 0.08 0.000001 80,000
Magnesium Mg 0.07 0.0004 <1,000
Sulfur S 0.06 0.0004 <1,000
Chlorine Cl 0.06 0.0008 <1,000
Sodium Na 0.04 0.0006 <1,000
Iron Fe 0.02 0.00007 <1,000
Boron B 0.001 0.00001 <1,000
Manganese Mn 0.0007 0.0000015 <1,000
Zinc Zn 0.0003 0.000001 <1,000
Cupper Cu 0.0001 0.000001 <1,000
Molybdenum Mo 0.00005 0.0000003 <1,000
Cobalt Co 0.000002 0.000000005 <1,000

As a result of the vegetative cell’s multiplication may occur eutrophication at the

lake’s surface, who can be colored in red or blue-green, depending on the
predominant species of cyano-bacteria (Duce 2008). These colonial algae reach the
surface carried by the lake's currents or by the bubbles of gases.
For a proper analysis of the parameters responsible for the excess development of
vegetation were made measurements for the sediments and water characteristics for
three lakes, including Lake Vaduri. The results of quantitative determination from
this area are presented in Table 2.
Table 2. Average values of physical-chemical parameters of sediments

Nr Parameter Lake Lake Lake
Pangarati Vaduri Reconstuctia
1 Humidity (1050C) % 55.46 53.38 55.66
2 pH (upH) 6.80 6.65 7.04
3 Organic substance (%) 6.95 5.93 8.36
4 Mineral Substance (%) 93.05 94.07 91.64
5
(
NH 4+ mg / 100 g ) 5.85 7.27 8.01
6
(
NH 4+ mg / l ) 105.48 136.19 143.91
7
(
NO3− mg / 100 g ) 0.33 0.41 0.19
8
(
NO3− mg / l ) 5.95 7.68 3.41
9
(
PO43 − mg / 100 g ) 0.068 0.072 0.086
10
(
PO43 − mg / l ) 1.22 1.34 1.54
N − NH 4+ + N − NO3− (mg / 100 g )

11 4.61 5.74 6.27
P − PO43 − (mg / 100 g )

12 0.022 0.023 0.028
13 Ndissolved / Pdissolved 209.54 249.56 223.93
Previously tested solutions

The hydropower Lake Vaduri has multiple utilizations besides the electric energy
production. It assures the water supply for the surrounding population and is a
RAMSAR site, a Natural Reservation representing a biological ecosystem needed to
be protected. Due to the water supply for the population is necessary to be
maintained at a certain level of water’s quality as to protect also the existing flora
and fauna. The excessive growth of vegetation significantly reduced the volume of
water that can be processed for energy purposes, but also affect the life quality for
specific birds, of their nesting, etc. In the last decades have been tested several
solutions, some of them improper and inadequate for this lake.
Chemical products
Here were used two possibilities based on different types of developed vegetation.
Algaecides
The solution uses derivatives of the copper and is recommended on lake’s surfaces
covered by algae. The effect is rapid, destroying the vegetation. The mixture is
spread on water surfaces and has best results when is applied on a calm sunny day.
Generally, heavy infestations were treated, but only for small surfaces, in different
stages. At intervals of 5-7 days, the treatment should be repeated. The re-treatment
during the growing season (spring-summer) is absolutely required and is more
efficient when a new growth of algae begin to appear. The solution may be applied
only at small lakes, without water circulation. Because the lake Vaduri is also used
for water supply, the solution was rapidly abandoned.
Herbicides
Represent a better solution to control the development of the aquatic vascular plants,
easy to be applied, almost in the same manner as the algaecides. It is necessary to
pour the solution into the lake's water, in different locations with a high density of
vegetation. It is recommended to be used when the plants are actively growing, and
the water temperature is above 15oC. This solution does not destroy the algae roots
and is efficient in lakes where the water does not flow. In hydropower lakes, there is
a permanent current of water, produced by the turbine functioning during the electric
energy production. This solution was tested but without efficiency in Lake Vaduri.
In many European countries, this solution is completely forbidden, because affects
the bird’s life. This solution should not be applied, since the lake is a Natural
Reservation, used also for water supply of the population.
Biological additives
Utilization of the biological solutions to inhibit the algae growth generally assures
an improving of the water’s quality, but in this lake, the vegetation has reached high
values, difficult to be destroyed with this method. In these conditions would be
necessary high quantities of biological additives, with high concentration. Anyway,
the efficiency of this solution at large scale is reduced, due to the water movement.
The solution was tested for three months. Taking account that the water is used for
human supply, the Commissions of the Environmental Protection and of the Public
Health have rejected it immediately.
Grass Carp
This solution was tested with good results in different lakes, but outside Romania. It
is represented by populating the lakes with some carp species, which feed especially
with aquatic vegetation. These species were imported from China. In Romania, the
solution was not efficient. The local authorities tried two times to populate the lake
with such fish, in different years. Nobody checked the natural conditions needed for
the fish surviving. They are living only a temperature almost constant, around 150C -
240C. Into the Vaduri Lake, more than 7 months/year the temperature is around
100C or lower and generally, freezes most of it in winter. In these conditions, the
fish died. Anyway, the solution was not accepted by the ecologists, which were
afraid do not disturb the natural eco-system.

Mechanical control
There are two solutions of cutting and removing the vegetation mainly with the
same purpose, but with different efficiency and applicability.
Harvesters - remove the plants from the water, until depths of about 1 m, with a
conveyor system. It is solved the problems associated with the decay of the cut
plants, being disposed of onshore. Some harvesters are large enough to haul up to 13
tons of vegetation. Densely packed, the vegetation can weigh 200 tons for a lake
with a surface of around 100 m2. Unfortunately, this solution also kills the fish,
amphibians, reptiles, birds, bird nests, and other wildlife by including them in the
harvested plant material.
Rotovator - uses the rototiller blades, for cutting at 0.5-0.8 m from the lake’s
bottom, extracting the almost entire plant or the branched plants. It may be used for
plants with buoyant roots and crowns. The solution is adequate for large surfaces of
water, preferable to be used during winter or spring when most of the plants have
died. They disturb the sediments on the bottom, increase the water turbidity, releases
the nutrients from the sediments, but also the toxic residues bounded in the
sediments. They also disturb in the lake’s bottom the sinking animals, the fish's
spawn, and their migration. There are many EU countries where they are not used.
As a conclusion, the methods tested until now were not efficient solutions. The
chemical and biological methods to combat the vegetation in Natural Reservation,
due to the risk of destroying the local ecosystem, are impossible to be applied. The
parasitic species have a rapid growth in detriment of endemic fish species from the
protected area. The only accepted solution and tested, was with cutting vegetation
machines, but the reality proved that was not efficient in time. In the subsequent
years, the areas where the vegetation was trimmed, the remained roots of aquatic
species have developed stronger, more branched, more vigorous plants.

The proposed solution is a prototype (Romanian patent pending) placed on a mobile
pontoon, commanded from distance, and powered in co-generation by the
photovoltaic panels (PV). The Photovoltaic panels ensure the pontoon movement
and partially the energetic supply of the collecting, partial drying, and compacting of
the vegetation systems. The main advantage of this solution is that the extracted
vegetation can be consumed, immediately, and integrally, into a biomass power
plant. The moving model is based on three main blocks: the collecting system
coupled to PV noted Block 1, the system for compacting the vegetation noted Block
2 and the drying of the collected vegetation, coupled also at PV noted Block 3.
The partially dried vegetation is used further into biomass power plant, noted Block
4. Separately were designed and executed the propulsion system of the pontoon, the
command system from the lakeshore and the supply system from the PV panels. For
all blocks is in progress to be realized a system of automation and inter-connection,
permanently adapted to the meteorological conditions.

The Prototype functioning

The model is placed on a mobile pontoon, which may advance by propulsion,
depending on the amount of the collected vegetation, and commanded from the
lakeshore. When it moves, Step 1, it collects the aquatic vegetation with a circular
system with barrel equipped with a grater, rasps, and small holes. Rasps are
necessary to keep the collected vegetation and the holes to release the water, back to
the lake. The vegetation arrives directly, due to the barrel, into a system of
compacting noted Step 2. When the tank is filled, the supply is interrupted, Step 3
and the pontoon stops Step 4. At a time interval, pre-selected in conformity with the
vegetation density and atmospheric parameters, the compacting system starts, by the
barrel and eliminates the water back into the lake, Step 5. After compacting, the
vegetation is deposited into a fiberglass tank, Step 6, where is partially dried Step 7,
due to the circulation of the warm water, assured by the solar panels. The fiberglass
tanks are placed on the pontoon, under the PV panels. After being partially dried, the
vegetation is evacuated-Step 8 and consumed in a biomass power plant, placed on
the lakeshore. The entire installation intends to be autonomic after finishing the
automation. After the evacuation of the dried vegetation is commanded the advance
of the pontoon and the functioning cycle is re-loaded.
The main components
The photovoltaic system has been selected with a small weight, 18 kg for the panels
with Power 1 KW and 28 kg for the inverter. It is formed by an Off-Grid 1 kW-PV
with possible energy storage in network batteries, recommended in areas where
there is no electricity. The photovoltaic panels are reliable modules with high yield
and good efficiency.
The collecting system is designed for cutting and collect both the floating vegetation
and the grassroots from a depth of 1.1-1.6 m, Figure 1-a. It has a knife-shaped "U"
hydraulic adjustable in height, depending on the vegetation type, allowing the
pontoon's circulation easily through the dense vegetation. After cutting the
vegetation it assures the removing from the water, and bring it into the deck, with a
steel site acting as the conveyer belt. The prototype moves, and via the drum with
teeth collects the excess vegetation. It is conducted by a snail rotor system through a
pipe partially open (for compacting and squeezing). The collected plants are
deposited into a fiberglass tank on deck with a capacity of around 5 m3.
Figure 1. The collecting and the compacting systems for the vegetation
A silent engine environmentally friendly drives the hydraulic system of the
collector. The propellers prove to be durable and anti-winding, ensuring a maximum

maneuverability in both directions, back, and forth, even in shallow water with high
vegetation.
The compacting system refers to a compression of the extracted vegetation, based on
a screw system (augers), Figure 1-b. The screw is moving through a conic portion,
assuring the compacting the vegetation and evacuation of the extracted water. The
augers used to compact the vegetation will offer progressive compression into a
semi-solid state. The materials have to be of high density as possible to ensure a
maximum load concentration. A high volume and low density would be inefficient.
The compacted vegetation, partially drained of water will be stored in a fiberglass
tank as to be partially dried, placed on the pontoon, under the photovoltaic panels.
The vegetation is only partially dried when is evacuated. The direct current
generated by the solar modules feeds directly the heating element and convert into
useful heat with an electrical efficiency of 98-99%, without using an inverter. The
heating system allows a permanent control of water temperature, in accordance of
the atmospheric temperature, which saves costs and maintenance during functioning.
If the vegetation remains wet after a cycle, or if a huge amount of vegetation is
collected will be stored on a secondary drying rack, close to the biomass power
plant, at the solar heat, Figure 2. It is placed in the sun, to hasten aeration and the
final drying.
Figure 2. Storage system for vegetation
The pontoon stops when the fiberglass tank is full with the compacted vegetation. It
is filled with vegetation until the level and weight sensors interrupt the movement
and the alimentation of the pontoon. Here, through a pipeline system placed on the
bottom, where circulates hot water, starts the partial drying of vegetation. When its
weight decreased by 28% is considered a completed cycle, is downloaded the
vegetation and a new cycle begin.
Figure 3 presents the basic structure of the biomass power plant based on the
collected vegetation from the lake.

Figure 3. Schematic plan for the biomass power plant supplied with vegetation
The obtained warm water provides the heating for a building where is an aquatic
plant nursery, with specific plants, and a bird’s incubator from the local ecosystem
for species still reduced as a number. There is also an annex to store the equipment
during the winter.
Conclusions
The solution is ideal for cleaning the floating vegetation, and the developed aquatic
vegetation from lakes Natural Reservations. The prototype may be extended into the
future to collect some other solid floating material, like the plastic bottles, wood
materials, etc. The model has a double effect; besides the collecting of the excess
developed vegetation from the Lake Vaduri, this one is consumed as the main
natural resource into a biomass power plant. In this sense, the solution contributes to
the utilization of renewable technologies, the automation and embedded systems in
industrial equipment. Under normal conditions of temperature and humidity, the
amount of the harvested vegetation from a hydropower lake is between the values of
- 20-25 tons/ha/year dry, moisture content 0%
- 33-42 tons/ha/year at 40% humidity
The Vaduri Lake has a surface of 1500 ha, meaning
- 30.000 – 37.5000 tons/year dry, vegetation with moisture content 0%
- 49.500 – 63.000 tons/year, vegetation with 40% humidity
The average price for vegetation is approx.
- 35-40 Euro/ton for humidity approx. 40%
- 50-55 Euro/ton humidity 0%
References
Cole, JJ, Peierls, BL, Caraco, NF & Pace, ML 1993, ‘Nitrogen loading of rivers as a
human-driven process’, M.J. McDonnell-S.T.A. Pickett, Springer-Verlag, New
York, USA, pp. 141-157.
Duce, RA, LaRoche, J, Altieri, K, Arrigo, KR, Baker, AR, Capone, DG, Cornell, S,
Dentener, F, Galloway, J, Ganeshram, RS, Geider, RJ, Jickells, T, Kuypers,
MM, Langlois, R, Liss, PS, Liu, SM, Middelburg, JJ, Moore, CM, Nickovic,
S, Oschlies, A, Pedersen, T, Prospero, J, Schlitzer, R, Seitzinger, S, Sorensen,
LL, Uematsu, M, Ulloa, O, Voss, M, Ward, B, Zamora, L 2008, ‘Impacts of
Atmospheric Anthropogenic Nitrogen on the Open Ocean’, Science, vol. 320,
pp. 893–89.
Lawton, LA & Codd, GA 1991, ‘Cyanobacterial (blue-green algae) toxins-their
significance in UK and European waters’, Journal of Soil and Water
Conservation, vol. 40, pp. 87–97.
Martin, A & Cooke, GD 1994, ‘Health risks in eutrophic water supplies’, Lake Line
vol. 14, pp.24–26.
Rodhe, W 1979, ‘Crystallization of eutrophication concepts in North Europe,’
National Academy of Sciences, Washington D.C., Standard Book Number
309-01700-9, pp. 50-64.
Seteanu, I, Radulescu, V 1997, ‘Infiltratia, difuzia si transferul biologic in ape de
suprafata’, Romanian House of the Romanian Academy, vol. 56, no. 5-6, pp.
285-295.
Shumway, SE 1990, ‘A review of the effects of algal blooms on shellfish and
aquaculture’, Journal of the World Aquaculture Society, vol. 21, pp. 65–104.
Smith, VH, Tilman, GD & Nekola, JC 1999, ‘Eutrophication: impacts of excess
nutrient inputs on freshwater, marine, and terrestrial ecosystems’,
Environmental Pollution, vol. 100, no. 1-3, pp. 179–196.

OPTIMAL POLICY OF IRRIGATION AND DRAINAGE WELLS SYSTEMS

IN AFFECTED AGRICULTURAL LANDS
Victorita Radulescu
University Politehnica of Bucharest, Faculty of Energy, Department of Hydraulics, Hydraulic

machinery, and Environmental engineering, 313 Splaiul Independentei, district 6, Bucharest,
vradul4@gmail.com, Romania
Abstract
During the last decades, important areas of the Romanian agricultural lands are
confronted with some specific problems. In South, due to an inefficient system of
irrigation, appears the salting effect. In drought years, entire surfaces are covered
with white phosphates (used in excess thirty-forty years ago), destroying the
agricultural plant’s roots. Contrary, in East, due to improper management of
riverbeds, after floods, appear surfaces confronted with excess quantities of water
deposition (sometimes even for one entire month), destroying also the agricultural
plant’s roots. In the present paper, a solution for estimation the necessary level of
the water table is presented, assuming a correct correlation between the irrigation
during the vegetation period and the drainage during the rest of the year. An
agricultural land irrigated by gravity, from the Jiu River basin, is considered, long
enough and extended between two emissaries with low topographic incidence. The
computational scheme, for unsteady flow with the initial level of groundwater,
corresponding to a stationary regime of drainage or injection is adopted. The
boundary conditions consist of imposed groundwater levels at areas extremities, in
accordance with the known levels of the emissaries. The objective function is
defined as a sum of cumulated rates for standard deviations, between the ground-
water flow and the water table level, during two years. Some major coefficient’s
penalties for the waiting time intervals are assumed, to limit the excessive water
during the vegetation. A detailed analysis of the underground flow, the numerical
model, the obtained results, conclusions, and references are also mentioned.
Keywords: agricultural engineering, aquifer management, groundwater flow,

irrigation, numerical analysis
Introduction
The optimum exploitation of agricultural land in the presence of an aquifer polluted
by the surface sources requires close monitoring of the groundwater level during the
entire year. For the theoretical applications and numerical modeling is considered an
agricultural land with low topographic incidence, irrigated by gravity. The aquifer
associated with the surface model is assumed as a homogeneous medium, with
known permeability. The groundwater is fed by surface sources of pollutant and
drained into an existent emissary, a river, at a lower level, with a known

hydrological regime, with a date insurance. It is presented an optimum process of
the operating well’s control, having as the objective function the cumulative size
rates of the deviation between the level of the groundwater and the highest levels
maximum acceptable thereof. During two years was made the analysis weighted
with high penalty factors, where there is the possibility of exceeding dangerous
levels. There are indicated some aspects of the unsteady groundwater flow's
problem, for the same case study.

The non-steady flow of the groundwater in an aquifer can be described, with a good
approximation, by the Boussinesq equation with partial derivatives. Considering an
infinitesimal element of groundwater flow in porous media (Mailhol 2004), the
principle of continuity requires the following condition mass balance:
v x ⋅ H ⋅ dt + q ⋅ dx ⋅ dt − (v x ⋅ H )1 dt = n ⋅ dH ⋅ dx (1)
where: H - the water table above the impermeable layer from depth, q - the lateral
specific flow rate, n - the porosity and x - the horizontal coordinate of a cross-
section. Expressing the flow rate through a section 1 with the relation:
∂
(v x ⋅ H )1 = v x ⋅ H + (v x ⋅ H )dx
∂x
equation (1) becomes:
∂
− (vx ⋅ H ) + q = n ⋅ ∂H (2)
∂x ∂t
The Darcy law for groundwater flow is equivalent to a dynamic equation, where:
∂h
v x = −k (3)
∂x
with k - the Darcy infiltration coefficient and h the level above “datum,” a horizontal
reference plane. Denoting with I the slope of the impermeable layer may be written
the following geometric relationship between the levels H and h, where L - is the x
coordinate of the intersection between the impermeable layer and Datum.
h = H − I (L − x )
By eliminating the velocity between relationships 2 and 3 is obtained the system:
 ∂  ∂h  ∂H
q +  k ⋅ H =n
 ∂x  ∂x  ∂t (4)
H = h + I ⋅ x − I ⋅ L

which is equivalent with the Boussinesq equation:
∂   ∂h  ∂H
q+  k ⋅ H  − I   = n (5)
∂x   ∂x  ∂t
For the unsteady flow, the initial line of the ground water corresponds to the
stationary regime with drainage or injection. The boundary conditions consist in
levels imposed of the groundwater at the extremities of the analyzed area in
accordance with known levels of the emissaries, Figure 1. The specific lateral flow
rate q simulates the regimes of injection if q > 0 and the drainage if q < 0. It may be
imposed an unsteady flow regime of time evolution for the lateral flow rate, with
variable limit levels of the emissaries, as consequence of floods or drought periods.
Figure 1. The main parameters for the initial and boundary conditions
The drainage conditions are equivalent to the operating regimes in 2 or 3 rows of

wells, modeled with a negative flow rate, known in groups of two adjacent nodes.
The analytical solution of the Equation 5, with the above initial and limit conditions,
is quite complex, due to the nonlinearity and complexity of the bi-local limit
problem. It is defined as a variable mesh network in which are calculated the values
of H level, with constant time-steps and variable-space steps, both known. To
mitigate the non-linearity of the equation is advantageous to introduce a new
functions G=H2, instead of the original function H (x, t). The equation (5) becomes:
∂ 2G n ∂G 2 q ∂H
= − + 2I (6)
∂x 2 k ⋅ H ∂t k ∂x
It may have meshed:
Ai Gin++11 + Bi Gin +1 + Ci Gin−+11 = Di (7)
where G, the auxiliary dimensionless unknown function, and the coefficients are:
α 2(1 − α )
Ai = 1 − θ1 ; Bi = −2 − θ1 ; Ci = Ai ; (8)
H ' (0 )
i H 'i (0 )

α 1−α n α
Di = −Gin+ 1 + 2Gin − Gin−1 − θ1 ( G n − 2θ1
0 ) i +1 ( G − θ1
0) i
Gin−1 +
H' i H' i H ' (0 ) i
(
+ 2θ 2 H 'i + 1(0 ) − H '
i −1 ) (
(0 ) − 2θ q n − q n + 1
3 i i )
The apostrophe represents the dimensionless terms, a notation of the type Gni is the
function G at time n.∆t in the node xi; α is an over-relaxation factor α = 0.63, and θ1,
θ2 and θ3 are defined as functions
( )
θ1 = ξ 3 ⋅ ∆x' 2 / ∆t' where ξ1 = I ⋅ SL / SH
θ 2 = ξ1 ⋅ ∆x' (
ξ 2 = S ⋅ q ⋅ SL2 / k ⋅ SH 2 )
θ 3 = ξ 2 ⋅ ∆x' 2 ξ 3 = n ⋅ SL2 / (k ⋅ SH ⋅ ST )
Here: SL, SH, ST are suitable scale factors for the corresponding variables, namely
x-coordinate, the level H, the flow rate q, time T, while the upper index (0)
represents the mean intermediate values corresponding to the mean values between
two successive rows of nodes of type H. The system 7 can be solved with an
algorithm tri-diagonal. Connecting the variable Gin++11 and Gin +1 by the equation:
Gin++11 = Ei ⋅ Gin +1 + Fi , where i = 1.. M (9)

is obtained a system of recurrence relations:
Ci Di − Ai Fi
Ei −1 = ; Fi −1 = (10)
Ai Ei + Bi Ai Ei + Bi
Admitting as initial conditions the known levels, corresponding to the stationary
flow, the calculation starts from the downstream boundary condition:
n +1
HM = H 2 (n ⋅ ∆t ) (11)
The groundwater level is equal in this case with to entrance. The condition 11 is
identically satisfied if:
E M −1 = 0 , and FM −1 = H 22
(12)
The conditions 12 are imposed at any time moment, where M is the total number of
points of type x. Considering the relations (10) is computed EM-2, FM-2, etc., and
finally, E1 and F1. On the other hand, since H 1n +1 is given in the upstream (the
emissary level) can be calculated, H 2n +1 , H 3n +1 , etc. until the downstream.

It is noted that, if the coefficients A, B, C, D have some terms defined in
intermediary time point (n+1/2).∆T, it is necessary a process of successive
approximations, starting from their values at the time n . t and iterated of n times for
the same step of the calculation. Due to the non-linearity problem, the calculation
algorithm, even for stationary movement, must begin by indicating the first
approximation of the groundwater levels, which is modified during the calculation
process. The numerical modeling proves that the concrete form of the groundwater
levels as starting function has not a great influence on the convergence rate of the
algorithm, so a linear approximation can often be satisfactory (Seteanu 1998).
The case of a stationary bi-local problem has been solved in the same way, as in the
case of non-stationary, observing that in this case, the coefficients A, B, C, D, are:
ki  I ∆x  4(∆x )2
Ai = 1 −  Bi = −
 2 H ; (13)
2(∆x )2  i ki
ki  I ∆x 
Ci = 1 + ; Di = −qi
 2 H i 
2(∆x ) 2

An example of calculation is given hereafter, to determine the infiltration coefficient
from sand and clay, using three different methods (Letey 1998, Radulescu 2004).
Hazen Solution
Noting: A- coefficient pending of measure system, A=1 if k is expressed in m/day;
- c is a coefficient which depends on the clay content of the sand,
- de - the effective diameter in mm, defined by the granule's diameter lower than
10% of the entire weight of earth granules,
k = A ⋅ c ⋅τ ⋅ d e2 (14)
- τ is a coefficient of temperature correction; t0 is the temperature in Celsius degrees
τ = 0 ,70 + 0 ,03 ⋅ t o (15)
For the clean sands c = 1000-700, and for sand with clays c = 700-500. Hazen's
relationship is applicable to sands with a diameter between 0.1 - 3 mm. additionally
the earth’s non-homogeneity coefficient, the ratio d0 /de, d0 - the pitch diameter to
which 60% of the granules have a smaller diameter, less 5 mm. If in relation (15) it
is considered τ = 100 C, c = 860, k expresses in m/day, and de in mm, k = d e2
Kozeny Solution
p2
k = 7 ,94
(1 − p ) 2
τ ⋅ d k2 [cm/s] (16)
where: p is the porosity coefficient, dk the effective diameter [mm], and τ is a

coefficient for correction of the temperature, presented in Table 1.

Table 1. Values of temperature coefficient after Kozeny

T τ T τ T τ T τ T τ
0 0.588 6 0.721 12 0.854 18 1.000 24 1.155
1 0.612 7 0.744 13 0.878 19 1.025 25 1.180
2 0.635 8 0.766 14 0.902 20 1.052 30 1.313
3 0.656 9 0.786 15 0.926 21 1.080 40 1.620
4 0.676 10 0.807 16 0.950 22 1.107 50 1.926
5 0.698 11 0.837 17 0.975 23 1.131 60 2.231
E. A. Zamarin Relation
p2
k = 8 ,07
(1 − p ) 2
c p ⋅τ ⋅ d k2 [cm / s] (17)
where - dk is the effective diameter [mm], cp is a coefficient taking account of the

land porosity. The coefficient τ from relation (16) is taken from Table 1, and the
coefficient cp, from Table 2.
Table 2. Values of coefficient cp
p% cp p% cp p% cp p% cp
27 0.757 32 0.632 37 0.518 42 0.416
28 0.731 33 0.608 38 0.497 43 0.397
29 0.706 34 0.585 39 0.476 44 0.378
30 0.680 35 0.562 40 0.456 45 0.360
31 0.656 36 0.540 41 0.435 46 0.342

To obtain a technically acceptable groundwater level is necessary to impose as a
restriction for the top level of the groundwater to be under an imposed value in each
node x. Furthermore, while the low levels are basically admitted, there are
prohibited those nodes exceeding the ground level.
The searching method (Hooke & Jeeves 2007) has proven effective, generating a
series of approximations improved, consisting of searching and extrapolation steps.
In the step of exploration, each parameter is examined and is considered solved if
the objective function has not increased. The step of extrapolation consists in
amplification of the main parameter in the superior direction, but without
exploration (Gelting 2013). The convergence and the stopping processes of the
optimization scheme correspond in this stage when the exploration steps of the
parameters become smaller than certain limit values imposed.
The first choice of the objective function consists in choosing the maximum
difference DH, between the groundwater and soil. It is imposed a scheme of mini-
max, by minimizing the absolute value of the objective function, Figure 2. The
obtained errors were quite high, so there were necessary some corrections. To
ensure a more suitable position of the groundwater was chosen a new objective
function, defined by the standard deviation between the minimum distances between
the two curves. The obtained errors were smaller but still inconclusive, (Seteanu &
Radulescu 2001). To ensure a more balanced position of the groundwater
distribution, a new objective function was defined, the standard deviation. The third
hypothesis was assumed and the differences between the minimum deviations of the
two curves, admits an overcoming of the soil level in some x points, considered
discontinuities. After these corrections were obtained smaller errors, which confirms
the choice of the objective function. It consists of the cumulating of the absolute
values of difference DH, multiplied by a factor of penalties when these differences
are positive. The DS1 type areas, Figure 2, are however small, maintaining a
balanced appearance of the groundwater.
Figure 2. The optimization solution
The modified parameters during the optimization process consist of the spatial
coordinates and the drainage rates of the rows of wells. Two numerical cases, with
two rows, presented in Figure 3 have been analyzed. The calculation scheme was
applied in a sector river of 50 km, between two emissaries with different levels
H1=70 m and H2 = 50 m, above the base soil level. The slope for the waterproof
layer I = 4.10-5, the permeability k = 6.10-4, and porosity n = 0.38. It was chosen a
number of nodes x, noted M = 1200, imposing a uniform flow rate of injection
q=8.10-4 m3/s/m. The selected porosity coefficients are presented in Table 3 and the
optimum parameters for this case in Table 4.
Figure 3. The land scheme with a system with two rows of wells

Table 3. Values of the porosity coefficient for different soils

Soil nature Porosity Coefficient 0 %
Different limestone 10-17
Sand with diameter 1/2 - 1/4 mm 42
Sand with diameter 2 mm 36
Gravel diameter around 5 mm 37
Earth clay 46-35
Peat lands 81
Table 4. Optimum parameters, scheme with two rows of wells

x1 = -2,76.10-4 m3/s/m Flow through first wells
x2 = -2,9.10-4 m3/s/m Flow through second wells
x3 = 11251 m Position first wells
x4 = 15742 m Position second wells
Figure 4 presents the scheme with three rows of wells for drainage and the optimum
obtained parameters in Table 5. From the analyzed nodes in Table 6 are mentioned a
selection of the levels of the groundwater.
Figure 4. The land scheme with a system with three rows of wells
Table 5. Optimum obtained parameters with three rows of wells

x1 = -1,941.10-4 m3/s/m Flow through left wells
x2 = -2,227.10-4 m3/s/m Flow through right wells
X5 = -1,803.10-4 m3/s/m Flow through central wells
x3 = 7688 m Position right wells
x4 = 10501 m Position left wells
x6 = 27038 m Position central wells
Table 6. Obtained levels of groundwater

i h(m) i h(m) i h(m) i h(m) i h(m)
1 70.00 41 83.93 81 87.70 121 92.20 169 73.03
9 76.82 49 81.36 89 91.79 129 88.42 177 72.42
17 81.33 57 76.89 97 94.16 137 82.79 185 71.59
25 83.92 65 73.50 105 95.00 153 78.94 201 68.73
33 84.74 73 81.82 113 94.36 161 76.35 1200 50.00

Conclusions
This method of calculation may be used to determine the variations of the
groundwater in aquifer based on the propagation of waves produced by the floods of
emissaries.
The method may be used also in assessing the changes from the groundwater levels,
caused by the intensive exploitation of an irrigation-drainage system.
For other practical applications, there is a possibility of combining the calculation
scheme proposed with a model of spatial propagation of a front of pollutant in the
aquifer. In this case, the penalty coefficients imposed to the objective function vary
depending on the upstream, respectively downstream flow, compared with this front.
It is possible that in this variant, to be used the favorable influence of the
groundwater from the farmland in the unpolluted area, by imposing some gradual
restrictions of non-exceeding the maximum levels of pollutant advancement, in the
agricultural areas.
References
Gelting, RJ & Baloch, M 2013, ‘A Systems Analysis of Irrigation Water Quality in
Environmental Assessments Related to Foodborne Outbreaks’, Aquatic
Procedia, vol 1, pp. 130-137.
Letey, J, Dinar, A, Woodring, C & Oster, D 1998, ‘An economic analysis of
irrigation systems’, Irrigation Science, vol. 11, no. 1, pp. 37-43
Mailhol, JC, Zaı̈ ri, A & Slatni, A 2004, ‘Analysis of irrigation systems and irrigation
strategies for durum wheat in Tunisia’, Agricultural Water Management,
Elsevier, vol. 70, no.1, pp. 19-37.
Method of Hooke and Jeeves, Appendix B. Available from:
https://onlinelibrary.wiley.com/doi/pdf/10.1002 /9780470511824.app2. [29
August 2018].
Radulescu, V & Nistreanu, V 2004, ‘Hydraulic Adduction Systems. Fundamentals,
Calculassions, Exemples’, Series Hydraulics, Publishing Bren House,
Bucharest. In Romanian.
Seteanu, I, Radulescu, V & Seteanu, S 2001, ‘Convective-Diffusive Transport of
Pollutants at River Branching (k-ε Model)’, Proceedings Numerical
Simulation for Fluid Mechanics and Magnetic Liquids, Orizonturi, University
of Timisoara, pp.101-112.
Seteanu, I & Radulescu, V 1998, ‘An Objective Function to Predict Virus Pollution
on Saturated Fields’, ENVIROSOFT 98, Las Vegas, USA, Comp. Mechanics,
Wessex Institute of Technology, pp. 89-93.

PROTECTING SURFACE WATER RESOURCES THROUGH

SILVICULTURAL METHODS
Cristinel Constandache1, Lucian Dinca1, Nicu Constantin Tudose1, Casen Panaitescu2
1
National Institute for Research and Development in Forestry (INCDS) “Marin Dracea, 1 –
Focsani Station, 7 Republicii, cicon66@yahoo.com, 2,3 – Brasov Station, Closca street,
dinka.lucian@gmail.com; cntudose@yahoo.com, Romania
2
Petroleum-Gas University of Ploiesti, 39 Bucuresti blvd., Ploiesti, c.panaitescu@gmail,
Romania
Abstract
Water was considered an inexhaustible natural resource until reality has proven its
reverse. Climatic changes increase the pressure on surface runoff and groundwater,
amplifying regional differences. As such, the necessity to adapt to climatic changes
implies applying certain biologic/silvicultural works for protecting water resources.
Water is strongly connected with forests so that forests fulfil an exceptional
hydrological purpose. In this paper we presents some types of silvotechnical works
realized in the past for improving degraded lands from Vrancea area, as well as the
results of investigations concerning the efficiency of this kind of works in protecting
water resources. The investigations were realized in Caciu-Barsesti torrential
watershed, an affluent of Putna River (pilot area in CAMARO-D project) situated in
the Curvature Subcarpathians. The investigations have targeted forest ecosystem
installed on degraded lands mainly comprised of Scots pine and European black
pine, as well as the management/consolidation technologies used for eroded lands
and their effects in reducing soil and leakage erosions. Forest ecosystems realized
through the afforestation of degraded land have an important role in retaining,
filtering water and in regulating the course of surface waters, as well as in reducing
soil erosion and transporting alluvium. All these roles have an effect in protecting
water resources, in maintaining their quality and ensuring a permanent water flux.
Amongst the most important effects exerted by forest plantations from degraded
lands we mention: reducing soil erosion, improving pedostational conditions, and
regulating surface and depth leakages. In comparison with unafforested lands,
degraded afforested lands present surface leakages of 4 up to 10 times lower as well
as a much more reduced specific erosion (0.06 t.ha-1year-1, in comparison with 50-
300 t.ha-1year-1).
Keywords: afforestation degraded lands, runoff, soil erosion, water resources

Introduction
As ecosystems, water and forest are the most important natural resources of the
Planet as both provide nutrition, energy and shelter, having multiple functions and
services for both the environment and its inhabitants. On short, without water,
forests could not exist. On the other hand, through forests, water sources, their
distribution and circulation are modified while the quality of water is highly
improved. As a result, we can affirm that water and forest interact and are
influencing one another in a positive manner (Chang 2006).
Most drinkable water resources from Romania originate in afforested hill and
mountain areas. In present times, we must acknowledge that water and forests are
not two independent components of our environment as they are linked by a strong
bond. Among the most important result of these bond, with a direct impact on socio-
economic objectives, we mention leakage (expressed through its quantum) and
alluvium transportation. Forests act as a sponge and filter that retains precipitation
water, which it releases gradually, supplying springs. In the absence of forests, water
originating from precipitations is instantaneously drainage causing soil erosion,
landslides and floods.
As such, in the context of ecosystem degradations (as a consequence of climatic
changes and uncontrolled aggressive human interventions), waters can become
dangerous if proper management and land repartition measurements are not
undertaken. It is a well-known fact that approximately 90% of natural calamities are
caused by climatic phenomenon, especially precipitations. The statistic from the last
decade show that the total number of natural calamities, including
hydrometeorological ones, have an increased tendency of apparition and intensity.
Proper managed forest ecosystems play an important role in retaining and filtering
water, as well as in regulating surface water courses, reducing soil erosion and
transporting alluvium. All these aspects have an effect in maintaining water quality
and in ensuring a permanent water flux.
Amongst the measures and actions for rehabilitating degraded areas with a role in
protecting water resources, for whose achievement the silvicultural sector
contributes, we mention anti-erosion management plans and the ecological
reconstruction through the afforestation of degraded lands. These are followed
simultaneously by increasing the percentage of surfaces covered with forest
vegetation in adverse areas and ensuring a minimum afforestation percentage of
30% in torrential watershed (Constandache et al 2016, Popov et al 2017). For the
catchment situated upstream of accumulation lakes, the minimum forest percentage
should be of approximately 60% in mountain areas and 40% in hill areas (Giurgiu,
2010). It is estimated that from the total lake accumulation capacity of 13 billions
square meters, 3.6 billions cm are cogged (Costin 2006). The significant increase of
the afforestation degree of large watersheds represents an important request for
preventing and stopping floods, as well as for rehabilitating and maintaining an
equilibrated water regime (Clinciu 2008).
The present paper’s objective is to identify and analyse the most efficient types of
silvotechnical works realized in the past in Vrancea area for improving/ecologically
reconstructing degraded lands that have a hydrological and anti-erosional role, as

well as an impact on protecting water resources.

The investigations were realized in reclamation perimeters from Putna-Vrancea
watershed, situated in the Curvature Subcarpathian area. This region is one of the
areas most affected by land degradation processes as a result of inconsiderate forest
exploitations realized at the beginning of the 20th century. The research has targeted
forest ecosystems installed on degraded lands, the management/consolidation
technologies for eroded or clough lands, as well as their effect in reducing soil
erosion and leakage.
Table 1. The main characteristics of drainage parcels from Caciu – Barsesti

perimeter, during May-October 2014
Experi-
Exposi- Average
mental Average
Erosion tion, The vegetation’s synthetic specific
plot/ drainage
Degree (descent characterization erosion
S* (%)
degrees) (t/ha)
(m2)
Very White sea buckthorn, on 0.6
1C strong E S* (average height of 1.9-2.5
1.7 0.06
142 towards (38) m) and dogrose on 0.3 S
excessive (average height of 1.5-2.0 m).
Scots pine stand (80%), black
Very pine (20%) and disseminated
2C V
strong manna ash, 39 years old, 0,8 0.5 0.02
554 (30)
consistency; white sea
buckthorn on 0.4 S.
Black pine stand, 39 years old,
3C V
Very 0.7 consistency; white sea 0.6 0.03
318 (20)
strong buckthorn on 0.1S.
Black pine stand, 37 years old,
4C V
Very 0.7 consistency; white sea 0.7 0.05
276 (27)
strong buckthorn on 0.8 S.
Mixture Scots pine and Black
8C E
pine Stand, 39 years old, 0.6 0.7 0.05
195 Strong (11)
consistency.
Mixture Scots pine and Black
9C E
pine Stand, 39 years old, 0.8 0.5 0.02
230 Strong (11)
consistency.
S*=surface
The investigations concerning silvotechnical works had as main objective the

behaviour and efficiency of works realized for the ecological reconstruction of
degraded lands. As such, the research was realized in experimental areas situated on

strongly eroded lands from Caciu-Barsesti torrential hydrographic watershed

(tributary stream of Putna river).
Establishing the leakage coefficient (%) for turbidity (loading with suspension
sediments, g/l) and specific erosion (t/ha) was realized through measurements of
water volume and alluvium from well demarcated parcels situated in different stand
situations installed on strongly and very strongly eroded lands with the age of 37-39
years and a consistency between 0.6 and 0.9 (Table 1). The volume of water charged
with sediments was collected in specially located basins at the base of parcels.
Water volume was related with the parcel’s surface and the volume of precipitations
fallen in the analysed period.
The drainage sediments were gathered by filtering samples extracted from basins,
dried at 1050 C and then weighted. The resulted quantity was reported to the parcel’s
surface, resulting the quantity (or volume) or eroded soil after a rain with certain
characteristics from surfaces with different types of forest vegetations. The
precipitations were recorded with a pluviography and pluviometer installed near the
drainage parcels.

Silvotechnical works realized in the past for improving degraded lands
Amongst the silvotechnical works realized for improving degraded lands in
reception basins, the decisive role was played by biological works (afforestation),
both in regard to the soil’s recovery and conservation, as well as in regulating
drainage. These types of works represent an auto regeneration property, as well as
the generation of vegetal production. Biological works are also useful in
consolidating slopes, springs, banks and riverbeds (Figure 1 and Figure 2). The
necessity of afforestation works for degraded lands (eroded, clough, sliding) in
regard with hydrotechnical works is a fundamental principle in re-establishing and
maintaining an equilibrated water regime (Clinciu 2008).
Special consolidation works are necessary for slopes affected by erosion or clough
in order to stabilize sediments sources even at their formation place as well as for
ensuring the success of afforestation works (biologic). Examples of these types of
slopes are simple terraces, terraces supported by small or intersected fences, terraces
supported by benches or “vegetally armed” terraces.

Figure 1. Scaune-Valea Sarii Perimeter Figure 2. The same perimeter but

before afforestation (photo Costin 1954, afforested (photo Constandache 2012,
INCDS „Marin Dracea” archive) INCDS „Marin Dracea” archive)
The enterprise investigations have shown that the purpose of these works is: to
retain precipitation water and upstream eroded materials; to reduce drainage
volumes and the water’s drainage speed on slopes; to sustain seedlings in the first 2-
3 years from installation.
The research realized 30-50 years after the consolidation works (Constandache &
Nistor 2008, Constandache et al 2010) have shown that the most efficient were:
-terraces supported by benches from strongly eroded lands with stones on slopes that
survived even after 40 years; the plantations from terraces supported by benches
have led to very good results especially when pine seedlings with protected roots
were used, their maintenance rate being of over 90% (Traci & Untaru 1986).
-vegetally armed terraces (Figure 3) in most eroded, clough lands and detachment
ramps from areas in which white sea buckthorn is naturally installed; the white sea
buckthorn stems, branches and roots used for constructing terraces have entered in
vegetation in a high percentage (50…70%), leading to the formation of vegetal belts
that play a significant role in dissipating and stopping superficial drainage and in
stopping soil erosion; furthermore, this method has led to a considerable cost
reduction (with almost 60%) in comparison with other methods, while the definitive
success of the achievement’s duration was reduced with at least two years (Traci &
Untaru 1986); in plantations realized on vegetally armed terraces (Figure 4) the
growth of planted species (Black pine and/or Scots pine) were also considerably
higher in comparison with other types of works (Constandache et al 2016, Silvestru-
Grigore et al 2018); this fact is explained by the higher capacity of water retention
and the soils enrichment with nitrogen resulted from white sea buckthorns (Untaru
et al 2013, Dinca et al 2018).
Hydrological and anti-erosion efficiency

Water drainage causes erosion which causes lands to lose their retention and water
storage capacity with 20 – 90% (Untaru et al 2006). These lands represent one of the
most altered segments of the environment. They are favouring and increasing
ecological derangements, being the main focal points for sediments alimentation
during surface runoff, considerably affecting the biological and habitat diversity.
The effects of forest vegetations were constantly monitored over time in different
situations, emphasizing their hydrological and anti-erosion efficiency.
Figure 3. Consolidation of degraded lands Figure 4. The same terrain after

with “vegetally armed” terraces (photo approximately 35 years (photo
Untaru 1979, INCDS „Marin Dracea” Constandache 2015, INCDS „Marin
archive) Dracea” archive)
The following aspects were obtained based on observations made to the

pluviographic network and parcels for studying surface runoff situated in protection
forest cultures comprised of Black pine and/or Scots pine mixed with white sea
buckthorn, installed on strongly to very strongly eroded/clough lands (Table 2 –
precipitations recorded and that have caused surface runoff during May-October
2015 in Caciu-Barsesti experimental perimeter):
-22 rains were registered in the analysed period, leading to a cumulation of 471.9
mm; among these, 9 rains have caused surface runoff reaching 453.1 mm; the
maximum rain was registered during 01-28 July, having a quantum of 119.9 mm,
being also the rain with the maximum intensity (1.56 mm/min); May and July are
the richest months in rains, especially torrential ones;
-the maximum sediments loading was caused by rains of over 60 mm, on strongly
eroded lands with a reduced degree of vegetation cover; the maximum quantity (10
g/l) was registered in parcel 3C during a rain of approximately 111 mm recorded
during the end of May; the average turbidity (loading with suspension sediments) of
drainage waters reaches 84 g/l in un afforested very strongly towards excessive
lands and 7 – 13 g/l in afforested degraded lands; in the mature common beech
forest the average turbidity was of 2,6 g/l (Untaru 2000).

Table 2. The synthesis of data concerning precipitations recorded in Caciu-Barsesti

hydrographic basin during May-October 2014
Δt Δh I average I max
No. Period/ Day
min mm mm/min mm/min
0 1 2 3 4 5
1 30.05.2014 1880 111.1 0.059 1.46
2 05 - 06.06.2014 460 9.3 0.02 0.093
3 16.06.2014 845 26.5 0.031 0.17
4 20 - 21.06.2014 305 7.9 0.026 0.08
5 04.07.2014 1645 119.9 0.084 1.56
6 20.08.2014 1005 79 0.079 0.66
7 27.09.2014 685 29.5 0.043 0.36
8 17.10.2014 1275 27.2 0.038 0.2
9 19 - 20.10.2014 560 42.7 0.076 0.36
TOTAL 453.1
Previous results (Untaru et al 2013) have led to the conclusion that rains under 30
mm with a 50...55% of the total precipitation quantity that have generated drainages
generate under 15% of the erosion’s quantum, while the ones larger than 30 mm
generate over 85% of the quantity of eroded material.
The average surface runoff coefficient is larger in parcel 1C (1.7%). This fact is
caused by the lands’ high slope and strong towards excessive erosion and its
coverage with over 90% shrubs: white sea buckthorn and dogrose (Table 1). In all
the other parcels - 2C, 3C, 4C, 8C and 9C (37-39 year old pine stands) – the average
surface runoff coefficient is reduced with up to 35%, being situated in the interval
0.5 - 0.7%.
As such, the investigations realized on parcels created especially for the study of
surface runoff and installed on pine and sea buckthorn cultures (Barsesti perimeter)
have proved that the surface runoff is of 4 up to 10 times lower in the degraded
pastures.
The average specific erosion (t/ha) was reduced considerably on afforested parcels
to under 0.06 t.ha-1year-1, in comparison with 50 up to 300 t.ha-1year-1 as it was
previously eroded before the afforestation works (Untaru 2000) or before
excessively eroded lands without forest vegetation. As such, in 2014 the average
specific erosion values are situated between 0.02 t.ha-1year-1in parcels 2C and 9C
and 0.06 t.ha-1year-1 in parcel 1C.
The realized investigations have emphasized an increase of protection forest cultures
efficiency in regard with their evolution in time and structural diversity. If forest
cultures under 20 years old present average surface runoff coefficients between 1
and 3%, after the age of 25 this number is reduced to 0.5 - 1.8% and to 0.5 and 0.7%
after the age of 35. In the same manner, the average specific erosion was reduced in
regard with the culture’s evolution from 0.4...0.7 t.ha-1.year-1 after 25 years from the
installation of protection forest cultures (Untaru et al 2013), to under 0.06 t.ha-1.year-
1 at over 35 years.

As the diversity, number (abundance) of species or the degree of soil coverage with
arbustive or wood species is larger, as much the impact of precipitations and the
specific erosion decreases. The erosion of superior soil horizons significantly
changes water circulation conditions on slopes, reducing the water’s infiltration
speed and capacity in soil, as well the water availability that leaks on slopes.
Furthermore, the soil’s resistance towards the impact of rain drops is also reduced.
All these results emphasize the hydrological and anti-erosion efficiency of
protection forest cultures as well as of silvotechnical works realized on degraded
lands.
Conclusions
Forest ecosystems realized through the afforestation of degraded lands play an
important role in retaining and filtering water, as well as in regulating surface water
courses, in reducing soil erosion and transporting sediments. These lands represent
one of the most altered segments of the environment: they favour and amplify
ecological derangements, being the main focal points of sediments alimentation
during torrential rains, considerably affecting the habitats and their biological
diversity.
The efficiency of silvicultural methods applied for the afforestation of degraded
lands is proven by ensuring installation and development conditions for forest
cultures that have a hydrological and anti-erosion protection role. Their effect is
manifested in protecting water resources, maintaining their quality and in ensuring a
permanent water flux.
The role of silvotechnical works for managing degraded lands is to retain water from
precipitation and eroded materials from upstream; to reduce drainage volume and
the speed of water drainage on slopes; to sustain seedlings in the first 2-3 years from
plantation. On afforested degraded lands surface drainage was 4 to 10 times reduced
in comparison with unafforested lands, registering values under 0.5 and 0.7%, while
the specific erosion was reduced to under 0.06 t.ha-1year-1, in comparison with 50 up
to 300 t.ha-1year-1, as was eroded before afforestation works.
References
Chang, M 2006, Forest Hydrology – An Introduction to Water and Forest, second
edition, CRC Press, Boca Raton, Florida, U.S.A.
Clinciu, I 2008, 'Prof. Stelian Munteanu's scientific visions and forecasts, in the
context of the new European concepts and programs in the field of river basin
management', Silvologie, vol VI, Arranging of torrential basins, Romanian
Academy Publishing House, Bucharest, pp. 43-114. In Romanian.
Constandache, C & Nistor, S 2008, Ecological reconstruction of the ravishing and
sliding lands in the area of the Sub Carpathian and the Moldavian Plateau, II
Series, Silvica Publishing House, Bucharest. In Romanian.

Constandache, C, Nistor S, Ivan, V, Munteanu, F & Pacurar, VD, 2010, 'Functional

efficiency of forestry crop protection and the improvement works of degraded
lands', Forest Magazine, no.1, pp. 26-31. In Romanian.
Constandache, C, Dinca, L, Nistor, S & Crisan, V 2016, 'Causes of land degradation
in Vrancea. Forestry measures to improve degraded land ', Pedogenic Factors
and Processes in the Temperate Zone, vol. 1, no 15, pp. 57-68. In Romanian.
Constandache, C, Peticila, A, Dinca, L & Vasile, D 2016, 'The usage of Sea
Buckthorn (Hippophae Rhamnoides L.) for improving Romania's degraded
lands', Agro Life Scientific Journal, vol. 5, no. 2, pp. 50-58.
Costin, A 2006, 'Forest, the most important factor in maintaining hydrological
balance', in Silvologie, vol. V, Forest and water regime, Romanian Academy
Publishing House, Bucharest. In Romanian.
Dinca, L, Dinulica, F, Socaciu, C, Constandache, C, Blaga, T & Peticila, A 2018,
'Hipphophae Salicifolia D. Don - a miraculous species less known in Europe',
Notulae Botanicae Horti Agrobotanici Cluj-Napoca, vol. 46, no. 2, pp. 474-
483.
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marginalization of forests', Forest Magazine, no.2, pp. 3-16. In Romanian.
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review of forest shelter belt establishments in Bulgaria and Romania', Revista
de Silvicultura si Cinegetica, no. 41, pp. 16-23.
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& Crisan, V 2018, 'The radial growth behaviour of pines (Pinus sylvestris L.
and Pinus nigra Arn.) on Romanian degraded lands', Forests, vol.9, no.4, pp.
213.
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for forest cultures from degraded lands from experimental perimeters, ICAS,
II Series, Bucharest.
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river basins', Symposium River basin arrangement, Romanian Academy, pp.
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Academy Publishing House, Bucharest, pp. 232-244. In Romanian.
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for the ecological reconstruction through the afforestation of degraded lands
from Romania (II)', Forest Magazine, no.1, pp. 16-26.

THE BEST PRACTICES FOR THE ASSESSMENT OF THE RAINWATER

DRAINED BY THE URBAN SEWERAGE SYSTEMS
Daniel Scradeanu1, Giuliano Tevi2, Alexandru Balint1
1
University of Bucharest, 6 Traian Vuia, 020956, district 2, Bucharest,
daniel.scradeanu@gg.unibuc.ro, ioan.alexandru.balint@drd.unibuc.ro, Romania
2
Ecological University of Bucharest, 1G Vasile Milea, Bucharest, giuliano.tevi@ueb.ro,
Romania
Abstract
The current article includes a quantitative model which was developed based on the
natural conditions of a specific site and it proposes an easily applicable
methodology which allows estimates for: the quantity of rainwater collected by
surface runoff; the quantity of rainwater collected by groundwater flow, due to the
infiltration in aquifers; the quantity of rainwater collected by sewerage systems.
The case study was developed for a site located in the Pantelimon area (in eastern
Bucharest) and it compares the results of the standardised model and quantitative
model. Additionally, the article provides an interpretation of the differences obtained
between the natural and anthropic site conditions.
Keywords: coupled model, standards, surface drainage, vadose zone
Introduction
The assessment of the rainwater drained by the sewerage systems in urban areas,
specifically for Bucharest area, is currently conducted using a standardised model in
accordance with the following regulation acts and standards:
• Ministry Order no. 88 from 20 March 2017 on the approval of the
Framework Regulation for the water supply and sewerage services;
• SR 1846-1:2006 Sewages outside the buildings. Design specifications.
Part 1: Calculation of sewerage flows;
• SR 1846-2:2007 Sewages outside the buildings. Design specifications.
Part 2: Calculation of storm water flows. – standard which defines the
runoff coefficients for each type of building;
• Decision of the Bucharest Local Council (HCLMB – acronym from
Romanian language) no. 23/1993, considered for the case study, which
defines the specific quantity of rainwater for the economical operators in
Bucharest.
The standardised model is inaccurate and has a level of incertitude generated by the
surface runoff and groundwater flow characteristics of the site. The current paper

aims at identifying the differences between the rainwater drainage estimates through
standardised model and the actual values calculated at a specific site level.

Site Location
The assessment was conducted on a site located in the eastern part of Bucharest, at
375 Soseaua Pantelimon, District 2 hereby referred to as “Faur site”. The location of
the site is depicted in Figure 1 below.
Figure 3. Location of the Faur site in the eastern part of Bucharest
The site is located on the second terrace of the Dambovita River and its northern
boundary is delimited by the first terrace of the Colentina River. The relative
altitude of the site with regard to the Colentina River is approximately 7-8 m.
In accordance with the Land Registry no. 203292, the site has a total area of
78,644.00 m2 divided as follows: constructed areas which comprise 1,642.21 m2
accounting 2% of the total site area and non-constructed areas which comprise
77,001.79 m2 accounting 98% of the total site area.

Methodology and Information Sources

The assessment consisted in four stages as follows:
• Outlining the specific rainfall-associated characteristics of the site;
• Defining the surface runoff and groundwater flow of the site related to
topography, geology and hydrogeology;
• Correlating the rainfall and the surface runoff and groundwater flow
characteristics related to the existing sewerage systems;
• Comparing the results with the standardised calculation model.
The preliminary input data consisted of the following documents:
• Land Registry no. 203292, District 2, Bucharest containing data about the
existing constructed and non-constructed areas of the Faur site;
• Land survey conducted between April 4 and 13, 2018. The purpose of the
survey was to update the constructed and non-constructed surfaces with
regard to the surface runoff and infiltration characteristics;
• Documentation which provided the information necessary for the surface
runoff and groundwater flow assessment.
Meteorological Information
In order to estimate the surface runoff and groundwater flow characteristics, a
hydrologic balance in terms of evapotranspiration, runoff and infiltration was
defined using the following equation:
P = E + Y + I ± storage (1)
where P is precipitation, E is evapotranspiration estimated based on the temperature
(T), Y is the runoff based on the evaluation of the slopes through the digital
elevation model, I is the infiltration based on the permeability of the land cover,
which is the main factor for groundwater flow and storage is lakes, pools and
perched groundwater.
Table 1. Average values for temperature, humidity and rainfall for Bucharest
Avg. temperature Avg. humidity Avg. rainfall
Month
[°C] [%] [mm]
Jan -3.0 87 46
Feb -0.5 84 26
Mar 4.5 73 28
Apr 11.5 63 59
May 16.5 63 77
Jun 20.5 62 121
Jul 23.0 58 53
Aug 22.5 59 45
Sep 18.0 63 45
Oct 12.0 73 29
Nov 6.0 85 36
Dec 0.5 89 27

Precipitations were estimated by taking into account the monthly average values
recorded in Bucharest for rainfall, temperature and relative humidity, which are
depicted in Table 1.
Based on Table 1, the annual rainfall is approximately 600 mm. According to the
existing meteorological data, the minimum and maximum values for temperature
recorded in Bucharest were -32.2 °C recorded in January 25, 1942 at Bucharest
Baneasa and 42.4 °C recorded in July 5, 2000 at Bucharest Filaret.
Surface Runoff
In order to estimate the surface runoff, a digital elevation model (DEM) was
generated at a 20x20 m grid, which enabled to determine the flow direction of the
runoff, which was depicted in Figure 2.
It can be observed that most of the surface water is directed outside the boundary of
the site, except the
runoff reaching two
depressional areas
located in the centre
and south-western part
of the site, the stadium
and the tennis court,
respectively.
The water accumulated
in the two depressional
areas stagnates and
evaporates or it
reaches the aquifer
named “Colentina
gravel” (“pietrisuri de
Colentina” in
Romanian) through
infiltration, as
described in the
groundwater flow
section.
Figure 4. Surface drainage flow direction
The volume of the rainwater collected by the surface runoff (Y) is estimated as a
difference between the precipitation (P) and the annual real evapotranspiration (Era)
using the following equation: Y = P − Era (2)
The annual real evapotranspiration is determined using the following equation
(Castany 1972):

X
Era = [mm/year] (3)
X2
0.9 +
L2
where L = 300 + 25 ⋅ Tm + 0.05 ⋅ Tm2 ,X is the annual rainfall [mm] and Tm is the
annual average temperature calculated as a weighted average of the monthly
precipitation with the following equation:
X ⋅ T + X 2 ⋅ T2 + ... + X 12 ⋅ T12
Tm = 1 1 (4)
X 1 + X 2 + ... + X 12
It was determined that the annual real evapotranspiration for Bucharest area is 450
mm/year accounting for approximately 76% of the annual rainfall of 592 mm/year.
Consequently, the maximum rate of rainwater collected by the surface runoff is the
following:
mm m3
Y = P − Era = 592 − 450 = 142 = 0.142 2
year m ⋅ year
Based on the land survey,

runoff coefficients were
established for each
existing building and
paved area based on the
roof and drainage
construction material in
accordance with SR 1846-
2:2007 as follows: 0.00
for areas with drainage
outside the boundaries of
the site, 0.05 for non-
paved areas, 0.85 for
areas made out of asphalt
and 0.95 for buildings
with metal roofs.
The distribution of the
maximum rate of
rainwater is depicted in
Figure 3.
Figure 3. Distribution of the maximum rate of rainwater

The figure highlights the following areas:

• Surface runoff – includes all constructed areas with a runoff coefficient of
0.85 and 0.95 (44,041 m2 accounting approximately 56% of the total site
area);
• Water accumulation – includes horizontal and depressional areas with a
runoff coefficient of 0.0 and 0.05 which enable the evaporation and
infiltration (34,063 m2 accounting approximately 48% of the total site
area);
• Infiltration in the “Colentina gravel” – includes horizontal and
depressional areas with a runoff coefficient of 0.0 and 0.05 (34,063 m2
accounting approximately 48% of the total site area).
Groundwater Flow
The site overlaps the “Colentina gravel” aquifer, which collects the rainwater
infiltrations from the plains of the Colentina River and Dambovita River. The
aquifer has a maximum thickness of approximately 16-17 m in the centre of
Bucharest and a minimum thickness of 1-2 m in the western part, below 3 m
thickness in the north-western part and 0.5-1 m thickness under Fundeni and
Pantelimon Lakes.
Based on the piezometric surface for the “Colentina gravel” aquifer, it was
determined that the general groundwater flow is from NW to SE, with a
groundwater head of 87 m AMSL to 52 m AMSL, respectively. The hydraulic
gradients have values between 1.14-1.63‰. The piezometric surface map is depicted
in Figure 4 and a cross-section through the location of the site is depicted in Figure
5.
Figure 5. Piezometric surface of the “Colentina Gravel” aquifer

Figure 6. Cross-section through Faur site
Figure 5 depicts the fact that the “Colentina gravel” aquifer is drained by the
Colentina River in the area of the Faur site. Consequently, the rainwater infiltrated
over a surface of 34,063 m2 will reach the Colentina River.
Standardised Model
In accordance with the Ministry Order no. 88 from 20 March 2017 on the approval
of the Framework Regulation for the water supply and sewerage services, Art. 215,
the rainwater drained by the sewerage system is determined by multiplying the
specific quantity of rainwater for the previous month provided by the National
Administration for Meteorology (ANM – acronym from Romanian language) with
the total areas of the constructed and non-constructed surfaces and with the runoff
coefficients.
The quantity of rainwater drained by the sewerage systems using the standardised
model is determined using the following equation:
n
AM = qS ⋅ ∑ S ⋅ CS
i =1
i i (5)
where AM is the quantity of rainwater drained by the sewerage systems, qS is the

specific quantity of rainwater, Si is the area of the constructed and non-constructed
surfaces and CSi is the runoff coefficient.
The runoff coefficients used for the standardised model are established according to
the standard SR 1846-2:2007, similar to the coefficients established for the surface
drainage estimation. Based on the Land Registry no. 203292, district 2, Bucharest,
the following runoff coefficients were selected for the constructed and non-
constructed areas: 0.0 (53,125.79 m2), 0.05 (23,976.00 m2), 0.85 (175.38 m2) and
0.95 (1,466.83 m2).
In accordance with the Decision of the Bucharest Local Council (HCLMB –
acronym from Romanian language) no. 23/1993, the specific quantity of rainwater
for the economical operators in Bucharest is:
m3
qS = ⋅0.5
m ⋅ year
2

The quantity of rainwater drained by the sewerage systems calculated using the
standardised model is the following:
m3
AM = 0.5 ⋅ (53125.79 ⋅ 0.0 + 23976 ⋅ 0.05 + 175.38 ⋅ 0.85 + 1466.83 ⋅ 0.95) = 1371
year
The quantity of rainwater drained by the sewerage systems calculated using the
quantitative and the standardised model, is the following:
• Quantitative model which takes into consideration the natural conditions
of the site:
o rainwater discharged in the nearby lakes through surface runoff:
m3
≅ 6166.0 ;
year
o rainwater discharged in the aquifer through groundwater flow:
m3
≅ 4844.0 ;
year
m3
o rainwater discharged in the sewerage system: ≅ 0.0 .
year
3
• Standardised model: ≅ 1371 m
year
Conclusions
It can be concluded that the current practice does not provide a real and precise
value for the calculation of the quantity of rainwater drained by the sewerage
systems. As a result, the quantity of rainwater obtained through calculations which
take into consideration the natural conditions of the sites is significantly lower than
the values obtained through the standardised model.
Acknowledgements
We would like to thank SC Bega Utilaje Constructii SA, the Beneficiary of the current paper
for their support during the assessment.
References
Castany, G 1972, Prospecting and exploitation of groundwater, Technical
Publishing House, Bucharest. In French.
Decision of the Bucharest Local Council no. 23/1993 on the approval of the
“Indicative Norms for the functioning of the water supply and sewerage
systems in Bucharest”.
Ministry Order no. 88 from 20 March 2017 on the approval of the Framework
Regulation for the water supply and sewerage services.

Scradeanu, D & Gheorghe, A 2007, General Hydrogeology, Ars Docendi Publishing

House, Bucharest.
SR 1846-1:2006 Sewages outside the buildings. Design specifications. Part 1:
Calculation of sewerage flows.
SR 1846-2:2007 Sewages outside the buildings. Design specifications. Part 2:
Calculation of storm water flows. Standard which defines the runoff
coefficients for each type of building.

THE INDEXES IN ESTIMATING RAINFALL EROSIVITY – CASE STUDY

BUCHAREST
Marin Rusanescu1, Ion Durbaca2, Elena Valentina Stoian3

1
Valplast Industrie Bucharest, 9 Preciziei, Bucharest, marinrusanescu@gmail.com, Romania
2
Polytechnic University Bucharest, Faculty of Mechanical Engineering, 313 Splaiul
Independentei, district 6, 060042 Bucharest, Romania
3
Valahia University of Targoviste, Faculty of Materials Engineering and Mechanics,
Department of Materials Engineering, Mechatronics and Robotics, 13 Aleea Sinaia,
Targoviste, Romania
Abstract
The objective of this study was to investigate the spatial and temporal distribution of
annual precipitation erosivity in Bucharest (Romania). The analyzed period was
2009-2016, 1961-1990, using the indices: Fournier (IF), Fournier Modified (IFM),
adapted to pluviometric recordings obtained from the meteorological station at the
Polytechnic University of Bucharest, Faculty of Biotechnical Systems Engineering.
Given the abundant rainfall in the summer months with implications for the soil, it is
important to know the mathematical equations that can be quickly applied to assess
soil erosion. The indices Fournier and Fournier modified obtained fall largely under
the moderate aggressiveness class, but there have been years when the precipitation
aggressiveness was moderate (2012, 2014). Erosion calculated according to Silva
and Rufino is low throughout the analyzed period. This knowledge is very important
to avoid the negative effects of pluvial erosion on agricultural crops.
Keywords: erosivity index, Fournier indexes, Fournier modified index, rainfall

aggressiveness
Introduction
The erosive concept of rainfall describes erosivity as an interaction between the
kinetic energy of rain drops and the surface of the soil. This may lead to a greater or
lesser degree of detachment and reduction in the transport of soil particles
depending on the amount of energy and rainfall, taking into account the same soil
type, the same topographical conditions, and soil coverage (Ene et al 2010,
Radulescu 2008, Radulescu et al 2010, Radulescu et al 2011a, Radulescu et al
2011b).
On the one hand, various authors have found good relationships between the
Fournier index and annual values of rainfall erosivity (Bertoni & Lombardi Neto
1990, Oliveira & Medina 1990, Oduro-Afriyie 1996). According to Bertoni &
Lombardi Neto (1990), the ideal condition is to compute a data set of at least 20-
year rainfall, but it is possible to determine the erosivity using 10-year rainfall

records. Mannaerts & Gabriels studied in 2000 rainfall erosivity for Cape Verde
Islands by means of 7-year rainfall pluviometric records.
For Cape Verde Islands was calculated significant relations with exponential
equation by considering storms greater than 9 mm (erosive storms) (Mannaerts &
Gabriels 2000). This study proposes two regression models for estimating
precipitation erosiveness and identifying suitable models in Bucharest Romania,
based on daily, monthly, and annual rainfall data of the weather station. The detailed
objectives of this study can be summarized as follows: (a) to construct new models
for the large scale estimation of the erosive factor in Bucharest; and (b) to analyze
the spatial distribution of the daily, monthly and annual rainfall erosivity in
Bucharest. Excessive precipitation amounts lead to intense erosion of soils,
landslides, floods and floods (Balteanu 1984, Rusanescu & Rusanescu 2013).
The climate and topography of the surrounding area of Bucharest are suitable for
agriculture (Rusanescu 2014a).

In this paper, rainfall recorded by weather station at the Faculty of Biotechnical
Systems Engineering from Polytechnic University of Bucharest is located at
coordinates 44.4380N Latitude, 26.0470E Longitude and 76.6 m elevation.
AWS weather station model / EV has a range wireless transmission up to 300 m and
integrated set of sensors, stanchion 1.77 m and related tripod. It is equipped with
sensors for acquisition of meteorological parameters: temperature, pressure, relative
humidity, wind direction and speed, precipitation, solar radiation intensity
(Rusanescu & Rusanescu 2013). Data is transmitted every hour throughout the day
at the site. The system enables instant viewing of measurements of meteorological
parameters mentioned (Weather station Technical Paper 2009).
The maximum intensity of rainfall measurable: 0-300 mm / h.
The evaluation of pluvial aggression on the substrate was determined using the
following indices: Fournier Index (IF), Fournier Modified Index (IFM) and Angot
Index. These indices can be used to assess soil susceptibility to erosion, to calculate
the erodibility of land and soil losses, to assess sloping land sensitivity due to
intense precipitation (Scrinzi et al 2006, Sfiru et al 2011).
Interpretation of erosive classes determined by the Fournier index (Sfiru et al 2011,
Alexandre Marco da Silva 2004) is follow:
The classes of rainfall erosion based on IF are: 0-20 mm very low erosion; 20-40
mm low erosion; 40-60 mm moderate erosion; 60-80 mm severe erosion; 80-100
mm very severe erosion; > 100 mm extremely severe erosion (Oduro-Afriyie 1996),
(Alexandre Marco da Silva 2004). According to Rusanescu et al (2014b), classes of
rainfall erosion based on MFI are: 0-60 very low; 60 – 90 mm low; 90-120 mm
moderate; 120-160 mm high; > 160 mm very high. Pluviometric records were
obtained from the meteorological station at the Polytechnic University of Bucharest,
Faculty of Biotechnical Systems Engineering, Romania (Rusanescu 2016b). Data
recording was for periods 2009-2016, 1960-1990.

Fournier Index
Estimation of pluviometric erosion using the Fournier index (IF). The Fournier (IF)
index is calculated based on the rainfall in the rainy month of the year, and the
annual rainfall thus expressing rainfall (Rusanescu et al 2018, Rusanescu et al
2016a).
P2
IF = m (1)
P
where: IF - Fournier Index, Pm - rainfall in m month of the most rainy year in year
(mm), P - annual rainfall (mm).
Fournier Modified Index (MFI)

The Fournier Modified Index (IFM) is determined with equation (2):
12
pi2 (2)
IFM = ∑
1 P
where: pi - the average rainfall for the month i (mm), P - the average annual rainfall
and IFM - the modified Fournier index (Scrinzi et al 2006, Rusanescu 2014a).

The Fournier rainfall aggressive classes were calculated based on the amount of
precipitation recorded by the weather station at the Faculty of Engineering of
Biotechnical Systems Polytechnic University of Bucharest (2009-2016, 1960-1990).
The annual values of the Fournier (IF) index calculated for Bucharest during the
period 2009-2016, 1960-1990, reach values below 60 mm in the years: 2009, 2010,
2011, 2013, 2014, 2016 low rainfall aggressiveness. In 2015, 1960-1990 rainfall
aggressiveness is very low. In 2012 (64.9 mm), characterized by a severe rainfall
aggression, due to the conditions of the plain relief, the low degree of coverage with
forest vegetation, the problems related to wilting, soil washing and erosion in the
surface may increase. The soils in the area near Polytechnic University of Bucharest
are in a very low or low rainfall erosion class in most of the analyzed years, except
in 2012 when severe pluvial erosion was used using the scale of Oduro-Afriyie
1996.
The pluvial aggression classes based on IF calculated for Bucharest 2009-2016,
1961-1990 are as follows: in order the year followed by IF (mm): 2009 with 31 mm;
2010 with 20.1 mm; 2011 with 37.2 mm; 2012 with 64.8 mm; 2013 with 11.0 mm;
2014 with 24.6 mm; 2015 with 14.2 mm; 2016 with 22.3 mm; 2009-2016 with 16.7
mm; 1961-1990 with 10 mm.

Figure 1. Values obtained for the Fournier and Fournier index for Bucharest 2009-
2016.
Classes of flood erosion by MFI for Bucharest ranges 2009-2016 and 1961-1990
are as follows: for the years 1961-1990 with 53.6 mm; 2009-2016 with 66.6 mm;
2009 with 78.7 mm; 2010 with 75.0 mm; 2011 with 77.4 mm; 2012 with 96.6 mm;
2013 with 77.7 mm; 2014 with 105.6 mm; 2015 with 73.8 mm and 2016 with 87.9
mm.
In Bucharest the average values of this index range are from 53.6 mm to 105.9 mm.
According to the pluvial aggressive classes, MFI for Bucharest results in a low
aggressiveness for the years: 2009, 2010, 2011, 2013, 2015, 2016, 1961-1990. For
the years 2012 and 2014, there is a moderate aggressiveness.
The triggering of geomorphologic erosion processes may have as a determining
factor either a long duration of precipitation or a high intensity of precipitation,
which leads to the accumulation of a large volume of water, which flows on the
slopes in the form of sludge, favoring the production of the processes Irritation and
torrentiality.
Thus, as a result of the analysis of the IF and MFIs calculated for the period 2009-
2016, it is concluded that the soils in Bucharest are subject to a low, very low and
moderate rain aggressive risk, being classified as rainwater aggressive classes 1 and
2, but also to a risk of moderate pluvial aggressiveness depending on the
morphodynamic characteristics of the analyzed area and the duration and intensity
of precipitations falling within the time interval to be analyzed.
The annual distribution of the maximum amount of precipitation in 24 hours is not
uniform (Rusanescu et al 2010). Multiannual monthly distribution shows a
continuous rise in rainfall from January to June when it reaches the maximum
(197.4 mm in June 2012) and then decreases until February to a minimum (0.3 mm
in December 2013). In the cold season, due to low thermal convection and the
prevalence of anticyclonic circulation, the maximum amount of rainfall in 24 hours
is smaller and slightly erosive compared to summer precipitation. This is due to the
substrate and soil resistance due to low temperature. There are exceptions in the cold
season when the monthly averages are exceeded (in Bucharest, the maximum of

February was 84.8 mm on February 10, 2010, and the maximum of 152.9 mm took
place on December 17, 2014). These exceptions in the cold season are due to
exceptional synoptic situations, meaning the adhesion of moisture-loaded air
masses.
Research conducted by the Pedological and Agrochemical Research Institute shows
that the pluvial aggression in Romania has the following characteristics: it is smaller
in the Western part of the country (0.08), moderate in the Southern (0.13), Eastern
and Northeast (0.10) and high in the Center of the country, the Sub-Carpathian hills
(0.14), the Transylvania Plateau (0.12) and the Carpathians (0.15 – 0.16) (Costea
2012). Most torrential rains occur in the summer, especially in June and July.
Figure 2. Precipitation recorded in Bucharest during 2009-2016, 1961-1990.
The equations used to determine the monthly / annual values of erosivity according
to the surface of the territory and their authors. Equation (3), according to Rufino et
al 1993 is a linear model; Equation (4) according to Silva (2001) is based on
Fournier's model:
Rx = 19.55 + (4.20 ⋅ M x ) (3)
M2  (4)
Rx = 42.307 ⋅  x  + 69.763
 P 
where Rx is the factor R (MJ mm ha -1 h -1 year -1) for the month x, Mx is the average
depth of the monthly precipitation (mm) and P is the average annual precipitation
(mm) (Silva 2001). Class for interpretation of annual erosivity index (R) where
erosivity (MJ mm year - 1 ha - 1 h - 1) are as follows: R ≤ 2452 low erosivity; 2452 <
R ≤ 4905 medium erosivity; 4905 < R ≤ 7357 medium-strong erosivity; 7357 < R ≤
9810 strong erosivity; R > 9810 very strong erosivity.
It is noticed that the erosivity is low throughout the analyzed period. Erosion
calculated for the same period according to Silva 2001 is low.

2009- 1961- Table
2016 2015 2014 2013 2012 2011 2010 2009 2016 1990 3/Year
93.5 156.5 350.1 271.6 299.3 99.4 115.3 186.7 196.5 185.9 I
II
98.5 180.8 21.2 225.4 90.1 71.6 375.7 170.8 154.3 171.6
III
330.4 439.1 234.2 292.6 75.0 43.9 233.8 175.0 228.0 180.0
IV
329.5 249.7 494.2 143.5 247.2 170.8 240.5 90.1 245.7 212.8
V
379.1 225.4 561.8 385.0 848.6 596.6 521.9 269.0 473.4 314.4
VI
490.0 271.6 662.2 565.6 177.5 354.7 449.6 427.0 424.7 344.6
VII
86.8 271.6 292.6 137.2 138.4 331.2 310.2 620.2 273.5 289.6
VIII
481.6 388.3 267.4 271.6 180.4 247.2 129.6 310.2 284.5 264.4
IX
103.6 374.0 218.6 393.4 198.9 19.6 159.0 303.5 221.3 196.8
X
546.2 272.8 290.9 351.4 123.3 180.0 300.1 284.2 293.6 152.7
XI
recorded in Bucharest during the period 2009-2016, 1961-1990
204.4 446.7 182.5 196.0 62.8 31.3 101.0 121.2 168.2 224.5
XII
49.0 27.5 661.7 20.8 319.0 221.2 292.6 43.1 204.4 201.4
Table 3. Erosivity calculated according to Rufino et al 1993 according to the rainfall

1961- Table
2009-
1990 4/Year
2016 2015 2014 2013 2012 2011 2010 2009 2016
I
88.4 131.3 344.7 281.7 381.8 99.8 100.6 171.5 177.3 181.0
II
91.0 155.1 69.8 211.1 89.6 82.6 496.5 153.0 132.1 162.8
III
398.8 647.5 185.7 318.4 82.0 72.6 224.1 157.7 218.9 173.3
IV
397.0 243.6 636.6 121.0 276.4 177.7 233.9 87.9 245.3 219.9
V
510.0 208.8 809.7 515.3 2811 1643 918.5 296.4 777.1 419.5
VI
823.4 278.2 1109. 1065 169.2 600.3 692.0 674.2 633.5 494.9
VII
85.1 278.2 257.3 115.9 126.1 528.5 353.9 1383 291.2 363.2
VIII
796.7 516.0 224.3 281.7 173.0 314.5 110.5 377.4 310.8 311.0
in Bucharest during 2009-2016, 1961-1990
IX
93.8 482.1 169.5 536.0 198.0 69.8 135.2 363.3 209.5 196.1
X
1015 280.3 255.0 437.1 112.7 191.3 334.5 324.7 327.7 141.1
XI
186.1 668.5 136.6 173.6 77.2 70.4 92.1 107.4 145.7 238.8
Table 4. Erosion calculated according to Silva 2001 depending on rainfall recorded
XII

72.7 70.0 1108 69.8 427.4 261.7 320.5 71.8 187.0 202.8
Conclusions
Applying Fournier indices to assess aggressiveness of precipitation is a simple, rapid
method. The two indices are influenced by the pluviometric characteristics, thus the
monthly and annual values recorded at the representative stations for Bucharest,
which give them their local or regional character.
Both variants of the Fournier indices indicate the same classes of pluvial aggression.
The modified Fournier Index is more relevant to the study of aggressiveness of
precipitation because it takes into account the value of precipitation in different
months of the year and the variation over a given year. The indices obtained fall
largely under the moderate aggressiveness class, but there have been years when the
precipitation aggressiveness was moderate (2012, 2014).
From the analysis of the indices of pluvial aggression assessment on the substrate,
periodically, favorable conditions of occurrence and manifestation of the pluvial
erosion processes are created, their effect being stronger when they intervene after a
prolonged drought period, especially in the periods of march - April, July and
august, or in some cases from October to November. For the years 2013 and 2014,
the high values of over 2 - 2.5 and even 3 at some stations indicate the creation of
favorable conditions for triggering of slope and linear erosion processes. Erosion
calculated according to Silva 2001 and Rufino 1993 is low throughout the analyzed
period.
References
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57, pp. 251–259.
Balteanu, D 1984, Relief Yesterday, Today, Meat, Albatros Publishing House,
Bucharest, pp. 205.
Bertoni, J & Lombardi Neto, F 1990, Conservação do solo Ićone, Editora, Sao
Paulo, Brazil, pp. 355.
Costea, M 2012, Ùsing the Fournier indexes in estimating rainfall erosivity. Case
study – The Secasul Mare Basin`, Conference of air and water components of
the environment, Babes-Bolyai University, Cluj-Napoca, pp. 313-320.
Mannaerts, CM & Gabriels, D 2000, 'Rainfall erosivity in Cape Verde', Soil and
Tillage Research, vol. 55, pp. 207–212.
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quality in central and eastern parts of Romania using atomic and optical
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(AM) ', Revista Brasileira de Ciencia do Solo, vol. 14, pp. 235-239.
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Radulescu, C, Stihi, C, Popescu, IV, Busuioc, G, Gheboianu, AI, Cimpoca, GhV,

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in wild mushrooms and soil by EDXRF and FAAS techniques`, Ovidius
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microwave digestion and flame atomic absorption spectrometry', Scientific
Study & Research, vol. 12, no. 2, pp. 155.
Radulescu, C, Stihi, C, Popescu, IV, Nitescu, VO, Dulama, ID, Gheboianu, AI,
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da chuva do estado do Paraná', Revista Brasileira de Ciencia do Solo, vol. 17,
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Weather station Technical Paper 2009, Elettronica Veneta.

TRANSITION OF INCD ECOIND SIMCM TO THE REQUIREMENTS OF

THE NEW STANDARDS ISO 9001: 20015 AND ISO 14001: 2015
Virgil Criste
National Research and Development Institute for Industrial Ecology, 71-73 Drumul Podu
Dambovitei, district 6, 060652, Bucharest, mmc@incdecoind.ro, Romania
Abstract
In National Research and Development Institute for Industrial Ecology has been
developed a methodology for the transition of quality and environmental
management systems to the requirements of ISO 9001 and ISO 114001 revised in
2015. The proposed methodology includes eight steps: organizational preparation,
coordination team design, changes analysis, organizing courses, change
management, risk assessment and system documentation, internal audit and
management analysis. This methodology was applied for the transition of the quality
and environmental integrated system (SIMCM) implemented in the institute and
certified according to the requirements of the ISO 9001:2008 revisions and ISO
114001:2004 revision. The methodology has been successfully applied, the
management analysis proposed the transition of the system to the requirements of
the revised standards. Following the audit of the certification body, the system has
been certified according to ISO 9001: 2015 and ISO 114001:2015, respectively.
Keywords: environment, quality, standard, transition
Introduction
The quality and environmental management systems have emerged in the industry in
order to ensure the planned / projected quality of all products manufactured by an
organization in conditions of environmental protection. Then these systems have
been developed to ensure the demands of stakeholders in organization results.
The requirements for development and implementation of management systems are
laid down in international standards developed by the International Standards
Organization (ISO) Thus, were developed and published in 1987 families of ISO
9000 standards for quality management systems, respectively 14000 in 1996 for
environmental management systems. These standards have been reviewed. The last
revision took place in 2015.
This paper presents the methodology developed within the Management Systems
Department for the transition of quality and environmental management systems,
developed and implemented according to the requirements of the ISO 9001:2008

and ISO 14001:2004 reference standards, to the requirements of the 2015 revised
standards and the results of its application in practice.

The 2015 revision of the reference standards for quality and environmental
management systems includes the following changes:
- brings two new important approaches: the organization's background together
with stakeholders; the risk-based thinking;
- modify the structure of standards;
- introduces changes to terms.
The context of the organization and the importance of stakeholders
In order to assess his context, the organization must determine, monitor and control
the internal factors (infrastructure, employee professional level, organizational
culture) and external factors (social, economic, legislative) that are relevant to its
purpose or affect or are affected by the organization's results, and the environmental
conditions that may be affected by the organization or that may affect the
organization's environmental performance (ISO 9001:2015).
The stakeholders and their relevant requirements for products, services, and
environmental aspects generated by the organization's operation should also be
determined.
Risk-based approach
This approach requires a systematic identification and analysis of existing risks and
opportunities. The organization must determine the factors that could cause its
processes and management system to deviate from planned outcomes and that may
affect the product and service compliance and the ability to enhance customer
satisfaction (Anghel & Criste 2015). For the environment, the risks and
opportunities relate to significant environmental aspects, compliance obligations,
and product lifecycle perspectives. Environmental impacts that can be controlled
and influenced at each stage of the product lifecycle are taken into account:
procurement of raw materials, manufacturing, packaging, transport, delivery,
consumer use, end of life cycle and final disposal (ISO 14001:2015). Organizations
must make full use of emerging opportunities. Based on the analysis, actions are
planned for treating the risks (and opportunities) to prevent or reduce unwanted
effects.
Structure of standards
In order to facilitate the integration of the different management systems into one, a
common structure of all standards, an identical base text and a set of 21 common
terms and definitions have been established.
The new structure of standards includes 10 chapters (ISO 9001:2015):
• Application domain;
• Regulatory references;
• Terms and definitions;
• The organization context;

• Leadership;
• Planning;
• Support;
• Operation;
• Performance evaluation;
• Improvement.
Changes of terms (ISO 9001:2015)
Management's responsibility becomes leadership. The decisions focus on trust,
inspiration, attitude, behaviour, personal character.
The documentation becomes documented information and relates to communication
of information, providing of evidence, transmission of knowledge, dissemination of
experience, etc. There are no requirements for mandatory procedures or a
management manual.
Supply becomes products and services supplied from outside.
Product becomes products and services.
Continuous improvement becomes improvement.
Organizational knowledge required for system and process operation.
For the transition of the integrated quality and environmental management system to
the requirements of the new standards we have developed a methodology that takes
place in eight stages:
- preparing the organization
- designation of the coordination team
- analysis of changes
- organizing trainings
- management of change
- risk assessment and system documentation
- internal audit
- management analysis
1. Preparing the organization
This requires acquisition of standard ISO 9001:2015 edition, identification and
analysis of changes. It establishes a team of auditors who will perform the analysis
and timeframe for the analysis and communicate to employees what is being done
and why.
2. Designate the coordination team
The management of the organization designates by decision the team that will
coordinate the project. Team members must have the necessary knowledge and
authority to make decisions and allocate resources for the project.
3. Analysis of changes
The team of auditors performs a diagnostic analysis comparing the current SIMCM
with the requirements of the new standards and establishes the necessary changes to
be made to make the transition to the new requirements of the standards. For this,
the team draws up and uses a checklist that includes the requirements of the new
standards written in the form of questions.

The diagnostic analysis is carried out in the form of an audit and includes the stages
of an audit: planning the audit, conducting the audit and presenting the results
through the audit report.
For each requirement (or set of requirements) the standard identifies the status of the
current system.
The conclusions of the audit are summarized as a list comprising:
• the processes that comply with the standard and are documented.
• the processes that comply with the standard and need to be documented.
• the processes that do not comply with the standard and need to be redesigned.
• the processes imposed by the standard and not currently.
4. Organizing trainings
For effective implementation of the new standards requirements, the organization
has to train staff to understand their role in achieving SMC performance and
relevance. Thus, courses will be organized for:
• training the managers and the project and work team leaders
• training all employees on: what changes provide the new standards, what is the
process approach, what is risk-based thinking, what is the impact on the workplace
and how it can impact on the quality and the environment
• training the work teams so that all team members understand the standards in detail
to do their job properly.
• training internal auditors with the new requirements of standards
5. Change management
In order to achieve the improvements associated with the changes, the organization
should consider all types of changes that may occur. These changes can be
generated, for example, in processes, documented information, equipment,
employee training and supplier selection.
Change management includes:
5a. Planning the changes
Changes must be made in a planned and systematic manner. The organization must
consider:
- the purpose of the changes and their potential consequences;
- the integrity of the quality management system,
- availability of resources;
- allocation or reallocation of responsibilities and authorities
Operational planning is reflected in the Design and Implementation Program.
5b. Designing and developing changes
During the design and development process are identified changes that will be
implemented and controlled to ensure that there is no impact on product or service
compliance, environmental performance, and compliance with legislation.
To determine priorities, the organization considers:
• consequences of the change
• likelihood of consequences
• impact on customers
• impact on stakeholders
• impact on the environment

• impact on quality and environmental objectives
• the efficiency of processes that are part of the SIMCM
5c. Check for changes
Analysing and controlling changes in production or supply of services to the extent
necessary to ensure continued compliance with the requirements.
The organization retains the documented information, describes the results of the
review of the changes, establishes the persons authorized to modify it, as well as any
necessary actions arising from the review.
6. Risk assessment and system documentation
Risk is an event that can affect your goals.
Once the processes are determined, once the changes are introduced, the risks and
opportunities associated with these processes will also be identified.
Risks can be related to any element of the process, such as inputs, resources, people,
activities, controls, measurements, outputs, etc.
The team will identify the risks for each process under review and propose control
measures for risks that go beyond acceptable limits.
The methodology for identifying and assessing risks has been developed within the
Managing Internal Control System. Identified risk management is done through the
Risk Register (Criste 2011).
As the requirements for documenting the management system are reviewed,
particular attention will be paid to identifying the documents that are required for the
system and for the production or service processes.
For system documentation, work teams are created for each section of the standard.
These are made up of employees and managers who will be responsible for the
process.
While the coordination team is leading the project, the work teams will develop
processes and establish documented information to meet the standard's
requirements. The coordination team will review processes and documents and
monitor the progress of work teams.
Although the new standards do not require documented procedures, we believe that
existing procedures need to be kept by making the necessary revisions to meet the
new requirements. A management manual, structured to the new standards, to
describe the system is also useful.
7. Internal Audit
In order to find and correct the deficiencies in the management system before the
certification audit, an internal audit is planned and performed, leaving time for the
application of any corrective measures established as a result of the audit findings.
In order to perform the internal audit, the audit team will be trained. Auditors will
use the checklist established for the diagnostic audit.
8. Analysis conducted by management
Management analysis is another key factor in getting a management system ready
for the certification audit. In the meeting it analyses the information from the

internal audit, the corrections and corrective actions proposed and undertaken, the
information from the system monitoring and the results.
Additional corrective action can be taken to resolve problems and improve system
performance. Records will be made and maintained.

The established methodology has been applied in the institute for transition of the
SIMCM, certified according to ISO 9001:2008 respectively ISO 14001:2004, to the
requirements of the 2015 revisions.
A project coordinating team was formed by two senior executives with experience
in management systems and audit experience, one is responsible for the project. The
responsible drafted the Strategic transition program of SIMCM to the requirements
of the new standards.
According to the program, the team carried out the following activities:
- reviewed the changes made to the two standards and prepared the Checklist
according to the requirements of the new standards.
- carried out an internal audit to determine the status of the current system against
each requirement of the revised reference standards. The results of the audit were
presented in the Audit Report.
- developed two course supports: ISO 9001:2015 and ISO 14001:2015 Changes in
requirements and implementation for training the auditors and Transition of ISO
9001:2008 to ISO 9001:2015 and ISO 14001:2004 to ISO 14001:2015 for staff
awareness on SIMCM transition to the new standards.
- organized two courses with developed course support: one for auditors training and
one for training quality-environment compartments responsible
- identified the environmental risks, the risks to the achievement of environmental
objectives and environmental compliance risks, established the risk management
actions and control measures and completed the Risk Register.
- reviewed the SIMCM documentation as follows: a new management manual was
developed on the structure of the new standards, the system and working procedures
were revised in line with the requirements of the new standards.
- has conducted an internal audit to prepare the certification system
- was conducted a management analysis in which were discussed the results and
was decided the SIMC transition to the requirements of the revised standards
Conclusions
The transition methodology of SIMCM to the requirements of the ISO 9001:2015
and ISO 14001:2015 standards was successfully applied in the institute because,
after the management analysis, was decided the transition of the system and the
proposal to certify it at the first surveillance audit of SIMCM.

Following the audit of the QS CERT certification body in April 2017, the system
obtained the ISO 9001:2015 and ISO 14001:2015 conformity certificates, as shown
in Figure 1.
Figure 1. Certificates of conformity
At present, the methodology is part of the Management Systems Department

portfolio and is used in consulting. The methodology was used in the consultancy
offered to SC ISAF SA in a contract concluded within the project Promotion,
identification and realization of partnerships for transfer of knowledge in the
field of industrial ecology, in the Competitiveness Operational Program
competition.
Acknowledgements
The study was carried out whithin the Romanian Nucleu Programme, Project PN 09-13 04 16
Transition methodology of quality management systems to the new requirements for the risk
based assessment approach on the organization’s processes and PN 16 25 04 03 Transition of
environmental management systems to the new requirements of the ISO 14001:2015 standard
and its integration with the quality management system according to ISO 9001:2015
References
Anghel, A & Criste, V 2015, The transition of the quality management systems to
the new requirements regarding the approach based on the risk assessment in
the organization’s processes, International Symposium The Environment and
The Industry, National Research and Development Institute for Industrial
Ecology, Bucharest, pp. 138-144.
Criste, V 2011, Managing Internal Control System of the National Research and
Development Institute for Industrial Ecology.
ISO 9001:2015 Quality management systems. Requirements.
ISO 14001:2015 Environmental management Systems. Requirements with guidance
for use.

USE OF REMOTE SENSING DATA IN INVESTIGATIONS OF

ECOLOGICAL STATE OF WATER BODIES IN URBAN AREA OF KYIV
CITY
Viktor Vyshnevskyi, Sergiy Shevchuk
Institute of Water Problems and Land Reclamation, 03022, Kyiv, 37 Vasylkivska,

vishnev.v@gmail.com, sergey_shevchuk@ukr.net, Ukraine
Abstract
There are several hundreds of water bodies within the territory of Kyiv city. The
biggest river is the Dnipro with many small urban rivers, lakes and ponds. Upstream
of the city on the Dnipro river the Kyivske reservoir was constructed. Near the city
another big river Desna flows into the Dnipro river. The ecological states of these
water bodies differ greatly and it is worthy to note that the routine monitoring of
these objects is irregular and limited. This resulted in the need of applying a new
approach to the investigation of their ecological states. The investigation included
field studies, using and processing of high-quality satelite images as well as
analysing some hydrometeorological data. The field studies were carried
simultaneously with the satellite survey. This enabled to get some dependences
between measured and calculated data. Some patterns regarding water temperature,
ice regime, water transparency, algal bloom as well as the ecological state of water
objects in a whole were obtained. The Kyivske reservoir located upstream is an
essential factor impacting on the Dnipro river and its gulfs. Another important
factor which has a great effect on the ecological states of water objects is water
exchange in them. In general, the ecological state of water bodies, connected with
the Dnipro river is much better, than those without that connection.
Keywords: Dnipro river, ecological state, Kyiv, lakes, remote sensing
Introduction
There are many cities within the territories of which there are a large number of
water bodies. Kyiv is considered to be one of them. Besides the Dnipro river there
are several hundreds of water bodies in the territory of the city: small rivers, lakes
and ponds. The length of the largest lakes and ponds can exceed 1 km. In many
cases the creation of lakes and increasing their sizes were caused by sand mining
which was used for construction needs. That is the reason of prevailing location of
the largest lakes on the left-bank flood plain of the Dnipro river (Figure 1).
The large number of water bodies does not enable to study them properly using
routine monitoring. Under these conditions it is desirable to use remote sensing data.
Relevant images cover all territory of the city that enables to compare ecological
states of different water bodies simultaneously and repeatedly over the whole year.
It is important to add that using the satellite images of medium spatial resolution is
free of charge. Another important factor is obtaining of colored images, which are
very illustrative.
Figure 1. Kyiv and its main water bodies: 1– the Kyivske reservoir, 2 – the Dnipro
river, 3 – the Desna river, 4–6 – the largest lakes: respectively Almazne, Vurlitsa,
Tjagle, Zaplavne

The images obtained by the Landsat and Sentinel satellites were used for the
investigation of Kyiv water bodies. These data are freely available on the site of the
US Geological Survey [www.glovis.usgs.gov]. The spatial resolution for the most of
spectral bands of Landsat satellite is 30 m, of Sentinel satellite is 10 m.
These data were processed using GIS-technologies. Water temperature and some
other indexes such as NDTI, NDPI, NDVI etc., which are the ratio of spectral bands
mainly in the visible part of spectrum, were calculated. Many digital colored images
were obtained and analyzed afterwards.
Besides obtaining satellite images and their processing, the field study was carried
out. Water temperature, water transparency and total suspended solids were
measured.
The hydrometeorological data such as air temperature, wind direction and speed
were collected from the data bases of Hydrometeorological Survey.

The carried out investigation enabled to specify some features of water temperature,
ice regime and ecological state of the Dnipro River, its gulfs and other water bodies.
Throughout the year their ecological states change greatly. The water temperature in
the water bodies depends not only on season and air temperature, but on water
exchange in them as well. The water temperature of the Dnipro River also depends
on the distance from Kyivska hydroelectric power station, so in summer the coldest

water is usually observed downstream of the Kyivska HPS. Water temperature rises
as the distance from HPS and on the southern suburb of Kyiv city it can be 2 ºС
higher than it is near power station (Figure 2).
a b
Figure 2. Surface water temperature: а – 13.07.2016, b – 29.07.2016
The temperature of water in the Desna River and lakes in summer is higher than the
temperature of discharged water from Kyivska HPS. The irregular operation of the
power station during twenty-four hours causes some differences in water
temperature along the Dnipro River.
The vicinity of Kyivska HPS to the city has the essential impact on the ice cover in
the river as well. As a rule even in cold winters a long ice-hole downstream the
station can be observed. Another important factor influencing the ice regime of the
Dnipro River is the operation of some industrial Kyiv enterprises, mainly thermal
power plants (TPPs) near the Dnipro River. TPP-5 which uses water for cooling, is
one of them. As a result of discharging heated water from that TPP an elongated ice-
hole is usually formed near the right bank of the river. In the satellite images one can
see the effect of one more enterprise – Bortnitska water treatment station, which is
located on the south-eastern suburb of Kyiv city. The water discharge of this station
exceeds 800 thousand cubic meters per day and the temperature of treated
wastewater in winter is much higher than 0 °C. As the result of this, ice cover
downstream the water treatment station is absent (Figure 3).

Figure 3. Ice cover in the Dnipro river on 07.12.2016
The important problem of the water bodies, located in Kyiv, is their ecological state.
The specific phenomenon in them is algal bloom. During some last years which
tended to be rather warm, the algal bloom was more intensive than in previous
years. The peak of algal bloom is usually observed in the first part of August, while
the water transparency at the same period is rather small: by the Secchi disk in the
Dnipro River it can decrease to 1 m and in some lakes to 0.40 m. In cold seasons the
differences in water transparency in the river and lakes become less (Figure 4).
a b
Figure 4. Algal bloom in the water bodies of Kyiv city on 17.08.2017:
a – in the north part of city, b – in the south-eastern part of city

This figure shows the essential differences in water color of the Dnipro River and
lakes. It is clearly seen the intensive algal bloom in Tjagle lake and some others
located in the south-eastern part of Kyiv city.
Based on the obtained field and satellite data on algal bloom, water transparency and
other characteristics some dependencies have been determined. There are correlation
between water transparency measured with Secchi Disk and values of spectral bands
B2, B3, B4 and B5 of Landsat 8 satellite. The close correlation is observed between
water transparency and value of B3 spectral band that corresponds to green color.
The correlation between water transparency and B4 spectral band that corresponds
to red color is not so strong. The strongest correlation between water transparency
and satellite data was obtained for the expression SD = (B4–B2) / B3 in summer
conditions (Figure 5).
When using the data obtained in other seasons the above stated correlation is not so
strong. It can be explained by the significant effect of algal bloom on the water
transparency during summer (Vyshnevskyi & Shevchuk 2016, 2018). The similar
results were obtained by other authors in relevant studies (Allan et al 2007,
Gholizadeh et al 2016, Shumakov 2008).
Figure 5. Correlation between water transparency by Secchi Disk and the values of
(B2–B4) / B3 obtained for Kyiv water bodies during summer
NDTI index, which is the ratio of (B4–B3) / (B4+B3) was used for the evaluation of
the ecological state of water bodies (fig. 6). The ratio of ((2/3)*B5–
(1/3)*B3) / ((2/3*B5+(1/3)*B3), proposed in paper (Burnis et al 2011), gives similar
results.

a b
Figure 6. The images of water bodies located in Kyiv city calculated by NDTI
index: a – 13.07.2016, b – 21.08.2016
The obtained figures show great differences in ecological states of the Dnipro River
and lakes. Rather bad ecological states are usually observed in two largest Kyiv
lakes: Almazne and Tjagle. There are some reasons for that. The poor ecological
state of Almazne lake can be explained its specific shape. This lake is rather deep
(up to 20 m) and characterized by a rather small shallow area. That is way the spread
of macrophytes is not essential. As the result of that nitrogen and phosphorus
compounds are mainly absorbed by blue-green algae (Shevchuk et al 2017,
Romanenko et al 2015).
Conclusions
The remote sensing and GIS-technologies are a useful toolkit, which enables to
determine the ecological state of water bodies. During warm period water
temperature in the Dnipro River near Kyiv city downstream of Kyivska HPS can
have a rise by 2 °C. Kyivska HPS has a great effect on the ice cover near city as
well. During winter time two enterprises, namely Kyivska TPP-5 and Bortnitska
water treatment station influence the ice cover too. Great differences in ecological
states of water bodies in Kyiv city can be observed. The most intensive algal bloom
in water bodies is usually observed in the first part of August. At that time the water
transparency in the Dnipro can drops up to 1 m and in lakes – up to 0.4 m. In general
the ecological state of the Dnipro River is considered to be much better than it is in
the lakes with small water exchange. For the evaluation of the ecological state of
water bodies NDTI and some other indices can be used.
References
Allan, M, Hicks, B, Brabyn, L 2007, ‘Remote sensing of water quality in the
Rotorua lakes’, CBER Contract Report, vol. 51, pp. 27.
Burnis, D, Bushuev, E, Voloshin, V 2011, ‘Automatic technology of urban territory
classification with use of data WORLDVIEW-2’, Ecology and nature use,
vol. 14, pp. 55–71.
Gholizadeh, M, Melesse, A, Reddi, L 2016, ‘A comprehensive review on water
quality parameters estimation using remote sensing techniques’, Sensors,
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www.glovis.usgs.gov – site of the US Geological Survey

WATER QUALITY ASSESSMENT USING PHYSICAL-CHEMICAL

PARAMETERS OF THE DANUBE RIVER (DELTAIC AREA) INCLUDING
RAZIM AND GOLOVITA LAKES, ROMANIA
Irina Catianis, Gabriel Iordache, Dumitru Grosu, Marian Malageanu, Iulian Pojar,
Ana Bianca Pavel
National Institute of Marine Geology and Geoecology – GeoEcoMar, Bucharest, 23 – 25

Dimitrie Onciul Street, 024053, Bucharest, irina.catianis@geoecomar.ro, Romania
Abstract
The present study assessed the spatial water quality variation of physical and
chemical variables. The water quality data were collected during May 2018 from
several sampling stations distributed between Ceatal Izmail and Sf. Gheorghe
branch and up to the Dunavat Canal, as well as Razim and Golovita lakes. The
sampling stations were selected on the basis of their contamination susceptibility,
i.e., the station located along the above-mentioned sector of the Danube River were
tended to be more impaired by the human related activities. Instead, the stations
downstream to the Danube River (the lower course – deltaic area), i.e., Razim and
Golovita lakes were supposed to be less impaired by the urban and rural
contamination. The investigated sites are of particular interest since they belong to
the Danube Delta Biosphere Reserve (DDBR). The following water quality
parameters were measured: depth (m), temperature (oC), pH (units), dissolved
oxygen content (mg/l), electrical conductivity (µS/cm), total dissolved solids (mg/l),
sulphates (mg/l), nitrite-nitrogen (mg/l), nitrate-nitrogen (mg/l), orthophosphates
(mg/l), chlorophyll ”a” (µg/l), turbidity (NTU), total suspended solids (mg/l), Secchi
visibility (m), silica content (mg/l) etc. Overall, the results indicated that some
variables presented comparable values that have not exceeded those limits
recommended by the reference standard. Instead, the fall in the quality of water (any
abnormal values encountered in a few situations) may be related to a wide range of
local natural environmental circumstances, as well as anthropic factors. The
outcomes obtained from the present study shall be useful in the future environmental
assessment of the aquatic ecosystems in DDBR area.
Keywords: ecosystems, evaluation, physical-chemical parameters, transitional

waters, water quality
Introduction
Generally speaking, the water quality is fundamental for life, basic human needs and
environmental issues sustaining ecological processes that support the development
of plant and animal communities. Surface water resources are vulnerable to
chemical, physical and microbiological contamination through natural and/or
human-related activities. There are many sources that might cause water stress and
quality impairment, but most are one of physical and chemical categories such as
land disposal of sewage effluents, sludge and solid waste, septic tank effluent, urban
runoff and agricultural, mining and industrial practices (Close et al 2008). The
stability of aquatic environments, including transitional waters as coastal lagoons,
and their variations under contemporaneous conditions (effects of natural and
anthropogenic stressors) are settled by the Water Framework Directive (WFD
2000/60/EC). This ordinance requires the achievement or maintenance of a good
ecological status in order to provide for a sustainable future for aquatic systems and
their habitats. The coastal wetlands are very important vulnerable ecosystems
assuring suitable environment for a large community of plants and animals.
Subsequently, they are also centers of economic activities as they ensure the
environment for fishery exploitation, farming practices, reed exploitation, water
tourism etc. The lagoons have particular characteristics which include the
ecological, morphological and hydrodynamic aspects. Also known as transitional
environments, they act as receptors and diluters of several inputs of substances
(hazardous substances, nutrients) and other water pollutants originating from a
variety of sources, both natural and artificial. The water circulation in a lagoon is
rather limited to be able to withstand the ecosystem changes in water quality so that
they become susceptible to anthropogenic pressures (Johnson et al 2007). Some
examples of anthropogenic pressures that may have a strong impact on coastal
ecosystems are: land-use change, freshwater withdrawal from ground and surface
water sources, sedimentation, point and nonpoint water pollution, shoreline
hardening, and overfishing (U.S. EPA 2007). Evaluation of the water quality in the
Razim-Sinoie Lagoon Complex is required for surveying of ecosystem features and
dynamic processes that support them. In this lagoon system consists of several large
brackish lagoons located in the southeastern part of Romania, the attainment of a
good ecological status is interfered by several natural and anthropogenic factors. In
recent years, there have been many studies about the effects of the natural and
anthropogenic changes to geomorphological environments and ecosystems of the
Razim-Sinoie Lagoon Complex (Panin 1974, Panin 1996, Romanescu 2009,
Vespremeanu et al 2013). The lagoon system has undergone through gradual
changes as a result of increasing man-made pressure that led to adverse
consequences, regarding the residence time, eutrophication and salinity of the
lagoon system (Dinu et al 2015). The artificial introduction of fresh water negatively
affected the salinity of the water system in the lagoon complex (Stanica 2012) with
repercussions on the levels of fauna and flora density. The differences in
environmental state of Razim-Sinoie Lagoon Complex as a response to the shifts in
salinity regime distinctly affected the local species diversity, abundance and trophic
status (Teodorescu-Leonte et al 1956, Teodorescu-Leonte 1977). Likewise, human
interference through the medium of different artificial structures (i.e., system of
dams and dikes, drainage systems, opening/closing of sluice-gate) designed to
control natural processes are among the most common cause of coastal erosion
(Spataru 1990, Vespremeanu-Stroe et al 2007). The present study assessed the
spatial water quality variation of physical and chemical variables. The aim was to
identify the main potential water stress and deteriorating water quality sources in the
Razim and Golovita lakes, and in a particular sector of its major connection -
Danube River - the main supply of water and sediment. The investigated sites are of
particular interest since they belong to the DDBR. The outstanding universal value
of the DDBR has been recognized (e.g., Romanian Government Decision no.
983/1990) through the inclusion within an international network of biosphere
reserves. The purpose of this study is to reveal the extent to which the natural factors
and/or human related activities performed around the investigated lakes has
impacted on its physical-chemical parameters. The environmental quality of the
investigated sites is greatly influenced by many variables. For instance, expected
shifts in physical-chemical characteristics of these relatively shallow waters (i.e.,
Razim L. and Golovita L.) range from changes in the freshwater inputs (connections
with Sf. Gheorghe branch), the local climatic conditions (wind stress, waves,
precipitation to evaporation balance), sedimentation rates and erosion processes etc.
In addition to the water quality assessment, a preliminary mapping of emergent
aquatic vegetation existing in the Razim Lake i.e., in the southeastern part of it
(Holbina Gulf), was performed to estimate the evolution of aquatic vegetation in
recent years. The importance of topo-geodesic mapping and monitoring of the
stability of the Danube Delta's riparian associations is imperative because they are
the main habitat for the fish fauna and other wildlife species. Aquatic plants play a
decisive role in the absorption of the nutrients from eutrophic waters, the reduction
of heavy metal concentrations and the sediment retention. Several studies have
found that the Phragmites australis (common reed), play an important role in the
removal of zinc in waste water. The quantity and the composition of aquatic plants
has a great influence on water quality, affecting temperature and light conditions,
carbon dioxide concentration, organic matter quantity and water movements.
Aquatic plants can indirectly diminish water turbulence by preventing its
movements and thus preventing sedimentation disturbances. It is known that aquatic
plants reduce the growth potential of phytoplankton by decreasing the availability of
nutrients (Huhta 2009). The increased amount of aquatic plants decreases the flow
of nutrients from the sediment and therefore the amount of nutrients in the water. It
also removes nitrogen from the water ecosystem.

Study Area and Sampling Sites
The Razim and Golovita lakes belong to the Razim-Sinoie lagoon complex, which is
situated to the south of the Danube Delta and on the western coast of the Black Sea
(Figure 1a). The lagoon complex comprises the only brackish lakes in Romania that
are connected both to the Danube River and to the Black Sea (Figure 1b). The
lagoon's total drainage area is 1145 km2 of which the lagoons and limans expand
approximately 863 km2. Razim Lake is the largest freshwater lagoon in Romania,
with an area of 415 km2 and a maximum depth of 3.5 m. The surface area of
Golovita Lake is 118.7 km2. The freshwater inflow to the lagoon is facilitated by the
Sf. Gheorghe branch via Dunavat and Dranov canals, where receives a contribution
coming from the Danube River. The environmental impairment trend of the Razim-
Sinoie Lagoon Complex began in the last decades as a result of different hydro
technical works (e.g., levees, dikes, cut-offs, canalization) performed for the
development of irrigation systems and the fishery exploitation potential of its water
bodies. The field measurements were carried out in the investigated perimeters on
RV ”Istros” owned by the National Institute of Marine Geology and Geoecology –
GeoEcoMar, Romania. The water quality data were collected during May 2018 from
several sampling stations distributed along a sector of the Danube River (i.e., the
lower course – deltaic area), namely between Ceatal Izmail and Sf. Gheorghe branch
and up to the Dunavat Canal, as well as Razim and Golovita lakes (Figure 1c). The
sampling stations were selected on the basis of their contamination susceptibility,
i.e., the station located along the above-mentioned sector of the Danube River were
tended to be more impaired by the human related activities. Instead, the stations
downstream to the Danube River (the lower course – deltaic area), i.e., Razim and
Golovita lakes were supposed to be less impaired by the urban and rural
contamination.
Figure 1. The geographical setting of the study area in Romania (a), within the
Danube Delta Biosphere Reserve (b), and distribution of sampling sites (c) along a
sector of the Danube River (the lower course – deltaic area), between Ceatal Izmail
and Sf. Gheorghe branch and up to the Dunavat Canal, and in Razim and Golovita
lakes.
The water samples were gathered from surface (0.5 m) using Niskin Water Sampler
(Figure 2). In situ parameters such as depth (m), temperature (oC), pH (units),
dissolved oxygen content (mg/l), electrical conductivity (µS/cm), turbidity (NTU)
along with water transparency/visibility (VDS) using a Secchi disc (25 cm diameter)
were measured at the sampling spots aboard the RV ″Istros″. The other parameters,
i.e., nitrite-nitrogen (mg/l), nitrate-nitrogen (mg/l), orthophosphates (mg/l), total
dissolved solids (mg/l), sulphates (mg/l), total suspended solids (mg/l), chlorophyll
”a” (µg/l), silica content (mg/l) etc., were analyzed ex situ at different laboratories.
The values of the above parameters were acquired with WTW Multiline P4

Multiparameter (Figure 2), (e.g., temperature, pH, dissolved oxygen, conductivity,

total dissolved solids, oxidation-reduction potential), HACH 2100Q (e.g., turbidity),
and HACH 5000 – UV-Vis-Spectrophotometer (e.g., nitrites, nitrates, phosphates,
sulphates). The obtained results were related to national standard guideline value for
surface water quality (Order No. 161/2006), as well as other available environmental
standards for variables as total dissolved solids (DeZuane 1997), turbidity
(Romanian Standard - STAS 6323 – 88), total suspended solids (ANZECC 2000
Guidelines), oxidation-reduction potential (Sigg 2000) and the silica content
(http://www.freedrinkingwater.com/water_quality).
Figure 2. Collecting and measuring in situ and ex situ water quality parameters
Moreover, different topo-geodesic measurements were performed on the south-

eastern part of the Razim Lake (i.e., Holbina Bay) for preliminary mapping of
emergent aquatic vegetation changes during the last years. Wetland plants as reeds
and marsh grasses may provide a natural, efficient and sustainable filtration system,
thus contributing to the state of water quality. High-precision GPS measurements
have been made to topo-geodesic mapping of the vegetation, that have highlighted
the limit contour of the vegetation permeated in two areas of the Holbina Bay
(Razim L.): the south-western part, i.e., Cosburunu Mare (about 4.4 km), and the
eastern part of the bay (about 3 km) up to near the mouth of the Dranov Canal.

This research investigation covered the first interval of May 2018 and took place at
13 stations in the Danube River branches and rivulets, as well as 25 stations at
Razim L., and respectively, 15 stations at Golovita L. (Figure 1c). The control
sections located along the sector of the Danube River (the lower course – deltaic
area) are specified further on: Ceatal Izmail – Mm 43.5 (DD18-02 station), Chilia
Branch-km 115.5 (DD18-05), Tulcea Branch - Mm 42.5 (DD18-08), Ceatal Sf.

Gheorghe– km 108 (DD18-11), Tulcea Branch – Mm 34 (DD18-14), Sulina Branch
– Mm 33 (DD18-17), Sf. Gheorghe Branch – km 85 – downstream of Mahmudia
village (DD18-20), Sf. Gheorghe Branch – km 63 – downstream of Murighiol
village (DD18-24), Old Danube Meander – km 65 (DD18-27), Sf. Gheorghe
Branch – km 59 (DD18-30), Sf. Gheorghe Branch – km 57+500 (DD18-31), Sf.
Gheorghe Branch – the first cut-off meander (DD18-32) and Dunavat Canal (DD18-
37).
In general, the results of the investigation showed uniform environmental conditions
(i.e., Low local fluctuations), the variables appear quite plain, with nearly regular
distribution. A synthetic presentation will be made in the following. The sampling
period was characterized by the oscillating thermal regime, sunny days respectively,
heavy rain days and strong winds with gusts, undeveloped underwater vegetation
and a higher mean value of the river water level (295.23 cm) registered in May
2018. Climate factors that act on the water surface temperatures measured during the
investigation period showed uniform trends with insignificant fluctuations in the
measured values. Water temperature (T) is one of the most important physical
characteristics of aquatic ecosystems and influences a number of water quality
parameters (Chapman 1996). The minimum T at all stations situated on the control
section of the Danube River was measured at Tulcea Branch-Mm 42.5 (20oC), while
the maximum T was registered at Dunavat Canal (21.9oC). Similarly, the mean
value of water T was consistent with the normal seasonal variations for the period of
May, e.g., Razim L. (20.28 oC) and Golovita L. (20.06 oC).
Dissolved oxygen (DO) is one of the important parameters in water quality
assessment and reflects the biological and physical processes predominating in the
water. The dissolved oxygen is an important factor for aquatic life and the chemical
characteristics of the environment (Chapman 1996). In the present study, DO
concentration among the control section of the Danube River, as well as investigated
lakes, showed little variation. The measurements of DO concentration revealed that
all investigated water samples were well-aerated, with dissolved oxygen
concentrations in excess of 5 mg/l. A minimum DO concentration of 5 mg/l is
recommended to adequately support aquatic life (www.niwa.co.nz/our-
science/freshwater/tools/kaitiaki_tools/impacts/dissolved-oxygen). The variations
recorded are roughly similar. In the control sections of the Danube River, the highest
value of DO concentration was encountered in Dunavat Canal (9.17 mg/l), while the
lowest was recorded in Sf. Gheorghe Branch – km 85 – downstream of Mahmudia
village (7.58 mg/l). As well, the mean value of DO concentration was higher than 5
mg/l, also in Razim L. (9.02 mg/l), and Golovita L (9.35 mg/l). The results showed
almost the same trend of the average concentration of DO content, regardless of the
sample station localization, i.e., the Danube River waters, as well as the lakes.
In agreement with the USEPA (1980), accepted water quality criteria specify a pH
of less than 6.5 units may be harmful to many species of fish. Therefore, the pH
range of 6.5-9.0 units would be suitable for the protection of aquatic habitats. In this
study, the measured water samples generally ranged from a normal pH to a slightly
alkaline pH in the majority of sampling sites. The pH of investigated water samples

compared favorably with the national water quality standard. So, in the control
sections of the Danube River, the lowest value was measured in Sf. Gheorghe
Branch – km 85 – downstream of Mahmudia (7.67) and the highest value was
observed in Old Danube Meander – km 65 (8.04). The pH values did not vary much
between the control sections of the Danube River. The water reaction (pH) tested in
the water of the investigated lakes is in the pH range with normal-slightly alkaline
mean values, such as Razim L. (7.82) and L. Golovita (7.99). The results showed
that pH is almost similar in the Danube River waters, as well as in the lakes.
Nitrates and nitrites are the most common inorganic nitrogen compounds in the
environment, and are present in waters, soils, foodstuffs and biota. The phosphates
represent a form of the element phosphorus that is a fundamental support for living
organisms. If the nutrients exceed certain limit concentrations are potentially
dangerous substances. The increasing levels of phosphates and nitrates can have a
detrimental effect on the ecological balance of rivers and lakes, and can cause harm
to human health (Chapman 1996). In the present study, nitrate-nitrogen (N-NO3-)
content tested among the control section of the Danube River, as well as
investigated lakes, showed little variation. The N-NO3- levels showed very low
values that are below the limit parameter corresponding to Class I of water quality
(high status), (Order 161/2006). Instead, it was noticed that the nitrite-nitrogen (N-
NO2-) content, examined among the control section of the Danube River, as well as
investigated lakes, showed some little variation. Therefore, it was noticed that the
limit of the maximum allowable content corresponding to Class I was slightly
attained or exceeded in some samples taken from: Tulcea Branch - Mm 42.5 (0.019
mg/l), Ceatal Sf. Gheorghe– km 108 (0.012 mg/l), Tulcea Branch – Mm 34 (0.01
mg/l), Sulina Branch – Mm 33 (0.011 mg/l), Sf. Gheorghe Branch – km 85 –
downstream of Mahmudia village (0.011 mg/l), Sf. Gheorghe Branch – km 63 –
downstream of Murighiol village (0.019 mg/l), Old Danube Meander – km 65
(0.016 mg/l), Sf. Gheorghe Branch – km 59 (0.017 mg/l), Sf. Gheorghe Branch –
km 57+500 (0.018 mg/l) and Sf. Gheorghe Branch – the first cut-off meander (0.019
mg/l). The N-NO2- content also presented a range of variation in the investigated
lakes, as Razim L. (0.005 – 0.015 mg/l, mean = 0.00975 mg/l) and Golovita L.
(0.004 – 0.006 mg/l, mean = 0.00467 mg/l). The ortophosphate (P-PO43-) values
obtained in the present study showed a range of variation, so that, the lowest value
of this parameter was recorded at Ceatal Sf. Gheorghe – km 108 (0.073 mg/l), while
the highest was measured at Sf. Gheorghe Branch – km 59 (1.953 mg/l). It has been
noticed that the limits of the maximum allowable content specified in the reference
standard (Order 161/2006) have been exceeded, covering more or less, almost all the
categories characteristic of the five water quality classes (high, good, moderate, poor
and bad), as follows: Chilia Branch-km 115.5 (0.303 mg/l), Tulcea Branch - Mm
42.5 (1.66 mg/l), Ceatal Sf. Gheorghe– km 108 (0.073 mg/l), Tulcea Branch – Mm
34 (1.65 mg/l), Sulina Branch – Mm 33 (1.57 mg/l), Sf. Gheorghe Branch – km 85 –
downstream of Mahmudia village (1.8 mg/l), Old Danube Meander – km 65 (1.853
mg/l), Sf. Gheorghe Branch – km 59 (1.953 mg/l), and Sf. Gheorghe Branch – km
57+500 (0.103 mg/l). A similar situation was also found in the investigated lakes,
so that the P-PO43- widely varied in Razim L. (0.026 – 1.703 mg/l, mean = 0.0289
mg/l) and Golovita L. (0.0366 – 1.816 mg/l, mean = 1.13287 mg/l). The levels of
chlorophyll "a" concentration measured in some control sections of the Danube
River, including the investigated lakes varies widely between 1.24 - 45.35 μg/l and a
mean of 14.60 μg/l. As a result, it was observed that some of the tested samples
showed values that exceeded the limit corresponding to Class I (L. Razim - 26.86
μg/l, L. Golovita - 39.90 μg/l and Gura Portitei - 45.35 μg/l). Presence of silicate in
aquatic environments is very important for growth of group of microorganisms as
diatoms (Egge & Aksnes 1992). Based on the silica content in natural waters
(www.freedrinkingwater.com) that specify values between 5-25 mg/l, the majority
of the investigated water samples showed lower silica content. Therefore, the
highest value was identified at Old Danube Meander – km 65 (7.74 mg/l), while the
lowest was recorded at Chilia Branch-km 115.5 (2.76 mg/l). The distribution of SiO2
concentration in water samples investigated in lakes had the following values:
Razim L. (0.05 – 3.31 mg/l, mean = 0.57 mg/l) and Golovita L. (0.075 – 0.6975
mg/l, mean = 0.3041 mg/l).
According to imposed limit sets of national standard (Order 161/2006), the
conductivity (EC) values determined in water samples among the control section of
the Danube River, were at normal and low levels. For example, the lowest value was
obtained at Sf. Gheorghe Branch – km 85 – downstream of Mahmudia village (382
µS/cm), while the highest value was obtained at Old Danube Meander – km 65 (397
µS/cm). The obtained values do not exceed the limit imposed by the current
legislation, corresponding to Class I. The values of the EC level recorded in Razim
L. showed values ranging from a relatively wide range (396-612 μS/cm, mean = 481
μS/cm), values that exceeded the limit corresponding to Class I. Slightly increased
levels of electrical conductivity recorded in Golovita L. were also noted, so they fall
within a relatively wide range (45 -780 μS/cm, mean = 592.4 μS/cm), values that
exceeded the limit corresponding to Class I and II.
Natural waters have a broad range of total dissolved solids (TDS) that may come
from natural sources, sewage, urban and agricultural run-off, and industrial
wastewater. Concentrations of TDS from natural sources have been found to vary
from less than 30 mg/l to as much as 6000 mg/l (WHO/UNEP GEMS 1989),
depending on the solubility’s of minerals in different geological regions. At most,
freshwater can have 2000 mg/l of total dissolved solids and most sources should
have much less than that (US-EPA 2009). Several environmental standards that
regulate water quality consider that TDS values in lakes and streams are typically
found to be in the range of 50 to 250 mg/L. In the present study, the variation in
total dissolved solids (TDS) content trend is similar to EC, since the TDS
measurements are derived from conductivity. According to the above-mentioned
limits, the TDS values determined in the investigated samples were generally at
normal and low levels.
The sulfate (SO42-) content did not show any significant variations among the
measured water samples. According to national standard limits (Order 161/2006),
the investigated samples could be categorized below the limit corresponding to

Class I. According to these limits, it was noticed that the lowest value was obtained
at Sf. Gheorghe Branch – km 59 (26 mg/l), while the highest was recorded at Chilia
Branch-km 115.5 (35 mg/l). Similar values have been reached in the investigated
lakes as Razim L. (28-52 mg/l, mean = 36,125 mg/l) and Golovita L. (37 – 46 mg/l,
mean =42 mg/l). Mostly, in accordance with the results obtained for the salinity
parameters e.g., EC, TDS and SO42- levels, the water samples investigated in lakes
showed freshwater features.
The results of water analyses for turbidity (NTU units) revealed that some values
above the maximum allowable content were remarked in most of the samples. These
values were related to STAS 6323-88, which stipulates 5 NTU - admitted values,
respectively 10 NTU - exceptionally admitted values. As regards the control section
of the Danube River, the highest value was met at Sf. Gheorghe Branch – km 59
(30.2 NTU), while the lowest was met at Old Danube Meander – km 65 (5.87 NTU).
The turbidity values measured in water samples gathered from lakes varied in a
relatively wide range with high values, such as: Razim L. (3.33 - 56.9 NTU, mean =
27.92 NTU) and Golovita L. (10.9-105 NTU, mean = 49.68 NTU)
The concentration level of TSS (total suspended solids) showed a number of
variations found in the control sections on the Danube. The highest value was
encountered at the Sf. Gheorghe Branch – the first cut-off meander (32 mg/l), while
the lowest was found at Old Danube Meander – km 65 (8 mg/l). The results have
been compared to the ANZECC 2000 Guideline standard (which provides values of
<40 mg/l-acceptable levels of TSS in the freshwater environment, and, respectively
<10-acceptable levels of TSS in the marine environment). The distribution of TSS
concentration in water samples investigated in lakes has the following values: Razim
L. (7-62 mg/l, mean = 35.9 mg/l) and Golovita L. (8-73 mg/l, mean = 49.6 mg/l).
Significantly increased TSS levels above 40 mg/l have been noted, largely from the
water samples tested from the two lakes.
The values of Secchi transparency (m) were ranged in the control sections of the
Danube. The highest value was encountered at Old Danube Meander – km 65 (1,3
m), while the lowest (0,5 m) was measured at several stations such as: Ceatal Izmail
– Mm 43.5, Tulcea Branch - Mm 42.5, Ceatal Sf. Gheorghe– km 108, Tulcea
Branch – Mm 34 and Sulina Branch – Mm 33. In. Razim L the transparency was
registered in a range of 0.2-1.3 m, mean = 0.5 m, and in Golovita L. it ranged
between 0.2 - 0.5 m, mean = 0.27 m. Regarding the trophic status of lakes, the
following situations are illustrated, based on the OECD, (OECD 1982) system: if
Secchi disc depth is between 0.8 and 1.5 m, the lake is eutrophic; if it is between 1.4
and 2.4 m, the lake is mesotrophic and if it is between 3.6 and 5.9 m, the lake is
oligotrophic (Ryding & Rast 1989).
The oxidation-reduction potential (ORP) showed little variation at all sampling
stations. The obtained results were within the normal range of variation for natural
waters (-500 mV + 700 mV) (Sigg 2000).
Synthesizing, the values recorded for the physical-chemical parameters in the
present study are generally comparable with other previous investigations acquired
at different water bodies from the DDBR area (Radan et al 2000, Dimitriu et al
2008, Munteanu et al 2012).
The various environmental conditions existing in the Danube Delta have led to the
development of rich and diversified vegetation. The most common unit of the
landscape of the DDBR is represented by the common reed habitats covering
approximately 199,600 ha, of which the mono-dominant reed beds totalize
approximately 117,000 ha (Hanganu et al 2002). The distribution of aquatic
vegetation is influenced by anthropogenic or natural factors i.e., seasons, frequency
of floods, erosion, accumulation etc. The mapping of emergent aquatic vegetation is
important and necessary to observe its evolution in the deltaic area and the changes
occurring in the aquatic ecosystems. It is also important to know, map and monitor
floating reed islets in the Danube Delta. They can be fixed or movable under the
action of waves or currents. Floating reed islets dynamics is absolutely necessary to
be known because these formations by their movement can partially or completely
close some channels may endanger navigation on lakes etc.
Floating reed islets formations also have an impact on water quality and
biodiversity. So, under beneath of large stretches, the aquatic life water quality
resources are improper because the sun's light cannot penetrate, the aeration is
deficient, the pH of the water and the amount of oxygen is very low (Banu &
Rudescu 1957). As a result, drastic decrease of biodiversity in these areas may occur
(Doroftei & Covaliov 2013).
After data processing few interesting findings were noticed, highlighting the current
limit expansion of emergent vegetation along lake shores, as well as its dynamics in
the last years. Three periods were selected for shaping the vegetation: 2006, 2013
and 2018, based on the data available in the portfolio. A first finding is the tendency
of expansion of emergent vegetation along the lake, specifically in the Cosburunu
Mare sector. These changes in emergent vegetation boundaries could be explained
by the positioning of each lakeshore sector in the predominant wind direction and,
implicitly, wave action. In the above-mentioned area, but on the inner side of the
Holbina Bay, the tendency of wind and climate-induced vegetation changes in the
lake show a retraction phenomenon of the vegetation and shoreline, too. This may
be due to the direct exposure of the wave action generated by the winds blowing in
the area, predominantly in the north-eastern sector. Wave movements act on the
existing vegetation of the lakeshores, implicitly on the unconsolidated underwater
sediment, producing under certain conditions the dislocations of some parts of the
vegetation. In this way reed islets begin to evolve floating freely on the surface of
the water under the influence of the wind and currents. These dislocations may
affect the structure of the habitats established in these favorable areas of wildlife
environment. Concerning the second area where topo-geodetic measurements were
made i.e., Holbina Bay, near the mouth of the Dranov Canal, no significant changes
were found about the limit of the vegetation. It can be assumed that the vegetation
on the eastern lakeshore of the Holbina bay has a relative stability. An explanation
for this phenomenon could be found in the fact that this part of the bay is protected
from the action of waves generated by winds blowing from the north-eastern sector.
Conclusions
According to the results, some variables (e.g., temperature, pH, dissolved oxygen
content, electrical conductivity, total dissolved solids, nitrate-nitrogen, sulphates,
silica content and chlorophyll ”a”) at most stations located along the above-
mentioned sector of the Danube River showed comparable values that have not
exceeded those limits recommended by the reference standard. Instead, other
variables (e.g., nitrite nitrogen, orthophosphates, turbidity and total suspended
solids) showed concentration that exceeded those mentioned by the regulations in
force, for some sampling points. The results of the assessment that characterized the
Razim and Golovita lakes in terms of the physical and chemical properties revealed
that the water quality is fairly good. Variables as water temperature, pH, dissolved
oxygen content, total dissolved solids, nitrate-nitrogen, sulphates, silica content and
chlorophyll ”a” were within desirable limits. Oppositely, the concentrations of
electrical conductivity, nitrite nitrogen, orthophosphates, turbidity and total
suspended solids exceeded the guideline values only in a few cases. The abnormal
values encountered in few situations may be related to a wide range of local natural
environmental circumstances, as well as anthropic factors. Presumably, the self-
purification ability and the dilution capacity of natural waters are key factors to
successfully adapt to changing conditions influenced by natural or human-related
activities. The outcomes obtained from the present study shall be useful in the future
environmental assessment of the aquatic ecosystems in DDBR. Future assays with
environmental samples are necessary to continue research in order to obtain an
overall picture of the state of the water quality of the lower course of the Danube
River, as well as other aquatic environments from the DDBR area. Everything that
occurs in the lower course of the Danube River is the result of what occurs
upstream, and, respectively the impact of the river water quality upon the aquatic
environments from the DDBR area.
Acknowledgements. The research leading to these results was financed from the Ministry of
Research and Innovation – MCI –Romanian Nucleu Programme 13N/2018 – Project PN 18 16
01 02.
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POLLUTION CONTROL AND MONITORING
Section Pollution Control and Monitoring 332

A BASELINE ASSESSMENT OF WATER QUALITY FROM PRIVATE

WELLS LOCATED IN CONSTANTA COUNTY AND RISK
IMPLICATIONS FOR COMMUNITY HEALTH
Gina Vasile Scaeteanu, Roxana Maria Madjar
University of Agronomic Sciences and Veterinary Medicine, Faculty of Agriculture, 59

Marasti Blvd., 011464, Bucharest, rmadjar@yahoo.com, Romania
Abstract
The aim of the research was to evaluate the quality of drinking water from five
private wells (W1-W5) located in Negresti-Cobadin, Constanta County, Romania.
The evaluation consisted in determination of some specific parameters as pH,
electrical conductivity (EC), total hardness (TH), ammonium, nitrate and nitrite
concentrations and oxidisability index. The results were compared with quality
standards for drinking water imposed by Council Directive 98/83/EC and also with
Romanian legislation. The pH, EC, nitrite and ammonium levels for all water
samples are within recommended ranges. The TH values are higher and range
between 27.41 and 47.14 mg CaO/L. Concerning nitrate levels, it is noteworthy to
mention that excepting W4 sampling point, all water samples exceeded (as average)
maximum admitted level. Oxidisability parameter indicates for wells W1-W4 values
were below 5 mg O2/L, meanwhile in the case of W5 found value exceeded slightly
limit value.
Keywords: conductivity, nitrate, nitrite, pollution, water.
Introduction
Protecting the quality of drinking water is a major challenge considering that the
presence of undesirable pollutants may be unacceptable due to their health effects
and decrease of water quality. Among the contaminants of water, nitrate and nitrite
species occupy an important place and is a common problem in many parts of the
world and it is generated by agriculture (fertilizers and manure), domestic activities,
municipal wastewater and sludge, septic systems (Scaeteanu et al 2014). The main
manifestation of high nitrate levels in drinking water or food is methemoglobinemy,
which appears mainly to babies or to elder people (Santamaria 2006).
Given that drinking water quality is an actual and astringent problem and the
presence of some chemical species above limits are harmful for human health, it was
evaluated some specific parameters (pH, electrical conductivity (EC), total hardness
(TH), nitrate, nitrite, ammonium, oxidisability) for well water samples collected
from Negresti-Cobadin, Constanta County, Romania, during 2016-2017.
Measurement of various water quality parameters provides information to facilitate
protection of the community health, to investigate and identify pollution sources.
Monitoring long-term trends in source water quality leads to prepare for future
challenges of regulations.


Water samples were collected from five wells (labelled W1-W5) located in
Negresti-Cobadin, Constanta County, Romania. The samples were collected from
wells during three sampling campaigns: S1 (October 2016), S2 (January 2017) and
S3 (April 2017). Selected wells represent sources of drinking water and are used
also for domestic usage as cooking, washing, etc. It was analyzed 15 water samples
in triplicate (5 wells x 3 sampling moments) and the results are average of the
determinations. All samples were collected in polyethylene bottles rinsed with
sample water before collection and were carried to the laboratory where were stored
at 4oC to avoid possible degradation of chemical species that are present in water.
Chemical analyses were conducted within 48 hours of collection. A presentation of
the analyses, methods and apparatus used for analytical determination of the
subjected parameters are presented elsewhere (Scaeteanu & Madjar 2017).
The experiment was designed as a bifactorial one and the studied factors are: A
factor - the location and B factor - the sampling moment.

The obtained results (as average of determinations) are presented in Table 1.
Table 1. The average values of the quality parameters for well water
Well pH EC TH NO3- NO2- Oxidisability
S/cm (mg CaO/L) mg/L mg/L mg O2/L
W1 7.12 1343 28.33 64.23 0.048 2.52
W2 7.25 1505 32.10 145.31 0.082 2.37
W3 7.21 1274 30.90 50.46 0.020 1.89
W4 7.04 1124 27.41 19.55 0.019 2.16
W5 7.18 2207 47.14 235.56 0.110 5.22
Limits 6.5-9.5* 2500* min.5* 50* 0.5* 5*
20-30**
*According to Official Journal of the European Communities, Council Directive
98/83/EC (1998) and to Law no. 458/2002 (2011); **STAS 1342/1991
The influence of location (A factor) and sampling moment (B factor) on pH value

from water samples collected from Negresti –Cobadin, Constanta County
The average of the determinations for pH parameter is between 7.04 and 7.25, these
values being within limits imposed by legislation (6.5-9.5). There are no significant
differences between W2, W3 and W5 sampling points and significant as against W1
and W4. The results of the analyses indicate a neutral to slightly alkaline reaction for
analyzed water samples. The influence of the sampling moment on pH average
values indicates significant differences with the highest value in S3 moment (7.64).
Similar pH values for well water collected from Patarlagele and Paltinis villages,
Buzau County (Senila et al 2017) and Maneciu-Ungureni, Prahova County
(Scaeteanu & Madjar 2017) were reported. According to literature, drinking water
should be almost neutral with pH values between 6.8-8.5 (Cohl et al 2014).

Table 2. The influence of location (A factor) and sampling moment (B factor) on

pH value from water samples
B
A S1 S2 S3 Average A
W1 a6.80b a7.20a b7.37a b7.12
W2 a6.85c a7.15b a7.75a a7.25
W3 b6.64c a7.27b a7.72a a7.21
W4 b6.54c b6.95b a7.63a b7.04
W5 b6.60c a7.22b a7.74a a7.18
Average B 6.69c 7.16b 7.64a
Average A: LSD 5%= 0.10* ; LSD 1%=0.15; LSD 0.1%=0.23
Average B: LSD 5%= 0.08*; LSD 1%=0.11; LSD 0.1%=0.16
1
B constant A variable: LSD 5%= 0.18*; LSD 1%=0.25; LSD 0.1%=0.35
2
A constant B variable: LSD 5%= 0.19*; LSD 1%=0.26; LSD 0.1%=0.36
There were made interpretations by LSD 5% indicated in the table by “*”
1
Means with different letters in a column (in front of data) are significant different.
2
Means with different letters in a row (in back of data) are significant different.
The influence of location (A factor) and sampling moment (B factor) on EC value

The average values of EC (S/cm) for analyzed water samples indicate significant
differences for all sampling points, the highest average value being encountered for
W5 (2207 S/cm), but lower than maximum admitted limit (2500 S/cm).
Table 3. The influence of location (A factor) and sampling moment (B factor) on EC

(µS/cm) value from water samples
B
W1 c1366a c1375a c1288b c1343
W2 b1472b b1545a b1497b b1505
W3 d1288a d1295a d1239b d1274
W4 e1129a e1109b e1135a e1124
W5 a1733b a1748b a3140a a2207
Average B 1398c 1414b 1660a
Average A: LSD 5%= 10.44*S/cm ; LSD 1%=15.19S/cm; LSD 0.1%=22.83 S/cm
Average B: LSD 5%= 9.73* S/cm; LSD 1%=13.27 S/cm; LSD 0.1%=17.95S/cm
1
B constant A variable: LSD 5%= 19* S/cm; LSD 1%=27 S/cm; LSD 0.1%=37 S/cm
2
A constant B variable: LSD 5%= 22* S/cm; LSD 1%=30 S/cm; LSD 0.1%=40S/cm
1
2
Significant differences are given by sampling moment, but with average values
lower than 2000 µS/cm, excepting S3 sampling moment for W5 sampling point
(3140 µS/cm). Similar results were reported for well water collected from Buzău
County (Senila et al 2017), meanwhile much lower values for EC were found for
water samples collected Prahova County (Scaeteanu & Madjar 2017).

The influence of location (A factor) and sampling moment (B factor) on TH value

The values for TH parameter is between 28.33 and 47.14 mg CaO/L, higher than the
minimum value of 5 mg CaO/L imposed by legislation (Law no. 458/2002 2011),
with no significant differences between W1, W2, W3 and W4 but with significant
differences as against W5. The influence of the sampling moment on TH average
values indicates significant differences, the highest value being encountered in S3
for W5 (67.08 mg CaO/L), 2.23 times higher than recommended value of 30 mg
CaO/L. This result is concordance with slightly alkaline reaction of water samples.
Drinking water with high total hardness may produce nephrolithiasis, influence iron
absorption or produce laxative effects. Also, the degree of water hardness is
correlated with aesthetic acceptability by consumers (WHO 2011).

TH (mg CaO/L) value from water samples
B
W1 a37.63a a28.00b c19.37c b28.33
W2 a43.45a a27.32b b25.53b b32.10
W3 a40.76a b23.96b b28.00b b30.90
W4 a38.08a b19.26b b24.91b b27.41
W5 a40.32b a34.03c a67.08a a47.14
Average B 40.05a 28.51c 32.98b
Average A: LSD 5%= 5.14* mgCaO/L; LSD 1%=7.49 mgCaO/L; LSD 0.1%=11.25
mgCaO/L
Average B: LSD 5%= 3.64* mgCaO/L; LSD 1%=4.97 mgCaO/L; LSD 0.1%=6.73
mgCaO/L
1
B constant A variable: LSD 5%= 7.68* mgCaO/L; LSD 1%=10.73 mgCaO/L; LSD
0.1%=15.10 mgCaO/L
2
A constant B variable: LSD 5%= 8.15* mgCaO/L; LSD 1%=11.12 mgCaO/L; LSD
0.1%=15.05 mgCaO/L
1
2
The influence of location (A factor) and sampling moment (B factor) on nitrate

levels from water samples collected from Negresti –Cobadin, Constanta County
The average content for nitrate in water samples indicate significant differences with
concentrations higher than limit value of 50 mg/L for four sampling points (W1,
W2, W3, W4). The highest average value is 235.56 mg/L for W5, this being 4.71
times higher than maximum admitted level. The influence of sampling moment on
average values indicates significant differences with concentrations that exceed the
limit value. The highest concentration is 141.30 mg/L for S3, for this sampling
moment being found also the value 400.17 mg/L for W5, 8 times higher than
maximum admitted level. The lowest concentrations are recorded for W4, with an
average of 19.55 mg/L and the sample collected at S3 present the lowest nitrate level
of 16.90 mg/L.
A study developed in Romania during 2009 (Tudor & Staicu 2009) revealed that
58% from reported cases of infant methemoglobinemy appeared when consumed
well water was 101-500 mg /L nitrate-contaminated. Also, 20% of cases were

reported when nitrate levels were between 0-50 mg/L.

nitrate levels (mg/L) value from water samples
B
W1 c61.10b c76.35a c55.25c c64.23
W2 b110.83c b139.78b b185.34a b145.31
W3 d51.05a d51.49a d48.86b d50.46
W4 e21.32a e20.44a e16.90b e19.55
W5 a158.23b a148.29c a400.17a a235.56
Average B 80.51c 87.27b 141.30a
Average A: LSD 5%= 2.35* mg/L; LSD 1%=3.43 mg/L; LSD 0.1%=5.15 mg/L.
Average B: LSD 5%= 0.65* mg/L; LSD 1%=0.88 mg/L; LSD 0.1%=1.20 mg/L.
1
B constant A variable: LSD 5%= 2.07* mg/L; LSD 1%=2.97 mg/L; LSD 0.1%=4.38 mg/L.
2
A constant B variable: LSD 5%= 1.45* mg/L; LSD 1%=1.98 mg/L; LSD 0.1%=2.68 mg/L.
1
2
The influence of location (A factor) and sampling moment (B factor) on nitrite

levels from water samples collected from Negresti –Cobadin, Constanta County
The influence of location on nitrite concentrations indicates no significant
differences between W3 and W4 and significant as against the other locations. The
found values are between 0.019-0.110 and are below limit value of 0.5 mg/L. The
influence of sampling moment an average values present significant differences with
values that are below limit value, the highest concentration (0.169 mg/L) being
found in the case of W5 at S3 sampling moment.
Having in view the cumulative hazardous effect of the simultaneous presence nitrate
and nitrite in drinking water according to Council Directive 98/83/EC, there must be
ensured the relation: [nitrate]/50 + [nitrite]/3≤ 1, where the square brackets represent
the concentrations in mg/L for both species. The results in our study conducted to
the following values: 1.30 for W1, 2.93 for W2, 1.01 for W3, 0.39 for W4, 4.74 for
W5. As it may be observed, for W1, W2, W3 and W5 the calculated parameter
exceeded the limit value, the highest value being found in the case of the well with
highest nitrate and nitrite levels.
There are many studies that deal with nitrate and nitrite levels found in well water
collected from different areas in Romania. Extreme values of nitrate, higher than
300 mg/L were reported for Matca (Galati County), Sahateni (Buzau County) and
Clinceni (Ilfov County) (Pele et al 2010). Concerning nitrite, values above 0.5 mg/L
were detected in well water from Matca (Pele et al 2010). Also, in well water from
Ozun village (Covasna) nitrate levels exceeded the limit value even 3 times,
meanwhile nitrite concentrations were within safe limit (Raduly & Farkas 2017).


nitrite levels (mg/L) value from water samples
B
W1 b0.074a b0.050b d0.020c c0.048
W2 c0.038c a0.074b b0.134a b0.082
W3 e0.010b c0.023a c0.028a d0.020
W4 d0.029a c0.018b e0.011c d0.019
W5 a0.109b b0.053c a0.169a a0.110
Average B 0.052b 0.044c 0.072a
Average A: LSD 5%= 0.005* mg/L; LSD 1%=0.007 mg/L; LSD 0.1%=0.011 mg/L.
Average B: LSD 5%= 0.002* mg/L; LSD 1%=0.003 mg/L; LSD 0.1%=0.004 mg/L.
1
B constant A variable: LSD 5%= 0.005* mg/L; LSD 1%=0.008 mg/L; LSD 0.1%=0.012
mg/L.
2
A constant B variable: LSD 5%= 0.005* mg/L; LSD 1%=0.0071 mg/L; LSD
0.1%=0.0103 mg/L.
1
2
There are many studies that deal with nitrate and nitrite levels found in well water
collected from different areas in Romania. Extreme values of nitrate, higher than
300 mg/L were reported for Matca (Galati County), Sahateni (Buzau County) and
Clinceni (Ilfov County) (Pele et al 2010). Concerning nitrite, values above 0.5 mg/L
were detected in well water from Matca (Pele et al 2010). Also, in well water from
Ozun village (Covasna) nitrate levels exceeded the limit value even 3 times,
meanwhile nitrite concentrations were within safe limit (Raduly & Farkas 2017).
The influence of location (A factor) and sampling moment (B factor) on oxidisability
(mg O2/L) from water samples collected from Negresti –Cobadin, Constanta County
Oxidisability parameter indicates water pollution and is expressed as amount of
oxygen that oxidize organic species. Clean water usually has oxidisability between
2-4 mg O2/L (Cohl et al 2014).

oxidisability parameter (mg/L) from water samples
B
W1 b2.16b b2.80a b2.61a b2.52
W2 b2.08c c2.32b b2.70a b2.37
W3 c1.92a d2.00a c1.76b d1.89
W4 c1.84b b2.80a c1.84b c2.16
W5 a4.40b a3.20c a8.07a a5.22
Average B 2.48c 2.62b 3.40a
Average A: LSD 5%= 0.15* mg O2/L; LSD 1%=0.22 mg O2/L; LSD 0.1%=0.34 mg O2/L
Average B: LSD 5%= 0.10* mg O2/L ; LSD 1%=0.13 mg O2/L ; LSD 0.1%=0.18 mg O2/L
1
B constant A variable: LSD 5%= 0.21* mg O2/L; LSD 1%=0.30 mg O2/L; LSD 0.1%=0.43 mg O2/L
2
A constant B variable: LSD 5%= 0.22* mg O2/L; LSD 1%=0.30 mg O2/L; LSD 0.1%=0.41 mg O2/L
1
2
The average values for oxidisability parameter indicate no significant differences for
W1 and W2 and significant as against W3, W4 and W5 with values between 1.89-
5.22 mg O2/L. For one well was found a slightly higher value (5.22 mg O2/L) than
limit (5 mg O2/L). The influence of the sampling moment on average values
indicates significant differences with values lower than imposed limit. The highest
value is found for W5 at S3 (8.07 mg O2/L), 1.61 times higher than limit value. The
lowest values were encountered for W3 (1.89 mg O2/L, as average), the sample
collected from W3 at S3 presenting the lowest oxidisability value (1.76 mg O2/L).
Conclusions
The main objective of the research was to monitor water quality parameters such as
pH, electrical conductivity (EC), total hardness (TH), oxidisability, nitrate, nitrite
and ammonium concentrations in wells located in Negresti–Cobadin, Constanta
County during 3 sampling campaigns (during 2016-2017) from 5 wells. The results
of the analyses led to the conclusions presented below:
The pH and EC for all water samples are within reccomended ranges, 6.5-9.5 pH
units and 2500 S/cm, respectively.
The TH values are higher and range between 27.41 and 47.14 mgCaO/L (as
average), these values being often encountered for well water.
Violations of the parametric value for nitrate (50 mg/L) imposed by European and
Romanian legislation were detected for a large number of water samples (73.33%
from total). Excepting W4 sampling point, all water samples exceeded (as average)
maximum admitted level. For W5 the found value was 4.71 times higher than limit
value.
Nitrite levels were below maximum admitted level, the highest average
concentration (for W5) being 4.54 times lower than limit value (0.5 mg/L).
Ammonium levels for all sampling points and sampling moments were below
detection limit of the method.
Oxidisability parameter for wells W1-W4 presented values below 5 mg O2/L,
meanwhile in the case of W5 found value exceeded slightly limit value (5.22 mg
O2/L, as average).
As a general conclusion, the values of some subjected parameters (pH, conductivity)
are similar with those already reported for other areas (Maneciu-Ungureni, Prahova
County, Patarlagele and Paltinis villages, Buzau County). Nitrate contents of W1-
W4 analyzed water samples are similar with those found for water collected from
Clinceni, meanwhile for W5 nitrate concentrations are comparable with those found
for some wells located in Sahateni. The identified values of nitrite are similar with
those reported for Branesti but higher than those from Sahateni. Oxidisability
parameter determined in this study presents values higher than those reported for
Maneciu-Ungureni, Prahova County (1.33-2.61 mgO2/L).
References
Cohl, M, Lazar, L & Balasanian, I 2014, 'Study on the quality of water supply
sources for Iași city, Romania', Environmental Engineering and Management
Journal, vol. 13, no.9, pp 2301-2310.
Law 458/2002 (r1) 2011, regarding drinking water quality, republished and amended
by Order no 22/2017. In Romanian.

Official Journal of the European Communities, Council Directive 98/83/EC 1998,

on the quality of water intended for human consumption.
Pele, M, Vasile, G & Artimon, M 2010, 'Studies regarding nitrogen pollutants in
well waters from Romania', Scientific Papers UASMV Bucharest, Series A,
Agronomy, vol. LIII, pp 145-151.
Raduly, OC & Farkas, A 2017, 'Nitrate, nitrite and microbial denitrification in
drinking water from Ozun village (Covasna County, Romania) and the
association between changes during water storage', Studia Universitatis Babes-
Bolyai Biologia, vol. LXII, no. 1, pp 17-28.
Santamaria, P 2006, 'Nitrate in vegetables-toxicity, content, intake and EC
regulation', Journal of the Science of Food and Agriculture, vol. 86, pp 10-17.
Senila, M, Micu, D, Hoaghia, A, Levei, E, Cadar, O, Kucsicsa, G & Balteanu, D
2017, 'Multivariate statistical analysis of water chemistry in wells from Sub-
Carpathians of Curvature, Romania', AES Bioflux, vol. 9, no.1, pp 64-71.
Tudor, A & Staicu, C 2009, 'Methemoglobinemia acuta infantila generata de apa de
fantana în anul 2009', National report.
Scaeteanu Vasile, G & Madjar, RM 2017, 'Evaluation of well water quality collected
from Maneciu-Ungureni, Prahova County, Romania', SGEM 2017 Vienna
GREEN Conference Proceedings, vol. 17, no.33, pp 151-162.
Scaeteanu Vasile, G Madjar, RM, Penescu, A, Dinca, EP &Terzea, IA 2014, 'Nitrate
monitoring in private wells from Prahova District', Scientific Papers Series A,
Agronomy, vol. LVII, pp 68-73.
WHO 2011, Hardness in drinking-water. Background document for development of
WHO Guidelines for Drinking-water quality.

ASSESSMENT OF DRINKING WATER QUALITY FROM TREATMENT

PLANTS AND CONSUMERS
Mariana Popescu1,2, Diana Puiu1,3, Madalina Mihalache1,4, Vasile Ion Iancu1,4*, Marius
Simion1,4, Marcela Antoaneta Niculescu1, Daniel Manolache1,4, Liliana Cruceru1
1
National Research and Development Institute for Industrial Ecology-ECOIND, 71-73
Drumul Podu Dambovitei, district 6, 060652, Bucharest, *vasileiancu10@gmail.com, Romania
2
Titu Maiorescu University of Medicine and Pharmacy, Faculty of Pharmacy, 22
Dambovnicului, 040441, Bucharest, Romania
3
University of Bucharest, Faculty of Biology, 91-95 Splaiul Independenei, 050095, Bucharest,
Romania
4
University Politehnica Bucharest, Faculty of Applied Chemistry and Materials Science, 1-7
Polizu Street, 011061, Bucharest, Romania
Abstract
The present study investigated the quality of potable water that was taken from the
treatment plants in three counties from Romania (Ialomița, Gorj and Tulcea) for a
two-year period (2016 and 2017). A series of organic and inorganic indicators have
been analyzed in the drinking water from the respective locations.
Out of the 37 samples collected in Ialomița county in 2016, the following indicators
have exceeded the maximum admissible concentrations (MAC): sodium in 8% of
the total samples, nitrogen in 38%, copper in 27%, manganese in 5%, iron, nickel
and chromium in 3% of the samples. In Gorj County, samples from 25 locations
were analyzed during 2017. Exceedings of MAC were recorded for hardness in 36%
of the samples, for boron in 16%, for ammonium, iron and manganese in 12%, for
sodium and for chloride in 4% of samples. In 2017 a total of 33 samples were
analyzed in Tulcea County; the following indicators have exceeded MAC
trihalomethanes and iron in 3% of samples and manganese and fluorides in 9% of
samples.
For the analyzed indicators that exceeded the maximum admissible concentrations a
database including the physical-chemical characteristics of drinking water at the exit
from the treatment plants was created.
Keywords: admissible values, drinking water, physical-chemical indicators,

treatment plants
Introduction
The term commonly used for water intended for human consumption is drinking
water. This is considered to be any type of water in its natural state or after
treatment, which is used for drinking, food preparation or other domestic purposes,
regardless of its source and its providing through distribution network, tanks, bottles
or other types of containers (Ordinance no. 22/2017).
In order to obtain drinking water in accordance with the requirements of the law in
force, used for human or industrial consumption, it is necessary that surface,
underground and marine waters to be treated in order to remove impurities and
pollutants of organic and inorganic origin, microorganisms existing in water
naturally occurring or due to accidental pollution (Radulescu 2017, Spataru 2017); it

is not to be neglected the contribution due to the level of air pollution by the intake
of wet and dry deposits (Petrescu et al 2017, Bucur et al 2010).
A drinking water required for human or industrial consumption, in order to meet
quality standards, must be treated by a succession of operations and unit processes,
where the degree of treatment varies function of the quality of the source used and
the requirements of the consumer (Galaon et al 2017).
A drinking water is considered to be of adequate quality when the set values for the
tested parameters (microbiological and physical-chemical indicators) are in
accordance with the maximum admissible concentrations (MAC) imposed by
legislation for different types of sampling points (distribution network, the
consumers tap, points where water is taken up in various production processes)
(Ordinance 22/03.09.2017)

Sampling
During 2016, samples of drinking water were collected and analyzed from a number
of 37 locations in Ialomita county. In 2017, in Gorj County, a number of 25 samples
were taken, while in Tulcea County a number of 33 samples were taken from
different sampling locations. Samples were collected in glass or plastic recipients
function of the organic or inorganic nature of the tested parameters.
Methods
For all samples, a series of organic and inorganic indicators were analyzed by
standardized physical-chemical methods: arsenic, benzene, benzo (a) pyrene, boron,
bromate, cadmium, total cyanide, free cyanide, total chromium, 1,2-dichloroethane,
fluoride, PAH, mercury, nickel, nitrate, nitrite, total pesticides, organochlorine
pesticides, organophosphate pesticides, triazine pesticides, lead, selenium, antimony,
tetrachloroethene, trichloroethene, trihalomethanes, aluminum, ammonium, total
organic carbon (TOC), chlorine, free residual chlorine, conductivity, color, total
hardness, iron, manganese, oxidation (CCO-Mn permanganate index), pH, sodium,
sulfates, sulfides, hydrogen sulphide, turbidity and zinc.
Results and discussions

For the 37 samples taken in 2016 in Ialomița county, most of the analyzed indicators
were situated below the maximum admissible concentrations imposed by the
Ordinance no. 22/2017 for amending and completing the Law no. 458/2002 on the
quality of drinking water. Exceedances were recorded for nitrates (in 38% of
samples), sodium (in 8% of samples), copper (in 27% of samples), manganese (in
5% of samples), iron, nickel and chromium (in 3% of samples). In fig. 1 are
represented the exceedances of the maximum admissible concentrations for nitrates,
sodium, copper, manganese, iron, nickel and chromium for the corresponding
locations.

Nitrates
Sodium Copper
Iron Manganese
Nickel Chromium
Figure 1. Exceeding maximum admissible concentrations for nitrates, sodium,
copper, iron, manganese, nickel and chromium in samples from Ialomita county
In 2017, samples were taken from 25 locations in Gorj County. Most of the analyzed
indicators were situated below the maximum admissible concentrations given by
quality of drinking water. Higher values than the maximum admissible
concentration were recorded for hardness, ammonia, iron, manganese, sodium and
chloride. The total hardness was below the admissible limit in 36% of the samples.
Exceedances of the maximum admissible concentration were recorded for
ammonium and boron in 16% of samples, iron and manganese 12% and sodium and
chlorides for 4% of the total of 25 samples. In fig. 2, are represented the non-
compliance results compared with the law values for total hardness, ammonium,
iron, manganese, sodium, chloride and boron corresponding to the related locations.

Total hardness
Ammonium Boron
Iron Manganesse
Sodium Chlorides
Figure 2. Exceeding maximum admissible concentrations for total hardness,
ammonium, boron, iron, manganese, sodium and chlorides in samples from Gorj
county
Most of the indicators analyzed for the 33 samples taken in 2017 in Tulcea County
were situated below the maximum admissible concentrations under Ordinance no.
22/2017 for amending and completing the Law no. 458/2002 on the quality of
drinking water. Overdosed values were recorded for manganese and fluorides at 9%
of samples, trihalomethanes and iron in 3% of samples. Fig. 3 shows the exceedance
of the maximum admissible concentrations for trihalomethanes, fluorides, iron and
manganese corresponding to their respective locations.

THM Fluoride
Manganese Iron
Figure 3. Exceeding maximum admissible concentrations for trihalomethanes, iron,
manganese and fluorides in the mentioned locations
Conclusions
Following the monitoring of drinking water quality in Ialomița, Gorj and Tulcea
counties,the majority of the analyzed organic and inorganic indicators from the
drinking water samples studied were below the maximum admissible limits
stipulated by the Ordinance no. 22/2017 for amending and completing the Law no.
458/2002 on the quality of drinking water.
For all locations in the three counties (Ialomita, Gorj and Tulcea) where exceedances
of the maximum admissible values for different indicators were found, for exemple
sodium, iron and manganese, the waters do not meet the drinking standards.
References
Bucur, E, Ionita, L, Petrescu, M 2010, 'Consideration concerning impact assessment
of pollution with breathable PM 2.5 particulate matters. Part 1. Pollution
monitoring in urban areas with intense road traffic, Journal of Environmental
Protection and Ecology, vol. 11, no. 3, pp. 809-814.
Galaon, T, Petre, J, Iancu, V, Cruceru, L, Niculescu, M, Chiriac, LF, Puiu, DM &
Mihalache, M 2017, 'Detection of cytostatic drugs in municipal waste water
and their transfer to surface water', 20th International Symposium "The
Environment and The Industry", SIMI 2017, National Research and
236.
quality of drinking water.
Petrescu, M, Bucur, E, Diodiu, R, Bratu, M, Serbanescu, A, Barbu, ME 2017,
'Chemical characterization of wet depositions in urban and rural area', 20th
International Symposium "The Environment and The Industry", SIMI 2017,
Radulescu, V 2017, 'Control of inorganic and organic contamination, asessment of

water quality in hydropower lakes on Jiu river', 20th International Symposium
"The Environment and The Industry", SIMI 2017, National Research and
228.
Spataru, P 2017, 'Influences of organic ammonium derivatives on the change of
concentrations of NH4+, NO2-, NO3- in river water', 20th International
Symposium "The Environment and The Industry", SIMI 2017, National

COMPARATIVE STUDY REGARDING THE ANALYSIS OF THE METALS

CONTENTS FROM BIOMASS WASTES THROUGH DIFFERENT
METHODS OF DIGESTION
Gina Alina Traistaru (Catrina)1, Agnes Serbanescu1, Mona Barbu1, Ileana Nicolescu1, Nicolae
Ionut Cristea1, Bogdan Stanescu1, Ileana Cristina Covaliu2
1
National Research and Development Institute for Industrial Ecology - ECOIND, 71-73
Drumul Podu Dambovitei, district 6, 060652 Bucharest, evmt@incdecoind.ro, Romania
2
University Politehnica of Bucharest, Faculty of Biotechnical Systems Engineering, 313
Splaiul Independentei Street, Bucharest, cristina_covaliu@yahoo.com, Romania
Abstract
The paper presents the characterization of the content of metals from three different
waste biomass using ICP-MS and AAS techniques. The purpose of the study was to
finding an appropriate method of analysis for the complex matrix of waste biomass
by comparing two methods of digestion using a closed system (microwave) and an
open system (sand bath).
For this study were analyzed six metals (Al, Mg, K, Ca, Na, Fe) in three different
waste samples from agriculture, forestry and related industries (horticultural and
wine waste).
It was observed that the highest concentrations of metals were recorded for the
sample P3 horticultural and wine waste through both analysis techniques.
The results obtained were compared with a certified reference material (CRM) and
value to demonstrate the precision of the method and the quality of the results.
The concentration obtained for Al, Mg, K, Ca, Na and Fe by microwave digestion in
a closed system analyzed using ICP-MS technique were better than the AAS
technique. The method of analysis chosen in this study was emphasized as being
optimal for the analysis of biomass waste using performance parameters: precision,
accuracy, detection limit, quantification limit and extended uncertainty.
From the obtained results it can be said that the method of digestion by using
microwave systems of the metals` analysis from biomass waste is within the desired
purpose.
Keywords: AAS, biomass waste, ICP-MS, major elements, solid biofuels
Introduction
Sustainable management of solid waste is a priority for all the countries. A
significant increase in municipal solid waste and beyond is one of the main
environmental problems in all developed countries and developing countries (Chen
et al 2018). The waste composition is very important in terms of management as
waste must be collected, transported, exploited and eliminated separately (Arama &
Kim 2016). Classification of waste in a category of waste: inert, non-dangerous and
dangerous waste is depending on its composition (Guta et al 2017).
According to the European legislation, preventing the waste generation and
performing an adequate management (recovery/disposal) is a strategy focusing on

the prioritization of practical actions taking into account the sustainable

development principles (Arama & Kim 2016). The term “waste” means any solid,
liquid or contained gaseous material that is discharged by being disposed of, burned,
incinerated or recycled (Puiu & Cruceru 2016). Biomass fuels usually contain high
levels of alkali/alkaline metals, in particular potassium, and high chlorine content, as
well as low sulphur concentrations, which make the deposition of corrosive ash in
biomass-fired boilers a more severe issue than that in traditional coal-fired boilers
(Lalak et al 2016). Biomass is the biodegradable fraction of agricultural residues (of
plant and animal), forestry residues and co-products of wood, residues from related
industrial sectors and products energy crops (Grigore 2016). Biomass ensure energy,
construction materials, paper, fabrics, medicines and chemicals. Currently biomass
fuel is used both for room heating and electricity production (Grigore 2016). By
determining the metal content of a waste biomass the amount of ash resulting in a
power plant after the combustion process can be estimated. The amount of ash may
influence the wear of a combustion plant. In literature there are presented a number
of methods of preparing samples of waste, in order to determine the heavy metals in
them, such as digestion in open systems and closed systems (microwave),
combustion, extraction with ultrasound and solvents dilution (Kim et al 2017).
This study shows two experimental models of characterization and analysis of
content of the major elements (Al, Mg, K, Ca, Na and Fe) from the biomass waste.
We have used two metal analysis techniques such atomic absorption spectrometry
(AAS) and inductively coupled plasma mass spectrometry (ICP-MS). The best
method of analysis was emphasized with performance parameters.

All the chemicals were of analytical reagent grade (Merck quality).
To examine the optimal method, a Soy Bean Meal B2271 certified reference
material was used. To determine the calibration plot of the metals content was used a
standardization method (EN ISO 16967: 2015).
For the mineralization of waste samples in a closed system (microwave) was used a
Milestone Up Ethos equipment.
The metal concentrations were determined in comparison with the techniques: mass
spectrometer with inductively coupled plasma (ICP-MS) and atomic absorption
spectrometer (AAS). For the ICP-MS analysis was used a Bruker Aurora M90
equipment and for the AAS analysis was used a Perkin Elmer Pin AAcle 900T
equipment.
To accomplish the study were selected three types of biomass waste coming from
agriculture (P1), forestry (P2) and related industry (waste horticultural and wine)
(P3). To determine the metals content of the three samples were used two methods
of digestion for the decomposition of organic matter.
To verify the performance parameters was selected the waste from industries related
P3 sample due to high content of metals in this sample than the other two samples.
The performance parameters of the study were: the precision, accuracy,
quantification limit, detection limit and extended uncertainty for the P3 sample of
the six metals. The waste biomass was dried and crushed under 1mm.
In method I, the samples were digested in microwave system (closed system): 0,25 g
of sample was weighed and was added to 2 mL H2O2 and 8 mL of HNO3. The
samples were introduced into the digester for digestion at 1800C for 15 minutes
under method I. Digestion parameters used were those of the cook book of the
digester equipment.
In method II, the samples were digested in a sand bath: 8 ml of HNO3 and 1 g of
sample with 2 ml of H2O2 for 90 minutes at 1200C.
Determination of metals from biomass samples was performed by inductively
coupled plasma mass spectrometry (ICP-MS) in concentrations range from 10-50
µg/L and by atomic absorption spectrometry (AAS) in the range of concentrations
from 0,1 to 0,5 mg/L. The results were reported in mg/kg.
For each sample were performed three folds and the obtained concentration was the
average of three determinations.

Performance parameters
There were performed ten determinations for the repeatability and precision,
quantification limit, detection limit and extended uncertainty for each metal
concentrations in part to the 10-50 µg/L and 0,1-0,5 mg/L for the sample (P3) from
related industries.
The results of the performance parameter in the case P3 sample (related industries)
are shown in tables 1 and 2.
Table 1. Performance parameters for the P3 sample by ICP-MS technique

Detection Extended
Major Precison Accuracy limit Quantification uncertainty
elements (mg/kg) (mg/kg) (mg/Kg) limit (mg/kg) (%)
Al 0.29 1.29 0.88 2.92 12.40
Mg 0.29 1.37 0.87 2.90 12.51
Ca 0.24 1.20 0.73 2.44 10.18
K 0.30 1.84 0.91 3.03 14.53
Na 0.30 1.22 0.93 2.10 12.97
Fe 0.30 1.34 0.91 3.04 13.07
Table 2. Performance parameters for the P3 sample by AAS technique

Detection Extended
Major Precison Accuracy limit Quantification uncertainty
elements (mg/kg) (mg/kg) (mg/Kg) limit (mg/kg) (%)
Al 1.45 3.51 4.34 14.47 16.55
Mg 1.58 4.27 4.73 15.75 18.84
Ca 1.63 4.52 4.90 16.32 19.81
K 1.61 3.77 4.82 16.07 18.66
Na 1.77 4.05 5.31 17.71 20.90
Fe 1.71 3.60 5.13 17.08 19.65
The results in Table 1 and Table 2 show that the detection and quantification limits
present the lowest limits for the ICP-MS technique compared to AAS technique.
ICP-MS technique shows a high sensitivity for complex matrices of biomass wastes.
It can be concluded that the performance parameters studied in this work fit the
intended purpose only for the ICP-MS technique.
Method I of digestion
The results obtained by the method I for the three-biomass waste samples are shown
in Figures 1 and 2.
In method I, the digestion of samples were conducted in a closed system in a

digester equipment at a temperature of 1800C. The P3 waste sample is a complex
matrix composed of a mixture of grape seed, grape vine shoots, leaves and fruit of
the trees. Since the matrix is very complex, hydrogen peroxide was introduced in the
digestion step to remove chlorine and sulphur from the waste biomass composition.
By eliminating the interference, we managed to obtain better results using ICP-MS
technique.
Figure 1. The results obtained from method I digestion using ICP-MS technique for
the three waste samples
In figure 1 it is observed that aluminium is the predominant component in samples

P1 and P3 (horticultural waste and wine), followed by magnesium, calcium,
potassium, sodium and iron. Iron is present in very small quantities in all three
samples (Figure 1). In P2 sample the predominant component is the magnesium
concentration followed by calcium, potassium, sodium, aluminium and iron. The
highest concentrations of metals were determinated for P3 sample, from
horticultural and wine waste (Figure 1).
Figure 2. The results obtained from method I digestion using AAS technique for the
three waste samples
In Figure 2 it was observed that the P3 biomass waste sample shows higher content
of metals compared to the other two samples of waste by the microwave digestion in
closed systems (method I). In P3 waste sample the major component is aluminum
followed by magnesium, calcium, potassium, sodium and iron. The decreasing order
of metals content for the P1 sample is: Mg>Al>Ca>K>Na>Fe.
For the P2 sample the decreasing order of metals content is: Mg>Ca>K>Na>Al>Fe
(Figure 2).
Method II of digestion
In method II of mineralization were recorded lower values of metals concentrations
compared to method I, for all the samples. The reason of these results is the
technique of digestion (in an open system on a sand bath) (Figure 3 and Figure 4).
Figure 3. The results obtained from method II digestion using ICP-MS technique
for the three waste samples
The major element for the P3 sample was calcium, followed by magnesium,
aluminum, potassium, sodium and iron.
As in method I, the iron shows the smallest concentrations in all three samples. In
P2 sample the decreasing order of metals content is: Mg>K>Ca>Na>Al>Fe (Figure
3). In P1 sample the decreasing order of metals content is: Ca>Mg>K>Al>Na>Fe.
Figure 4. The results obtained by method II digestion using AAS technique for the
three waste samples
The P3 sample presented high concentrations in all six metal elements. In P3 sample
the predominant component is calcium, followed by magnesium, aluminum,
potassium, sodium and iron. In P1 and P2 samples the decreasing order of metals
content are: Ca>Mg>K>Al>Na>Fe (Figure 4).
By comparing the two analysis techniques (ICP-MS and AAS) it was observed that
the highest concentrations of metals presents the P3 sample using the ICP-MS
techniques. It was recorded the smallest concentrations of iron with both analysis
techniques for all the samples.

The method of mineralization in an open system recorded lower values for all metal
concentrations of the three waste samples compared to the mineralization in a closed
system (microwave).
Results obtained for the MRC

Besides performance parameters studied in this paper, the obtained results were
compared with a certified reference material with the certificated values. Results for
the MRC obtained in the laboratory were reported in percentages to compare the
results with the analysis certificated for Soy Bean Meal B2271.
The results obtained for the MRC are presented in the Table 3.
Tabel 3. The results obtained for the MRC by ICP-MS and AAS
MRC obtained in MRC obtained in
Technical Analyzed MRC certificate the laboratory the laboratory
analysis element (%) (method I) (%) (method II) (%)
Al 0.0111 ±0.0004 0.010±0.0012 0.0070±0.0018
Mg 0.0039 ± 0.0004 0.003±0.0013 0.002±0.0019
K 2.47 ±0.22 2.11±0.0015 1.42±0.0021
ICP - MS Ca 0.33 ± 0.04 0.32±0.0010 0.30±0.0017
Na 0.02±0.25 0.019±0.0013 0.017±0.0020
Fe 0.0146 ±0.003 0.0144±0.0013 0.0140±0.0021
Al 0.0111 ±0.0004 0.0090± 0.025 0.0040± 0.033
Mg 0.0039 ± 0.0004 0.0020±0.0033 0.0019±0.0045
K 2.47 ±0.22 1.66±0.0036 1.01±0.0048
AAS Ca 0.33 ± 0.04 0.23±0.0035 0.21±0.0042
Na 0.020±0.25 0.013±0.34 0.011±0.44
Fe 0.0146 ±0.003 0.0130±0.0043 0.0100±0.0052
The results obtained for the MRC analyzed in the laboratory with ICP-MS were
satisfactory compared to the results obtained with AAS. We have obtained good
results using ICP-MS technique for the MRC compared to AAS analysis technique,
because of the sensitivity analysis techniques (Table 3).
Depending on the biomass composition, metals content can vary. Using the
mineralization method in a closed system (I) were obtained higher concentrations of
metal for all of the three waste samples compared to the open system mineralization
method (II).
Conclusions
The aim of this study was to characterize three different biomass wastes by two
digestion ways and two analysis techniques and to demonstrate the quality of the
results obtained in the laboratory by using a certified reference material. The metal
concentrations were recorded by AAS and ICP-MS techniques.
From all results of the samples it was observed that the highest concentrations of
metals showed P3 sample as compared to the other two samples. The predominant
elements were aluminum, calcium and magnesium and were analyzed by ICP-MS
and AAS. Iron concentrations are very low in all three samples using both methods
of analysis. The most efficient way to analyze the biomass waste is by microwave
digestion in a closed system and analyzing samples by ICP-MS. Interference from

the compounds of chlorine and sulphur coming from biomass waste was removed by
the addition of hydrogen peroxide in the sample mineralization step. Good and
reproducible results were obtained by digestion in a closed system at a temperature
of 1800C for 15 minutes and analysing the samples by ICP-MS technique. This
method of decomposition of organic matter is fast and safe. The results obtained by
microwave digestion (method I) sustained the application of this method for the
characterization of the metals` content from biomass waste.
Acknowledgements
This work was carried out through the Romanian Nucleu Programme, financed by the Ministry
of Research and Innovation, Project PN 18 05 04 01.
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ECOIND, Bucharest, pp. 189-196.
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V 2017, ’Experimental models of characterization and analysis of industrial
waste’, 20th International symposium “The Environment and The Industry”,
SIMI 2017 National Research and Development Institute for Industrial
Lalak, J, Martyniak, D, Kasprzycka, A, Żurek, G, Moroń, W, Chmielewska, M,
Wiącek, D & Tys, J, 2016, ‘Comparison of selected parameters of biomass
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Si, Na, Ti, Solid biofuels’.

CONSIDERATIONS REGARDING THE CONTROL OF BIOCHEMICAL

OXYGEN DEMAND AND CHEMICAL OXYGEN DEMAND FROM DEJ
WASTEWATER TREATMENT PLANT
Marius-Daniel Roman, Roxana Mare, Adriana Hadarean
Building Services Engineering Department, Technical University of Cluj-Napoca, Boulevard

128-130 December 21 Blvd., 400604, Cluj-Napoca, marius.roman@insta.utcluj.ro, Romania
Abstract
Biochemical Oxygen Demand (BOD) and Chemical Oxygen Demand (COD) are the
most commonly used parameters for the characterization of the organic pollution of
wastewaters. Both of these parameters have advantages and disadvantages and the
choice usually depends on many factors such as the time period required to
determine each one of them. It is essential to obtain a control between BOD and
COD for various wastewater treatment plants, to help in the design and operation of
these plants. In this paper the modelling results of BOD and COD for an aeration
tank from Dej wastewater treatment plant by Matlab/Simulink software program has
no significant difference, because the results are close enough to the real ones that
allow the user to make a good prediction regarding this parameters. A true validation
of these results, including experimental validation of simulations of the entire
collecting data was realistic.
Keywords: Biochemical oxygen demand, Chemical oxygen demand, wastewater,

simulation, parameters
Introduction
Wastewater is characterized in terms of physical, chemical and biological
composition (Hur et al 2010). Depending on the level of pollutants and local
regulations; physical, chemical and biological treatment may be used
(Tchobanoglous et al 2003, Cossu et al 2017). Before any wastewater can be treated,
it must first be characterized, because knowing the composition of the influent
wastewater is essential for successful design and operation of wastewater treatment
plants (Sincero & Sincero 2003). The impact of an effluent or wastewater discharge
on the receiving water is predicted by its oxygen demand (Sawyer et al 2003,
Ahmed et al 2013). The two most common parameters used to recognize the
composition of wastewater are the biochemical oxygen demand (BOD) and the
chemical oxygen demand (COD). BOD5 is a measure of how much dissolved
oxygen is consumed by aerobic bacteria in 5 days at 20̊C. It is the broad measure of
the strength of the organic matter in a waste stream. The typical range of BOD5 in
domestic wastewater ranges is between 100 to 300 mg/L. COD is chemical oxygen
demand and is measured chemically by digestion with acid. There exists a definite
correlation between the COD and BOD under certain conditions and by determining

the COD, the information about the BOD of the wastewater can be derived, but it is
highly waste dependent (Sawyer et al 2003, Khaled & Gina 2014, Henze et al 2000).
These two parameters have advantages and disadvantages and the choice usually
depends on many factors such as, the reproducibility of the determinations, time
period required location of the test (Evangelou et al 2017). COD analysis estimates
the amount of organic matter in wastewater in only three to four hours, rather than
the five days required by the BOD5 test and can be used as an alternative. COD
results are typically higher than BOD5 values and the ratio between them will vary
depending on the characteristics of the wastewater.
In this case for a model is important to have something representative in the design
and operation of wastewater treatment systems, it must be possible to evaluate
parameter values which are wastewater specific and to estimate concentrations of
important components in the influent (West & Dellana 2008). The first step is to
identify the components of relevance in the model. In this case these are BOD and
COD. The second step is to identify the biological processes occurring in the
system, for example the transformations or the conversions that happen and write
mathematical relations that describe the process. The third step is to use a simulation
program. In this study was used Matlab/Simulink. Although a number of
environmental factors can influence the parameter values, these are specific factors
in the wastewater, pH and temperature.
The purpose of this model is to find a mathematical model able to determine certain
effluent levels, for BOD and COD concentrations depending on influent and
effluent. Khaled & Gina (2014) obtained in the case studies, for parameters COD
and BOD in different plants of variable types and treatment capacities, that the
correlation between BOD5 and COD is generally linear, except in some rare cases
where the relation was polynomial and sometimes doesn’t have a definite pattern.
However, this rare indefinite pattern might be due to inaccuracy in determination of
the BOD5 and COD parameters in such cases. Since the BOD and COD are
correlated, the estimation of BOD5 values using the quick COD test, and plant
specific biodegradability index (which is the slope of the plotted correlation) became
possible and relatively reliable. Thus, it can be used as a check parameter to evaluate
performance for quick action. In order to establish the BOD and COD correlation for
a particular existing wastewater, one should have both COD and BOD5 values for
several representative wastewater samples. From graphics the BOD5 values versus
the COD values then use the regression analysis to develop the correlation. The
plotted BOD5 and COD figures indicated that there is a clear linear positive
correlation for most case studies, which differs from plant to another (Khaled &
Gina 2014).

We consider a tank which has: width 35.1 m and height of 4.95 m, with the volume
of 8947 m3. It was considered as a static system with a piston-type flow with
changing parameters as the water moves into the tank.
Were taken into account the following simplifying assumptions:

• All parameters are constant in radial section of the reactor (flow piston
type).
• The flow rate is considered constant.
• Flow regime is considered ideal (flow regime shift (type D).
• Density and water temperature are considered constant and have not been
taken into account.
• The influence of pH was not taken into account, which is assumed constant.
• Ammonification was considered constant.
• Biomass concentration in the tank was considered constant (specific death
rates, the increase is much smaller than reaction rates).
• The vapour pressure of the water surface was not been considered.
To achieve simulation method was used Matlab/Simulink software. The
mathematical model of the aeration tank consists of a system by a differential
equation for each parameter to be determined. For numerical solutions of differential
equations using the method of integration ODE45 (Dormánd-Prince) with variable
step and relative tolerance of 10-3. For calculation was used Matlab program version
7.14.0.739.
Knowing the size of the tank could calculate the cross section area as follows:
Wetted area is calculated first using the formula:
Au = H ⋅ l (1)
where: Au is the wetted area [m2], H is the height of the tank [m] and l is the width
of the tank [m].
Wetted perimeter is then calculated:
(
Pu = 2 ⋅ H + l ) (2)
where: Pu is the wetted perimeter [m].

This is necessary to determine equivalent diameter, which has the following
formula:
Au
D ech = 4 ⋅ (3)
Pu
where: Dech is the equivalent diameter [m].
Having calculated the equivalent diameter of the cross-sectional area can be

calculated:
π ⋅ (Dech )2
A= (4)
4
where: A is the cross-sectional area of the tank considered [m2].
Input flow is known from experimental data and calculated using the above area can
cause water flow rate:
F
w= (5)
A
where: W is the water flow rate [m3/h] and F is the experimentally measured water
flow [m3/h].
All these equations are part of the mathematical model, namely the algebraic
equations of the model.
Differential equations of the model are:
For BOD5:
dBOD 5
= −Y1 ⋅
(BOD5 − C i ) (6)
dt w
For COD:
dCOD
= −Y2 ⋅
(COD − C i ) (7)
dt w
where: dBOD5/dt is the the changes in biochemical oxygen demand after 5 days, Y1
is the theoretical stoichiometric ration, Y2 is the theoretical stoichiometric ration, Ci
is the standard oxygen concentration (1.5 mg/ml).
In the last decade, stringent quality standards are being applied to effluent plants,
whether by regulatory authorities or environmentally concerned plant management.
More often than not now, limits on nitrates, ammonia, phosphates, suspended solids,
etc. are applied to outfalls (Turak & Fsar 2004).
To realise an optimum biological process, it is necessary to assure the best
environment for the bacteria. A few important parameters are oxygen, pH and
temperature, as well as suspended solids which indicate the bacteria concentration in
the tank. Advanced monitoring of the bacteriological processes based on oxygen,
ammonia and nitrate makes it possible to satisfy strict legal regulations and to
optimize energy consumption at the same time.

For BOD were obtained 20 simulations with increasing values of inflow starting
from 188.88 m3/h up to 314.67 m3/h. Influent flow values and the influent
concentrations were taken from experimentally determined data from treatment plant
using the analysis method according to SR EN 1899-2/2002 (NTPA-001/2005).
Simulation results from data obtained were compared with those determined
experimentally. In the case of biochemical oxygen demand after 5 days was obtained
the graph from Figure 1. It may be noted that the data obtained from simulation and
the data obtained experimentally keeps tendency, which otherwise have no trend.
The data measured at the plant can vary widely from day to day even for the same
rate, this being also very difficult to simulate. But with this mathematical model
results are close enough to the real ones that allow the user to make a good
prediction of biochemical oxygen demand after 5 days, knowing the inflow of water
and oxygen concentration standard.

Table 1. Experimental values for BOD
Influent Influent Influent Effluent

EffluentBOD InfluentBOD
Sample flow BOD Sample flow BOD
m3/h mg/l mg/l m3/h mg/l mg/l

1 188.88 190 4 11 256.71 100 14
2 197.42 195 6 12 261.33 200 10
3 201.79 140 4 13 262.54 125 8
4 214.00 125 6 14 267.04 110 8
5 224.17 105 10 15 272.63 105 6
6 226.08 150 10 16 281.71 70 10
7 229.13 205 10 17 289.54 100 10
8 236.29 155 8 18 301.17 150 8
9 244.46 160 10 19 302.00 125 12
10 247.67 100 6 20 314.67 160 10
Figure 1. Simulated and measured values of BOD from Dej WWTP
As was shown in the graphic all data were simulated in according to normative
NTPA-001/2005, below 25 mg/l, although influent concentrations values were
between 70 and 205 mg/l. The dissolved oxygen concentration can be measured by
an optical sensor for continuous determination of oxygen (Haimi et al 2009). For
COD, were performed 20 simulations for the increasing values of flow starting from
188.88 m3/h up to 314.67 m3/ h. Concentration values from the influent and effluent
have been determined experimentally by potassium dichromate method according to
SR ISO 6060/1996 (NTPA-001/2005).

Table 2. Experimental values for COD

Influent Influent Effluent Influent Influent Effluent
Sample
Sample flow COD COD flow COD COD
m3/h mg/l mg/l m3/h mg/l mg/l
1 188.88 674 47 11 256.71 422 58
2 197.42 505 37 12 261.33 307 38
3 201.79 269 29 13 262.54 238 48
4 214.00 307 58 14 267.04 269 29
5 224.17 317 38 15 272.63 189 28
6 226.08 217 19 16 281.71 269 48
7 229.13 490 28 17 289.54 378 57
8 236.29 422 58 18 301.17 400 38
9 244.46 384 38 19 302.00 422 38
10 247.67 211 67 20 314.67 355 29
The results obtained of the simulation are compared to the experimental ones as was
shown in Figure 2. If in the case of biochemical oxygen demand after 5 days the
results can vary widely from one day to another day, from a flow or even at the same
flow, in case of oxygen concentration determined by the COD also from the
influent and effluent varies more than in the previous simulation.
This linearity is present as well in simulation of this parameter, but the trend keeps
organized pattern of actual data. However data from simulation is close to the real
values and the mathematical model can be used to predict the effluent of the oxygen
concentration normally determined experimentally with COD method.
Figure 2. Simulated and measured values of COD from Dej WWTP
All simulation data are below to the maximum allowed by the normative NTPA-
001/2005, below 125 mg/l. Block diagram of the model in Simulink can be seen in
Figure 3. In the left diagram can be seen the three input quantities of inflow in m3/h
and BOD after 5 days from the entry into the tank and COD from the entry into the
tank. The three enter in a multiplier which forwards them to the position S.
After completing the steps in the S output as is represented in figure 3, but also are
sent to the workspace in the form of a matrix. Simulation time is set to 120 minutes.
Figure 3. Block diagram of the model in Simulink
Data collected from the wastewater treatment plant keeps a uniform trend, this was
underlined by the results of simulations. In simulation we can see a very good
overlap of simulated results over determined experimentally, because the tank is
rectangular, which is enough close to ideal form.
Conclusions
In this paper, a procedure for getting a set of solutions for development of a
mathematical model must incorporate the major events occurring within a system in
a manner which is consistent with established knowledge about that system.
Validated process models can be used for dynamic simulations, for example, with
different kinds of input data. In simulations the mathematical equations of process
model are solved and the results given. Models and software for simulation have the
possibility to control and evaluate the parameters. The presented control strategies
use mainly ideal conditions, given the circumstances, for controllers and plant
operations.
The formal modelling of systems has been done with a mathematical model, which
attempts to find analytical solutions enabling the prediction of the behavior of the
system from a set of parameters and initial conditions. Modelling techniques include
statistical methods, computer simulation, system identification, and sensitivity
analysis; however, one of these is as important as the ability to understand the
underlying dynamics of a complex system. Models applied for prediction aim at
providing an accurate and fast image of a real systems behavior under different
conditions.
Models may be linear with respect to variables or parameters; furthermore, a model
can be nonlinear to parameters and linear to variable. Linear models are used
frequently, because the analytical solution can be found. For nonlinear models
numerical solutions are predominant. Term mechanistic, physiological and white-

box are used to describe that models structure is based on physical, chemical and
biological laws.
References
Ahmed, S, Abdelhalim, H & Rozaik, E 2013, ‘Treatment of primary settled
wastewater using anaerobic sequencing batch reactor seeded with activated
EM’, Civil and Environmental Research, vol. 3, no. 11, pp. 130-136.
Cossu, R, Fantinato, G, Pivato, A & Sandon, A 2017, ‘Further steps in the
standardization of BOD5/COD ratio as a biological stability index for MSW’,
Waste Management, vol. 68, pp. 16-23.
Evangelou, A, Chintzios, V, Komilis, D & Sanchez, A 2017, ‘Effect of air flow rate
on the dynamic respiration activity of the raw organic fraction of municipal
solid wastes’, Bioresource Technology, vol. 224, pp. 748-752.
Haimi, H, Mulas, M, Sahlstedt, K & Vahala, R 2009, ‘Advanced operation and
control methods of municipal wastewater treatment processes in Finland’,
Helsinki University of Technology Water and Wastewater, pp. 7-17.
Henze, M, Gujer, W, Mino, TM & van Loosdrecht 2000, ‘Activated sludge models
ASM1, ASM2, ASM2d and ASM3’, Scientific and Technical Report, no.9,
IWA Publishing, pp. 6–8-16-26.
Hur, J, Lee, BM, Lee, THw & Park, DH 2010, ‘Estimation of biological oxygen
demand and chemical oxygen demand for combined sewer systems using
synchronous fluorescence spectra. ’ Sensors, vol.10, no.4, pp. 2460-2471.
Khaled ZA & Gina, H 2014, ‘Correlation between biochemical oxygen demand and
chemical oxygen demand for varoius wastewater treatment plants in Egypt to
obtain the biodegradability indices’, International Journal of Sciences: Basic
and Applied Research, vol.13, no.1, pp. 42-48.
NTPA-001/2005, Normative act regarding the determination of limits of loading
with pollutants of industrial and town wastewaters at evacuation in natural
receptors, 2005.
Sincero, AP & Sincero, GA 2003, ‘Physical-chemical treatment of water and
wastewater’, IWA Publishing, UK.
Sawyer, CN Parkin, GF & McCarty, PL 2003, ‘Chemistry for Environmental
Engineering’, 5thed. New York, McGraw-Hill.
SR EN 1899-2/2002, Determination of biochemical oxygen demand after 5 days
(BOD).
SR ISO 6060/1996, Determination of the chemical oxygen demand (COD).
Tchobanoglous, Burton, FL & Stensel, HD 2003, ‘Wastewater
Engineering:Treatment And Reuse’, Metcalf and Eddy.” 4th edition, New
York, McGraw-Hill.
Turak, UG &. Fsar, HA 2004, ‘Research of BOD and COD values of wastewater
that contain certain organic materials’, A Donor Menderes Univ. 4th AACD
congress Kusadasi-Aydin, Turkey, pp. 177.
West, D & Dellana, SA 2008, ‘Predictive modeling for wastewater applications:
linear and nonlinear approaches’, Environmental Modelling & Software, vol.
24, no.1, pp. 96-106.

DESTRUCTION CAVITATION ACTION

ON THE MICROBIAL CELLS SIZES
Iryna Z. Koval
Lviv Polytechnic National University, Department of General Chemistry, 12 Bandera street,

79013, Lviv, irynazk@gmail.com, Ukraine.
Abstract
Cavitation influence has different destruction action on the microbial cells that
depends on their size, shape, type of bacteria, etc, i.e. it depends on the
morphological features of the cells. The effectiveness of this process also depends
on the nature of bubbled gas into reactive cavitation zone. Ar/US has shown the
highest effectivity of cells destruction conditions regardless of the size of their cells
compared with Не/US, О2/US and СО2/US. Concerning of gas/US-action on the
type of microorganisms it was found that yeast cells were destroyed most rapidly,
because their sizes are several times larger than bacterial cells.
Keywords: bacteria, cavitation, cells size, destruction, gas bubbling, yeast
Introduction
Biological pollution of water is caused by bacteria, viruses, fungi and higher
organisms (Jyoti & Pandit 2001, Koval 2016, Voloshko 2008, Zhang et al 2006). It
is a problem for environment nowadays and needs progressive technology for water
treatment. Water treatment is an important factor in ensuring the ecological integrity
of water systems (An & Park 2017). There are many methods of water treatment, but
currently, the modern method of water purification is the use of cavitation. It is well
known about destructive action of cavitation on the microorganisms (MO) cells in
the water medium (Koval et al 2011, Koval et al 2012, Koval et al 2016, Stamper et
al 2008). However, these effects could have different influence on the cells,
depending on the variety of bacteria. Microbes are characterized by different cell
sizes and forms of the outer shells, which may have an ambiguous effect on the
process of their destruction and its duration under cavitation action. Therefore, the
purpose of the present research is to investigate cavitation influence on the bacteria
and yeasts destruction, depending on the size of their cells.

The objects of investigation for destruction process of microbial cells were the
following waters: model waters created based on distilled water with adding some
types of MO. Micrococcus luteus, Pseudomonas fluorescens, Bacillus cereus,
Sarcina lutea bacteria and Saccharomyces cerevisiae yeasts were used as microbial
cells for investigations. Effective rate constants of cells destruction (kd) were
calculated after combined action of cavitation and gas influence. Oxygen (O2),
carbon dioxide (СО2), argon (Ar) and helium (He) were used as an additional source
of bubbles in an aqueous medium. The aqueous medium was aerated during whole
process of cavitation action on the cell. Saturation of the treated aqueous medium by
different types of gases created additional cavitational embryos in reactive zone.

Hence, simultaneous action of gas and ultrasound (US), namely Ar/US, Не/US,
О2/US, СО2/US on the individual bacterial cells were used.
The source of cavitation was US waves with oscillation frequency of 22 kHz, power
of 91W and intensity of 1.65 W/сm3. US oscillation were transmitted by the
magnetostrictive emitter immersed into the volume of investigated water (V=75
сm3). Experimental conditions were T = 298±1K, P = 0.1MРa, process duration (t) –
2 hours.
A nutrient media for cell growth after cavitation treatment was used: for bacteria –
meat water (1dm3), peptone (10g), agar (15g) and for yeast – malty mash (1dm3)
containing solids (6-8%) and agar (2%). Petri dishes were placed in thermostat at the
370C for 48 h (for bacterial cells) and 300C for 96 h (for yeast cells).

The specific cavitation effects on the cells wall as well as intergenetic difference in
the structures of cells’ wall were explained by the resistance of investigated MO.
This fact is consistent with some articles during destruction effect of cavitation on
different MO: Gram-negative bacteria (total coliforms, fecal coliforms,
Pseudomonas spp.), Gram-positive (Clostridium perfringens and fecal streptococci)
(Drakopoulou et al 2009); spores of Aspergillus flavus and fungi of Penicillium
digitatum (López-Malo et al 2005); E. coli (Patil et al 2009), Microcystis aeruginosa
algae (Zhang et al 2006).
As a result, some morphological features, namely cells sizes of investigated MO
were detected and presented in Table 1.
Table 1. Morphological features of investigated microorganisms

Morphological features
Investigated
Coloration by Width, Length,
microorganisms
Gram micrometers micrometers
Bacteria
Bacillus
Gram + 1.3 3.42
cereus
Micrococcus
Gram + 0.7 -
luteus
Sarcina
Gram + 2.2 -
lutea
Pseudomonas
Gram - 0.53 1
fluorescens
Yeast
Saccharomyces
Gram + 5.17 8.67
cerevisiae
It was observed that the larger size cells were easily damaged by gas/US treatment,
i.e. the cell stability in cavitation conditions was reversely proportional to the cell
size. The value of kd is in the range of (4.52 ÷ 7.94) 10-4 s-1 for Saccharomyces
cerevisiae yeast unlike the value of kd in the range of (2.0 ÷ 5.0) 10-4 s-1 for
investigated bacteria types (Table 2), cells size of which is approximately in 10
times smaller from yeast cells size (Table 1).

It could be created dependencies of effective rate constants of MO destruction on

their cells size under conditions: Ar/US, Не/US, О2/US, СО2/US (Table 2). kd values
as a function of MO size, where the increase of kd values was observed for larger
cells. This pattern was observed for all investigated gases, especially for argon.
Hence, MO destruction under cavitation action depends on the nature of gas
bubbling during whole process. The analysis of nature of gas influence on cells
destruction under cavitation conditions showed that these processes occur most
effectively in the atmosphere of argon in the reaction medium, independently on
genetic origins of the studied MO, their morphological features, initial quantity of
cells in the unit volume of water system and size of their cells.
Hence, the relative series of effective MO destruction during gas/US treatment was
described below:
kd (Ar/US) > kd (O2/US; He/US; CO2/US) (1)
The highest effectivity of cells destruction was observed under Ar/US conditions
regardless of the cells sizes. The values of effective rate constants of cells
destruction under gas/US-action are presented in Table 2.
Table 2. The values of effective rate constants of cells destruction under gas/US
conditions
kd 104, s-1
Microorganisms
Ar/US Не/US СО2/US О2/US
Bacteria
Micrococcus luteus 3.29±0.03 1.70±0.04 – –
Pseudomonas
3.96±0.02 0.91±0.20 2.10±0.15 1.63±0.05
fluorescens
Вacillus cereus 5.02±0.03 2.89±0.04 2.51±0.04 3.11±0.06
Sarcina lutea 5.95±0.07 3.30±0.09 – –
Yeast
Saccharomyces
7.94±0.09 5.73±0.08 5.36±0.03 4.52±0.01
cerevisiae
Experimental results were shown almost complete water refinement from yeast for a
shorter process time comparing with bacteria (yeast cell size is almost 10 times
larger) (Table 1). Thus, among spherical shapes of MO, the most effective
destruction was observed for Sarcina lutea, comparing with Micrococcus luteus (the
size differs approximately 3.5 times) (Table 1). Similar behavior is observed for rod-
shaped bacteria: Bacillus cereus and Pseudomonas fluorescens.
Conclusions
The values of еffective rate constants of cells destruction were compared, depending
on the gas nature bubbling under cavitation conditions, and it was found that the
efficiency of cell destruction under Ar/US is approximatelly two times larger unlike
O2/US, He/US and CO2/US, regardless of cell sizе. It was discovered the
dependence of the values of effective rate constants of investigated MO destruction
of size of their cells that for all studied gases under cavitation conditions was shown
growth of kd with an increase of cell size. It was found that yeast cells were

destroyed aproximatelly two times faster than bacterial cells, that could be explained
by larger sizes of yeast cells.
References
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Value in Traditional Korean Villages: The Case of Oeam Village, Asan City, Korea',
Sustainability, no 9, pp. 1145-1159.
Drakopoulou, S, Terzakis, S, Fountoulakis, M.S, Mantzavinos, D, Manios, T 2009,
'Ultrasound-induced inactivation of gram-negative and gram-positive bacteria
in secondary treated municipal wastewater', Ultrasonics Sonochemistry, vol.
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cavitation', Biochemical Engineering Journal, no 7, pp. 201-212.
Koval, IZ 2016, 'Cavitational influence on the Bacillus cereus bacteria and
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Environment and The Industry”, SIMI 2016, National Research and
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Koval, I, Shevchuk, L, Strogan, O 2012, 'Equipment for magnetic-cavity water
disinfection', Chemistry & Chemical Technology, vol. 2, no. 6, pp. 219-223.
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contaminated water', 15th Meeting of the European Society of Sonochemistry
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DETERMINATION OF RHODIUM FROM WASTEWATER SAMPLES

USING ICP-EOS TECHNIQUE
Anda Tenea1, Cristina Dinu1,2*, Eleonora-Mihaela Ungureanu2, Gabriela-Geanina Vasile1,

Marius Simion1
1
Podu Dambovitei, district 6, 060652, Bucharest, *cristinadinu_2006@yahoo.com, Romania
2
University Politehnica of Bucharest, Faculty of Applied Chemistry and Materials Science, 1-7
Polizu Street, 011061, Bucharest, Romania
Abstract
A rapid, sensitive and accuracy method was developed for detection of rhodium in
wastewater samples. The recovery test indicate that 343.489 nm is the proper
wavelenghts for Rh determination.
Keywords: ICP-OES, rhodium, water
Introduction
Rhodium is part of Platinum group elements together with iridium (Ir), osmium
(Os), palladium (Pd), platinum (Pt) and ruthenium (Ru). Over the last decade, the
platinum metal concentration of environmental samples such as soil, surface water,
sediment and vegetation has increased significantly, the main source of
contamination with these platinum metals being catalytic converters. Platinum group
elements are used in catalysts which reduce pollutants in the exhaust system.
Catalysts containing platinum metals are applied especially to motor vehicles but
can also be used in industry as stationary catalyst used for oxidation of ammonia.
The main sources of platinum metals emissions in Europe: 50.4% come from
catalysts, 24.7% of jewelry, 6% from electrical industry, 4.8% from chemical
industry, 4.6% from glass industry, 2.6% from oil industry and 6.8% from other
sources (Pawlak 2014).
Large platinum concentration have been found near mines, especially those that
extract nickel ores (Dinu 2017). Concentration of platinum metals were found also
in different types of water (river, rainwater, groundwater, surface water) (Ravindra
2004, Kim 2017). Due to the use of catalysts, harmful gases (CO, HC, NOx) emitted
by cars are oxidized and reduced to harmless gases (CO2, H2O, N2) (Yajun 2012).
In high concentration platinum metals give mutagenic effects in bacterial and
mammalian cells and tumor growth. The platinum metal concentration in the
environment are low and their health effects are poorly studied (Merget 2001).
Rhodium is present at about 0.001mg/L in the earth’s crust. Rhodium is a white-
silver metal with a higher melting point and a lower density than platinum. Platinum
elements usually do not form oxides and are not affected by the most acids. It is
completely insoluble in nitric acid, poorly soluble in aqua regia, but only sulfuric
acid can dissolve completely when it is in the form of a powder. Being a noble
metal, pure rhodium is chemically inert, but becomes very reactive in chemical

combinations. Rhodium is used in combination with platinum for thermocouples,

crucibles, evaporating dishes, etc. (Panahi 2009).
Rhodium found in nature consists of one isotope, 103Rh of the thirty-eight discovered
so far (Parker 2012).
The most commonly used analytical techniques for rhodium determination are:
graphite furnace atomic absorption spectrometry (GFAAS) (Su 2001,
Zimmermann 2003), instrumental neutron activation analysis (INAA) (Dai 2001),
adsorptive stripping voltammetry (ASV) (Georgieva 1997), inductively coupled
plasma-atomic emission spectrometry (ICP-AES) (Kovacheva 2002) and inductively
coupled plasma-mass spectrometry (ICP-MS) (Petrucci 2000, Niemela 2004,
Djingova 2003, Gomez 2000, Resano 2007, Muzikar 2006).
The aim of this study was to develop a method for the determination of rhodium
from wastewater samples using ICP-OES technique.

Reagents : Standard solution for Rhodium calibration, 10 mg/L ICP-MS Standard,
Sigma – Aldrich quality; nitric acid for trace analysis ≥ 69%, Fluka; ultrapure
water; argon 99,996% purity; nitrogen 99,999% purity (Linde-Gas quality).
Equipment: Inductively Coupled Plasma Optical Emission Spectrometer ICP-OES
Type Optima 5300 DV Perkin Elmer.
Optimized instrumental parameters are summarized in Table 1.
Table 1. Parameters for ICP-EOS

Spectrometer parameters
Rh Wavelengths: 233.477 nm; 343.489 nm Replicates 3 times
Integration time: 0.05 s Purge Gas Flow normal
Transient Read Time 30.0 s Transient Read Delay 0.0 s
Plasma parameters
Plasma flow rate 15L/min Power RF 1400
Auxiliary flow rate 0.2L/min Plasma View Axial
Nebulizer flow rate 0.7 L/min View distance 15.0 mm
Method verification
In order to validate the developed method under the established optimized condition
were investigate the performance parameters: limits of detection (LOD), limits of
quantification (LOQ), linearity, accuracy (precision, recovery). The tests performed
are indicated in Table 2.
Table 2. Experimental design for method verification

Linearity test 5 solutions in the range 0.1 mg/L to 0.5 mg/L Rh
LOD, LOQ 5 independent fortified blank solution of 0.04 mg/L Rh
Repeatability 10 independent standard solution of 0.3 mg/L Rh
Intermediate 4 independent standard solution analyzed by 2 chemists in 2 different
precision days, 16 independent standard solution of 0.3 mg/L Rh
Recovery 6 independent fortified drinking water samples, respectively 3 wastewater
samples with 0.04 mg/L Rh

The mathematical equation for relative standard deviation (coeficient of variation)

and recovery are:
Recovery, %
𝑋𝑋𝑓𝑓− 𝑋𝑋𝑏𝑏 (1)
ƞ= ∗ 100
𝑋𝑋𝑎𝑎
where Xf is mean value of fortified samples, mg/L; Xb is mean value of unfortified

samples, mg/L; Xa is concentration of added standard solution, mg/L.
Relative standard deviation, RSD
𝑆𝑆𝑟𝑟 (2)
𝑅𝑅𝑅𝑅𝑅𝑅 = ∗ 100
𝑥𝑥
where Sr is standard deviation of concentrations, mg/L; x is mean value of
concentrations, mg/L.

The calibration standards were prepared in the range 0.1 to 0.5 mg/L Rh in 3% nitric
acid for trace analysis using a 10 mg/L Rh Certified Reference Material. The
calibration curve and all tested parameters was performed at two different
wavelengths: 233.477 nm, respectively 343.489 nm. In Figures 1 and 2 are plotted
the calibration curve, the determination coefficients were higher than the minimum
accepted value (0.995).
Figure 1. Calibration curve, 233.477 nm Figure 2. Calibration curve, 343.489 nm
The working range is linear between 0.1mg/L and 0.5 mg/L for both wavelengths
(233.477 nm and 343.489 nm) and the value for coefficient of variation (0.36% for
233.477 nm and 0.92% for 343.489 nm), less then 2% according to Horwitz function
(Hibbert 2007), situate the test method as good spectrometric method (Table 3).

Table 3. Linearity test coefficients

Rh, 233.477 nm
y = 93062x - 354
y-Intercept Sensitivity = slope of the Correlation coefficient
a = -354 mg/L calibration curve R = 0,99995
b = 93062 mg/L
Residual standard Standard deviation of the Coefficient of variation of the
deviation method method
SY = 101.1 mg/L Sx = 0.0011 mg/L Vx01 = 0.36 %
Rh, 343.489 nm
y = 92355x + 152.91
y-Intercept Sensitivity = slope of the Correlation coefficient
a = 152.91 mg/L calibration curve R = 0,9994
b = 92355 mg/L
Residual standard Standard deviation of the Coefficient of variation of the
deviation method method
SY = 255 mg/L Sx = 0.0028 mg/L Vx01 = 0.92 %
Five independent blank samples (ultrapure water) were fortified with 0.04 mg/L Rh
in order to quantify the detection limit (LOD) and the quantification limit (LOQ).
The results obtained are presented in Table 4.
Table 4. Parameters in experiments for LOD and LOQ

Rh, 233.477 nm
Measured values
0.047 0.047 0.043 0.043 0.034
(mg/L)
Standard deviation of the results, s = 0.005 mg/L
Limit of detection, LOD = 3s = 0.016 mg/L
Limit of quantification, LOQ = 10s = 0.05 mg/L
Rh, 343.489 nm
Measured values
0.031 0.037 0.035 0.036 0.038
(mg/L)
Limit of detection, LOD = 3s = 0.01 mg/L
Limit of quantification, LOQ = 10s =0.03 mg/L
For precision in terms of repeatability of the method, ten samples of 0.3 mg/L Rh,
prepared from 10 mg/kg Rh (III) in nitrate solution were analyzed. The precision test
was performed by one analyst with the same equipment and method, in one day. In
Table 5 are presented the experimental data for precision test.
Table 5. Experiments for repeatability

Rh, 233.477 nm
Measured values 0.298 0.301 0.300 0.299 0.298
(mg/L) 0.306 0.299 0.298 0.302 0.308
Mean value, xmean = 0.3009 mg/L
Repeatability = 2.8*s= 0.0102 mg/L
Relative standard deviation of the repeatability, RSDr= s/(xmean*100)= 1.21%

Rh, 343.487 nm
Measured values 0.301 0.303 0.305 0.298 0.299
(mg/L) 0.301 0.301 0.305 0.305 0.309
Test for intermediate precision (Table 6) have been performed by two analysts (four
determination in two different days for each analyst) using the same method and the
same equipment.
Table 6. Experiments for intermediate precision
Rh, 233.477 nm
Measured values 0.288 0.272 0.294 0.279 0.316 0.301 0.311 0.291
(mg/L) 0.276 0.294 0.321 0.307 0.312 0.319 0.297 0.306
Rh, 343.487 nm
Measured values 0.298 0.297 0.296 0.300 0.302 0.302 0.310 0.312
(mg/L) 0.296 0.299 0.299 0.300 0.307 0.303 0.297 0.309
Relative standard deviation of the repeatability, RSDr= s/(xmean*100)=2.00%
The studies for recovery test was performed using two different drinking water
samples and one wastewater sample enriched with 0.4 mg/L Rh. For each type of
matrix, three separate samples were digested with nitric acid ultrapure in order to
eliminate organic matter and then analyzed. The obtained results are in Tabel 7.
Table 7. Results for recovery tests

Rh, 233.477 nm
Parameter Drinking water Drinking water Wastewater sample
sample 1 sample 2 3
Xf, mg/L 0.0043 0.0053 0.0223
Ƞ, % 10.83 13.33 55.83
Sxf, mg/L 0.0006 0.0015 0.0023
Sƞ, % 1.44 3.82 5.77
Rh, 343.487 nm
Parameter Drinking water Drinking water Wastewater sample
sample 1 sample 2 3
Xf, mg/L 0.0417 0.042 0.0427
Ƞ, % 104.2 105 106.67
Sxf, mg/L 0.0012 0.001 0.0006
Sƞ, % 2.89 2.50 1.44

For 10 to 100 μg/L level of concentration, the recovery percentage must be situated
in the 60-115% range (Tanase 2007).
The recovery test indicate that at 233.477 nm wavelength the recovery percentage is
very low, even if the other performance parameters are very good. It is found that
only 343.487 nm is suitable for determination of rhodium from drinking and
wastewater samples, recovery percentage higher tahn 104%.
Conclusions
The method for rhodium determination at 343.487 nm using inductively coupled
plasma optical emission spectrometry is precise, sensitive and fast, with a good
recovery performance and can be used for drinking and wastewater samples.
Acknowledgements
The authors acknowledge the financial support offered in 2018 by the Romanian Nucleu
Programme through Project PN 18 05 01 01.
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preconcentration system using polyamine Metalfix–Chelamine resin for the
on-line determination of palladium(II) and platinum(IV) by inductively
coupled plasma optical emission spectrometry', Talanta, vol.70, pp.1081-
1086.
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platinum and rhodium in dust and plant samples using microwave-assisted
sample digestion and ICP-MS', Analytica Chimica Acta, vol.521, pp.137-
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Mahmoudi, F 2009, 'Amberlite XAD-4 functionalized with m-
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for preconcentration and determination of rhodium (III) in water samples by
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DETERMINATION OF SULFUR COMPOUNDS WITH A STRONG

OLFACTORY IMPACT ON THE POPULATION
Raluca Diodiu, Toma Galaon, Vasile Iancu, Mihaela Petrescu, Mihai Bratu, Valeriu Danciulescu,
Andreea Cozea
National Research and Development Institute for Industrial Ecology –ECOIND, 71-73 Drumul
Podu Dambovitei, district 6, 060652, Bucharest, raluca.diodiu@incdecoind.ro, Romania
Abstract
The aim of this study was to develop an analytical method capable to determine
mercaptans in air at low concentrations, lower than the ones that produce an
olfactory discomfort. A reliable, rapid, and simple high performance liquid
chromatography (HPLC) method was developed for the determination of
mercaptans, a sulphur compounds class. The developed method can be successfully
applied to the quantitative determination of four compounds (Methyl mercaptan,
Butyl mercaptan, Ethyl mercaptan and Propyl mercaptan).
Keywords: Butyl mercaptan, Ethyl mercaptan, mercaptans, Methyl mercaptan,

Propyl mercaptan, thiols
Introduction
A number of studies conducted by our team revealed the presence of sulphur
compounds in different environmental matrices (Petrescu et al 2017, Nicolescu et al
2017). Of the sulphur compounds, particular attention is given to mercaptans (thiols)
due to the olfactory discomfort they can create at very low concentrations.
These are regulated in Romanian legislation only for Methyl mercaptan, but it has
been found that the limits in the legislation are higher than the threshold at which an
olfactory discomfort occurs. The methods used and implemented at present in the
country are designed to meet the limits of the legislation. The technique of
molecular absorption spectrometry is the one recommended for these compounds
according to the standards in use. The performance of this technique cannot detect
low levels of sulphur compounds at the level at which an olfactory discomfort
occurs.
The implementation of new analytical techniques, suggested in the literature
(Moliner-Martı'nez et al 2013, Toyo'oka et al 1988, Bramantis et al 2004), such as
liquid chromatography high performance for mercaptans would compensate for this
drawback and could determine and quantify concentrations below the detectable
olfactory threshold.


All reagents and standards were prepared with ultrapure water (0.1 S/cm) from a
ultra pure water purification systems MilliPore.
The standards were purchased commercially and were from SPEX CertiPrep. The
standards were realised in methanol. All intermediate dilutions were also carried out
in methanol. Standards were of the folowing concentrations: 1000 μg/ml of methyl
mercaptan, 1000 μg/ml of ethyl mercaptan, 1000 μg/ml of propyl mercaptan and
1000 μg/ml of butyl mercaptan.
These can also be prepared in the laboratory by purchasing the pure substance and
dissolving it in methanol.
The ortho-phthalaldehyde reagent - OPA (C8H6O2) was commercially purchased but
can be realised in the laboratory by dissolving the o-phthalaldehyde in distilled
water with 1% methanol.
The isoleucine reagent (C6H13NO2) was prepared and brought to dry distilled water
purchased as such from the trade. For the 7.4x10-3 M concentration, 0.9694 g of
isoleucine is dissolved in 1000 ml of ultrapure water.
The borate buffer solution at pH = 10 was prepared by dissolving boric acid and
adjusting the pH with 1M NaOH. Dissolve 31 g of boric acid in 1000 ml of ultrapure
water. Sodium hydroxide used for pH adjustment was prepared in the laboratory
from NaOH pellets and ultrapure water by dissolving 40 g of NaOH in 1000 ml of
ultrapure water.

Determination of thiols by liquid chromatography implies their derivatization to a
more stable form using derivatizing agents. Subsequently, the derivatization
compounds are analysed on a liquid-chromatograph.
A high-performance liquid chromatograph of Agilent 1200 coupled with a
quaternary pump, autosampler and Fluorescence detector was used to perform the
method. The chromatographic column used was Acclaim Carbonyl C18 with the
following characteristics: 250 mm*4.6 mm, and particle size of 5 μm.
The mobile phase used was a mixture of methanol with gradient water and a flow
rate of 1 ml / min. In the literature, it is specified in case of derivatization with
OPA-leucine eluting with methanol and water (Moliner-Martı'nez et al 2013).
Table 1. Gradient of the mobile phase.

Timp (minute) MeOH H2O
(%) (%)
0.0 25 75
15.0 100 0
17.0 100 0
17.1 25 75
In this method of mercaptans determination, various ratios between the mobile phase
components (methanol: water) were tested to obtain the best separation in the
shortest possible time. Separation was done using gradient elution in order to obtain
efficient peaks in a short time period. The best gradient for the separation was a
5%/minute methanol increase in 15 minutes as can be seen in Table 1.
The stock standards were purchased commercially in a matrix of methanol (SPEX

Certi Prep) containing 1000 μg / ml for each mercaptan (methyl mercaptan, ethyl
mercaptan, propyl mercaptan, butyl mercaptan)
From the stock standards, intermediate standards were realised, containing a mix of
each mercaptan, of 100 μg/ml and 2.5 μg/ml concentrations containing a mix all four
thiols. From this, the points for the calibration curves were made and then
derivatized.
The calibration curves ranged between 10-1000 μg / L (ppb) for each of the four
mercaptans. The calibration points were 10, 25, 50, 100, 250, 500, 1000 μg / L ppb).
The injection volume used in this analytical method was 50 μl.
The reaction of mercaptans (R-SH) with OPA and isoleucine underlies a very good
capture / preconcentration / derivatization method minimizing the analytical
problems specific to this analysis (instability and instability). According to the
literature (Moliner-Martı'nez et al 2013), the best sensitivity to o-Phthaldialdehyde
(OPA) and isoleucine derivatization was obtained with OPA 7.4 x 10-3 M and OPA:
isoleucine (1: 1) ratio. With this in mind, each standard was derivatized as follows:
0.6 ml of supernatant was added 0.4 ml of borate buffer (pH = 10), 1 ml of the
standard in methanol, 1 ml of OPA followed by 1 ml of isoleucine. It is expected to
form a foam that leads to detergents.
The derivatization products are stable for 24 hours at room temperature, or 14 days
(maximum study time) if stored at 4°C. Under these conditions, derivatized
mercaptan solutions were stored at 4°C in the refrigerator.
The determination coefficients - R2, had values greater than 0.999, as follows:
methyl mercaptan - 0.9994, ethyl mercaptan - 0.9996, propyl mercaptan - 0.9998
and butyl mercaptan - 0.9999.
Table 2. Retention time of compounds

Methyl Ethyl Propyl Butyl
mercaptan mercaptan mercaptan mercaptan
Retention time
10.89 11.41 12.54 13.17
(minutes)
The analytical method of determination manages to separate the four mercaptans in

a relatively short time, they eluted in less than 20 minutes, as can be seen in Table 2.

Figure 1. Chromatographic separation of mercaptans for the 500 ppb standard.
Figure 1 shows a chromatogram of a standard sample used to perform calibration

curves. Within this, one can follow the elution pattern of the compounds of interest.
Conclusions
In the present paper an analytical method was developed to identify and determine a
class of sulfur compounds with strong olfactory impact on the receptors called
mercaptans or thiols.
The analytical method was performed on a high performance liquid chromatograph
and is able to identify and quantify under the limits of the legislation and near the
olfactory threshold four compounds of the mercaptan class (mercaptan metal, ethyl
mercaptan, propyl mercaptan and butyl mercaptan) in ambient air and indoor air
samples.
The developed analytical method from this article can be reproduced by other
analyst thus being able to be easily implemented in another laboratory. It also offers
an alternative to methyl mercaptan determination by molecular absorption
spectrometry, being more accurate in identifying methyl mercaptan from other
mercaptans.
Acknowledgements
This work was carried out through the Romanian Nucleu Programme, developed with the
support of MCI; the authors would like to thank all those who contributed to this study.
References
Bramanti, E, D’Ulivo, L, Lomonte, C, Onor, M ,Zamboni, R, Raspi, G & D’Ulivo,
A 2004, ’Characterization of denatured metallothioneins by reversed phase
coupled with on-line chemical vapour generation and atomic fluorescence
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Avella-Oliver, M & Campıns-Falco, P 2013, ’More about sampling and
estimation of mercaptans in air samples’, Talanta, vol. 106, pp.127–132.
Nicolescu, IC, Bucur, E, Serbanescu, A, Diodiu, R & Barbu, ME 2017,
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Petrescu, M, Bucur, E, Diodiu, R, Bratu, M, Serbanescu, A & Barbu, M 2017,
Toyooka, T, Uchiyama, S, Saito, Y & Imai, K 1988,’Simultaneous determination of
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fluorescence detection’, Analytica Chimica Acta, vol. 205, pp. 29-41.

HEAVY METALS EMISSIONS TO AIR FROM INDUSTRIAL PLANTS:

CRITICALITIES AND SOLUTIONS
Elena Cristina Rada
University of Insubria, Department of Theoretical and Applied Sciences, via G.B. Vico 46,
21100 Varese, elena.rada@uninsubria.it, Italy
Abstract
In the European Union, the regulation in the sector of emissions into the atmosphere
from industrial plants did not evolve homogeneously. As demonstrated in this
article, the sector of waste to energy plants has shown important improvements in
the latest 20 years, whilst other industrial plants were subject to less stringent
regulations. As consequence, the human exposure resulting from industrial plant
authorisations depend on the plant to be authorised. Examples of consequent
inequalities and related criticalities concern both macro and micro-pollutants. The
present article concerns a category of micro-pollutants: heavy metals emissions into
the atmosphere. The sector of thermo-chemical treatment of waste is presently
analysed in details in the University of Insubria in the frame of a research in
progress. The present article refers to some aspects emerged in that research and
integrates them by a preliminary analysis of the underestimated criticalities of other
industrial sectors. In both cases, the core of the problem is the demonstrable
excessive simplification of the control of heavy metals emissions. Large industrial
plants are controlled through an approach that does not exploit in details the
available information of toxic effects of each heavy metal. Small industrial plants
can be subject to simple authorisations with no analysis of the local impact of their
emissions. In both cases, secondary and diffused emissions can have an impact
higher than the conveyed ones, as discussed in this article. A methodology of control
that integrates the present regulation, avoiding under-estimated human exposures to
heavy metals is mandatory.
Keywords: emissions, industrial plants, heavy metals, health, regulation
Introduction
The European Union (EU) regulation for emissions into the atmosphere from
industrial plants did not show a homogeneous evolution in the recent decades. The
sector of waste to energy (specifically of thermo-chemical plants) showed a clear
improvement in the environmental performances of the authorised plants thanks to
an approach more sensible to the reduction of the human exposure to emitted
atmospheric pollutants. Other industrial sectors were not subject to the same
restrictions in spite of potential high impacts, as explained below.
An example is the case of NOx. A cement factory must comply with an emission
concentration at the stack that may be even one order of magnitude higher than the
one of an incinerator. Moreover, the flowrate of a cement factory could be even one
order of magnitude higher than the one of an incinerator. Thus, the load of NOx
emitted from the stack of a cement factory could be even two orders of magnitude
higher than the load released from an incinerator. Supposing the same characteristics
of release into the atmosphere (stack height, off-gas temperature, off-gas velocity,
same site) the consequent incidence on the air quality at ground level can change of
two orders of magnitude.
Examples like this one, of consequent inequalities and potential criticalities, can be
seen not only for macro-pollutants like NOx but also for micro-pollutants. The
present article concerns a specific category of micro-pollutants: it concerns heavy
metals emissions into the atmosphere. The core of the problem analysed in the
present article is the demonstrable excessive simplification of the control of heavy
metals emissions in some industrial plants.
Readers of scientific journals could have caught some concerns on the management
of the risk from heavy metals emitted into the atmosphere from industrial plants.
The concern on this topic is clear in China as demonstrated by the visible presence
of Chinese authors in the Scopus database on this subject. In China, regulation and
control organisation in the sector of environment are not yet developed like in EU,
thus the present criticalities could be expected. A question remains on the
criticalities present in the EU for under-estimation of the role of heavy metals. The
present article demonstrates that some criticalities are still present in the EU in spite
of a modern regulation.

The sector of industrial plants can be divided in two sub-sectors: waste to energy
plants (the ones not related to biogas production) and other industrial plants involved
in heavy metals release into the atmosphere.
For both the sub-sectors, a link among case studies of interest was sought in order to
make more understandable the criticalities to be pointed out. In order to do that,
international databases were analysed containing proceedings papers and scientific
journal articles. Additional analyses concerned the literature not related to the most
known databases. Indeed by this way specific charactarisations of the environment
and the stack emissions may be found in technical documentation.
In order to consider relevant a case study, not only the concentrations of the
emissions at the stack of a plant were taken into account. Indeed the human exposure
to persistent atmospheric pollutants like heavy metals depend on many factors (the
following list reports only the main ones):
- Emitted load (obtained multiplying the flow-rate and the concentration);
- Dynamics of the emissions (cyclic, 24/24h etc.);
- Stack height of the conveyed emissions;
- Off-gas temperature at the stack;
- Off-gas velocity at the stack;
- Secondary emissions characteristics;
- Diffused emissions characteristics;
- Meteorologic parameters specific for the site of the plant;
- Toxicological characteristics of each heavy metal emitted.
Considering this last point, data on the toxicity of each compound are available in
form of Cancer Slope Factor (SF) for the carcinogenic substances. SF, expressed in
(mg kgbw-1 d-1)-1 where “bw” means body weight, is defined as the incremental
cancer risk associated with a unit dose of a carcinogen. It is the slope of the curve
representing the relationship between dose and cancer risk. Depending on the

exposure pathway, inhalation or ingestion, we distinguish between SFinhal and SForal.

Table 1 reports the toxicologic parameters available for the considered pollutants.
Table 1 - Toxicologic characteristics of the considered pollutants
SFinhal SForal
[(mg kgbw-1 d-1) -1] [(mg kgbw-1 d-1) -1]
Cadmium 6.30E+00 -
Tallium - -
Arsenic 1.50E+00 1.50E+00
Chromium III - -
Chromium VI 2.94E+02 -
Nickel 9.10E-01 9.10E-01
From Table 1 we can remark that (Rada 2018):

- Heavy metals show SFs in a range of two orders of magnitude.
- In spite of that, the regulation in force sums heavy metal concentrations with no
regard to their specific toxicity; as examples:
- in the regulation for incineration emissions at the stack, Cd + T₁ are summed even
if only one has a SF;
- arsenic, chromium and nickel are summed with other six heavy metals even if only
three have a SF.
Just to understand the complexity of the sector, planst like the steel making ones are
characterised by conveyed, secondary and diffused emissions.
It is clear that a plant constructed in a near-desert area has a very limited impact on
the health of the population. The analysis presented in this article considers the
criticalities as related to a densely populated areas.

Two links have been found among the case studies selected from the literature:
- CrVI emissions as demonstration of the no optimised approach for the management
of heavy metals from industrial stacks; additional details on this issue can be found
in (Rada 2018).
- Low height emissions of heavy metals into the atmosphere.
In the case of residual municipal solid waste (RMSW) and special waste
incinerators, supposing to consider a limit value of Cd at the stack as 50 µg/Nm3, it
is easy to understand that for CrVI, carcinogenic, the emission at the stack must be
coherent with what requested for Cd. In spite of that, the regulation in force asks for
Cr only the value of Crtot. Its value must be considered in the frame of a sum with
other heavy metals. Taking into account the different carcinogenicity of CrVI, along
the pathway adopted to authorize the emissions of an Italian plant (PAT 2009) it was
proposed a maximum value of CrVI to be guaranteed at the stack. The proposed
value was 1 µg/Nm3 calculated on yearly basis (being a carcinogenic compound, its
relevance is on a long period of exposure) (PAT 2009). It is an approach that even
10 years ago recognized the limits of the regulation in force for the sector. However,
no one focused in details on the matter of the equivalent impact given by different
carcinogenic compounds.
Concerning tannery sludge and its thermochemical treatment, two big leather-
tanning industrial areas are present in Italy. Since long time, the attention was put on
the role of Chromium. It is used as CrIII in the tanning activities. The potential risk
depends on two main reasons (Rada 2018):
- It can be found in trace in the leather product, causing allergic reactions; that limits
also the possibility of the reuse of the material;
- It is transformed into CrVI if the final treatment of the generated sludge (from
wastewater treatment plants) if based on oxidative conditions; that limits the energy
recovery from this sludge in spite of the fact that it is assimilated to a discarded
biomass, thus being a renewable source of energy.
In order to find a solution, the Italian Authorities promoted and financed many
researches on this topic. What emerges from the analysis of role of CrVI emission in
this sector, is the inadequacy of the regulation on emissions to air: the high content
of CrIII in sludge can cause high concentrations of CrVI at the stack in case of
combustion, with no problems in complying the national regulation on heavy metals
emissions. Just to have an example, a concentration of CrVI equal to 100 µg/Nm3 and
the rest of the heavy metals equal to 400 µg/Nm3 results acceptable from the
regulation even if the health risk only from CrVI results significantly higher than the
risk from PCDD/F assumed equal to the limit (0.1 ngTEQ/Nm3) (Rada 2018).
The problem cannot be not avoided in full in the case of gasification: a local
formation of CrVI can be found for local oxidizing conditions, even if the global
conditions in terms of free Oxygen availability are sub-stoichiometric. Pyrolysis is
worst: the combustion of the produced char (the solid output of the plant) offers to
CrIII there contained the possibility to be oxidized to CrVI. At the end, an important
solution is prevention: tanning without Cr (called wet white leather) is a growing
reality in the sector; however long time is needed to get a full conversion of the
approach because of higher costs compared to the use of CrIII. It is clear that an
integration of the regulatory approach is compulsory.
Woody waste combustion can find problems from CrVI. In the latest years, EU has
started a review of the regulations on combustion of woody biomass. In Italy, virgin
wood belongs to the category of fuels. Treated wood even if derived from wood-
furniture industry rejects is considered as waste. That has consequences on the
option of combustion: its combustion is subject to more stringent requests (in term
of process monitoring and emission limit). A question debated recently in Italy
concerned the possibility to classify slightly treated wood as fuel. A research was
developed and analyses before and after combustion (on pilot scale) were made,
dealing with organic micropollutants (Passamani et al 2017) and heavy metals (but
not detailing on CrVI). What is interesting for the present paper is the analysis of the
heavy metals content in virgin wood. If the supplied wood comes from a polluted
land, an anomalous heavy metals amount (Cr included) can enters a burner without
any control of its emissions. This problem, not yet analysed in Italy, is clear in
Germany: there, some limits are set. In this case, the approach of Germany could
become a reference for other countries where no control on wood composition is
requested. However, the problem remains in case treated wood were burnt because
its Cr content usually is not characterized.
Concerning the case of special waste gasification, a recent proposal (gasification
followed by immediate combustion of the generated syngas) has been put forward in
the Italy (Appa 2018). Also in this case, the authorization pathway suffers from the
aggregation of heavy metals in the limit values to be complied with at the stack:
- The sum of Cd and Tl has a limit with no consideration of each toxicologic
characteristic;

- The sum of antimonium, arsenic, lead, total chromium, cobalt, manganese, nickel e
vanadium (Sb + As + Cr + Pb + Co + Cu + Mn + Ni + V) has a limit, again with no
specific attention to the toxicologic effects of each pollutant.
Dispersion modeling and assumptions on the potential presence of CrVI
demonstrated that this heavy metal can be the dominant pollutant in the health
impact of a plant, higher than the impact of dioxins and furans (PCDD/F) (Rada
2018). In spite of that, this result is not taken into account by the regulation in force
as the value of CrVI is not known as not requested in the analytical characterization.
The sector of SRF (Secondary Refused Fuel) may have potential problems from
CrVI emissions. This criticality is demonstrated by a few cases in the sector of
cement works. There, some plants are authorized for co-combustion of special
waste. An interesting case is the one of an Italian cement factory (Province of Como
2017) where SRF and sewage sludge (after thermal drying) are authorized for co-
combustion. An attention to the underlined problem is demonstrated by the fact that
those fuels are accepted at the gate of the plant only if they comply with limits of
some pollutants including total Chromium and CrVI.
Small painting works and small printing activities can be authorised with a release at
the stack that could give a local impact higher than the one of an incinerator. That is
demonstrated in a recent study (Appa 2018). In the case of painting activities, it was
demonstrated that closing a painting plant to give an adequate area to a modern
gasifier may allow a reduction of the local impact of CrVI (referring to the authorized
values). That is the consequence of the fact that small activities are authorized to
emit at low height with a consequent (often not estimated) limitation of the dilution
capability of the pollutants released. After analysing the complexity of the link
(among case studies) offered by CrVI, another overview of criticalities, linked by the
way of release, was studied. To this concern, it can be pointed out that steel making
plants are characterised by secondary and diffused emissions that could create a
significant local impact even if the conveyed emissions are managed with the best
available technologies. Indeed, the main stack is the only kind of emission that can
be monitored with a high detail. Unexpected potential emissions could come also
from bio-mechanical plants of RMSW. The problem could be related to the biofilter
that is often used to manage the emissions from the biological process. The height of
the biofilter is around 2 m. The temperature of release is around the room
temperature. The hydraulic load of release is around 100 m/h. As a consequence
the dilution is reduced. Until now, no criticality has been pointed out in the literature
(only few data were produced in Austria and Germany about 20 years ago, generally
not published in scientific papers). The produced values showed generally a high
variability. What was not analysed in that period is the risk associated to the local
contribution of the plant from the point of view of heavy metals. Indeed, a release of
one order of magnitude higher than a background value could be associated to an
individual health risk higher than 10-6.
Taking into account what found in the discussed case studies, an enhanced approach
to take CrVI impact under control is compulsory. A recent proposal focuses on it
(Rada 2018). The steps are:
- Ask for total Cr values at the stack from the laboratories involved in emission
characterization (avoiding receiving only sum of multiple heavy metals)

- Set a preliminary threshold for total Cr (taking into account comparatively the
toxicity of the other pollutants emitted and the typical ratio CrVI/total Cr in the
sector) so that, when total Cr analyses result beyond it:
- specific analyses of CrVI will be performed (case specific) in addition to total Cr
analyses
- a risk analysis will be developed in order to verify if a different threshold set for
the total Cr emissions at the stack must be introduced
It is clear that in case the plant is already authorised, the collaboration of the
company managing it is compulsory.
Moreover, the focus on the role of CrVI in specific contexts shown in this article
should be extended to other heavy metals.
Conclusions
The presented overview on the role of heavy metals in the industrial sector
(concerning their emissions into the atmosphere) demonstrates that their potential
impact may be underestimated.
That depends on a too simplified regulation that does not valorize the results of the
toxicological studies on heavy metals characteristics. The simplification is so hight
that, for the case of one of the most carcinogenic compounds, CrVI no analyses must
be made according to the regulation in force.
This simplification causes an anomaly in the EU approach as some inequalities in
the human exposure can be created. Solutions should be made integrating the
regulation in force with additional methodologies of emission characterisation based
on the valorisation of the toxicological information available for each heavy metal.
An additional problem can come from the way of release into the atmosphere.
Indeed, in case of low height releases, secondary emissions and diffused emissions,
the reduced dilution can cause an accumulation of heavy metals in the surroundings
of the plant.
References
APPA-Provincia autonoma di Balzano, 2018. Available from:
http://ambiente.provincia.bz.it/valutazioni-ambientali/archivio-procedure-via-
vas-screening-aia.asp.[12 July 2018]. In Italian.
Passamani, G, Rada, EC, Tirler, W, Tava, M, Torretta, V & Ragazzi, M 2017,
‘PCDD/F emissions from virgin and treated wood combustion’, International
Journal of Energy Production and Management, vol. 2, no. 1, pp. 17-27.
Rada, EC 2018, ‘Special waste valorisation and renewable energy generation under
a circular economy: which priorities’, 3rd International Conference on Energy
Production and Management: The Quest for Sustainable Energy, 10-12
September 2018, New Forest, UK.
PAT 2009, Studio di Fattibilità,‘Concessione di lavori per la progettazione,
realizzazione e gestione dell'impianto di combustione o altro trattamento
termico con recupero energetico per rifiuti urbani e speciali assimilabili in
località Ischia Podetti, nel Comune di Trento’, (Feasibility Sudy-combustion
plant or based on other thermal process with energy recovery for MSW and
special assimilable waste), Authonomous Province of Trento. [June 2009]. In
Italian.

INTERDISCIPLINARY STUDY REGARDING THE COLOIDAL SILVER

SOLUTIONS EFFECT ON MOMORDICA CHARANTIA L. DEVELOPMENT
Adriana Bira1,3, Zoltán Marosy2, Cristian Ion3

1
Hofigal Export Import SA, 2 Intrarea Serelor Street, district 4, Bucharest,
adrianaflorinabira@yahoo.com, Romania
2
Ecological University of Bucharest, Bucharest, 1G Vasile Milea Boulevard, district 6,
Bucharest, marosy.zoltan@gmail.com, Romania
3
University of Bucharest, Faculty of Physic, Doctoral School of Biophysics and Medical
Physics, 405 Atomistilor Street, Bucharest-Măgurele, alexandru.cristianion@yahoo.com,
Romania
Abstract
In the 21st century the world faces ecological problems due to the industrialization.
One of these issues may be intensive agriculture. The next study reflects the attempt
to use a natural means compounds in organic farming. Considering the antibacterial
capacity of the coloidal silver solutions was born the idea of using it in organic
farming for medical plants development.
Over the course of several years, the observations made have favored the balance to
lower concentrations of colloidal silver water solutions.
During this study was observed that the plants were more healthy and the production
and the quality of the fruits was also modiffyed.
The plant specie of Momordica charantia L. was chosen for its high interest in its
effects. The fruit being used in alternative medicine, also being called „natural
insulin”. The seeds used in the experiment were organic certified and were obtained
from already acclimatized plants. The experiment unfolding in partially protected
environment on an area of about 400 square meters.
This paper highlights the effects of seeds treatament and watering treatment with 3
different concentations (5 ppm, 15 ppm and 30 ppm) of colloidal silver watter
solutions on the development of Momordica charantia L. plants. It is worth
mentioning that in previous studies these concentrations attracted the most attention.
The most favorable results could be seen in plants treated with colloidal silver
solution at the higher concentrations.The Momordica charantia L. plants being
obtained by using organic farming method, this study can reflect an inovative
method of organic fertilization.
Keywords: colloidal silver, Momordica charantia L., organic farming
Introduction
Colloidal silver contains a suspension of silver nanoparticles in liquid solution. The
qualitty of a colloidal solution it is determinated by the dimension and the
concentration of the silver particles.
Silver nanoparticles (AgNPs) were prepared in aqueous colloidal dispersions by
reducing Ag + with glucose in alkaline medium.

The company uses Momordica charantia L. to produce food supplements with a

real economic success, so it is very important for it to be produced in an eco-friendly
way and to be of a good quality.
After applying successive treatments with colloidal silver water solutions, from seed
hydration to the end of the biocycle, no silver compounds were found in chemical
structure of plants. During the experiment, germination, plant growth, fructification,
and mineral content were pursued.
For three consecutive years 2016, 2017 and 2018 the experiment was repeated, the
results being similar in terms of plant quality.

On each trawl of approximately 100 square meters sowed 2 rows with a number of
71 nests per row, and each nest was sown with 3 seeds of Momordica charantia L.
organic certified. Insisting we have 142 nests on each trawl and a total of 426 seeds
sown properly.
The seeds sown in the first 3 trawls were kept hydrated for 2 hours in a colloidal
silver water solution with a suspension of 5 ppm and then another 22 hours in plain
potable water at a temperature of about 45 degrees Celsius.
Seeds sowed in the control trawl as a control were kept hydrated in heated water at
about 45 degrees Celsius for 24 hours after being seeded in the field.
After seed drilling in the field, 3 treatments with aqueous colloidal silver solutions
were performed of private origin (Aqua Nano 2018 ).
The observations have been made for three consecutive years.
Although the action of each element in the plant body manifests only in
interdependence with other elements, it can be shown that the physiological role of
the different anions and cations is appreciated by their participation in the functional
systems of the cell and the specific functions they exercise in normal, inadequate or
excess doses. Green plants predominantly absorb mineral substances, of which
organic substances are synthesized by chlorophyll assimilation.
Plant mineral nutrition is a physiological process of supplying plants with nutrients.
Green plants predominantly absorb mineral substances of which organic substances
are synthesized by chlorophyll assimilation.
Laboratory analyzes for the mineral content were performed during peak harvest by
the atomic absorption method. For laboratory analyses we made plant sampling
(dried fruits) from each study trawls, V1, V2, V3 (treated with 3 different
concentations, 5 ppm, 15 ppm and 30 ppm) of colloidal silver water solutions and
V4 named MARTOR representing the control (untreated).
Atomic absorption spectrometry can be defined as a method for determining the
concentration of an element in a sample by measuring radiation absorption in atomic
vapor produced by the sample at a specific wavelength and characteristic of the
element to be studied. Obtaining a population of free atoms is one of the main
functions of atomic absorption devices. It can be done by analyzing the sample in
the flame or electrothermal in the graphite furnace (Nitech 2018).
The flame occurs as a result of a combustion process involving a fuel (acetylene)
and an oxidant (air or nitrous oxide in the case of refractories). The flame is a source
of free atoms and at the same time a space in which they are continuously similar to
a cuvette of UV-VIS molecular absorption spectrometry (Nitech 2018).

The used device was an absorbtion and emission spectrometer AVANTA PM – air
acetylene – flame equipped with computer and cathodic lamp for each element. The
samples have been suposed to HNO3, H2O2, and HCl mineralization (Council of
Europe 2010), using an under pressure Berghof-MWS-Microwave digestion
apparatus (Popescu et al 2011, Popescu et al 2017, Ionescu et al 2014).

The mineral content influences the good development of the plants. (Pennazio 2005,
Hans et al 2015) An optimal content determines their correct development. The
analyses made by atomic absorption spectrometry on dried fruits, highlighted the
most important compounds for plant development.
Calcium is the most important element for root development. High calcium content
stimulates mitochondrial biosynthesis and regulates the elasticity of cell walls, so it
favours the stretching and division of the cells. (Shapoval et al 2011)
300
200
100
0
V1 - 5ppm V2 - 15ppm V3 - 30ppm V4 -
MARTOR
Figure 1. Calcium content in the dried fruits [mg/100g]
Analysing the calcium content from plant dried fruits, we observe in Figure 1 that
the samples from V3 trawl has the best content compared with those of V1 and V2
and with control plants from V4.
Magnesium is indispensable in the process of chlorophyll formation in plants as well
as in the synthesis of proteins, carbohydrates and lipids. It can also be considered an
enzyme activator for plant breeding.
150
100
50
0
V1 - 5ppm V2 - V3 - V4 -
15ppm 30ppm MART OR
Figure 2. Magnesium content in the dried fruits [mg/100g]
In the Figure 2 we observed that the best magnesium content was for V2 compared
with V1 and V2 plant samples and with V4.

Potassium is a stimulant in plant physiological processes, regulates the intensity of

photosynthesis, nitrogen metabolism and vitamin synthesis. This element influences
plants ability to absorb water and increases resistance to frost and drought.
3000
2500
2000
1500
1000
500
0
V1 - 5ppm V2 - 15ppm V3 - 30ppm V4 - MARTOR
Figure 3. Potassium content in the dried fruits [mg/100g]
In the case of potassium content, we observe that the V3 samples have the best
values compared with those of V1, V2 and with V4 (Figure 3)
Manganese is important for plant growth because it activates many enzymes
necessary for the formation of vitamins and reduces the content of nitrates absorbed
by the plants.
2
1.5
1
0.5
0
V1 - 5ppm V2 - V3 - V4 -
15ppm 30ppm MART OR
Figure 4. Manganese content in the dried fruits [mg/100g]
Manganese has a significant value at V3 samples, compared with V1, V2 and with
V4 (Figure 4).
Iron is absorbed by plants through the root system as ferrous and ferric salts. This
macronutrient influences photosynthesis, nitrogen metabolism and biosynthesis of
carotenoid and chlorophyll pigments. It is very important because the iron
deficiency slows plant growth. (Volker & Gabriel 2011)

60
40
20
0
V1 - 5ppm V2 - V3 - V4 -
15ppm 30ppm MART OR
Figure 5. Iron content in the dried fruits [mg/100g]
This important plant nutrient, iron, has the best value at V3 treated plants compared
with V1 and V2 plants and with untreated ones V4 as it was observed in Figure 5.
Zinc is very important for plant growth and development, fertilization, increased
frost and drought resistance, nitrogen fixation and chlorophyll synthesis.
10
8
6
4
2
0
V1 - 5ppm V2 - 15ppm V3 - 30ppm V4 -
MARTOR
Figure 6. Zinc content in the dried fruits [mg/100g]
The zinc value was significant increased, as we observe in Figure 6 and the best
value was obtained at V3 samples compared with V1, V2 and with V4.
We also studied quantitative differences between fruit harvested from each study
trawl, treated and untreated ones in Figure 7.
60
50
40
30
20
10
0
V1 - 5ppm V2 - 15ppm V3 - 30ppm V4 -
MARTOR
Figure 7. Quantitative difference in harvesting the fruit on an area of approximately

100 square meters for 5 successive weighing [Kg]

Comparing the fruit quantities from each 100 square from each studied trawl, we
conclude that was obtained a significant value for V3 sample compared with V1 and
V2 and all of them with V4 - untreated trawl.
We also made a germination study, between all of the sampling treated and
untreated, used for planting in nests on each studied trawl, V1, V2, V3 and V4.
70
65
60
55
50
V1 - 5ppm V2 - 15ppm V3 - 30ppm V4 -
MARTOR
Figure 8. Seeds germination in the field (%)
We observe in Figure 8, that the best germination value, as percentage, was for V2
trawl, around 70 % compared with V3 aproximate 65%, V1 less than 65 % and V4
untrated less than 60%.
From the below images (Figure 9, Figure 10) we can observe consistent growth
differences betwen the control plants (untreated) – V4 named MARTOR and the
sample plants (treated with a solution having a silver concentration of 30 ppm ) –V3.
Figure 9. Momordica charantia L. V4 – MARTOR (the weakest results)

Figure 10. Momordica charantia L. V3 – 30 ppm (the best results)
The results were favourable in the case of colloidal silver aqueous solutions with
higher silver concentrations and this aspect is important for Momordica charantia L.
development, which has a great economic importance. Therefore, the growth of
production in the cultivation process is being pursued, in this case the fruit of the
plant is very much used. It is therefore intended to obtain as large quantities as
possible.
Conclusions:
After the Momordica charantia L. studies, we could conclude that: there were
obtained good effect results regarding the use of seeds treatment and watering
treatment with colloidal silver aqueous solutions on the plants, as important aspect
in development of an inovative method of organic fertilization.
After applying successive treatments with colloidal silver water solutions, from seed
hydration to the end of the biocycle, we made analyes regarding mineral fruit
content because that content could demonstrate the benefits of the tratement on the
good development of the plants. So, we used atomic absorption spectrometry on
dried fruits and the results were: the highest calcium concentrations were found in
plant treated with colloidal solution 15 and 30 ppm (V3 and V2); a good content of
magnesium for V3 and V2 dried fruits; potasium content was the highest for V3 (30
ppm); Manganese and Iron content in the dried fruits was very good for V3 (30
ppm); high levels of Zinc was detected at V2 (15 ppm) and V3 (30 ppm).
Regarding the quantities of fruits harversted from each trawel, large amounts of
fruits have been harvested from the plants of Momordica charantia L. treated with
colloidal silver aqueous solutions at 15 and 30 ppm (V2 and V3).
We also made a germination study and we observe that the best germination was for
V2 (15 ppm).
The final conclusion was that the results were favourable in the case of colloidal
silver aqueous solutions with higher silver concentrations and the best version in the
development of the plants was the one that aimed at their treatment with aqueous
colloidal silver solution at a concentration of 30 ppm – V3.
This study represents a development point for the other next studied related with
aqueous colloidal silver solution use on other interest plants.
References
Agricultural Sciences, Available from: http://agris.fao.org/agris-
search/search.do?recordID=RU2016001637. [20 March 2018].
Aqua Nano, Colloidal silver and the environment, Available from:
https://www.coloidale.ro/index.php/en/colloidal-silver/53-centru-argint-mediu.
[19 June 2017], in Romanian.
Council of Europe 2010, European Pharmacopoeia, Seventh Edition, Strasbourg,
France.
Hans, L, Patrick E, Hayes, E, Laliberte, RSO & Benjamin, LT 2015, 'Leaf
manganese accumulation and phosphorus-acquisition efficiency', Trends in
Plant Science, Elsevier, vol. 20, no. 2, pp. 83-90.
Ionescu, D, Popescu, M, Rizea, GD, Mihele, D, Bulearca, G, Ivopol, M & Mihalcea,
F 2014, 'Polyphenols and minerals, antioxidants in the plants used in the
natural treatment of hepatobiliary disorders', Revista de Chimie, vol. 65, no. 5,
pp. 507-511.
Nitech, Instruments, Available from: http://www.nitech.ro/pagini/noutati/tehnic/pg-
instruments-990fgf-spectrofotometru-de-absorbtie-atomica-514.html.
[22 February 2018]
Pennazio, S 2005, ‘Mineral nutrition of plants: a short history of plant physiology’
Rivista di Biologia, vol. 98, no. 2, pp. 215-36.
Popescu, M, Puiu, D, Mihalache, M, Bordei, N, Raiciu, AD, Cristea, I, Galaon, T &
Pascu, LF 2017, 'A study of the content in volatile oils and their composition
of various aromatic herbs from ecological soils', 20th International Symposium
"The Environment and the Industry", SIMI 2017, National Research and
212.
Popescu, M, Danciu, T, Danciu, E, Ivopol, G & Manea, S 2011, 'Natural
antioxidants, free-radical-scavengers and minerals, in fresh juices and
vegetables', Revista de Chimie, vol. 62, no. 8, pp. 761-765.
Shapoval, OA, Mukhina, MT, Pryanishnikov, A, Klimov, AI & Kudrinsky, AA
2015, Central Scientific Agricultural Library, Russian Academy of
Agricultural Sciences, Available from: http://agris.fao.org/agris-
search/search.do?recordID=RU2016001637. [20 March 2018].
Volker, R & Gabriel, S 2011, 'Iron transport in plants: Future research in view of a
plant nutritionist and a molecular biologist', Soil Science and Plant Nutrition,
vol. 50, no. 7, pp. 1003-1012.

MEMBRANE FILTRATION EFFICIENCY ON TRIAZINE HERBICIDES IN

ORGANIC AND AQUEOUS SOLUTIONS
Roxana-Elena Scutariu1, 2, Vasile Ion Iancu1, 2, Gheorghe Nechifor2, Gabriel-Lucian Radu2,

Marius Simion1, Marcela Niculescu1
1
Podu Dambovitei, DISTRICT 6, 060652, Bucharest, roxgrigoras@gmail.com, Romania
2
University Politehnica Bucharest, Faculty of Applied Chemistry and Materials Science, 1-7
Polizu Street, code 011061, Bucharest, Romania
Abstract
The filtration efficiency of organic contaminants like triazine herbicides class
(simazine, atrazine and propazine) has been tested using more types of filter
membranes (PTFE, glass, cellulose acetate, regenerated cellulose) from synthetic
solutions with variable content of organic modifiers (acetonitrile and methanol).
Thus, 2 mL of synthetic solutions (10%, 25%, 50%, 75% and 100% methanol and
respectively acetonitrile) were filtered on each of the membrane filters. Simazine
pesticide responds very well on PTFE, glass and regenerated cellulose filter
membrane when the organic modifiers was acetonitrile. An excellent recovery was
obtained when filtering simazine with 25% ACN on PTFE, glass and regenerated
cellulose. In case of atrazine was observed a good recovery on the four filters when
the solution contained 100% acetonitrile and 75% methanol. The propazine has an
efficient filtration on all four membranes, on hydrophobic and hydrophilic
membranes, contrary to theoretical prediction. For the samples prepared in 100%
organic solvent (methanol), PTFE filters provided excellent recovery (>95%) for all
three pesticides (simazine, atrazine and propazine). The study is useful in the
filtration stage of organic extracts resulting from processing of environmental
samples (water / soil).
Keywords: environmental, liquid chromatography, membrane filters, pesticides
Introduction
Triazine herbicides (simazine, atrazine and simazine) are the most widely used
group of herbicides since their discovery in the 1950s, constituting a group of
chemically similar compounds used to control certain annual broadleaf weeds and
grasses throughout the world (Grover 1988). Current research documents with
increasing frequency show that many synthetic organic micro- pollutants, such as
pesticides are present in drinking water sources throughout the world (Novotny
1999). The presence of pesticides in water sources and soil is becoming a concern in
drinking water production, wastewater treatment, and water reuse applications due
to potentially adverse health effects associated with these compounds. Numerous
studies performed on laboratory animals have shown that a series of pesticides is
involved in endocrine disruption, while many of the well-known herbicides (such as
atrazine) are blamed for long term toxicity and carcinogenicity. For this reason, they
are considered as the most thoroughly tested and regulated substances in use today.

Simazine (C7H12ClN5) is adsorbed especially in particulate form and rarely in

gaseous form (gas/particle ratio may be in the range of 20%/80%)
(Tissier et al 2005). It is used to control broad-leaved weeds and annual grasses and
it remains active in the soil for 2-7 months after application. Atrazine (C8H14ClN5)
use was denied by the EU, due to its contamination of drinking water and
subsequent problems for humans (Ackerman 2007). However, it continues to be one
of the most widely used herbicides in the world. It is considered to be persistent due
to its moderate water solubility (33 mg/L) and small soil sorption partition
coefficient (Kd=3.7 L/kg) (Smalling & Aelion 2006).
The large use of triazines and the similarity of their physicochemical properties such
as water solubility, high polarity, low degree of adsorption in soils and high
persistence, are the cause of the frequent occurrence of these chemicals and their
metabolites in groundwater.
Micro-membrane filtration is a mandatory step in developing new chromatographic
methods for the detection of organic pollutants in the environment (Galaon et al
2017, Kim et al 2017, Popescu et al 2017).
The objective of this work is to study the performance of membrane filters in the
filtration of organic extracts from processing of environmental samples (water, soil).
In Table 1 the chemical structure and the IUPAC chemical name of the selected
pesticides are presented.
Table 1. Chemical structure and IUPAC chemical name of the pesticides

Compounds/ Molecula Chemical Molecular Log Aqueous
IUPAC chemical r formula structure weight Kow solubility
name (g/mol) (mg/L)
Simazine C7H12Cl 201.7 2.18 5.0
6-chloro-2-N,4-N- N5
diethyl-1,3,5-
triazine-2,4-diamine
Atrazine C8H14Cl 215.7 2.61 33
6-chloro-4-N-ethyl- N5
2-N-propan-2-yl-
1,3,5-triazine-2,4-
diamine
Propazine C9H16Cl 229.7 2.93 8.6
6-chloro-2-N,4-N- N5
di(propan-2-yl)-
1,3,5-triazine-2,4-
diamine
Solvent type, membrane filters type and percent of solvent volume were examined
respectively. The reverse-phase high performance liquid chromatography (RP
HPLC) separation with Multi-Wavelength Detection (MWD) was applied for the
determination of triazines from the samples. Selection of a filtration device with an
appropriate pore size ensures effective particulate removal while minimizing sample
loss. In table 2 the membrane filter used on filtration was described.

Table 2. Description of membranes used to filter solutions

Membrane Diam Pore Resistance of membrane Hydrophobicity/
eter Size Hydrophilicity
(mm) (µm)
PTFE 25 0.45 All kinds of solvents Hydrophobic
Glass Microfiber 13 0.45 Aqueous and/or organic Hydrophilic
Cellulose acetate 25 0.45 Aqueous and/or alcohols Hydrophilic
Regenerated 25 0.45 Aqueous and/or organic Hydrophilic
cellulose solvents

Reagent and solvents
Pesticides: simazine (99.2 purity), atrazine (99.2 purity) and propazine (99.2 purity)
were all purchased from Riedel-de Haën (Germany), with certified quality. HPLC-
grade acetonitrile, methanol was supplied by Scharlab (Barcelona, Spain) and Merck
(Darmstadt, Germany). High purity water was produced by passing double distilled
water through Milli-Q water purification system (Millipore, Bedford, MA, USA).
The filters were purchased as follows: glass microfiber filters (0.45 µm GMF) from
Whatman (United Kingdom); membrane filters (0.45 µm Cellulose Acetate) from
Frisenette (Denmark); membrane filters (0.45 µm PTFE) from Macherey-Nagel
(Germany) and Econofilter (0.45 µm RC) from Agilent Technologies (Romania).
Stock standard solutions of simazine, atrazine and propazine were prepared in
methanol to achieve the final concentration of 500 μg/mL each. Standard mix
solutions (synthetic) were prepared at 5μg/mL in 10%, 25%, 50%, 75% and 100%,
v/v methanol/ultrapure water and acetonitrile/ultrapure water. From each of the
mixed solutions a volume of 0.25 mL was taken and then diluted in a 25 mL
volumetric flask. All stocks and diluted standard solutions were protected against
light in amber vials and were stored at 4°C.
Equipment
The samples were analyzed by using a liquid-chromatographic Agilent 1100
(Agilent Technologies, USA). The system was equipped with a degasser, quaternary
pump, autosampler, a column thermostat and multiple wavelength detectors
(MWD). The separations were performed on a BDS Hypersil C8 analytical column
(150 mm length, 4 mm i.d, 5 µm particle size) acquired from Thermo Scientific
(Waltham, Massachusetts, USA) protected by a BDS Hypersil C8 (10 mm x 4.6 mm
i.d., 5 µm) guard column. System control and data acquisition were achieved by
means of a computer equipped with an Agilent Chem Station program.
HPLC-MWD conditions and calibration

For this study a rapid LC-UV method was developed for the determination of the
three pesticides (atrazine, simazine and propazine) in the synthetic solution.
The optimized conditions were as follows: a mobile phase flow rate of 1 mL/min
and an injection volume of 5μL were used. Solvent A is ultrapure water (H2O) and
solvent B is acetonitrile (ACN). The elution of analytes was isocratic with 52.5%
H2O and 47.5% ACN, performed over a time of 6 minutes. The temperature of the
column was 20°C. The detection was performed at 223 nm for all compounds which
was determined to be at the optimum wavelength in preliminary studies performed
on a scanning spectrometer. There were compounds identified in the chromatograms

comparing the retention time of the peaks with that of the corresponding compounds
in the standard solution. Five concentration levels injected in triplicate were used to
build the calibration curves, by means of an external standard method based on peak
areas. Good linearity was found for all compounds in the concentration range of
0.57-11.97μg/mL with correlation coefficient (R2) values higher than 0.99. Table 2
shows the quality parameters of the analytical procedure for each compound:
regression equations, correlation coefficients, concentration range, repeatability
(intra-day precision).
Table 3. Figures of merit for the analytical procedure of simazine, atrazine and
propazine
Concentration
Regression Repeatability
Compound R2 range
equation (RSD) (n=4)
(μg/mL)
Simazine y=51.51x- 4.69 0.99963 0.57-11.40 3.2
Atrazine y=48.01x- 5.07 0.99961 0.52-10.40 3.9
Propazine y=47.70x- 6.72 0.99953 0.59-11.97 3.6
Filtration of synthetic solutions

A volume of 2 mL for each synthetic solution with different percent of solvent
(10%, 25%, 50%, 75% and 100% v/v methanol/ultrapure water and
acetonitrile/ultrapure water) was manually passed through PTFE filter, glass filter,
cellulose acetate and regenerated cellulose using 2 mL glass syringe. The filtrate was
collected into an autosampler vial and was injected in the LC system.

The efficiency of acetonitrile solutions filtration
The significance of each parameter in case of pesticides filtration is directly related
to the particular solute properties (molecular weight, molecular dimensions: length
and width), the polarity (dipole moment), the acid dissociation constant (pKa), and
hydrophobicity/hydrophilicity (logKow) which determines the strength of the
pesticide-membranes physicochemical interaction.
The filtering behaviour of the triazine herbicides class on the membranes filters:
PTFE, glass, cellulose acetate and regenerated cellulose using different percentages
of organic solvent (acetonitrile) is shown in Figure 1. The data consists of
percentages indicating the recovery of compounds passed through the filters, as
calculated from the peak areas integrated in the HPLC chromatograms.

(a) (b)
(c) (d)
Figure 1. Filtration recovery evaluation results for aqueous/ acetonitrile sample
media on PTFE (a), glass (b), cellulose acetate (c) and regenerated cellulose (d)
Adsorption of the selected chlorinated herbicides (atrazine, simazine and propazine)

was observed on all four membrane filters employed. The adsorption is different,
depending on the solute and the membranes properties, but it is mainly facilitated in
the hydrophobic region of membrane materials due to hydrophobic interactions.
From Figure 1 it was observed that the simazine has an efficient filtration on PTFE,
glass and regenerated cellulose (recovery between 90.4 and 101.7) compared to the
CA for which were obtained lower values (78.4% - 94.0%). The maximum recovery
rate was obtained when filtering the solutions with 25% ACN (PTFE, glass and
regenerated cellulose). In the case of PTFE membranes it was achieved a recovery in
the range 90% -101% for solutions in ACN% between 10 and 100%.
The atrazine pesticide has presented the following recovery range for use of
acetonitrile as a solvent: PTFE 85.6% (10%) - 102.3% (100%); glass 80.1% (10%) -
100.9% (100%); cellulose acetate 95.8% (10%) - 101.9% (100%); regenerated
cellulose 86.3% (10%) - 101.9% (100%). Low efficiency is shown for PTFE, glass
and regenerated cellulose membranes in the case of a low percentage of organic
modifier (10% and 25% acetonitrile). Starting with 50% ACN, the herbicide shows
maximum efficiency on all membranes.

The propazine has an efficient filtration across all four membranes, both on
hydrophobic PTFE membranes corresponding to the lowest polar character (log
Kow=2.93, Table 1) and on other hydrophilic membranes, contrary to theoretical
prediction. The recoveries ranged for PTFE between 94.0% (25% ACN) and 100.7%
(100% ACN); for glass 93.2% (25% ACN) and 100.9% (100% ACN); for cellulose
acetate 94.9% (25% ACN) and 99.4% (100% ACN); and for regenerated cellulose
95.0% (25% ACN) and 103.8% (100% ACN).
It has been noticed that the use of ACN as a solution preparation solvent leaded to
filtration efficiencies higher than MeOH of up to 16% (in case of atrazine the use
cellulose acetate as a membrane filter with 100% ACN generated a recovery of
101.9% compared to 85.6% at 100% MeOH).
The efficiency of methanol solutions filtration

The potential adsorption of the triazines class on to membranes filters PTFE, glass,
cellulose acetate and regenerated cellulose using different percent of organic solvent
(methanol) is shown in Figure 2.
(a) (b)
(c) (d)
Figure 2. Filtration recovery evaluation results for aqueous/methanol sample media
on PTFE (a), glass (b), cellulose acetate (c) and regenerated cellulose (d)
For the samples in 100% organic solvent (methanol) PTFE filters provided excellent
recovery (>95%) for all pesticides (simazine, atrazine and propazine). However,
glass filter, cellulose acetate and regenerated cellulose (RC) caused loss of atrazine
pesticide during filtration.
The simazine pesticide presented the following recovery ranges for use of methanol
as solvent: PTFE 76.8% (10%) - 100.2% (100%); glass 76.6% (10%) - 99.6%
(100%); cellulose acetate 72.4% (10%) - 95.3% (100%); regenerated cellulose
78.6% (10%) - 100.8% (100%). Excellent recovery was obtained for PTFE, glass
and regenerated cellulose membranes in case of a high percentage of organic
modifier (100% methanol). The retention of compounds in filters by adsorption in
case of aqueous solution (10%) can be due physical interactions between simazine
and sorbent. It is recommended to avoid filtering the simazine in aqueous solution
by this type of membrane.
Excellent and consistent recoveries (>95%) were evident for atrazine when using all
syringe filters with a proportion of methanol/water 75:25 (v/v). The results showed a
decrease of recovery (<92%) when using PTFE, glass and regenerated cellulose
filters with low percentage of methanol. Similar behavior was observed in case of
simazine and propazine by use of aqueous (10%) solutions on PTFE, glass and
regenerated cellulose.
In case of propazine, good overall recovery (>95%) in all three filter materials
(PTFE, CA and RC) was obtained when the proportion of MeOH in the sample was
100%. For glass filter the best recovery was obtained at 50% (96.3%). Propazine
recoveries were in the following ranges: for PTFE 88.2% (75% MeOH) - 100.0%
(25% MeOH); for glass 90.3% (10% MeOH) - 101.6% (25% MeOH); for cellulose
acetate 82.6% (10% MeOH) - 91.6% (75% MeOH); and for regenerated cellulose
87.32% (75% MeOH) - 99.1% (100% MeOH).
The PTFE, glass and RC filters gave the worst recovery when the samples contained
MeOH at 10%. Once the MeOH concentration was increased to at least 25%, all
three filters gave similar high recovery results for all analytes. This study showed
that if the sample needs filtration, the sample should contain at least 25% MeOH to
prevent recovery losses due to filter absorption.
Conclusions
Filtration using syringe filters was shown to be a simple, easy and efficient step for
the analysis of triazine pesticides. The membrane can affect the potential adsorption
of pesticide during filtration, and therefore selection of the appropriate filters,
including membrane type, pore size and filter dimension is critical to achieve
accurate and precise results.
The performance of PTFE, glass, cellulose acetate and regenerated cellulose
membrane filters in retaining three pesticides (atrazine, simazine and propazine)
from synthetic solutions was studied. The results showed that the recovery varied
according to the proportion of water/solvent (acetonitrile and methanol) and the
material of the membrane. The recovery of pesticides increased when the percentage
of solvent was higher. The results confirm that the PTFE membrane shows a better
performance for all pesticides compared to the glass membrane.
In conclusion, PTFE syringe filters were shown to be an excellent choice for
filtering of triazine pesticides, by providing excellent filtration recovery.

References
Ackerman, F 2007, 'The economics of atrazine', International Journal of
Occupational and Environmental Health, vol. 13, no. 4, pp. 441-449.
Galaon, T, Petre, J, Iancu, V & Niculescu, M 2017 'Determination of estrogenic
steroids in sewage sludge samples from eight domestic wastewater treatment
plants', 20th International Symposium "The Environment and The Industry",
Grover, RA 1988, 'Environmental Chemistry of Herbicides', CRC Press, Boca
Raton, Florida, pp. 45-88.
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2017 'Experimental models of characterization and analysis of industrial
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Science and Technology, vol. 39, no. 3, pp. 1-13.
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Pascu, LF 2017, 'A study of the content in volatile oils and their composition
of various aromatic herbs from ecological soils', 20th International Symposium
"The Environment and The Industry", SIMI 2017, National Research and
212.
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atrazine in coastal aquatic sediments', Chemosphere, vol. 62, no. 2, pp. 188-
196.
Tissier, C, Morvan, C, Bocquené, G, Grossel, H, James, A & Marchand, M 2005,
'Les substances prioritaires de la Directive cadre sur l'eau', Ifremer, Fiches de
synthèse.

MICROSTRUCTURAL AND CHEMICAL CHARACTERIZATION OF

SOME WESTES FOR PHONOABSORBANT MATERIALS OBTAINING
Mihai Bratu, Luoana Florentina Pascu, Cristea Nicolae Ionut, Nicolescu Ileana
National Research and Development Institute for Industrial Ecology – ECOIND, 71-73
Drumul Podu Dambovitei, district 6, 060652, Bucharest, poluare.aer@incdecoind.ro, Romania
Abstract
Composite materials obtaining, based on wastes mixing, can have both, economical
and social positive impact, and also the use of such composites materials leads to a
level of environmental pollution reduction, generally, and in the level of noise
pollution, particulary. This aim of this study is essential for the future development
of such materials because, the results will give us informations regarding the
formulation of oxide and polymeric composite materials, by associating the
components and leads us to superior properties products, having the property to
absorb sound waves. In this paper we characterize a number of wastes that are
resulting from industrial technological processes. The wastes are characterized by
granulometry, oxide composition and apparent porosity that are specific properties
for obtaining composite materials with sound-absorbing properties.
Keywords: apparent porosity, granulometry, oxide composition, sound-absorbing

properties, wastes
Introduction
The increase of the world population related with human activities from the last
century, esspecially from industry and transports, have lead to an accentuate
deterioration of the environmental air, with significant effects on climate, affecting
the environment and also human health (Bucur & Danet 2016, Danciulescu et al
2015, Minghua et al 2009, Petrescu et al 2017). This paper have an great importance
theme with economic and ecological impact regarding the different wastes use
which by their storage can affect the quality of the environment, in order to obtain
composite materials with sound absorbing properties. Thus, two interest objectives
will be achive, based on that study, namely the reduction of environmental pollution
through the reuse of various wastes and the reduction of the noise pollution. One of
the many environmental problems threatening our planet, a major one is, without a
doubt, wastes (Lilliana et al 2013). These wastes are resulting from multiple human
activities, and are representing an issue due to the continuous increase of the
quantities and of their types (which by natural degradation can represent a danger for
the environment and the population health) as well as the significant quantities of
reusable materials and energy, that can be recovered and entered into the economic
circuit (Serbanescu et al 2017, Guta et al 2017). National Rules in waste
management domain must be adapted to General European Reglementations
regarding the prevention of generate wastes and reducing resource consumption and
practical aplication of wastes hierarchy (Danciulescu et al 2017, Directive 2008/98,
Emergency Ordinance 195/2005, Law 211/2011).
Studied wastes from this paper are made from organical or anorganical matter
(oxidic wastes) such us: wooden wastes, thermal plants fireplace slag, domestic
sterile wastes, sunflower husks seeds ash and metallic waste smelting slag
(Figure 1). The aim is to obtain composite materials with sound absorbing properties
by combining selected wastes with the oxide matrix - binder matrix obtained from
selected and activated CaCl2 + CaO (Bratu et al 2016, Stoleriu & Teoreanu 2006,
Stoleriu et al 2004, Teoreanu et al 2005, Teoreanu & Stoleriu 2002) wastes or
polymeric matrix and therefore the selected wastes are characterized in terms of
granulometric distribution, oxidative composition and apparent porosity, important
physical properties for phonoabsorbent composites.

Firstly the wastes used for studing in this project were dried, in accordance with in
force standard (SR ISO 5264-1995). Total humidity was determined by summing the
of Wî ibibation humidity and of Wh hygroscopic humidity, according to the
ecuation (1), and the resulting values are shown in the Table 1.
Wt = Wî + Wh (1)
where: Wî- inbibation humidity; Wh- hygroscopic humidity
Table 1. Total humidity for studied wastes
Sample Total humidity
Wastes
No. Wt (%)
S1 Wooden waste 36.42
S2 Thermal plants fireplace slag 48.75
S3 Thermal plants ash 53.20
S4 Sunflower husks seeds ash 55.44
S5 Metallic waste smelting slag 50.02
S6 Domestic sterile wastes 49.86
After drying, large grain wastes were grinded (thermal and metallic waste smelting
slag) according to in force standard (SR ISO 2591-1: 2003). The drying process was
necesary esspecialy due to storage conditions of these materials.
Secondly the selected wastes used in this paper were analyzed in terms of
granulometric distribution by sifting for the coarse fraction, as the case may be, for
wooden waste, thermal plants fireplace slag, domestic sterile wastes, thermal plants
slag, thermal plants ash, sunflower husks seeds ash, metallic waste smelting slag
according to in force standard (SR EN-933-1:2002). The sifting operation was
carried out with the Verder A5200 basic device, which can fit up to 8 sites. Fine
fractions were identified using the MALVERN MASTERSIZER 2000 laser beam
granulator (SR ISO 13320-1: 2001). All of these wastes were monitored to have a
well-controlled granulometric distribution to ensure the reproducibility of all the
data obtained. XRF analyzes were performed using a Rigaku Gas Cromatography
analyzer (Rigaku, Japan) equipped with a 50W - X-ray source with a Pd anode.
Detection was performed using a silicon drift detector (SSD) maintained at optimal
temperature via a Peltier system. To perform the samples, the internal calibration
was performed initially. Samples were pre-calcined at 550 ° C and homogenized and
then analyzed (SR 15309:2007). Samples representing the waste selected for the

production of composite materials with phonoabsorbant properties were also

analyzed in terms of apparent porosity.
Porosity determination was performed according with SR EN 993-1:1997. Thus, a
portion of each waste sample was initially weighed (mi), then in water immersed,
after which weighed the mass (mf).
The apparent porosity (na) is determined with the (2) relation:
na = (mf – mi)/ρl (%) (2)
where: mf - final mass ; mi - initial mass ; ρl - density of the liquid
Figure 1. Images for analised waste samples

S1-Wooden waste
Wooden waste are the result of making wooden boards. The dimensions of the
shanks are different: ranging from 0.1mm to 15 mm as seen in Figure 2. The siving
was performed at 0.25, 0.5, 2, and 4 mm.
Figure 2. Granulometric distribution of wooden shanks waste

From the mass of material suposed to the granulometric analysis, different
proportions were obtained as follows: remaining on the 4 mm sieve – the qantity of
47.2%; between 2 ÷ 4mm the remaining quantity was 6.5%; between 0.5 ÷ 2mm the
remaining quantity was 8.2%; between 0.25 ÷ 0.5mm the remaining quantity was
22.5%; sieved through 0.25 mm the ramaining quantity was 15.6%. Thus, a large
proportion of the material representing the wood shanks remaining on the 4 mm
sieve is observed. The distribution of the varied granulometric distribution of this
waste, with very few fine fractions and a large proportion of coarse fractions over
4.00 mm (almost 47.2%), can condition the formation of a non-homogeneous

structure of the reinforced composite with variable porosity and very large pores
alternately with small pores.
S2-Thermal plants fireplace slag and S3-thermal plants ash

Most of the thermal power plants operate with solid fuel and the result of the
combustion process is the combustion slag and the ash of the thermal plant. Figures
3a and 3b show the granulometric distributions of coarse fractions (Figure 3a for
slag) and fine fractions (Figure 3b for thermal ash). Figure 4 also shows the oxide
composition for these types of waste.
(a) (b)
Figure 3. Granulometric distribution of thermal plants fireplace slag (a) and thermal
plants ash (b)
Figure 4. Oxide compozition of thermal plants fireplace slag and of thermal plants
ash
We observe a weight of slag remaining on the 0.25 mm sieve of 56.9% and for the
ash of the thermal power the fine particles with the size between 2-800 μm.
Depending on the composition of the processed ore, the slags are characterized by a
complex chemical oxide composition; along with the main oxides: CaO, MgO, P2O5
and K2O, they also contain small amounts of Al2O3 and SiO2 MnO, TiO2, P2O5,
Cr2O3, etc. Therefore, the crystalline phases of the blast furnace slag represent a
mixture of silicates, silico-alumina and, as the case may be, calcium and magnesium
aluminates, as well as very small amounts of oxidic-silcate combinations in
particular with iron, titanium, manganese; it is also noted the presence of small
amounts of sulphides and combinations with phosphorus - phosphates and
phosphosilicates.
S4- Sunflower husks seeds ash (from thermal plants)

Because of the storage conditions and for this type of waste, it was necessary to
perform the drying operation and determine the total moisture Wt according to the
relation (1), after which the resulting ash at the seed husks burning was subjected to
the sifting operation and determination of the granulometric distribution Figure 5a.
Also, the ash resulted from the burning process, was analyzed from the point of view
of the oxide composition shown in Figure 5b.
Figure 5. (a) granlometric distribution; (b) oxide composition for the resulting ash
from the burning of sunflower husks seeds
The granulometric distribution for this type of waste has a large proportion with the
material passed through the sieve of 0.25 mm, namely - 50.5%. Also, a large
proportion of the material was also determined on the 0.25 mm sieve - 36.8%, while
the other quantities were lower. The ash resulting from the burning of seed husks is
a powder whose oxide composition presents CaO in a higher amount but also K2O,
MgO, SiO2 and P2O5 in smaller quantities, as shown in Figure 5b. In order to obtain
ash-based oxide composite materials resulting from the burning of sunflower seed
husks, the hydration process must be activated to provide an adequate kinetics as
well as an adequate basicity of the system. So, the presence of the oxides shown
above may influence the binder system and, of course, the obtaining of the
composite material.
S5- Metallic waste smelting slag

Due to the very high temperature of the slag obtained from the electrical melting of
metallic wastes, cooled with water, which means a sudden cooling with pore
formation on the surface of the material. It is a property acquired for smelting slag
which can have an advantage in terms of phonic wave absorption, because the
porosity of a material influences in a positive sense the absorption coefficient of the
sound waves. The smelting slag is a high density, hardness and porosity material,
which is in the form of large boulders. Thus, it was necessary the grinding process
as a first step, then sieving, to determine the granulometric distribution shown in
Figure 6a and the oxidic composition shown in Figure 6b.
Figure 6. (a) granlometric distribution; (b) oxide composition for the metallic waste
smelting slag
A granulometric weight with a maximum of 0.5-2.00 mm of approximately 40%
was observed. Also, the granulometric fraction approximately to 2.00-4.00 mm is
present in proportion of 30%. The fine fractions were by 0.25-0.5 mm and present in
proportions lower than 6.6% and 14,1%, respectively, similar to coarse fractions
over 4.00 mm. This granulometric distribution, with a significant proportion of
mono-grain fractions of 0.5-2.00 mm and 2.00-4.00 mm, respectively, can give the
composite material a uniformity, high porosity structure and can give the composite
good sound-absorbing capacity. The slag resulting from the melting of metallic
wastes is a by-product of melting arc. The oxide composition, seen in Figure 6b,
shows a higher amount of Fe2O3 followed by CaO and SiO as well as MgO, Al2O3,
MnO and Na2O in smaller quantities.
S6-Domestic sterile wastes

It is a mixture of household wastes. The sample was brought to the laboratory after
sterilization at 120oC. Due to the storage conditions it was necessary to carry out the
drying operation and the determination of the total humidity; the material was
screened by the granulometric distribution shown in Figure 7a. Also in Figure 7b is
the oxidic composition of this type of waste.
Figure 7 (a) Granulometric distribution; (b) the oxidant composition for domestic
waste.
From Figure 7a, a very small amount of coarse remaining material on the 4 mm
sieve (0.7% of the entire amount of sieve material) is observed. On the other site, the
amount of sieve material increases, so that it passed the 0.25 mm sieve, represents a
quantity of about 45.2%. The sterylated domestic waste sample, and studied in terms
of the oxide composition, contains a larger amount of oxides such as: SiO2, CaO,
Na2O, Al2O3 and K2O. Also, anions of the type of SO42-, SO32- were identified in the
composition of this waste. The selected samples were identified for the production
of composite materials with phono absorbing properties, were also analyzed in terms
of apparent porosity. In order to obtain composite materials where the absorption of
sound waves to be hight, it is necessary to obtain materials with higher porosity.
Thus, Figure 8 shows the result of the determination of the apparent porosity of the
analyzed samples.

Figure 8. The aparent porosity of waste samples: S1- Wooden waste;S2- Thermal
plants fireplace slag; S3- Thermal plants ash; S4- Sunflower husks seeds ash; S5-
Metallic waste smelting slag; S6- Domestic sterile wastes
The porosity is the principle property that gives composite material the ability to
absorb sound waves. The formation of voids on the surface and in the depth of the
sample influences the retention of the sound waves and implicitly the reduction of
the sound pressure level. As a result of the apparent porosity, it is as certained that:
for the metallic waste smelting slag, a good apparent porosity has been obtained, so
that the use of this type of waste by incorporating it into the oxide matrix can give
the composite material a good sound waves. absorption capacity. The same as S1-
wooden waste and S4- sunflower husks seeds ash. can be used as reinforcement
material both in the oxide matrix and in the polymer matrix.
Conclusions
In this paper were selected and characterized from a microstructural and chemical
point of view six different types of potentially usable wastes for obtaining phono-
absorbing composite materials: S1- wooden waste; S2- thermal plants fireplace slag;
S3- thermal plants ash; S4- sunflower husks seeds ash; S5- metallic waste smelting
slag; S6- domestic sterile wastes. The porosity is the principle property that gives
composite material the capacity to absorb sound waves, while particle sizes (based
on granulometric test results) can provide information about the possibility of using
wastes as reinforcement material and/or binder. The possibility of using oxidic waste
as a binder for the preparation of composite materials is evidenced by the proportion
in which CaO, SiO2, Al2O3, MgO. Based on the obtained results, we can conclude
that: i) wood wastes can be successfully used as reinforcement materials; ii) as well
as the thermal plants fireplace slag and metallic waste smelting slag can be used as
reinforcement materials due to porosity and granulometry; iii) the fine fractions of
the other wastes can be used in binder matrix for obtaining oxide composite
materials.
The studies will be continue by conducting experiments to obtain composite
materials and testing their absorption capacity.
Acknowledgements
This work would not have been possible without the financial support of the Romanian Nucleu
Programme.

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ORGANIZATION OF HYDROGEOLOGICAL MONITORING WITHIN

THE UKRAINIAN PART OF THE TISZA RIVER BASIN
Lidiia Davybida
Department of Geotechnogenic Safety and Geoinformatics, Ivano-Frankivsk National

Technical University of Oil and Gas, Karpatska 15, Ivano-Frankivsk, 76000,
davybida61085@gmail.com, Ukraine
Abstract
The Ukrainian part of the sub-basin of Tisza, the largest left tributary of the Danube,
which is located within five countries (Romania, Hungary, Slovakia, Ukraine,
Serbia), is considered. This area due to the interaction of a number of natural and
man-made factors is characterized by high risk of natural phenomena occurrence,
particularly, floods, mudflows and landslides. There is a negative tendency in
Ukraine to reduce the hydrogeological observation network. Obviously, that for the
study area, further development of the monitoring system (restoration of stopped
wells and construction of new wells) is expedient. In a geoinformation environment,
a single monitoring geodatabase was created, that allowed maximum consideration
of the results of hydrogeological surveys, ensured integration heterogeneous data
and their overlay analysis, provided opportunities for effective design and
optimization of the observation network based on the hydrogeological, analytical
and statistical criteria.
Keywords: catchment area, groundwater, geodatabase, wells
Introduction
In recent decades Ukrainian hydrogeological observation network was extremely
reduced due to insufficient financing. Thus, in 2014, monitoring of groundwater
levels was carried out only at 350 hydrogeological monitoring wells and research on
the chemical composition of water was not carried out at all. This situation is
critical, especially given the fact that in the early 90's the state network of
hydrogeological monitoring had 7,000 wells, the absolute majority of which are
stopped or abandoned at all now (Shestopalov & Lyuta 2016). As result, the long-
term series of continuous observations are lost, which makes impossible the
implementation of reasonable estimates and predictions of dynamic hydrogeological
processes. Obviously, it is necessary to develop urgent measures for the restoration
of the observation network and its gradual harmonized to European norms and
requirements. It should be noted that one of the main principles of water
management in most developed countries is monitoring and territorial management
at a river basin (catchment area) level instead of an administrative territory. Basin
principle of management is based on the unity of surface water and groundwater
within the river basin. Particular attention is paid to transboundary catchment areas,
located on the territory of several countries (Berezko & Vasneva, 2012, Davybida &
Kuzmenko 2018, EUR-Lex Access 2018).


The 8% of the catchment area of Tisza, the largest left tributary of the Danube,
account for the territory of Ukraine, namely, the upper part of the basin on the
southwestern slopes of the Ukrainian Carpathians and the Trans Carpathian lowland.
The Ukrainian part of the Tisza basin is located within the Alpine folded structure of
the Carpathians and covers the central part of the Ukrainian segment of the folded
Carpathians and the Trans Carpathian Trench. The Ukrainian Carpathians are a
complex hydrodynamic system where the Carpathian and Trans Carpathian basins of
underground waters are distinguished by geostructural features and conditions for
the formation, accumulation and circulation of groundwater (Basin Department of
Water Resources of the Tisza River 2018).
In the framework of international cooperation within the territory of the Tisza
catchment area, a flood control complex has been implemented, a monitoring system
of the dynamics and quality for surface water has been established, using automated
hydrogeological posts and a river basin management plan has been developed.
However, if one considers the measures for monitoring groundwater, it is necessary
to note their recommend and declarative character. Thus, the boundaries of the
allocated transboundary groundwater bodies (presented in Table 1) are still not
coordinated with neighboring countries, the planned extension of the monitoring
network at the border areas is not implemented. Moreover, according to official data
of State Scientific and Production Enterprise “Geoinform of Ukraine” there was a
significant reduction in the number of hydrogeological monitoring wells of the state
network level (from 56 wells in 2010 to 6 wells in 2016), that is shown in Figure 1.
Under the conditions of limited funding, an important task is the development of an
effective strategy for reforming the system of hydrogeological observations.
The analysis of the accumulated research experience allows distinguishing two main
approaches to the organization of hydrogeological monitoring networks. The first is
based on the formal statistical estimation of the density of observation points, taking
into account the given error of extrapolation of the studied parameters. The second is
based on the assessment of conditions and factors for the groundwater formation and
their regime, zoning of the territory taking into account different principles and the
placement of regime monitoring points within typical areas. Using modern
techniques (GIS) that allows effective combining of these approaches, operatively
testing and evaluating various variants of the monitoring network within any
territorial units (Davybida & Kuzmenko, 2018).
Also, it should be noted that the European Union Water Framework Directive
provides only a platform and recommendations for managing transboundary water
resources. When the boundaries of groundwater bodies for Ukrainian transboundary
territories is being defined and substantiated and the optimal monitoring network is
being organized, both the experience of European countries and existing national
scientific and practical results in the field of hydrogeological research of the
territories should be taken into account, as well as the features of recharge,
movement and unloading of natural groundwater, which are determined by the
geological, physical-geographical conditions and the level of anthropogenic pressure
within a particular territory (Koshliakov et al 2017).

Table 1. Groundwater identified bodies within Ukrainian part of Tisza river basin
(ICPDR 2018)
Area within
Groundwater body Age ID Distribution Type of use
Ukraine (km2)
Aquifer Middle Transboundary
Household
Pleistocene and distribution
(a, laPII- UA_TIS_ and drinking
Quaternary Alluvial, 3883 (Romania,
III+aH) GW_ 4 water supply;
Lacustrine-Alluvial Hungary,
Agriculture
Deposits Slovakia)
Aquarium complex
Transboundary Household
of lake-alluvial
(aE- UA_TIS_ distribution and drinking
deposits of Chop 1302
laE+P1čp) GW_204 (Hungary, water supply;
suite and alluvium of
Slovakia) Agriculture
high terraces
Aquarium complex
Household
in the fracture zone
and drinking
of Upper Miocene- (αβ,α,l- UA_TIS_
1816 Within Ukraine water supply;
Pliocene aN1-2) GW_ 220
Agriculture;
volcanogenic
Balneology
formations
Household
Transboundary
Aquarium complex and drinking
UA_TIS_ distribution
in Upper Miocene- (N1-2) 1788 water supply;
GW_240 (Romania,
Pliocene sediments Agriculture;
Slovakia)
Balneology
Local-aquifer Transboundary Household
complex in the distribution and drinking
UA_TIS_
deposits of the (N1s) 3638 (Romania, water supply;
GW_263
Sarmatian regional Hungary, Industry;
tier Slovakia) Balneology
Transboundary
Local-aquifer Household
distribution
complex in the UA_TIS_ and drinking
(N1b) 4769 (Romania,
deposits of the GW_283 water supply;
Hungary,
Baden regional tier Balneology
Slovakia)
Household
Local-aquifer
UA_TIS_ and drinking
complex in the (P) 2842 Within Ukraine
GW_300 water supply;
Paleogene deposits
Balneology
Household
Local-aquifer
and drinking
complex in the UA_TIS_
(K+P) 4241 Within Ukraine water supply;
Chalk and Paleogene GW_425
Industry;
deposits
Balneology

Figure 1. The studied area and state hydrogeological monitoring network

In a geoinformation environment, which includes general and special geospatial
information, a single geodatabase was created. The significant part of the database is
the layers of hydrogeological zoning according different approaches. The complex
geological structure of the studied area has caused a great variety of its
hydrogeological conditions, which are unequal for the groundwater using and its
vulnerability to the industrial pollution. The hydrogeological areas identified by
various principles are considered as a territorial basis to conduct the groundwater
monitoring as well as projecting and improvement of the current network of
observation wells. In this paper, the zoning scheme based on groundwater formation
conditions as well as the scheme of functional zoning pursuant to the basin principle
are chosen as the initial cartographic materials that characterize conditions creating
the regime on the area.
The zoning scheme of the groundwater formation is based in accordance with the
geological and structural principle of hydrogeological zoning, which takes into
account the heterogeneity of the earth's crust composition and structure. The regions,
which are covering the largest geo-structural units – the hydrogeological massifs as
well as artesian basins, are allocated at the core of the scheme. There are smaller
taxonomic units that include the hydrogeological areas representing a part of the
groundwater basin expressed on the certain territory, which is characterized by a
specific combination of geological structure, relief, climatic, hydrological and,
eventually, hydrogeological conditions. The smallest taxonomic units of typing,
which characterize the stratigraphic features of the conditions for the groundwater
formation in the profile, are the landscape hydrogeological complexes, which
includes separate areas, where the first water bearing horizon is deposited having the
defined stratigraphic sections, reflecting the structure of the aerated zone, water-
bearing and waterproof layers and, to certain extent, stipulate peculiarities of the
groundwater recharge and discharge as well as the reservoir properties of the upper
layer of rocks where their formation takes place. (LHC) are azonal units of zoning
and they are characterized by common features of the most hydrogeological areas,
mainly within the groundwater basins. In general, 26 varieties of plain LHC and 6
varieties of mountainous LHC are identified in Ukraine. There are 10 varieties (4
plain LHC and 6 mountainous LHC) within the Ukrainian part of the Tisza basin
(Ruban & Nikolishina 2005).
The functional zoning scheme according to the basin principle (under conditions of
water exchange in the upper hydrogeological layer, shown in Figure 1) may be
considered as the basic one for reorganization of the state system for the
groundwater monitoring, in accordance with the principles of the EU Water
Framework Directive. The system for studying of the groundwater drainage is based
on the dynamic features of objects allocated according to the principle of
groundwater runoff unity from the areas of drainage formation to its main discharge,
which is controlled by a single closed balance of the groundwater. Within the
hydrogeological structures, one may allocate water exchange basins of the first
order, which are characterized by single or close trends of the regional water
exchange. The hierarchy of this zoning is as follows: there are basins of sea drainage
(regions) and main rivers that flowing into the seas (provinces). The next zoning
level takes into account peculiarities of the hydrogeological conditions as well as the
close trends of lateral water exchange, thanks to that, the basins of rivers’
groundwater flow are united within the bounds of the single zoning units
(provinces), where the subareas corresponding to water exchange basins of different
main rivers tributaries are allocated. The water exchange basins, sizes and
boundaries of which are determined by sizes and configuration of the river basins as
a rule, should be considered as characteristic systems with homogenous regime in
forecasting changes in level of the ground water, that is a part of underground
hydrosphere the most closely related to the external surface factors forming the
groundwater recharge and discharge. The expediency of monitoring study for both
surface and underground water is also confirmed by synchronicity of the long-term
variability of the mid-annual surface water flow and the annual average depth of the
groundwater level (Davybida & Kuzmenko 2018).
The studied territory belongs to the hydrogeological province of the Danube River,
which coincides territorially with the hydrogeological district of the Tisza River (B-
1) within the studied region. The hydrogeological district includes two sub-districts
–B-1-1 (the Uzh River) and B-1-2 (the Latorytsia River).
In order to integrate the spatial data, the spatial binding of raster maps was
conducted and they were transferred into the vector format by digitalization.
It has been created geodatabase that includes the following layers with the relevant
attributes: hydrogeological monitoring stations (code, number, type, depth,
coordinates X and Y, type of water-bearing horizon, regime type, disturbance of
regime); levels of groundwater surface (code, level); contours of distribution of
groundwater bodies (code, type, international index, geological age, distribution,
area within Ukraine, type of use); hydrogeological provinces (code, index, water
exchange basin); hydrological districts (code, index, water exchange basin); water-
resource regions (code, index, departmental subordination); hydrogeological basins,

allocated under the conditions of formation and groundwater occurrence (code,
index, basin); hydrogeological district (code, index, district); hydrogeological sub-
district (code, index, sub-district); landscape hydrogeological complexes (code,
index, age of rocks of the aeration zone, rocks of the aeration zone, chemical
composition of the aeration zone, limit values of aeration zone depth, limit values
peculiar to the coefficient of the aeration zone filtration, age of rocks contained in
the water-bearing formation; rocks of the water-bearing formation; chemical
composition of waters contained in the ground water-bearing horizon, limit values
peculiar to the filtration coefficient of water-bearing horizon, age of watercourse
rocks, filtration coefficient of watercourse rocks, limit values of mineralization,
water hardness and pH index); additional information layers of hydrological and
meteorological points; vector layers of the basic information including
administrative boundaries, settlements, roads, rivers, vegetation, relief.
Results of long-term regime observations over the groundwater levels, presented in
the form of average monthly values of groundwater depth levels calculated under the
data of timing observations, as well as results of observations on the variability of
annual surface water discharge, weather and climate characteristics (average annual
air temperature, amount of precipitation), long-term change of numerical
characteristics peculiar to the geological features (the energy of earthquakes) and the
cosmogenic features (solar activity) required to form the hydrogeological regime.
Results of the routine dynamics observations are stored in the external relational
database and can be attached to the spatial objects (meteorological, hydrological and
hydrogeological monitoring stations) using unique codes of the supervisory stations.
The development of the network of hydrogeological monitoring for the studied area
should be carried out in compliance with the following basic principles: maximum
possible preservation and restoration of monitoring wells that functioned earlier;
congestion of the network (first of all, in the border zones); the involvement of
sources and household wells as observation points; taking into account hydroisobath
maps for designing of the quantitative monitoring network and maps of landscaping
and hydrogeological complexes for the qualitative monitoring network; estimation
of an expected accuracy of hydrogeological models for the projected network;
carrying out optimization of the hydrogeological monitoring network and
clarification of groundwater bodies boundaries after 2-3 years of the observation
period, using analytical or geostatistical criteria (Ben-Jema et al 1994, Hudak &
Loaiciga 1992).
Obviously, that the number of hydrogeological monitoring points should be
increased for the Ukrainian part of the sub-basin of Tisza. Thus, not only for
groundwater bodies, but also for each hydrogeological district, allocated on the
hydro geodynamic principle within the water exchange basins of the Dniester and
the Danube, it is necessary to position the posts in such a way that they would be
representative on the river, terrace and watershed types of groundwater regime.
Another criteria for choosing the location of the observation point is the distribution
of LHC. Such placement of monitoring points will enable to capture observations of
the areas with different conditions of the hydrogeological regime formation and to
obtain more complete information about the spatial and temporal variability of the
groundwater regime elements.

Conclusions
Consequently, the basic current network of the state hydrogeological monitoring
within the studied area, which in 2016 included only 6 observation wells, does not
fulfilled assigned functions and it requires serious reorganization. The observation
network and the monitoring program for the Ukrainian part of the sub-basin of Tisza
should be developed on the basis of a comprehensive analysis of the
hydrogeological conditions and the results of observations on elements of the
hydrogeological regime using geoinformation systems and technologies. It should
also be taken into account that the cost of any measures to improve groundwater
status is much higher than the cost of optimizing the monitoring system.
Acknowledgements
This work would not have been possible without the information support of the State
Scientific and Production Enterprise “Geoinform of Ukraine”. I am especially thankful to the
employees of the Department of Accounting of Groundwater Resources, who worked to
provide the research with actual hydrogeological monitoring data.
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PHYSICO–CHEMICAL CHARACTERISTICS AND WASTEWATER

QUALITY INDEX FOR EVALUETING THE EFFICIENCY OF
TREATMENT PROCESS EFFLUENT
Florinela Pirvu, Jana Petre, Liliana Cruceru, Iuliana Paun, Marcela Niculescu, Luoana
Florentina Pascu, Nicoleta Vasilache, Florentina Laura Chiriac
Podu Dambovitei, district 6, 060652, Bucharest, florinela_pirvu@yahoo.com, Romania
Abstract
As is known all forms of life depend on water. Water is a vital part of many
metabolic processes inside the body. By increasing the world population, increasing
global pollution and global warming, fewer people benefit from water. This problem
can be solved by increasing water production, better distribution and disruption
existing resources. For this reason, water is a strategic resource for many countries.
Regarding to this, is important to protect the water resources from the action of
pollutants and to monitor the quality of the water already existing. Wastewater is
composed of different proportions of residual water from domestic or industrial
origin and rainwater. To evaluate the quality of wastewater various parameters are
available but for common people it is difficult to understand the meaning of this
values. The concept of Water Quality Index (WQI) has been developed by
representing it as numeric value for easy and quick understanding of quality of the
water. This study aimed to assess the wastewater quality of 8 sampling stations in
Valcea County. The data were collected over a five years’ period (2013-2017) from
each sampling point and the physical-chemical parameters were analysed to evaluate
the variations registered in the study period.
Keywords: basic statistical, quality index, wastewater
Introduction
The influent composition at the entrance of the wastewater treatment plant is due to
the different types of contaminants present in the initial waters. For example, the
wastewater can contain mainly organic compounds and various microorganisms
(bacteria, viruses, parasites) while the rainwater can contain especially inorganic and
mineral compounds (Petrescu et al 2017, Bucur et al 2010).
In 1970s the concept of Water Quality Index (WQI) has been developed for easy
understanding of water quality by representing it as numeric value between 0 (Poor)
to 100 (Excellent) (Mudiya 2012, Vijayan et al 2016). Similarly, the wastewater
quality index (WWQI) may be considered as a useful tool to provide information
about the degree to which the wastewater is polluted by human activities.
Wastewater quality index is a dimensionless number that depends on the
combination of chemical, physical, and microbiological parameters. It consists of
sub-index scores attributed to each parameter by comparing the measurement values

with the specified parameter estimation curve and calculated in the final index (Dede
et al 2017).
In this paper the wastewater quality index of the effluents from different wastewater
treatment plants was evaluated. The samples were taken with a monthly frequency
between 2013 and 2017, from eight sampling points situated in Valcea County. The
parameters considered for this study were. The wastewater quality assessment was
based on the comparison of the experimentally determined values with the limits
imposed by the legislation, NTPA-001 Quality Norm (NTPA 001 2005). The
analytical results were used for the evaluation of the wastewater quality index
(WWQI) and, based on basic statistical technique, were correlated with sampling
points.

Sampling
This study evaluates the quality of effluents from eight wastewater treatment plants
situated in Valcea County, Romania: Ramnicu Valcea, Govora, Babeni, Olanesti,
Calimanesti, Dragasani, Horezu and Voineasa (Figure 1). The effluents are
discharged in local emissaries or directly in Olt River. The samples were taken with
a monthly frequency between 2013 and 2017. Samples were collected in polythene
bottles and preserved, function of the type of indicators, by acidulation at pH <2 or
by keeping them at 40C, in the dark.
Figure 1. VALCEA County, location of sampling points
Reagents and chemicals

For calibration of the equipment, for calculation of the uncertainty of measurement,
and also for plotting points in control charts Reference Materials (MR) and Certified
Reference Materials (MRC) were used. All the reagents (Merck and Sigma) used in
the determinations were of analytical purity.
Methods
The physical-chemical parameters: pH, Suspended solids (SS), Total dissolved
solids (TDS), Chemical Oxygen Demand (COD), Bio-chemical Oxygen Demand
(BOD5), chlorides (Cl-), ammonia (NH4+), Total Phosphorus (P), Sulphides (S2-),
Total oil and grace (TOG), Anionic surfactants (AS), sulphate (SO42-), Total
Nitrogen (TN) were analysed using electrochemical, volumetric, UV-VIS
spectrometry and combustion methods. All analyses were performed under
accreditation system, according to SR EN ISO 17025:2015 reference standard (SR
EN ISO 17025:2015, 2005).
Water Quality Index

The Water Quality Index has become an important decision-making tool for the
authorities. In the same sense, the development of Water Quality Indicators has
become an important tool for authorities and is easy to understand for population
various methodologies are available for determining the quality of wastewater.
The Canadian Water Quality Index (CCMEWQI) (CCME 2001, 2005) provides a
comprehensive method of calculating quality index that allow the transmission of
water quality information to the management involved in water quality testing.
The wastewater quality index (WQI) measures the scope, frequency and amplitude
of water quality over runs and then combines the three measures into a score. The
higher the score, the better the water quality is. The wastewater quality (WQI) index
is a useful tool for assessing the degree of wastewater pollution.
The mathematical expression for the Quality Council of the Canadian Council of
Ministers for the Environment (CCMEWQI) is:

where: Scope (F1) = number of quality indicators determined, whose values exceed
the maximum allowed by law, Frequency (F2) = Number of tests of determined
quality indicators, the values of which exceed the maximum allowed by the
legislation, and Amplitude (F3) = individual value for each test of the determined
quality indicators, the values of which exceed the maximum allowed by the
legislation. The index values function of the main characteristics of wastewater are
described in Table 1.
Table 1. Criteria according to Canadian Council of Ministers of the Environment,
Water Quality Index (CCMEWQI)
Designation Index Value Description
Excellent 95-100 All measurements are within objectives virtually all of the time
Good 80-94 Conditions rarely depart from natural or desirable levels
Fair 65-79 Conditions sometimes depart from natural or desirable levels
Marginal 45-64 Conditions often depart from natural or desirable levels
Poor 0-44 Conditions usually depart from natural or desirable level

Using the Water Quality Indicator of the Canadian Environment Ministers Council
(CCMEWQI), the quality of effluents from 8 wastewater treatment plants from
Valcea county was assessed.
The results obtained for the analysed parameters were compared with the maximum
limits allowed by the NTPA-001 (Table 2).
Table 2. Maximum admissible value (MAV) according to NTPA-001 Quality Norm

Determined parameter MU MAV
pH pH units 6.5-8.5
SS mg/L 35(60)
TDS mg/L 2000
COD mg O2/L 125
BOD5 mg O2/L 25
Cl- mg/L 500
NH4+ mg/L 2(3)
P mg/L 1(2)
S2- mg/L 0.5
TOG mg/L 20
AS mg/L 0.5
SO42- mg/L 600
TN mg/L 10(15)
In this study, for the assessment of wastewater quality, 4184 samples were taken
monthly, in a period of 5 years. 13 Parameters have been tested for WQI
determination. On the basis of monthly average values, the descriptive statistics as
average, minimum, maximum, standard deviation were evaluated. Function of the
results obtained for all the analysed parameters only that one exceeding the imposed
limits were selected (Table 3÷ Table 10).
Table 3. Basic statistics of physical and chemical variables for Ramnicu Valcea
effluent (2013–2017)
Spring Summer Autumn Winter
Analyte Mea Mea
MU Mean Min Min Min Mean Min
s n± n
± SD Max Max Max ± SD Max
SD ± SD
33.80 26.60 30.27 24.00 29.07 24.00 36.92 26.00
SS mg/L
±8.3 46.40 ±6.33 36.4 ±5.54 34.40 ±12.5 50.25
5.92 3.99 3.68 3.18 3.24 2.61 5.83 1.82
NH4+ mg/L
±1.95 8.69 ±0.58 4.28 ±0.79 4.11 ±4.65 10.40
1.00 0.54 0.72 0.56 0.87 0.68 0.66 0.43
P mg/L
±0.47 1.52 ±0.59 1.70 ±0.20 1.06 ±0.28 0.95
The parameters which exceeded the maximum admissible limits from Ramnicu
Valcea wastewater Treatment Plant, were: suspended solids, ammonia and total
phosphorus (Table 3).
Suspended solids presented average values between 36.40 mg/L to 50.25 mg/L.
These values provided information on effluent turbidity during four seasons.
Ammonia resulting from the degradation of N-containing organic substances in their
molecule indicates a very high concern (Paun et al 2017). The values obtained for

ammonium indicator varied from 4.11 to 10.40 mg/L. The highest value obtained for
phosphorus indicator was up to 1.70 mg/L was recorded in summer time.
Table 4. Basic statistics of physical and chemical variables for Govora effluent
(2013–2017)
Mea
Analytes MU Mean Min Min Mean Min Mean Min
n±
± SD Max Max ± SD Max ± SD Max
SD
51.53 39.20 41.17 32.80 47.20 40.80 71.33 42.00
SS mg/L
±13.6 64.20 ±9.34 50.80 ±8.05 56.00 ±30.0 99.00
1663 846.4 1202 965.2 1625 1230 2112 1096
TDS mg/L
±902 2761 ±469 1850 ±454 2103 ±1112 3199
mg 143.0 67.20 124.0 80.66 171.4 92.16 258.3 131.9
COD
O2/L ±75.76 229.4 ±78.8 228.4 ±83.0 249.6 ±114 345.6
mg 49.28 25.80 43.40 28.49 60.65 37.32 89.15 46.05
BOD5
O2/L ±25.0 78.62 ±27.4 79.76 ±25.7 85.14 ±40.7 125.4
16.47 8.13 27.40 22.54 38.90 35.24 25.17 16.38
NH4+ mg/L
±9.96 27.38 ±8.62 38.98 ±3.56 42.20 ±9.90 35.84
0.78 0.41 0.69 0.43 1.07 0.60 1.05 0.54
AS mg/L
±0.50 1.20 ±0.23 0.87 ±0.57 1.69 ±0.62 1.41
Table 5. Basic statistics of physical and chemical variables for Babeni effluent
(2013–2017)
Analytes MU Mean Min Mean Min Mean Min Mean Min
± SD Max ± SD Max ± SD Max ± SD Max
36.27 29.80 33.60 24.60 29.20 19.60 35.33 29.00
SS mg/L
±9.14 52.40 ±10.2 44.40 ±7.72 34.40 ±6.97 44.50
7.52 4.62 5.03 3.48 5.12 4.26 7.27 4.06
NH4+ mg/L
±2.70 10.50 ±1.59 6.59 ±0.48 7.44 ±2.78 9.97
0.26 0.19 0.28 0.19 0.27 0.18 0.36 0.24
AS mg/L
0.15 0.53 ±0.10 0.38 ±0.08 0.35 ±0.13 0.53
Table 6. Basic statistics of physical and chemical variables for Olanesti effluent
(2013–2017)
Analyte
MU Mean Min Mean Min Mean Min Mean± Min
s
± SD Max ± SD Max ± SD Max SD Max
34.60 31.00 38.93 26.00 33.87 24.80 32.33 27.00
SS mg/L
±11.2 50.20 ±13.9 53.20 ±8.75 41.60 ±5.75 38.00
46.40 41.44 89.60 61.44 101.8 78.72 62.40 45.60
COD mg O2/L
±13.2 67.20 ±25.7 107.5 ±24.4 126.9 ±23.3 81.60
15.63 14.26 29.62 17.28 37.14 26.73 20.28 9.53
BOD5 mg O2/L
±9.79 28.06 ±11.1 37.97 ±11.3 48.64 ±11.5 31.69
9.21 8.98 22.12 17.89 14.95 12.48 9.29 4.32
NH4+ mg/L
±5.95 18.26 ±5.19 27.23 ±2.28 16.95 ±5.11 14.39
0.05 0.02 0.76 0.41 0.62 0.32
S2- mg/L - -
±0.18 0.55 ±0.34 1.07 ±0.45 1.08
0.34 0.29 0.54 0.39 0.30 0.20 0.28 0.22
AS mg/L
±0.26 0.71 ±0.33 0.90 ±0.26 0.59 ±0.08 0.37

Table 7. Basic statistics of physical and chemical variables for Calimanesti effluent
(2013–2017)
Analyte Mea Min
MU Min Mean Min Mean Min Mean
s n Max
Max ± SD Max ± SD Max ± SD
± SD
36.27 26.00 32.93 29.20 34.13 31.2 38.58 30.50
SS mg/L
±15.8 64.80 ±4.27 36.60 ±6.55 42.40 ±9.93 49.00
mg 157.4 72.26 220.5 142.0 208.0 122.8 216.8 132.0
COD
O2/L ±63.9 223.3 ±57.6 250.6 ±84.9 272.6 ±86.2 297.6
mg 53.79 25.63 73.84 48.52 74.24 43.24 74.23 44.39
BOD5
O2/L ±21.8 74.76 ±17.5 80.82 ±24.5 88.68 ±32.0 106.4
1876 1376 2179 2041 1938 1747 1947 1723
Cl- mg/L
±321 2285 ±251 2502 ±251 2222 ±223 2165
10.31 8.02 12.22 10.23 11.35 6.29 10.98 8.82
TN mg/L
±4.94 21.78 ±2.73 15.32 ±2.13 25.93 ±2.30 13.33
0.79 0.47 1.19 0.73 1.04 0.56 1.14 0.52
P mg/L
±0.33 1.15 ±0.43 1.51 ±0.39 1.33 ±0.79 2.03
0.27 0.20 0.41 0.25 0.46 0.34 0.29 0.21
AS mg/L
±0.16 0.61 ±0.14 0.61 ±0.15 0.60 ±0.10 0.40
Table 8. Basic statistics of physical and chemical variables for Dragasani effluent
(2013–2017)
± SD Max ± SD Max ± SD Ma ± SD Max
42.87 36.60 37.00 28.00 35.60 26.00 42.17 33.50
SS mg/L
±11.4 60.20 ±10.1 47.00 ±10.5 46.00 ±9.71 51.50
31.83 19.89 23.81 12.75 34.75 21.36 24.76 18.04
BOD5 mg O2/L
±12.9 42.28 ±10.9 34.36 ±14.5 49.92 ±7.86 33.33
16.01 11.95 17.66 10.96 10.23 9.63 11.05 7.84
NH4+ mg/L
±3.69 19.05 ±9.26 25.63 ±0.57 10.67 ±2.97 13.40
1.86 1.55 1.81 0.79 2.16 1.71 1.66 1.24
P mg/L
±0.47 2.39 ±0.99 2.70 ±0.53 2.72 ±0.40 1.99
0.82 0.43 1.01 0.51 1.32 0.92 0.78 0.45
AS mg/L
±0.47 1.36 ±0.59 1.51 ±0.63 2.05 ±0.29 0.98
Table 9. Basic statistics of physical and chemical variables for Voineasa effluent
(2013–2017)
Analytes MU Mean Min Mean Min Mean Min Mea Min
± SD Max ± SD Max ± SD Max n± Max
SD
37.53 26.20 41.60 30.40 38.00 24.80 44.50 34.00
SS mg/L
±13.9 63.40 ±11.5 52.00 ±14.4 52.40 ±10.5 54.50
42.56 38.40 164.1 155.5 30.72 28.80 45.60 42.00
COD mg O2/L
±32.6 111.3 ±12.2 172.8 ±2.72 32.64 ±5.85 51.60
10.21 4.95 26.59 2.67 9.88 4.63 10.91 3.95
BOD5 mg O2/L
±14.8 42.86 ±32.7 61.92 ±5.51 15.17 ±8.61 20.28
8.64 4.67 4.12 1.98 6.30 4.46 9.95 4.91
NH4+ mg/L
±5.59 18.51 ±3.10 6.84 ±2.78 8.82 ±6.28 16.53
0.32 0.23 0.35 0.26 0.26 0.19 0.26 0.15
AS mg/L
±0.13 0.54 ±0.12 0.46 ±0.09 0.36 ±0.12 0.37

Table 10. Basic statistics of physical and chemical variables for Horezu effluent
(2013–2017)
± SD Max ± SD Max ± SD Max ± SD Max
49.27 28.80 52.20 38.00 44.93 31.60 41.00 31.00
SS mg/L
±20.2 80.60 ±20.8 75.40 ±15.4 61.60 ±13.7 57.50
mg 70.72 49.92 103.3 74.88 80.64 69.12 53.75 53.75
COD
O2/L ±31.6 97.92 ±39.7 144.0 ±13.2 92.16 ±22.9 86.15
10.17 5.66 19.63 10.49 15.78 12.67 17.33 7.13
NH4+ mg/L
±7.25 16.99 ±10.3 28.49 ±3.67 19.82 ±9.57 24.63
0.54 0.45 0.88 0.57 1.18 0.68 0.46 0.26
AS mg/L
±0.10 0.70 ±0.47 1.41 ±0.72 1.98 ±0.12 0.57
Regarding to Wastewater Treatment Plant from Govora, parameters that have

overtaken the maximum admissible limits were: suspended solids, total dissolved
solids, chemical oxygen demand, biochemical oxygen demand, ammonia, anionic
surfactants (Table 4). For the suspended solids average values were situated between
50.80 mg/L to 99.00 mg/L, COD varied from 228.4 to 345.6 mgO2/L, and CBO5
from 78-62 to 125.4 mgO2/L. The ammonia levels were found from 27.38 to 42.20
mg/L.
In WWTP from Babeni, higher values than maximum admissible limits were
recorded for: suspended solids, ammonia, anionic surfactants (Table 5). Suspended
solids values were situated between 44.40-52.40 mg/L, ammonia concentration
ranged from 6.59 mg/L to 10.50 mg/L, some of which are about 5 times higher than
the maximum admissible NTPA 001.
Regarding the wastewater Treatment Plant from Olanesti, the parameters with higher
values than the maximum admissible limits were: suspended solids, chemical
oxygen demand, biochemical oxygen demand, ammonia, sulphides, and anionic
surfactants (Table 6). The suspended solids values ranged from 41.60-53.20 mg/L in
summer, for COD the highest value was 126 mg O2/L, the maximum level obtained
for CBO5 was 48.64 mg O2/L, while for ammonia the highest average value of the
concentration was about 13 times higher than the value admitted by NTPA 001 and
recorded in summer time. For sulphides parameter values were found between 1.07
mg/L and 1.08 mg/L.
In WWTP from Calimanesti the exceeding parameters were: suspended solids,
chemical oxygen demand, biochemical oxygen demand, chlorides, total nitrogen,
and anionic surfactants (Table 7). Suspended solids varied from 36.60 to 64.80
mg/L, the COD concentrations were found in the range of 223.3 and 297.6 mg O2/L,
CBO5 varied from 74.76 to 106.4 mgO2/L. Chlorides ranged from 2165 mg/L to
2502 mg/L, total nitrogen from 13.33 to 21.78 mg/L and total phosphorus from 1.15
to 2.03 mg/L.
Parameters with concentration higher than the maximum admissible limits for
WWTP from Dragasani were: suspended solids, biochemical oxygen, Ammonia,
total phosphorus, anionic surfactants (Table 8). Suspended solids varied from 46.00
to 60.20 mg/L, BOD5 ranged from 33.33 to 42.28 mgO2/L and the highest value for
ammonia was 13 times higher than the maximum admissible limit. Total phosphorus
levels ranged between 1.99 and 2.72 mg/L, while anionic surfactants were situated
between 0.98 to 2.05 mg/L.
In WWTP from VOINEASA parameters exceeding the maximum admissible limits

were: suspended solids, biochemical oxygen demand, chemical oxygen demand,
ammonia, anionic surfactants (Table 9). Suspended solids were determined to be
from 52.00 to 63.40 mg/ L, COD levels ranged from 51.60 to 111.3 mg O2/L, while
the highest average concentration found for CBO5 was 61.92 mg O2/L. The
ammonia results varyed from 6.84 to 18.51 mg/L and for anionic surfactants the
highest value was 0.54 mg /L.
The parameters which exceeded from maximum admissible limit for WWTP from
Horezu were: suspended solids, chemical oxygen demand, ammonia, anionic
surfactants (Table 10). Suspended solids values were situated between 57.50 to
80.60 mg/L, the highest value for COD was 144 mg/L, while the ammonia
concentration was about 14 times higher than the admitted value by NTPA 001 and
was recorded in summer time.
Based on determined results, sub-index used to obtain the water quality index of the
Canadian Council of Ministers for the Environment (CCMEWQ) were calculated
(Table 11).
In Table 11, the value of the Canadian Environment Ministers' Water Quality
Indicators corresponds to fair designation which means acceptable quality class for
the effluent of the Ramnicu Valcea Wastewater Treatment Plant. For the other
effluents the calculated index corresponds to marginal designation, which means
that the values of the determined parameters often break the limits imposed
(NTPA001)
Table 11. Values of water quality sub-index and index (CCMEWQ) calculated for
each sampling point
Sampling point F1 F2 nse F3 Index Value Designation
Govora 14.29 7.62 2.067 67.39 59.98 Marginal
Ramnicu Valcea 36.36 10.45 0.861 14.67 76.57 Fair
Olanesti 77.78 13.64 0.305 462.6 47.16 Marginal
Babeni 55.56 16.99 0.324 24.49 63.60 Marginal
Horezu 62.50 30.50 0.904 47.48 51.38 Marginal
Voineasa 62.50 16.49 0.375 27.28 59.49 Marginal
Dragusani 66.67 38.05 1.145 53.38 46.02 Marginal
Calimanesti 72.73 44.67 0.628 38.58 45.92 Marginal
Conclusion
In this study, a new index has been proposed for evaluating the wastewater quality
index regarding to the efficiency of the effluent treatment process, to represent the
quality of the final effluent and to quickly evaluate whether it would be adequate for
its final destination. The developed wastewater quality index can be very useful in
managing treated wastewater for reuse or disposal purposes. The application of this
types of indexes is that it can help in decisions for reuse purposes and assessing the
improvement in treatment procedure.
References
Bucur, E, Ionita, L, Petrescu, M 2010, 'Consideration concerning impact assessment
of pollution with breathable PM 2.5 particulate matters. Part 1. Pollution
monitoring in urban areas with intense road traffic, Journal of Environmental

Protection and Ecology, vol. 11, no. 3, pp. 809-814.
CCME 2001, Canadian water quality guidelines for the protection of aquatic life:
CCME Water Quality Index 1.0, user’s manual. In Canadian environmental
quality guidelines, 1999, Canadian Council of Ministers of the Environment,
Winnipeg, Manitoba. Available from:
http://www.ccme.ca/assets/pdf/wqi_usermanualfctsht_e.pdf. [29 March 2007]
CCME 2005, Canadian environmental sustainability indicators. Freshwater quality
indicator: Data sources and methods. Catalogue no. 16-256-XIE. Available
from: http://www.statcan.ca/bsolc/english/bsolc?catno=16-256-
XIE#formatdisp. [29 March 2007]
Dede, OT Mısır, FY Telci, İT 2017, 'The Using of Principal Component Analysis
for the Assessment of Water Quality in Kirmir Basin', 20th International
Symposium “The Environment and The Industry”, SIMI 2017, National
https://ro.wikipedia.org/wiki [02.07.2018]
Mudiya, BN 2012, 'Development of Wastewater Quality Index for Disposal in to
Environmental Sink–Inland Surface Waters', International Conference on
Emerging Frontiers in Technology for Rural Area (EFITRA), International
Journal of Computer Applications® (IJCA), pp. 3-4.
NTPA 001 Quality Norms on the determination of the limits of pollutant loading of
industrial and urban wastewater into natural receptors, according to HG
352/2005.
Paun, I Chiriac, FL Marin, NM Cruceru, LV Pascu, LF Lehr, CB Ene, C 2017,
'Water Quality Index, a Useful Tool for Evaluations of Danube River Raw
Water', Revista de Chimie), vol.68, no. 8, pp. 1732-1739.
Petrescu, M, Bucur, E, Diodiu, R, Bratu, M, Serbanescu, A, Barbu, ME 2017,
International Symposium “The Environment and The Industry”,SIMI 2017,
SR EN ISO/CEI 17025:2005, General requirements for the competence of testing
and calibration laboratories.
Vijayan, G, Saravanane, R & Sundararajan, T 2016, 'Wastewater Quality Index – A
Tool for Categorization of the Wastewater and Its Influence on the
Performance of Sequencing Batch Reactor', International Journal of
Environmental Engineering and Management, vol. 7, no. 1, pp. 69-88.

QUANTIFICATION OF ANIONIC AND NONIONIC SURFACTANTS IN

DOMESTIC WASTEWATER SAMPLES COLLECTED FROM ROMANIA
Daniel Mitru, Catalina Stoica, Mihai Nita-Lazar
Podu Dambovitei, district 6, 060652, Bucharest, mihai.nita@incdecoind.ro, Romania
Abstract
Surfactants are substances that reduce surface tension and they are worldwide used
in all branches of industry such as householder products, cosmeticals,
pharmaceuticals, petroleum.
The large utilization of surfactants is reflected in their accumulation in the domestic
and industrial wastewaters and subsequently into the waste waster treatment plants
(WWTP) and the environment. Once in the environment, the surfactants could harm
it by inducing important changes in water quality which could directly affect the
human life.
This paper is a monitoring study of anionic and nonionic surfactants from domestic
wastewaters during three seasons (winter 2018, spring 2018 and summer 2018). The
samples were taken from specific sampling points along Romanian counties: Ilfov,
Prahova, Giurgiu, Dambovita and Braila.
The results showed that the concentration of the surfactants varied between 0.85
mg/L and 6.73 mg/L for anionic surfactants and 0.81 mg/L up to 6.48 mg/L for
nonionic surfactants related to the accepted value of surfactants concentration (as
sum of anionic and nonionic) of 25 mg/L (Romanian legislation, HG 352/2005,
NTPA 002 and Annex 2/2005). Moreover, the study revealed that the highest
concentration of both anionic and nonionic surfactants were detected in Dambovita
County during summer.
Keywords: anionic, counties, nonionic, sewages, surfactants
Introduction
Surfactants or surface-active agents are substances that reduce surface tension and
they have two types of functional groups in their structures: hydrophobic and
hydrophilic (Mulligan 2007). The hydrophilic part remains in contact with water,
while the hydrophobic part did not have any contact with the aqueous phase. The
classification of surfactants relies on their ionic behaviour in solution: anionic,
cationic, nonionic or amphoteric (Pereira & Souza 2015).
Surfactants are worldwide used in all branches of industry from domestic use
(household products, personal care products and pharmaceuticals) to petroleum
products and. Their extensive application translated in a large production of
surfactants waste represents a global environmental problem (Bosnar & Čačić
2014). Considerable amount of surfactants are released in rivers, where they could
accumulate (up to 30 µg/Ls) causing serious problems inducing pollution of the
aquatic systems (Odokuma & Okpokwasili 1997). Moreover, surfactants could also
accumulate in the sludge sewage treatment flow (18.2 mg/L concentration of anionic

surfactant measured for the influent) which could affect WWTP’s treatment
processes (Cserhati & Forgacs 2002).
In the past, before 1960, the major surfactant used in the United States especially for
laundry activity was propylene tetramer benzene sulphonate (PT benzene) (Scott &
Jones 2000). This chemical compound was a very resistant to degradation and
accumulated in the discharged water sewages and subsequently into the
environment. Due to thas situation, this surfactant was replaced with biodegradable
straight alkyl surfactant chains and recently, the major anionic surfactant in use has
been the linear alkylbenzene sulphonate (LAS) (Scott &Jones 2000).
The aim of this study was to quantify the presence of anionic and nonionic
surfactants in domestic wastewaters from different counties of Romania (Ilfov,
Prahova, Giurgiu, Dambovita and Arges) during three seasons (winter, spring, and
summer) of 2018.
Considering the fact that about 90% of the total production of synthetic surfactants
comes from the sum of anionic and nonionic surfactants (Bosnar & Čačić 2014).

The Metylene Blue Active Substances (MBAS) method was applied for the
quantification of anionic surfactants. The Methylene Blue reagent was prepared
according to the standard method (SR EN 903:2003). The reference used for this
method was methyl ester of dodecyl benzene sulfonic acid (C19H32O3S, MDS, 99%
purity, M= 340.53 g/mole (Merck, Germany). The main reaction in this method was
the separation between two matrix: water matrix and organic matrix. For this
reaction was used chloroform (99,4% purity) (Honeywell, USA). A buffer solution
was obtained by dissolving sodium carbonate (Na2CO3) and sodium hydrogen
carbonate (NaHCO3) in water and added to every sample worked to sustain the pH.
According to the standard method (ISO 7875-2:1984), the Dragendorff method was
used for quantification of nonionic surfactants. The reference material used as
control was nonylphenol polyethylene glycol ether
99% purity, M= 616.82 g/mole (Sigma Aldrich,
USA).The precipitation agent, Dragendorff reagent was made from two mixed
solutions, A and B. The solution A comprise a mix between bismuth oxynitrate,
glacial acetic acid and potassium iodide, and the Solution B comprise barium
chloride which was dissolved in water. To complete the Dragendorff reagent, two-
thirds solution A with one-third solution B in volume was mixed.
The equipment used for both anionic and nonionic quantification by absorbance
reading was Specord BU 205 spectrophotometer (Analytic Jena, Germany). The
wavelength for detection of anionic surfactants was at 650 nm (using a optical cell
length path of 10 mm and of nonionic surfactants at 263.5 nm (using an optical cell
length path of 20 mm).
The concentration of MBAS was detected by the formula:
(1)
where: py is masic concentration of MBAS ( mg/L);

A1 is the absorption of sample;
f2 is the calibration factor which was the amount of anionic surfactant

represented in milligrams (it was calculated as sodium salt of dodecyl
benzenesulfonate acid);
V0 is the volume was represented in milliliters.
The formula used for nonionic determination was:
(2)
Where: py is masic concentration of nonionic surfactants (mg/L);
C2 is the absorption of sample;
V0 is the volume was represented in milliliters.
The study was carried out during three seasons (winter 2018, spring 2018 and
summer 2018) in order to identify the variation of anionic and nonionic surfactants
from domestic wastewaters. The samples were taken from specific sampling points
along Romanian counties: Ilfov, Prahova, Giurgiu, Dambovita and Braila.The
sampling points from each county were noted: S1-Arges, S2-Dambovita, S3-
Prahova, S4-Giurgiu, S5-Ilfov (Figure 1).
Legend
S1-Arges
S2-Dambovita
S3-Prahova
S4-Giurgiu
S5-Ilov
Figure 1. The samples points from the specific counties

The results revealed the presence of anionic surfactants in all sampling points
Arges (S1), Dambovita (S2), Prahova (S3), Giurgiu (S4) and Ilfov (S5) during
winter 2018 (Figure 2). Thus, the highest concentration of anionic surfactants (6.10
mg/L) was detected in Dambovita County (S4), while the lowest of 0.85 mg/L was
in Ilfov (S5) (Figure 2a).

3
a) winter b) spring c) summer

Figure 2. The concentration of anionic surfactants detected from domestic
wastewaters during study period of 2018, a) winter; b) spring; c) summer. (Color
code: - surfactants concentration below 2 mg/L; - surfactants concentration
ranging between 2 and 3 mg/L; - surfactants concentration ranging between 3
and 4mg/L; - surfactants concentration ranging between 4 and 5 mg/L and
red - surfactants concentration higher than 5 mg/l).
In the spring season of 2018 (Figure 2b), an increase of anionic surfactants was
detected in S5 sampling site (3.75 mg/L). Similar with the winter season, a lower
concentration of 0.95 mg/L anionic surfactants was measured at S1 sampling site
(Figure 2a).
During summer of 2018 (Figure 2c), the concentration of anionic surfactants
detected from S4 and S5 sources were the highest in the all 2018 seasons (S2-6.72
mg/L and S1-4.33 mg/L). The anionic surfactants concentration from the samples
collected in S1, S2 and S3 sampling sites in summer year were lower (S5-1.18
mg/L, S3-2.11 mg/L and S4-2.71 mg/L than in spring.
The results of nonionic surfactants showed, in general, the same trend as in case of
anionic surfactants; thus, the highest concentration (5.64 mg/L) of nonionic
surfactants was detected in Dambovita County (S2), while the same County, Iflov
(S5), presented the lowest concentration (0.80 mg/L) (Figure 3).
3
a) winter b) spring c) summer

Figure 3. The concentration of nonionic surfactants detected from domestic
wastewaters during study period of 2018, a) winter; b) spring; c) summer. (Color
code: 1.18 mg/L - surfactants concentration below 2 mg/L; - surfactants
concentration ranging between 2 and 3 mg/L; - surfactants concentration
ranging between 3 and 4mg/L; - surfactants concentration ranging between 4
and 5 mg/L and - surfactants concentration higher than 5 mg/l).

However, according to the national legislation (HG 352/2005, NTPA 002 and
Annex 2/2005), the limit of concentration of surfactants was 25 mg/L. It means that
the sum of both anionic and nonionic surfactants concentration need to be less than
25 mg/L for the discharge in the sewage.
The concentration of nonionic surfactants detected in the sampling sites had the
same degree of magnitude as the anionic surfactants: S5 source (3.56 mg/L) and S3
source (0.80 mg/L).
The increase of nonionic surfactants at S5 source could be linked the spring season
when the weather became warm, so the domestic activities (like washing, cleaning)
were growing relative to winter.
Quantification of nonionic surfactants indicated that they have the same tendency as
the anionic surfactants (S2, S1 sources with increased concentration: 6.48 mg/L and
4.28 mg/L while S5, S3 and S4 sources decreased: 1.02mg/L, 1.96 mg/L and 2.68
mg/L).
The nonionic surfactants were in lower presence than the anionic surfactants which
means that can be a correlation between them (more anionic compounds than
nonionic).
However, in every season the results showed that the wastewater sample colected
from Dambovita (S2) had higher concentration of both anionic and nonionic
surfactants than Ilfov, which means that in Dambovita County were more domestic
activities due the superior number of population (523.730) and Ilfov 423.315).
(http://www.ilfov.insse.ro/, http://www.dambovita.insse.ro/).
In addition is very important to keep under control the concentration of surfactants
in domestic wastewaters; if this domestic wastewaters are undergoing to a treatment
plant, high concentrations of accumulated surfactants (can inhibit sewage sludge
microorganisms and compromise the way in which a wastewater treatment plant
(WWTP) removes pollutants and breaks down sewage, which was the case of a
Croatian study conducted on a sewage effluent where the anionic surfactant
concentration was extremely high (1090 mg/L). High concentrations of surfactants
means huge problems for the environment and expensive treatments in the WWTPs
(Ivanković & Hrenović 2010).
Also it is very important that the treatment plant to work properly like in the
Switzerland, where the highest concentration quantified fom wastewater effluent of
eleven sewage treatment plants was 2mg/L in Basseldorf, and the lowest in Stadel
with 1,1 mg/L ( Ahel & Giger 1994).
Conclusions
The concentration of both anionic and nonionic surfactants depends on the season
and also the amount of popualtion.
It was a corelation of concentration between both surfactants (anionic had higher
concentration than nonionic, and when one type had increase, the other one had the
same).
The importance of early quantification of domestic wastewaters means prevention
before treatment.

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Environmental Chemistry, Springer, Berlin, Germany, pp. 157-176.
Cserhati, T & Forgacs, E 2002, ’Biological activity and environmental impact of
anionic surfactants’, Environment International, vol. 28, no. 5, pp. 337-348.
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August 2018, Direcţia Judeţeană de Statistică Ilfov. Available from:
http://www.ilfov.insse.ro/contact/. [24 August 2018]. In Romanian.
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Environmental Issues, vol 1, pp. 279-298.
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contaminants to human and environmental health’, Environmental Science and
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Biochimica et Biophysica Acta, vol. 1508, no 1-2, pp. 235-251.

THE REMOVAL OF NITRATE FROM DRINKING WATER, NATURAL

WATER BY ION EXCHANGE USING ION EXCHANGE RESIN,
PUROLITE A520E AND A500
Nicoleta Vasilache, Liliana Cruceru, Jana Petre, Laura Florentina Chiriac, Iuliana Claudia
Paun, Marcela Niculescu, Florinela Pirvu, Giovanina Lupu
Podu Dambovitei, district 6, 060652, Bucharest, zegreanicoleta@yahoo.com, Romania
Abstract
Water pollution nitrates contamination of drinking water sources is a global
environmental problem causing eutrophication of receiving surface waters, higher
levels of nitrates being toxic for infants. Efficient removal of different levels of
nitrates in ground water and surface water by using two types of ion exchange resin,
A520E and A500 Purolite, was experimentally studied in a fixed bed adsorption
column in laboratory scale. Adsorption kinetics was well described by the Langmuir
and Freundlich isotherm models for an amount of 2 g resin and concentrations
between 10.18 to 66.8 mg NO3-.L-1. The maximum nitrate removal rate in the real
water used in this study was 87.2% for the Purolite A500 resin and 91.6% for the
Purolite A520E resin, indicating a higher efficiency of the A520E resin.
Keywords: ion exchange, kinetic adsorption, nitrate removal, Purolite A520,

Purolite A500
Introduction
Contamination with nitrates in groundwater and surface water is an important
problem for the whole world. Although nitrates are found in most natural waters at
moderate concentrations, elevated levels in groundwater stem mainly from human
and animal waste as well as excessive use of chemical fertilizers. Other sources of
nitrates are uncontrolled discharges of municipal and industrial wastewater into
natural receptors, the execution of septic tanks. Nitrate was involved in
methemoglobinemia, especially in children less than six months of age. Symptoms
include unusual blue gray skin, irritability, drowsiness and lethargy at higher levels.
Nitrates are an essential nutrient for plant growth and micro-organisms. The high
concentration of nitrates in water can cause eutrophication, which is a serious
environmental problem as it can lead to the abundant aquatic plants, algae growth,
have harmful effects on fish and other aquatic life and disturb the ecological balance
of present organisms in water.
Due to these adverse effects of nitrates, the World Health Organization has declared
nitrate as a regulated water pollutant, and it is necessary to reduce the concentration
before it is used for drinking. A requirement for the nitrate removal process is to
produce drinking water that meets the standard quality defined by the European
Economic Community in Directive 98/83/CE. This Directive limits nitrates to a
maximum admissible concentration (MAC) of 50 mg NO3-.L-1.
Techniques available to remove nitrates from water sources that can be treated for
drinking purposes have been investigated. Among other techniques such as catalytic
reduction, reverse osmosis, electrodialysis, coagulation and flocculation, the ion

exchange process seems to be best suited for small suppliers of nitrate contaminated
water due to its simplicity, efficiency, selectivity, recovery and relatively low costs.
A variety of adsorbents have been used for the denitrification of drinking water.
Strong anionic microporous resins have the best selectivity for nitrates. A variety of
anion exchange resins have been used to selectively remove nitrate, such as Purolite
A520E, Purolite A100. The selectivity in the adsorption of the nitrate with these
resins in the presence of other anions varies depending on the length of the carbon
chain of the functional group in the resin. The longer the carbon chain of the
functional group in the resin, the selectivity of the nitrate adsorption is higher,
becoming more hydrophobic. The resin becomes more selective in the anions, such
as nitrate with lower hydration energies. The Purolite A520E resin with
triethanolamine functional group showed that the selectivity of anion adsorption
follows the order of NO3-> Cl-> SO42- which is the inverse order of hydration
energies. Although the A500 resin has characteristics similar to the A520E resin, the
effectiveness of the retention of nitrate ions is lower (Bulgariu 2010, Samatya 2006).
This study was aimed to investigate the nitrates removal efficiency from ground
water and surface water using two selective ion exchange Purolite A520E and A500
resins in fixed bed columns. The objective of this study was divided into two parts:
1) the kinetic study of the nitrate adsorption from two water samples with NO3- ion
concentrations exceed values using the two resins and 2) thermodynamic study.

Materials
The ion exchange resin
Two ion-exchange resin, Purolite A520E and A500 were supplied from Purolite
Romania and used as adsorbents. Purolite A520E is a strongly basic anion exchange
resin whose structure is composed of polypro polystyrene with divinylbenzene
crosslinked, with a triethylamine functional group, specially designed to remove
nitrates from drinking water. Microporous matrix and particular functionality of the
ion exchange group gives the ideal selectivity of nitrates from Purolite A520E,
making this particularly suitable resin for nitrate removal even when moderate
sulfate concentrations are higher. Therefore, this resin provides superior
performance in the nitrate removal applications compared to other standard ion
exchange resins (Modrogan 2010, 2013).
Purolite A500 is also a strong basic anion exchanger with microporous structure of
the styrene-divinylbenzene with a trimethylamine functional group designed to
fulvic and humic acids removal and tannins from the effluents with higher
selectivity for the organic load. Table 1 shows the physical-chemical characteristics
of the two resins.

Table 1. The physical - chemical properties of resins Purolite A520E and A500
PARAMETER A520E A500
Polymeric structure Polystyrene crosslinked Polystyrene crosslinked
with divinylbenzene with divinylbenzene
polypropylene polypropylene
Aspect Spherical yellowish Opaque, white spherical
Functional group Type I quaternary Type I quaternary
amine -N (C2H5)3 amine N (CH3)3
Ionic form Cl- Cl-
Total capacity [equiv.L-1] 0.9 1.15
Particle size [μm] 300 - 1200 800 -1600
Specific gravity [ g.ml-1] 1.07 1.08
Moisture [%] 50 - 56 53 - 58
Temperature range [°C] max. 100 max. 140
pH range 0 - 14 0 - 11
Samples
The investigated samples were from Tulcea County, Babadag and of the Olt county
areas groundwaters, nitrate concentrations exceeding permissible limit
55.1÷66.8 mg.L1. Surface water samples were colected from the upstream and
downstream Corbul Ucei River, which springs from the Făgăraș Mountains and
flows into the Olt River, having concentrations between 10.18 and 11.86 mg NO3-.L-
1. Drinking water samples were taken from an area in the vicinity of a leguminous
seed-producing farms with concentrations of 14.45 mg NO3-.L-1 to 36.39 mg NO3-.L-

1.
Table 2. Characteristics of the real waters used in this study

Parameter P1 P2 P3 P4 P5 P6 P7 P8 P9 P10
NO3-[mg-.L-
1 10.19 11.86 14.45 18.52 22.8 23.86 36.39 52.84 55.1 66.8
]
SO42-[mg.L-
1 - - - - - - - - 18.3 48.6
]
Turbidity
- - - - - - - - 0.38 1.09
[NTU]
pH - - - - - - - - 7.2 7.5
Nitrate concentrations analyzes were performed with UV/Vis spectrophotometer

Perkin-Elmer Lambda 25.
Column tests were performed with two lab scale glass columns having an inner
diameter of 1.3 cm and 25 cm height, fixed resin bed with a 2.5 cm height. (Figure
1).
(a) (b)
( (
Figure 1. Anion exchange column, schematically (a) and real (b), on a laboratory
scale

Column adsorption experiment was performed with real water sample with 66.8 mg
NO3-.L-1 concentration. Progress curves were obtained by collecting the fractions of
the effluent in the beakers.
Methods of Analysis
Determination of nitrate was carried out according to SR ISO 7890-3 on water
quality by salicylic acid spectrometric method.
Kinetic study of adsorption
In order to study the nitrate adsorption by time, they were used two water samples
with high nitrate concentration, P9 (55.1 mg NO3-.L-1) and P10 (66.8 mg NO3-.L-1).
The Purolite A520E and A500 resins were hydrated with distilled water for 24 hours
at 25°C and so maintained throughout the study. Adsorption studies were carried out
in static pots in the open, under magnetic stirring, at room temperature (25 ± 2°C).
0.2 grams resin quantities were contacted with 10 ml of the sample. Each container
was further stirred with a magnetic stirrer at 120 rot/min at various times 1, 3, 5, 10,
20, 30 and 60 minutes. After stirring, the solid was separated from liquid phase
filtration and the nitrate concentration in the filtrate was analyzed
spectrophotometrically at λ = 415 nm compared to the control solution.
Thermodynamic study of adsorption of nitrate on the two resins Purolite
An amount of 1 g of resin was contacted with 50 ml water samples with various
concentrations of nitrate. Allow to stand for 24 hours at room temperature (25 ±
2°C) considered necessary for reaching the equilibrium ion exchange process. The
samples were filtered and nitrate was analyzed. Calculate the nitrate removal
efficiency in water samples and analyzing the equilibrium adsorption isotherms
justifying the choice of the two resins as selective nitrates retention in groundwater
and surface water.
Results and Disscusion

Study of kinetic adsorption
Experimental data on the kinetics of ion exchange for the anionic microporous
morphology Purolite A520E and A500 samples, are shown in Figure 2, in the form
of full kinetic curves as adsorbed NO3- amount variation in time. Kinetic curves
reveal similar to the high-speed stage ion exchange process of onset and slowing the
rate of ion exchange is correlated with NO3- concentration in the solution decrease
and the progressive approximation of the steady state system. Figure 3 shows the
time variation of the rate of ion exchange A520E, and A500 resins using two water
samples with various nitrates concentrations (55,1 mg.L-1 and 66.8 mg.L-1). The rate
of ion exchange depends on the size and shape of the ion exchanger particles. The
ion exchange reaction is carried out at the interface and, as a rule, it is considered
that its speed is much higher than the diffusion processes speed in the liquid phase,
so the interface does not introduce resistance to mass transfer. The A520E resin
contains smaller size particles than A500, so their specific surface is higher. At high
nitrate concentrations the ion exchange speed is higher due to a better mass transfer.
From the variation rate of ion exchange in time graph is observed that the rate
decreases rapidly during the first 5 minutes, a part of nitrate ions are charged on the
surface of the resin particles and then slowly decreases to 30 minutes which was
maintained at equilibrium due to the fastening of nitrate.

Figure 2. The variation in time of adsorption capacity of nitrates with A520E (a)
and A500 (b) resin using two different concentrations (T = 25 °C; pH = 7.2/7.5)
Figure 3. The variation rate of loading in time of A520E (a) and A500 (b) resin (T =
25 °C, pH 7.2/7.5)
Figure 4. The effect of contact time of A 520E (a) and A500 (b) with two different
nitrates concentrations (T = 25 ° C; pH = 7.2/7.5)

When using the anionite A520E after 60 minutes of contacting, the nitrate
concentration decreased from 55.1 mg.L-1 to 2.06 mg.L-1 (P9) and from 66.8 mg.L-1
to 3.19 mg.L-1 (P10). In the case of using A500 anionite, nitrate concentration
decreases from 55.1 mg.L-1 to 2.60 mg.L-1 (P9) and from 66.8 mg.L-1 3.05 mg.L-1
(P10).
Figure 4 shows the load variation of the A520E (a) and A500 (b) resins in time.
Relatively similar kinetics ion exchange process proved to be a probability due to its
similar morphology, and that the ion exchange process is controlled by internal
diffusion. In the first 10 minutes nitrate retention was rapid, reaching a maximum at
30 minutes, followed by maintaining toward equilibrium. It was found that 30
minutes is sufficient for nitrate ions retention on both resins. The loading capacity
given by the amount of retained nitrate per unit mass of resin [mg.g-1] on
equilibrium, was higher on the A520E resin, in the range 2.25-2.74 mg.g-1, to A500
resin which was situated between 2.15 and 2.68 mg.g-1.
The effect of contact time is a parameter that shows the efficiency of ion exchange
process.
The amount retained nitrate on Purolite resins was calculated using the equation:
(1)
The removal efficiency of nitrate ions from an aqueous solution on the A520E resin
was calculated using formula:
(2)
where: a - is the adsorption capacity of resin (mg.g-1), at equilibrium; C0 - initial

nitrates concentration in different types of waters (mgNO3-/L); Ct - nitrate
concentration at time t; V- solution volume which was contacted the resin (10 ml);
m - mass of the resin (0.2 g).
A kinetic study was carried out for the prediction of adsorption rate constants,
equilibrium adsorption capacity and adsorption mechanism. The capability of
pseudo-first and second order kinetic models were examined in this study at two
different initial concentration of nitrate at constant temperature of 25 °C (Nujic
2017, Nur 2014).
The linear form of pseudo first-order model is generally expressed as follows:
- )= )- t (3)
where: aeq and at are the adsorption capacity of nitrate per unit weight of resin at
equilibrium and at time t (min), respectively (mg. g−1), and k1 is the pseudo first-
order rate constant (min−1). k1 and aeq values were determined from the slope.
The linear form of pseudo second-order model is expressed as follows:
(4)

Ion exchange rate was calculated using experimental models of the adsorption
pseudo-first order and pseudo-second order kinetics.
Ion exchange rate was calculated using experimental models of the adsorption
pseudo-first order and pseudo-second order kinetics (Simonin 2016). These models
were used to fit discontinuous ion exchange process. The values of the correlation
coefficients calculated with can be found in Table 3.
Table 3. The parameters of the two kinetic adsorption models

Pseudo first - order Pseudo second - order
aeq k1 aeq k2
R2 R2
[mg.g1] [min-1] [mg.g-1] [min-1]
A520E 2.63 0.00187 0.8199 2.63 0.00129 0.8298
P9
A500 2.60 0.00200 0.8128 2.60 0.00168 0.8374
A520E 3.18 0.00160 0.8889 3.19 0.00130 0.9070
P10
A500 3.19 0.00170 0.8903 3.19 0.00160 0.9112
The values of the correlation coefficient suggest that the pseudo - the second order
model is most suitable to describe the nitrates retention in the water samples on the
A520E and A500 resins, so that the ion exchange process is limited only by the
availability of nitrate ions and functional groups on the resin surface.
The efficiency of nitrate removal from water samples actual influenced by the initial
values of nitrate concentration was between 81.7 to 82.16% for the Purolite A520E
resin (a) and 78.1 to 80.31% for the Purolite A500 resin (b) for a maximum of 95%
in both resins. Experimental results show that the percentage of retention decrease
with pollutant concentration increasing.
Thermodynamic study of NO3- retention on the A520E and A500 ion-exchangers

Ion exchange is an efficient removal process of NO3- from water. This method is
suitable on a wide range of concentrations. Ion exchange processes are influenced by
a number of factors of which the most important are the nature of ion exchange
group of the anionite macromolecular structure and the specific surface of the ion
exchanger; the pH of the wastewater (Tumuzi 2014); the degree of contamination of
the wastewater with different chemical species.
Treatment by ion exchange of NO3- contaminated water can be achieved with
various types of anion: strongly basic, medium basic, and weakly basic. As
chemisorption occurs, the amount of NO3- linked to ion exchanger rise to its
maximum capacity. The ionic form, salt or hydroxyl (Cl-, SO42-, NO3-) of anion
exchangers used is a factor which can promote the preferential adsorption of NO3-.
The most commonly used form is as salt, typically of SO42- or Cl-. The purpose of
this part of the paper is the comparative study of the equilibrium and kinetic ion
exchange system: water containing NO3- anion exchanger, where the exchanger was
Purolite A520E and Purolite A500. For NO3- water removal, two basic chloride
anion form A520E, A500 resin was used. The first one is selective NO3- ion while
the second is one non-selective.
The objective of this study was to investigate the kinetic parameters for the nitrates
removal from groundwater, surface drilling and drinking water, by two adsorption
resin Purolite A520E and A500.

Study of the adsorption process of ion SO42-

A study of the SO42- ion adsorption process has been performed in order to
emphasize the influence of the selectivity on the nitrates removal from real water
samples by ion exchange. The experiment was based on identical conditions with
thermodynamic study of nitrates adsorption with the two types of resins.
The results showed a loading of the resin A520E of 0.33 mg.kg-1 SO42- compared to
2.5 mg.kg-1 NO3- and A500 resin loading 0.93 mg.kg-1 SO42- versus 2.9 mg.kg-1 NO3-
.
The conclusion of this study is that the A500 resin, which has wick selectivity for
NO3- will remove SO42- ions, reducing its efficiency.
The experimental data were processed by the two equilibrium isotherm models
(Langmuir and Freundlich model) in order to establish the best balance of ion
exchange adsorption. The Langmuir isotherm adsorption is based on homogeneous
monolayer on the surface. The model assumed that the forces are similar to the
forces of adsorption and chemical interactions can be used to estimate the maximum
retention capacity (a max), corresponding to saturation of the ion exchange resin
surface. According to this theory, once a busy center active molecule or another
adsorption can’t be held, at which the saturation has been reached (Radu 2012).
The former is expressed as follows:
(5)
where amax (mg. g−1) is the theoretical maximum monolayer adsorption capacity at
the constant temperature, and KL(L. mg−1) is the Langmuir constant related to the
energy of adsorption. The value of RL indicates the shape of Langmuir isotherm to
be either unfavorable (RL >1), linear (RL = 1), irreversible (RL= 0), or favorable (0 <
RL< 1). Also a smaller RL value indicates a highly favourable adsorption.
Freundlich isotherm describes the non-ideal and reversible adsorption, the formation
unrestricted relative monolayer molecules on the surface of the adsorbent. The
adsorption surface is applied to heterogeneous interactions between the adsorbed
molecules. This model considers that high affinity centers are busy first. The
Freundlich model is expressed as follows:
(6)
where KF (L mg−1) and 1/n are Freundlich constants related to the multilayer
adsorption capacity and the surface heterogeneity, respectively.
Table 4. Langmuir and Freundlich constants adsorption isotherms for the adsorption
of nitrate corresponding to A520E and A500
Langmuir constant Freundlich constant
a max KL R2 n KF R2
A520 2.723 0.4234 0.9787 2.30 0.8780 0.9207
A500 7.914 0.0659 0.9282 1.28 0.5457 0.9735

Figure 6. Langmuir-Freundlich overlapping of patterns and experimental data

obtained for ion adsorption nitrate in aqueous solution at 25°C with the resin,
Purolite A520E
Figure 7. Linearized form of the isotherm: Langmuir (a), Freundlich (b)
In Figure 6 are shown overlapping of Freundlich and Langmuir models with

experimental data obtained in the case of nitrates adsorption from water samples by
the Purolite A520E resin and their linearized forms: (a) Langmuir, (b) Freundlich,
Figure 7. The correlation coefficient R2 in the case of Langmuir model was 0.9787
and 0.9207 in the case of the Freundlich which shows that the adsorption is well
described by the Langmuir isotherm.
Figure 8. Langmuir-Freundlich overlapping of patterns and experimental data

obtained for ion adsorption nitrate in aqueous solution at 25°C with the resin,
Purolite A500
Figure 9. Linearized form of the isotherm: Langmuir (a), Freundlich (b)
In Figure 8 are shown overlapping and Langmuir-Freundlich models with

experimental data obtained in the case of nitrates adsorption from water samples to
Purolite A500 resin and their linearized forms: (a) Langmuir, (b) Freundlich, Figure
9. The correlation coefficient R2 in the case of Langmuir model was 0.9282 and
0.9735 in the case of the Freundlich adsorption which indicates that aqueous nitrates
solutions to Purolite A500 resin is better described by the Freundlich isotherm.
Anionite A520E's hold a greater amount of NO3- than anionite A500. NO3- removal
efficiency increase to an optimum value above which increase the efficiency of
nitrate removal is negligible. At equilibrium, NO3- concentration in the solution
increases with increasing initial concentration of NO3- in the solution.
Ion exchange isotherms have similar shapes and indicates close values of NO3-
retention capacities from water under static conditions, although they have total
different abilities. At equilibrium, the NO3- amount removed from water is almost
identical for the two ion exchangers. The decreased value of the NO3- concentration
in water, retention capacity presents high values for both anions which means that it
can achieve efficient treatment of water NO3- contaminated through ion exchange.
Due to 1/n values, the adsorption can be classified as: positive (0 ˂ 1/n ˂ 1), bad
(1/n> 1), the irreversible (1/n = 0). A value of 1/n = 0.435 for the A520E resin and
1/n = 0.779 for the A500 resin is between 0 and 1 which reflects the adsorption of
positive ions of nitrate throughout the range of concentrations subjected to this
study, indicating a strong link between ion sorbent nitrate anion exchange resin,
Purolite A520E or A500.
The maximum ion exchange efficiency of removing nitrates from actual water used
in this study was 87.2% for Purolite A500 resin and 91.6% for Purolite A520E resin,
which shows a higher efficiency of A520E resin. The maximum efficiency was
obtained at lower concentrations of nitrate.
Conclusions
Ionic equilibrium and kinetic tests were performed for the case of nitrates removal
from ground waters, surface waters and drill waters through the two Purolite A520E
and A500 resins. The experimental data were processed by methods widely used
(isothermal Langmuir and Freundlich) to balance pseudo first and second order
kinetic and dynamic study in columns fixed bed of resin. The results have
established that the resin A520E has a higher efficiency of ion exchange and higher
selectivity than the A500 resin to nitrates removal from different types of water
samples with very high nitrate concentration. The process of NO3- adsorption of the
anionic ion exchanger A520E was better represented from Langmuir isotherm while
the A500 resin was better represented from Freundlich isotherm. Increased
efficiency of the A520E resin was due to the high NO3- ion selectivity, as evidenced
by the progress curve of ion exchange. The maximum nitrate removal rate in the real
water used in this study was 87.2% for the Purolite A500 resin and 91.6% for the
Purolite A520E resin, indicating a higher efficiency of the A520E resin.
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Purolite A520E ion exchange resin: batch and fixed-bed column adsorption
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pp 1311-1320
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Radu/Radu-ro.pdf. [20 July 2018].
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from aqueous solution by nitrate selective ion exchange resins', Reactive and
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THE USE OF CORTICOLOUS LICHEN SPECIES TO ASSESS THE LEVEL

OF AIR POLLUTION WITH HEAVY METALS
Dorian-Gabriel Neidoni1,3, Ladislau Andres1, Valeria Nicorescu1, Carol Blaziu Lehr2, Elena
Bucur2, Adrian Sinitean3
1
National Research and Development Institute for Industrial Ecology- ECOIND Timisoara
Subsidiary, 115 Bujorilor, 300431, Timisoara, ecoind.tm@gmail.com, Romania
2
National Research and Development Institute for Industrial Ecology - ECOIND, 71-73
Drumul Podu Dambovitei, district 6, 060652, Bucharest, Romania
3
West University of Timisoara, Faculty of Chemistry, Biology and Geography, Department of
Biology, 16A Pestalozzi, 300115, Timisoara, Romania
Abstract
The paper presents the preliminary results obtained in a study aimed to assess the
level of air pollution with heavy metals in urban areas by means of using bio-
indicators. The tests were carried out in one of the most polluted cities in western
Romania, using as bio-indicators corticolous lichens collected from seven
representative sites for air quality in the city. The assessment level of air pollution
with heavy metals (Cd, Ni, Pb, Cu, Mn, Zn, Cr) was based on the effect that their
presence could induce on lichens. Thus, two methods were used for the
quantification of the effect such as: a) IAP method, variation in diversity and
abundance - calculation of the value of Index of Atmospheric Purity, IAP and b)
determining the content of heavy metals in the lichen thalli, respectively.
Classification of air quality from the seven sampling sites in pollution classes (low
pollution, moderate pollution, high pollution and very high pollution) was based on
the statistical tests for correlation between the metal concentration in the air and the
specific parameters for the two evaluation methods (the IAP index value for the first
method and the metals concentration in the lichen thalli for the second method). The
tests results revealed a differentiated air quality in the seven sites, also indicating the
method of biomonitoring with corticolous lichens as a viable option for assessing the
air quality in polluted areas with heavy metals.
Keywords: air pollution, biomonitoring, heavy metals, IAP, lichens
Introduction
Lichens are organisms resulting from the symbiosis of a green algae or a
cyanobacteria and a fungus. They are a very widespread group of plants around the
world, growing on any substrate (wood, earth, trees, stones, rocks, etc.) and under
the most unfavourable conditions, so they were named "pioneers of vegetation".
Air pollution from urban centres and around them reaches concentrations that are
large enough to have a damaging effect on vascular plants.
Lichens accumulate very efficiently minerals and pollutants, they grow slowly and
live for a long time and, therefore, can accumulate large amounts of toxic substances
over a long period of time while other types of plants usually remove large areas of
loaded leaves with toxins every year (Johnson 1979).
When they are hydrated, lichens absorb nutrients and contaminants all over the
surface. During dehydration, nutrients and many contaminants, concentrate by
absorbing on cell walls, inside cellular organisms, or crystallize before cells
(Nieober et al 1978).
Characterization of the chemical composition of atmospheric deposits is relevant for
the assessment of ambient air quality by providing information on the origin of
atmospheric pollutants (natural or anthropogenic), regional and long-distance
transport, and impacts on ecosystems (Petrescu et al 2017). Traffic arteries are
known to be contaminated with heavy metals emitted by the exhaust gases of motor
vehicles after combustion of fuels. It is well known that pollution of the natural
environment with heavy metals is an universal problem because these metals are not
biodegradable and many of them have toxic effects on micro and macro organisms
and implicitly on human health (Kim et al 2017).
The current study aimed to quantify heavy metals in the atmosphere by
unconventional methods (use of corticolous lichens) other than those already
existing. Our study was conducted in July 2017.

Study area
The study area of the present paper was Timisoara, one of the largest cities in
Romania, located in the Western Plain. According to the 2011 census, the city has
319,279 inhabitants and an area of 130.5 km2 (National Institute of Statistics 2017),
being the third largest city in Romania. This makes Timisoara an important
industrial centre which also leads to considerable pollution level of the environment
with various compounds. In addition to industrial pollution, the urban agglomeration
contributes to an augmentation of pollution with heavy metals resulting from mainly
by heavy traffic, which is a growing problem in large and crowded cities in
Romania.
Seven sampling sites were selected at a distance of ~2-3 km from each other on the
N-S axis as a study area (Figure 1). The influence of the road traffic on the
lichenological flora and the degree of accumulation of heavy metals in thallus were
considered. Sites 1 and 2 were not directly influenced by road traffic, sites 4 and 5
indicated a medium traffic, sites 3 and 6 were characterized by heavy traffic, and site
7 highlighted very heavy traffic.
Figure 1. Satellite view of the study area – Timisoara and the seven sampling sites.
In order to compare the heavy metals concentrations in lichen species harvested

from Timisoara with reference values from unpolluted areas, a control sample was
used: a lichen sample was collected from a forest area located at 70 km northeast of
Timisoara (Figure 2). This area was considered as one with low pollution.
Figure 2. Satellite view of the control sample area.
Index of Atmospheric Purity (IAP)

In July 2017, for each site, lichens were sampled from 2-4 trees with a distance of at
least 100 m. The identification of lichen species and the quantification of individuals
of each species was carried out on an imaginary surface of 20x20 cm metric scale,
across the entire circumference of the tree at 1-1.5 m from the ground. This distance
from the ground was used to avoid the influence of soil and precipitation water that
washed the road and came to the bottom of the trees. After this procedure, the
lichens were inserted into plastic bags and transferred to the laboratory to determine
the existing species.
Based on the number of individuals of each species on each studied tree, a scale of
measurement of the coverage abundance was proposed by us, starting from the scale
proposed by Braun-Blanquet (Stringer & Stringer 1974): 2= 1-10 individuals, 3=
11-20 individuals, 4= 21-40 individuals, 5= 41-70 individuals, 6= 71-100
individuals.
The degree of atmospheric pollution of each site was determined using the formula
of Index of Atmospheric Purity (IAP) proposed by LeBlanc and DeSloover (1970)
IAP = Σ(Q x F)/10 (1)
where”Q” is the association index for each species and ”F” represents the sum of the
abundance values for each species, according to the used scale.
The "Q" value for each species represents the sum of the species in each site where
the species are found and the resulting amount is divided by the number of sites
where the species referred to were present.
The number of individuals of crustose thalli species were could not be identified and
thus, the values for "F" were based on visual appreciation.

Determining the accumulation of heavy metals in the lichen thalli

Additional analysis of the abiotic factors affecting the lichenological communities
was necessary to identify the stress related to the decrease of lichen biodiversity. For
this reason, a spectrophotometric analysis was carried out to determine the content
of heavy metals in the lichen thalli (Cd, Ni, Pb, Cu, Mn, Zn, Cr). For this, the lichen
thallus was thoroughly washed with distilled water and dried in the oven at 105°C
(Labtech, South Korea) to determine the dry matter. From 0.25 to 0.50 g dry tissue
was weighed and calcined at 550°C (Daihan Labtech CO-LTD, South Korea). The
ash was digested with a mixture of HCl + HNO3 3:1 (aqua regia). The crucible was
washed three times with 3 ml of HCl 1:1. The solutions to take over the residue and
the solutions for washing were filtered through paper Sartorius filter papers 2-206
FT and quantitative moved in 25 ml flasks (rated baloon). They were filled to the
mark with the HCl 1:1. Determination of metals was carried out with a
spectrophotometer Avanta AAS type (GBC Scientific Equipment Pty Ltd,
Australia).

The values of the Index of Atmospheric Purity for each site, were presented in
Figure 3. Low IAP values indicated areas with high atmospheric pollution, and high
IAP values indicated areas with improved air quality.
30
IAP Values
20
10
0
SITE SITE SITE SITE SITE SITE SITE
1 2 3 4 5 6 7
Figure 3. IAP values for each site from Timisoara in July 2017.
The different values of the IAP were used to divide the study area into 4 sub-zones
as follows: zone I includes sites with IAP values between 0-5 (very high pollution);
zone II= 6-10 (high pollution); zone III= 11-20 (moderate pollution) and zone IV=
21-30 (low pollution). Table 1 showed the results of IAP values at each site and the
corresponding pollution degree.
Table 1. The grading of sites in the pollution sub-zones, based on IAP values
I (very high II (high III (moderate IV (low
Sub-zone pollution) pollution) pollution) pollution)
Site 3, 6, 7 4, 5 1 2
Moreover, the total amount of heavy metals determined in lichen thallus for each
site were presented in Table 2.

Table 2. Quantitative results of heavy metals detected in lichen thallus from the 7
sites from Timisoara
Total amount Concentrations of heavy metals [mg/kg d.m.]
Site
[mg/kg d.m.] Ni Zn Mn Cu Pb Cd Cr
Site 1
175 3.50 115 34.6 15.3 6.60 <0.11 <0.13
Site 2
151 4.00 87.1 37.5 21.3 1.00 <0.11 <0.13
Site 3
314 3.90 210 79.6 15.2 5.00 <0.11 <0.13
Site 4
317 9.50 218 66.5 22.2 0.500 <0.11 <0.13
Site 5
149 6.00 74.8 46.5 16.9 4.80 <0.11 <0.13
Site 6
205 3.60 103 69.8 17.2 11.1 <0.11 <0.13
Site 7
469 9.00 296 77.0 83.2 4.00 <0.11 <0.13
Control
159 1.60 47.7 97.0 3.60 8.22 <0.11 <0.13
sample
d.m.=dry matter
Table 2 indicate that Zn, Mn and Cu were found in the largest proportion in the
lichen thalli. The presence of zinc in the control site may be explained by the use of
fungicides and fertilizers containing Zn in the forest boundary area. In addition, the
presence of Zn in the urban areas might be a consequence of cars evacuation and tire
wear. The large amount of Cu in the urban environment was also an effect of diesel
and unleaded gasoline, these being the main sources of atmospheric Cu. The use of
Cu-containing products, such as fungicides in agriculture could be a possible source
of Cu in lichens in the control site.
Manganese is an abundant element in the lithosphere, and the appearance of this
element in the lichen thalli was derived at least partially from the upper layer of
wind-blown soil. Besides of this natural contamination, the presence of manganese
in high concentrations may also be caused by the abrasion of motor vehicles, due to
the fact that they release heavy metal particles into the atmosphere (Affum 2008).
Lead was described as a major toxic metal that causes multiple effects on human
health such as adrenal insufficiency, cardiovascular disease, hypertension,
Parkinson's disease etc. (Goyer & Clarkson 2001), so it is very important to know
the level of lead in the atmosphere, and lichens can give indications of the presence
of this element in the atmosphere. Lichens are highly efficient Pb-accumulation
through aerosols, leakage of metal particles or acid rain (Cervantes et al 2008).
The values obtained for nickel were compared to those reported by Loppi (Loppi et
al 1994) for the centre of Italy. He reports values between 1.19 and 4.59 µg/g d.m.
which are similar to those determined by us.
Cadmium and chromium had values below the detection limit of the method.
It was evident, however, that besides the anthropogenic sources heavy metal
contamination, their presence in lichens was also determined, at least partially, by
natural causes, and this was confirmed by the presence of heavy metals in the
control sample.
Considering the total amount of metals detected in the lichen thalli, it was possible
to divide the study area into 4 sub-zones with different degrees of atmospheric
pollution (Table 3). Zone I= 100-200 mg/kg d.m. (low pollution); Zone II= 201-300
mg/kg d.m. (moderate pollution); Zone III= 301-400 mg/kg d.m. (high pollution);
Zone IV= ≥401 mg/kg d.m. (very high pollution).
Table 3. The grading of sites in the pollution sub-zones, based of heavy metals
amount
II (moderate III (high IV (very high
I (low pollution)
Sub-zone pollution) pollution) pollution)
1, 2, 5,
Site 6 3, 4 7
control sample
Correlation of the two methods presented with reference values in the air
In order to achieve the study goal represented by the correlation of corticolous
lichens results with the intensity of air pollution measured from fraction PM10 of
the particles in suspension, the National Environmental Protection Agency (NEPA)
public database was used. In Timis County, there were six automatic stations, out of
which four in Timisoara. The quantification of heavy metals (only lead and nickel)
was done in three stations: TM1, TM2 and TM5. The analysis measured at the three
automatic stations as well as the lichen analysis for all sampling points, was noted a
good overlapping. Each sampling site was located near an automatic station: TM 1
station (Timisoara South) - site 3; site 4; site 5; TM 2 station (Timisoara Center) -
site 1; site 2; TM 5 station (Timisoara North) - site 6; site 7.
No mathematical relationship was established between the air quality determined by
the instrumental analysis and the two methods analysed in the present study,
therefore a conventional air quality assessment scale was introduced taking into
account the average annual values for 2017 from National Environmental Protection
Agency database: TM 1 - increased intensity; TM 2 - medium intensity; TM 5 - low
intensity.
The correlation between the results of air quality surveillance network and the
grading of sites according to heavy metals concentration, as well as IAP was
presented in Table 4.
Table 4. Correlation between the classification of the pollution level according to

heavy metal concentrations and indicator IAP and NEPA database
Grading according to Grading according to Grading according to
Harvesting
heavy metals in the thallus IAP values NEPA network
area
Site 1 Low pollution Moderate pollution Medium intensity

Site 2 Low pollution Low pollution Medium intensity
Site 3 High pollution Very high pollution Increased intensity
Site 4 High pollution High pollution Increased intensity
Site 5 Low pollution High pollution Increased intensity
Site 6 Moderate pollution Very high pollution Low intensity
Site 7 Very high pollution Very high pollution Low intensity
The three harvesting areas in the south of the municipality (site 3, site 4, site 5), and
the sites in the central area (site 1 and site 2), an acceptable correlation was
observed. For the other two sites it was not possible to make a accurate correlation,
based on the frames presented above, because these areas do not present a constant
and uniform pollution, these areas being influenced mainly by the road traffic. The
area located in the south of the city was likely to have a constant pollution, but
considering the ability of lichens to accumulate and store heavy metals over several
years, this bio-indicators might be used as warning system in air pollution

assessment studies.
Conclusions
In the present study, the intensity of air pollution was assessed in seven sampling
sites located on the north-south axis of Timisoara. Both the Index of Atmospheric
Purity and the metals concentrations in the lichen thallus were calculated, based on
which, an evaluation scale was made by 4 levels of pollution intensity (low,
moderate, high and very high pollution).
The highest quantities of heavy metals were recorded in heavy and very heavy
traffic areas, and the lowest values were presented in the areas that were not directly
affected by road traffic. The heavy metals with the highest concentrations detected
in the thallus were zinc, copper and manganese. The presence of these metals was
mostly caused by road traffic, which signals the existence of a growing problem for
highly developed cities from Romania.
Some of the study results were correlated with the National Environmental
Protection Agency data, about heavy metals detected in the air (lead and nickel). The
experiments carried out in the present study, lead to the conclusion that the
analytical experiments, both the heavy metal detection method and the method using
the IAP indicator, could be used as low cost alternatives for assessing air pollution
in areas with constant pollution. Moreover, using the IAP indicator, heavy metal
pollution can be determined through the mathematical formula based on species
abundance, the formula that does not involve any chemical analysis.
Therefore, the experimental study validated the fact that lichens were good
bioindicators of heavy metals in the air, and they can be used for the identification of
heavy metals in the air samples.
Acknowledgements
The present research was financially supported by the Romanian Nucleu Programme, Project
PN 16 25 01 16.
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405-426.

VERIFYING THE HEIGHT OF THE DISCHARGE CHIMNEY FOR

EMISSIONS RESULTING FROM HAZARDOUS WASTE INCINERATION
INSTALLATIONS
Loredana Irena Negoita, Maria Popa
Petroleum – Gas University of Ploiesti, 39 Bucuresti, 100680, Ploiesti,

irena.negoita@gmail.com, Romania
Abstract
The paper compares the results obtained by applying three calculation
methodologies for the height of the chimney of a hazardous waste installation.
Thermal waste treatment processes are a feasible option after recovery (collection,
sorting, recycling) and prior to controlled disposal.
Monitoring data at a hazardous waste incineration plant made it possible to calculate
three heights of the incinerator emission network.
The incineration plant is thus operated in such a way that the emissions of the
harmful substances of the chimney are in conformity with the VLE values
transposed into the national legislation by Law no. 278/2013 regarding industrial
emissions, Annex 6.
Three methodologies are used to determine the height of the chimney: according to
the Technical Instructions for Air Quality Control - "TA Luft", according to "Arrêté
du 25/01/91 relatif aux incinération de résidus urbains" and according to "RS
814.318." 142.1 Ordonnance sur la l'air (Opair) ".
Keywords: chimney, incineration, monitoring, waste treatment
Introduction
In the integrated waste management system, the incineration of hazardous waste is
considered together with their controlled storage and their chemical, physical and
biological treatment as a method of disposal of combustible wastes which are no
longer proprietary for material recovery and which due to their types, and quantities
are particularly dangerous to population health and environmental factors, are
explosive or flammable, contain or can generate pathogenic germs of transmissible
diseases. These are predominantly waste types that contain large amounts of organic
compounds or have a high potential for risk. (Lazaroiu 2005)
Incineration consists in the disposal of waste by burning it in an incineration plant at
a temperature of more than 850°C.
The incineration plant may be a fixed or mobile technical plant and equipment for
the thermal treatment of waste, with or without the recovery of the resulting
combustion heat (http://eippcb.jrc.ec.europa.eu/reference/BREF/wt_bref_0806.pdf ).
A waste incineration plant consists of the following operating areas:
 Takeover of waste;
 Temporary storage, pre-treatment (if necessary);
 Supply to the incineration plant;
 Removal and treatment of residual ash;
 Treatment and recovery of emissions

Monitoring data at a hazardous waste incineration plant made it possible to calculate
three heights of the incinerator emission network.
The incineration plant of BIC systems has a total incineration capacity of 23000
tonnes/year and 2880 kg/hour and consists of: a rotary kiln (primary combustion
chamber), a combustion chamber (secondary combustion chamber) with 2 burners +
1 (for each room), fuelled with conventional fuel (LPG), connected to an air
pollution control system, all controlled and monitored (http://www-
old.anpm.ro/upload/39867_Acord%20de%20mediu%20SC%20PRO%20AIR%20C
LEAN.pdf).
This type of incinerator is equipped with an analyser that continuously monitors
(record and print) independently the following parameters: temperature, oxygen,
CO, NO, NO2, SO2, HC measurement module (uncharged hydrocarbons).
Total organic carbon (TOC) and total dust are controlled by continuous monitoring
of combustion temperature, excess oxygen and uncharged hydrocarbons (HC).
The pollutants that could be emitted into the atmosphere and must be monitored in
accordance with the Law no. 278/2013 regarding industrial emissions, Annex 6 for
incineration activity are: dust, TOC, HCl, HF, SO2, NOx, heavy metals (Cd, Tl, Hg,
Sb, As, Pb, Cr, Co, Cu, Mn, Ni, V) dioxins and furans (Law no. 278/2013).
The determinations are made during the incineration step (Lazaroiu 2006,
Serbanescu et al 2017).
The incineration plant is thus operated in such a way that the emissions of the
harmful substances of the chimney are in conformity with the VLE values
transposed into the national legislation by Law no. 278/2013 regarding industrial
emissions, Annex 6. With the monitored data, is checked the actual emission
chimney height. Three methodologies are used to determine the height of the
chimney: according to the Technical Instructions for Air Quality Control - "TA
Luft", according to "Arrêté du 25/01/91 relatif aux incinération de résidus urbains"
and according to "RS 814.318." 142.1 Ordonnance sur la l'air (Opair)"(Arrêté de
25/01/91, R.S. 814.318.142.1, Ordonnance sur la protection de l'air, Neue TA-LUFT
2002).

Calculation the height of the chimney incinerator according to the Technical
Instructions for Air Quality Control - "TA Luft" (Neue TA-LUFT 2002)
The study was carried out on a hazardous waste incineration plant, 600 KW thermal
power, with a dry purification plant for waste gases discharged through the chimney.
The installation is characterized by: thermal power 600 MW, low caloric power Hu:
16 MJ / kg, oxygen reference value: 11 %; inner diameter of the chimney at the
outlet (d): 1.20 m; flue gases temperature (t): 80 ° C; Incinerator chimney height: 30
m.
Limit values to be met according to Law no. 278/2013 regarding industrial
emissions for the indicators of interest and in this paper are presented in Table 1.

Table 1. Emission limit values (VLE), daily averages for waste incineration plants
mg/Nm3 with 11% O2.
Polutant VLE, mg/Nm3 The confidence intervals values of 95% for

with 11% O2 the measurement techniques,%
dust 10 30
SO2 50 20
NOx, like NO2* 400 20
* for capacity installation less than 6t/h
In order to cover the chimney height, the calculations will be carried out using the
value of the upper limit corresponding to the confidence interval for VLE (13
mg/Nm3 for dust, 60mg/Nm3 for SO2 and 480mg/Nm3 for NOx, like NO2).
Step 1: Calculation of flue gases flow, R [m³/h], in normal conditions, (273.15K,
101.3 kPa)
 m3  (1)
R = 3600 ⋅ V ⋅ A  
  h
where: V - flue gases velocity at chimney exit (for capacity installation over 1 t/h
and less with 6t/h): 8.0 m/s ˂ V ˂ 12.0 m/s;
A - area of the chimney section at the exhaust gases outlet:
π ⋅ D2 ;
A= (2)
4
A = 1.13 m2 ; R = 32572.8 m3/h;
Flow rate of flue gases at 11 % oxygen content is 68403 m³/h.
Step 2: Calculation flow rate of emissions (Q in kg/h)
 Qdust = 68403m³/h·13mg/m³·10-6 = 0.89 kg/hQSO2 = 68403m³/h·60
mg/m³·10-6 = 4.10 kg/hQNO2 = 68403m³/h·480mg/m³ (NOx)·10-6·0,64 =
21.01 kg/h
The conversion factor from NOx to NO2, f= 0.64, is calculated as follows: in the case
of combustion, the percentage of NO2 in the NOx emissions in the waste gas is
approx. 10%, the rest (90%) is emitted as NO; approx. 60% of the resulting NO will
be oxidized, turning to NO2.
The percentage of NO2 from the limit value of CNOx = 400 mg/m³ shall be calculated
as follows:
C NO = 480 mg/m3·0.1 = 48 mg/m³
2
Percentage of NO2 by oxidation of NO in NO2:
NO = (480 mg / m³ - 48 mg / m³)·0.6 = 259.20 mg/m³
Determination of the transformation factor f, from NOx, into NO2:
C NO , total = 48 mg/m³ + 259.20mg/m³ = 307.2mg/m³
2
f = 307.20mg/m3 / 480 mg/m³ = 0.64
Step 3: Calculation ratio Q/S
S is a specific factor for pollutants used to determination the chimney height.

Table 2. S factor according Annex 7 from Technique Guide for Air (TA Luft)
S factor value
Dust (Material particles) SOx NO2 HCl HF CO
0.08 0.14 0.1 0.1 0.0018 7.5
Q/S for dust: 0.89 kg/h / 0.08 = 11.125 kg/h;

Q/S for SO2: 4.10 kg/h / 0.14 = 29.29 kg/h;
Q/S for NO2: 21.01 kg/h / 0.1 = 210.10 kg/h
Relevant is the highest coefficient Q/S ⇒ Q/S NO2 = 210.10 kg/h
Step 4: Height chimney of incinerator in diagram
From nomogram, fig. 1, for d = 1.20 m, t = 80 ° C, R = 68403 m3/h and Q/SNO2 =
210.10 kg/h corresponding for a chimney high, Hc, de 30m.
N ă d i
Figure 1. Nomogram for determination the chimney height of incinerator.
According to the TA Luft Technical Guide, the surface on which the assessment is
made is a circle with a radius of 1.50 km around the chimney. In this area, existing
or approved compact constructions according to the construction plan or compact
vegetation have less than 5% of the area of the assessed land, which does not
involve increasing the height of the chimney (Neue TA-LUFT 2002).
When determining the height of the chimney, a form of non-linear relief shall also
be considered if the installation is located in a valley or the dispersion of the
emissions is disturbed by an oscillation of level in the relief. If necessary, the height

of the chimney is then increased by a correction factor. The actual height of the
incinerator chimney is 30m.
Calculation the height of chimney incinerator according with ARRÊTÉ DU 25/01/91

RELATIF AUX INSTALLATION D' INCINÉRATION DE RÉSIDUS URBAINS
(Arrêté de 25/01/91, article10).
The minimum admissible height of the chimney, respecting to the condition of the
concentration of pollutants, is calculated by the relations (Lazaroiu 2005; Arrêté de
25/01/91, article10).
1 1
H c = S 2 ⋅ (R ⋅ ΔT )
− (3)
6
where: q ; (4)
S= k⋅
cm
Cm = Cr − C0 (5)
 k = coefficient with 340 value for SOx and NOx (gases pollutants) and
k = 680 for dust;
 q [kg/h], maximum theoretic flow rate of pollutant;
  mg  , maximum admissible concentration of pollutant to the soil level;
Cm =  3 
 m N 
 Cr – reference concentration, 0,15 value to ash and SO2, and 0,14 value to NOx
(Arrêté de 25/01/91)
 C0 – annual average to concentration at the soil level, to impact zone (Arrêté
de 25/01/91)
273 + t  m 3 
R = 3600 ⋅ V ⋅ A ⋅  
(6)
273  h 
ΔT[K ] - difference between flue gases temperature at the outlet in chimney and the
annual average air temperature from the site.
ΔT = 353,15 − 288,15 = 65[K ]
t - the flue gases temperature to the outlet chimney; t = 80 0C;
Maximum admissible concentrations for SOx, dust and NOx, according to Law no.
278/2013, Annex 6, of the 3 values calculated for q choose the highest value to
calculate S and Hc implicitly.
q = 42117.9 ∙ 480∙10-6 ⋅ 273 = 15.63 kg NO x
273 + 80 h
Hc = 30.82 m
It is found that by this method, between the value of the chimney height obtained
from the environmental agreement and the value of the chimney height in the sizing
calculation results a difference of 0.82 m.
Calculation the height chimney of incinerator according the R.S. 814.318.142.1

ORDONNANCE SUR LA PROTECTION DE L'AIR (R.S. 814.318.142.1, ANNEXE

6)
Method for determination the chimney height by Fig. 2 Nomogram starting from
rate value Q/S (Q expressed in g/h and S expressed in µg/m3) and the value of the F
factor (ascendant flow) calculated with the relation (7):
F = 3,18 ⋅ 10 −6 ⋅ R n ⋅ Δt = 15.23 (7)
where: Rn – volumetric flow rate of the flue gases in normal conditions, 68403
Nm3/h cu 11% O2.
Δt = t - 10 0C = 80 – 10 = 70 0C
Figure 2. Nomogram for determination the chimney height of incinerator (R.S.

814.318.142.1, Annexe 6)
For Q/S = 210.13  g / h  , for NO2 and F = 15.23 from nomogram is obtained an
 3
 μg / m 
initial value for chimney high, H0 = 24m, which takes into account only the
parameters of the transmitted emission. For value correction taking into account the
weather parameters that can influence the dispersion of pollutants in the air and of
the any obstacles due to the relief or buildings situated on the site the value H0 is a
series of corrections as follows:
1. Wind intensity correction for interest site, the f factor:
H1 = f ∙H0 (8)
For f = 1.25, intermediate intensity wind, H1 = f·H0 ⇒ H1=1.25·24 = 30m.
H1- the minimum height of the incinerator chimney placed on flat, unobstructed
land.
2. High obstacles correction: buildings, vegetation placed near the
incinerator by an overhang I1.
H2 = H1 + I1; (9)
There are no high obstacles in the incinerator's area and for those conditions the
correction will not be applied.

Conclusions
According to the Air Technical Guidelines (TA Luft), the imissions assessment area
caused by the incineration plant is the surface that is completely inside the circle
around the chimney, which is 50 times the real height of the chimney and in which
the additional pollution has more than 3.0% of the value of the long-term imissions
concentration.
The actual height of the incinerator chimney is 30m.With the help of dispersion
calculation, it is checked whether outside the scope of assessment there exists, for
example, additional dust pollution for dust, NO2 and SO2.
As a result of calculations according to the "Arrêté du 25/01/91 relatif aux
incinération de résidus urbains", between the value of the chimney in the
environmental agreement and the value of the chimney height in the sizing
calculation results a difference of 0,82m; it is specified that the average annual air
temperature in the site area is an important factor in determining the height of the
chimney, in determining the height of the flue and in calculating the dispersion of
the pollutants; the average gas velocity entering the sizing calculation is a parameter
chosen in the range of 8.0-12 m / s, depending on other parameters.
The third methodology for verifying the height of the emission dispersion chimney
results in the minimal height of the incinerator chimney located on flat, unobstructed
land areas of 30 m.
Through all three methodologies, the minimum chimney height, depending on the
pollutant categories and their concentrations, is at least 30 m, as is the actual height
of the chimney height.
References
Arrêté de 25/01/91 relatif auxinstallation d'incinération de résidus
urbains.https://aida.ineris.fr/consultation_document/5927. In French.
Directive 2000/76/EC of the European Parliament and of the Council on the
incineration of waste. Available from:
https://www.retim.ro/legislatie/Directiva_2000_76_CE.pdf.
Environmental agreement for the project “The installation for waste incineration”,
SC PRO AIR CLEAN SA. Available from: http://www-
old.anpm.ro/upload/39867_Acord%20de%20mediu%20SC%20PRO%20AIR
%20CLEAN.pdf.
Integrated Pollution Prevention and Control, Reference Document on the Best
Available Techniques for Waste Incineration. Available from:
http://eippcb.jrc.ec.europa.eu/reference/BREF/wt_bref_0806.pdf. [August
2006].
Lazaroiu, Gh, Patrascu, R & Gheorghe, C 2005, Impact of CTE on the environment -
applications, Politehnica Press Publishing House, Bucharest, pp. 145.
Lazaroiu, G 2006, Dispersion of pollutants, Agir Publishing House, Bucharest,
pp. 307.
Ordonnance sur la protection de l'air. Available from :
https://www.admin.ch/ch/f/rs/8/814.318.142.1.fr.pdf;/R.S.814.318.142.1. In
French.
Law no. 278/2013 regarding industrial emissions

Neue TA-LUFT. Available from:

http://m.bmu.de/fileadmin/Daten_BMU/Download_PDF/Luft/taluft_engl.pdf [24
July 2002]
Serbanescu, A, Barbu, ME, Nicolescu, IC & Bucur, E 2017, ‘Interdependence
between total organic carbon content and heating value of sewage sludge
samples’, 20th International Symposium “The Environment and The Industry”,
Technical Normative about waste incineration from 26/11/2004 published in
Official Monitor, parte I no.86 encore from 26/01/2005.

21ST INTERNATIONAL SYMPOSIUM

“THE ENVIRONMENT AND THE INDUSTRY”
Sponsors Presentation
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Bucharest
20-21 September 2018
ISSN-L 1843-5831
National Research and Development Institute for
Industrial Ecology - ECOIND

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PENTRU ECOLOGIE INDUSTRIALĂ

National Research and Development Institute for

21st INTERNATIONAL SYMPOSIUM

21st International Symposium “The Environment and the Industry” –

Ph.D. Chem. Luoana Florentina PASCU

Publisher: National Research and Development Institute for Industrial

2017 SYMPOSIUM PROCEEDINGS IS INDEXED IN WEB OF SCIENCE –

2015, 2016, 2017

Symposium Proceedings are

under Honorary Patronage of:

under Coordination of:

Ph.D. Chem. Luoana Florentina Pascu

Acad. Ioan-Aurel Pop, President of Romanian Academy

Chair: Ph.D. Chem. Luoana Florentina Pascu, INCD-ECOIND, Romania

Sustainable Environmental Technologies

Ph.D. Eng. Costel Bumbac, INCD-ECOIND, Romania

Pollution Assessment & Management System

Prof. Ph.D. Eng. Ioan Bica, UTC Bucharest, Romania

Pollution Control and Monitoring

Prof. Dr. Irinel Adriana Badea, University of Bucharest, Romania

PHOTODEGRADATION OF RHODAMINE 6G IN PRESENCE 99

Pollution Assessment & Management Systems

ASSESSMENT TERMS FOR LOCAL SUSTAINABILITY 186

USE OF REMOTE SENSING DATA IN INVESTIGATIONS OF 311

Pollution Control and Monitoring

A BASELINE ASSESSMENT OF WATER QUALITY FROM 333

MEMBRANE FILTRATION EFFICIENCY ON TRIAZINE 392

SUSTAINABLE ENVIRONMENTAL TECHNOLOGIES

Section Sustainable Environmental Technologies 16

A VARIANT OF GREEN CONCRETE WITH INDUSTRIAL AND

Catalina Mihaela Helepciuc (Gradinaru), Marinela Barbuta, Adrian Alexandru Serbanoiu,

Keywords: corn cob, density, fly ash, mechanical properties

Materials and Methods

Section Sustainable Environmental Technologies 18

- CCCFA 50-10 – a concrete with 50 vol.% of corn cob granules as partial

Results and Discussion

Section Sustainable Environmental Technologies 19

Figure 2. Concrete density at 28days, [kg/m3].

Figure 3. Compressive strength of the concrete [N/mm2].

Section Sustainable Environmental Technologies 20

Figure 4. Splitting tensile strength of the concrete [N/mm2].

Section Sustainable Environmental Technologies 21

Ashour, A, Amer, M, Marzouk, A, Shimizu, K, Kondo, R & El-Sharkawy, S 2013,

Section Sustainable Environmental Technologies 22

ADSORPTION OF Sr2+ IONS FROM AQUEOUS SOLUTIONS ON THE

Mihai Ciobanu, Tudor Lupascu, Tatiana Mitina, Igor Povar

Institute of Chemistry, 3 Academiei Street, MD2028, Chisinau, ipovar@yahoo.ca, Republic of

Keywords: activated carbon, adsorption, aqueous solution, chemical activation,

Materials and Methods

Figure 1. Adsorption isotherm (adsorption a versus equilibrium concentration Ce) of

Section Sustainable Environmental Technologies 24

The decrease of the filtration rate to 5.75 m/hr (Figure 3) demonstrates a

Section Sustainable Environmental Technologies 25

Figure 5 shows an increase in the adsorption value compared to Figure 4, the

Section Sustainable Environmental Technologies 26

Results and Discussion

where Vads. is the adsorbent volume.

Section Sustainable Environmental Technologies 28

Section Sustainable Environmental Technologies 29

Zhang, AY, Wei, YZ & Kumagai, M 2004, 'Synthesis of a novel macroporous

Section Sustainable Environmental Technologies 30

ANALYSING WOOD DENSITY AND BIOMASS: A CASE STUDY OF