SIMI 2019 Full Paper

INTERNATIONAL SYMPOSIUM “THE ENVIRONMENT AND THE INDUSTRY”,
SIMI 2019, PROCEEDINGS BOOK
22nd INTERNATIONAL SYMPOSIUM

“THE ENVIRONMENT AND THE INDUSTRY”
PROCEEDINGS BOOK
Bucharest, Romania
September 26-27, 2019
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2
22nd International Symposium “The Environment and the Industry” –

SIMI 2019
Editors:
Ph.D. Chem. Luoana Florentina PASCU

Ph.D. Eng. Carol Blaziu LEHR
Ph.D. Eng. Gabriela Geanina VASILE
Ph.D. Eng. Alina Mirela CONSTANTIN
Proofing:
Ph.D. Stefania GHEORGHE
Eng. Cristian SERBANESCU
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.2019
2017 SYMPOSIUM PROCEEDINGS IS INDEXED IN WEB OF SCIENCE –

CONFERENCE PROCEEDINGS CITATION INDEX-SCIENCE
2015, 2016, 2017, 2018
Symposium Proceedings are

indexed in:
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Organizers
International Symposium
“The Environment and the Industry” SIMI 2019
under Honorary Patronage of:

Romanian Academy
under Coordination of:

Ministry of Research and Innovation
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
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Introductory word
Dear colleagues,
Welcome to the 22st edition of the International Symposium “The
environment and the industry” to be held in Bucharest on September 26-27,
2019.
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 thank the authors for their submitted work and their professional
involvement and Scientific Committee for their thorough and timely
reviewing of the papers.
We wish you a pleasant and fruitful stay in Bucharest.
Ph.D. Chem. Luoana Florentina Pascu

Chair of SIMI 2019
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Honorific Committee
Nicolae Hurduc - Minister of Research and Innovation
Acad. Ioan Aurel Pop – President of Romanian
Academy
Acad. Marius Andruh – President of „Chemical Sciences Section” of
the Romanian Academy
Emeritus Prof. Dr. Eng. Sorin Rosca – President of Romanian
Society of Chemistry
Prof.Dr.Eng. Vladimir Rojanschi – President of Romanian
Environment Assoc. 1998
Felix Stroe – President of Romanian Water Association
Emeritus Prof. Dr. Eng. Gheorghita Jinescu (Vice-President of
Romanian Society of Chemistry, Romania)
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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

Prof. Dr. Asher Brenner (Faculty of Engineering Sciences, Israel)
SR Dr. Eng. Costel Bumbac (INCD-ECOIND, Romania)
Prof. Dr. Eng. Cristina Costache (University Politehnica Bucharest,
Romania)
SR Dr. Eng. Gheorghe Batrinescu (INCD-ECOIND, Romania)
SR Chem. Cristiana Cosma (INCD-ECOIND, Romania)
Prof. Tim Grotehnuis (WUR, Olanda)
Honored Prof. Dr. Eng. Gheorghita Jinescu (University Politehnica
Bucharest, Romania)
Dr. Mykola Kartel (CISC, Ukraine)
Dr. Pawel Krzeminski (NIVA, Norway)
Dr. Michela Langone (Trento University, Italy)
Acad. Dr. Tudor Lupascu (ICA, Moldova)
Prof. Dr. Ying Ma (Coimbra University, Portugal)
Prof. Dr. Eng. Ileana Nistor (University of Bacau, Romania)
SR Dr. Eng. Ines Nitoi (INCD-ECOIND, Romania)
Prof. Dr. Ovidiu Popa (USAMV Bucharest, Romania)
Prof. Dr. Eng. Mircea Teodorescu (University Politehnica Bucharest,
Romania)
Prof. Dr. Giuliano Tevi (Ecological University, Romania)
Dr. Eng. Valentin VLADUT (INMA)
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Pollution Assessment & Management System

Prof. Dr. Eng. Ioan Bica (UTC Bucharest, Romania)
SR Dr. Eng. Lucian Constantin (INCD-ECOIND, Romania)
SR Eng. Virgil Criste (INCD-ECOIND, Romania)
Dr. Biol. Stefania Gheorghe (INCD-ECOIND, Romania)
Prof. Dr. Tiago Natal da Luz (Coimbra University, Portugal)
SR Dr. Eng. Carol Lehr (INCD-ECOIND, Romania)
SR Biochem. Irina Lucaciu (INCD-ECOIND, Romania)
Prof. Dr. Rui S. Oliveira (Coimbra University, Portugal)
Dr. Robert Raschman (Dekonta, Czech Republic)
Prof. Dr. Eng. Geta Rasnoveanu (University of Bucharest, Romania)
Prof. Dr. Eng. Vladimir Rojanschi (Ecological University, Romania)
Prof. Dr. Daniel Scradeanu (University of Bucharest, Romania)
Prof. Dr. Jose Paulo Sousa (Coimbra University, Portugal)
SR Dr. Bogdan Adrian Stanescu (INCD-ECOIND, Romania)
SR Eng. Cristian Teodorescu (International Development, Norway)
Asst. Prof. Dr. Özlem Tunç Dede (Giresun University, Turkey)
SR Dr. Eng. Gabriela Geanina Vasile (INCD-ECOIND, Romania)
Dr. Caner Zanbak (Environmental Coordinator, Turkish Miners
Association, Turkey)
Pollution Control and Monitoring
Prof. Dr. Irinel Adriana Badea (University of Bucharest, Romania)
SR Chem. Elena Bucur (INCD-ECOIND, Romania)
Dr. Marius Bumbac (Valahia University, Romania)
SR Chem. Liliana Cruceru (INCD-ECOIND, Romania)
Acad. Gheorghe Duca (ASRM, Moldova)
Prof. Margarita Filipova (Rousse University, Bulgaria)
SR Dr. Chem. Toma Galaon (INCD-ECOIND, Romania
Dr. Biol. Stefania Gheorghe (INCD-ECOIND, Romania)
PhD Iryna Koval (Lviv Polytechnic National University, Ukraine)
Prof. PhD. Jean Louis Marty (Perpignan University, France)
Prof. dr. ing. Aurelia Meghea (University Politehnica Bucharest, Romania)
Prof. Dr. Eng. Gheorghe Nechifor (University Politehnica Bucharest,
Romania)
SR Dr. Biolog. Mihai Nita-Lazar (INCD-ECOIND, Romania
SR Dr. Chem Luoana Florentina Pascu, (INCD-ECOIND, Romania)
SR Dr. Chem Jana Petre (INCD-ECOIND, Romania)
Prof. Dr. Eng. Gabriel–Lucian Radu (University Politehnica Bucharest,
Romania)
Prof. Dr. Lucica Tofan (Ovidius University, Romania)
Prof. Dr. Chem. Luminita Vladescu (University of Bucharest, Romania)
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Sponsors
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Content
Sustainable Environmental Technologies
A NEW APPROACH TO DETERMINE THE DISCHARGE 17

PASSING OVER OGEE SPILLWAY
Alpaslan Yarar, Ali Yildiz, Ali İhsan Marti, Öznur Kocaer
CONVERSION OF LIGNOCELLULOSIC AGRICULTURAL 24
WASTES INTO ADSORBENTS FOR PHARMACEUTICAL
DRUGS
Anca Cruceanu, Monica Alexandra Vaideanu, Rodica Zavoianu, Elena
Bacalum, Octavian Dumitru Pavel
ENERGY-SAVING INTEGRATED FERRITISATION 32
TREATMENT OF NICKEL-CONTAINING WASTEWATER
Gennady M. Kochetov, D.M. Samchenko, B. M. Yemchura
EVALUATION OF ACTIVE SLUDGE AND AQUATIC FERNS 39
USAGE FOR REMOVAL OF ZINC IN A BIOLOGICAL
WASTEWATER TREATMENT SYSTEM
Amir Hajiali, Lacramioara Diana Robescu
EXPERIMENTAL EVALUATION OF A BIOLOGICAL 45
PRODUCTS' EFFICIENCY FOR HIGH-LOAD WASTEWATER
TREATMENT
Elena Elisabeta Manea, Costel Bumbac, Florin Găulea
EXPERIMENTAL STUDY ON USING COMMERCIAL 50
MEMBRANES FOR TREATMENT OF WASTEWATER
GENERATED BY COLLAGEN PRODUCTION
Mirela Alina Constantin, Lucian Alexandru Constantin, Ion Viorel
Patroescu, Gheorghe Batrinescu, Georgiana Dolete
Fe-Al RECOVERY FROM MINE WATER TREATMENT 56
RESIDUALS AND PRODUCT TESTING FOR WASTEWATER
TREATMENT - PHOSPHATE AND TURBIDITY REMOVAL
Laurentiu Razvan Dinu, Valeriu Robert Badescu, Gabriela Geanina Vasile,
Ionut Cristea, Ecaterina Anca Serban, Voicu Oncu, Marinela Moga
INVESTIGATION OF SERVICE BRIDGE PIERS LOCATED ON 63
SPILLWAY AND EFFECTS ON DISCHARGE
Ali Yildiz, Alpaslan Yarar, Ali İhsan Marti, Öznur Kocaer
MANAGEMENT STRATEGIES APPLIED IN WATER 71
STATIONS USED IN THE FOOD INDUSTRY IN ORDER TO
INCREASE THE QUALITY OF THE BIOGAS
Daniela Angela Buzoianu, Casen Panaitescu
MULTI-FUNCTION BIOSYSTEM BASED ON ARTHROSPIRA 77
PLATENSIS FOR SPACE APPLICATIONS
Gabriela Soreanu, Igor Cretescu, Mariana Diaconu, Maria Ignat, Valeria
Harabagiu, Corneliu Cojocaru, Petrisor Samoila
NEW MATERIALS FOR REMOVING NITRATE, MANGANESE 84
AND IRON FROM GROUNDWATER
Liliana Bobirica, Cristina Modrogan, Constantin Bobirica, Oanamari Daniela
Orbulet, Madelene Annette Dancila, Cristina Orbeci
10
REMEDIATION OF POPS POLLUTED SITES IN REPUBLIC OF 90

MOLDOVA
Tudor Lupascu, Oleg Bogdevich, Elena Culighin
THE ROLE OF FOREST VEGETATION IN THE MITIGATION 98
OF THE ECOLOGICAL IMBALANCES RESULTING FROM
CLIMATE CHANGE IN THE PUTNA-VRANCEA RIVER BASIN
Cristinel Constandache, Lucian Dinca, Laurentiu Popovici, Ciprian Tudor
TREATMENT OF HEMP RETTING WASTEWATERS: USE OF 107
BY-PRODUCTS FROM WINEMAKING INDUSTRY
Simona Gavrilas, Violeta Nastuneac, Florentina-Daniela Munteanu
VEGETABLE FOOD WASTE FOR COTTON DYEING-NEW 113
DIRECTIONS FOR ENVIRONMENTAL SUSTAINABILITY
Andreea Bujdei, Simona Gavrilas, Mihaela Dochia, Florentina-Daniela
Munteanu
Pollution Assessment & Management Systems
A FINITE ELEMENT METHOD FOR ENVIRONMENTAL AND 122

POLLUTANT TRANSPORT PREDICTION
Victorita Radulescu
ANALYSIS OF THE MIGRATION OF A POLLUTANT IN THE 130
SOIL STRUCTURE
Maria Popa, Loredana Irena Negoita
APPROACHES CONCERNING THE CONCEPTUAL MODEL 135
FOR THE ASSESSMENT OF THE NATURAL FUND VALUES
OF THE SOIL AND WATER IN NATURAL PROTECTED
ZONES
Bogdan Stanescu, Adriana Cuciureanu, Georgiana Cernica, Gina Alina
Catrina (Traistaru)
ASSESSMENT OF THE AIR POLLUTION DUE TO 144
COMBUSTION PROCESSES OF DIFFERENT WASTES
Mihai Bratu, Luoana Florentina Pascu, Mihaela Petrescu, Andrea Cozea,
Maria Pasca
BIOLOGICAL MONITORING USED IN ASSESSMENT OF THE 153
AIR POLLUTANTS
Andreea Cozea, Elena Bucur
COMPARATIVE TOXICITY EFFECTS OF CLEANING 160
PRODUCTS ON FISH, ALGAE AND CRUSTACEA
Stefania Gheorghe, Irina Lucaciu, Daniel Mitru, Lucian Ionescu, Mihai Nita-
Lazar
CPM AND PERT TECHNIQUES FOR SMALL-SCALE R&D 166
PROJECTS
Marius Simion, Gabriela Vasile, Cristina Dinu, Roxana Scutariu
ECOLOGICAL ASPECTS OF AGROECOSYSTEMS OF 175
SOYBEAN IN THE CONDITIONS OF THE SOUTH-EAST OF
KAZAKHSTAN AT CLIMATE CHANGE
Naziya Suleimenova, Margarita Filipova, Elnara Kuandykova, Gulnar
Orynbasarova, Kuanish Zholamanov, Kenzhe Erzhanova
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EVALUATION OF ASH RELATED PROBLEMS DURING 184

SEWAGE SLUDGE COMBUSTION
Agnes Serbanescu, Mona Barbu, Ionut Cristea, Gina Catrina, Georgiana
Cernica, Mihai Stefanescu, Ioana Bercu
IMPACT OF TERRESTRIAL AND MARINE POLLUTION ON 192
THE BLACK SEA QUALITY OF WATER
Victorita Radulescu
INFLUENCE OF THE pH INDICATOR ON DISSOLVED 200
ORGANIC CARBON FOR DETERMINATION THE
HAZARDOUSNESS OF INDUSTRIAL WASTE
Georgiana Cernica, Adriana Cuciureanu, Gina Catrina (Traistaru), Diana
Stroia
METHODOLOGY FOR QUICKLY DETERMINING THE 207
QUALITY OF PELLETS
Georgi Komitov, Violeta Rasheva, Ivan Binev
METHODS OF THE END-USE OF END-OF-LIFE TIRES 215
Nevena Ivanova, Margarita Filipova, Ivanka Zheleva
OPTIMIZING CHARACTERISTICS IN MINERAL INSULATING 222
OIL USED IN HIGH POWER TRANSFORMERS
Irina Alina Chera Anghel, Loredana Popescu
SOLUTIONS FOR OBTAINING HIGH QUALITY 229
VITICULTURAL PRODUCTIONS IN THE CONTEXT OF
CLIMATE CHANGE
Diana Elena Vizitiu, Lucian Dinca, Viorica Enache, Alina Donici, Ana-
Maria Radomir
STRUCTURAL MODEL OF FOREST ECOSYSTEM SERVICES’ 238
PAYMENT FOR WATER QUALITY IMPROVEMENT
Mariyana Lybenova, Alexandre Chikalanov, Yulian Petkov
STUDY OF THE POSSIBLITIES TO REUSE CONSTRUCTION 246
AND DEMOLITION WASTE
Denitsa Hvarchilkova, Margarita Filipova, Ivanka Zheleva
THE INFLUENCE OF EMISSION SOURCES ON PARTICULATE 253
MATTER POLLUTION IN ADJACENT AREAS
Valeriu Danciulescu, Luoana Florentina Pascu, Mihaela Petrescu, Andreea
Cozea, Raluca Diodiu, Gheorghita Tanase, Maria Pasca
THE ORIGIN OF AMMONIUM IN CARBONATED MINERAL 259
WATERS AND ITS UNDERGROUND TRANSPORT TO ONE
PRODUCTION WELL IN MIDDLE CIUC DEPRESSION FROM
EASTERN CARPATHIANS
Olariu Andra, Palcu Marin
TOXIC EFFECTS OF NON-ACUTE LEAD EXPOSURE ON 279
ANIMAL MODEL
Gheorghita Isvoranu, Daniela Ionela Popescu, Elena Codrici, Simona Mihai,
Ana-Maria Enciu, Gina Manda, Marco Peretto, Cristiana Tanase
VERIFYING COMPLIANCE OF A METALLIC SURFACE 285
TREATMENT COMPANY WITH BAT REQUIREMENTS, TO
MINIMIZE EMISSIONS OF POLLUTANTS IN WATER
Marius Kovacs, Angelica-Nicoleta Calamar, Lorand Toth, Sorin Simion,
Alexandru Simion
12
WASTE MANAGEMENT SYSTEM IN ROMANIA – STATUS 293

AND DEVELOPMENT FOR BIOECONOMY
Steliana Rodino, Marian Butu, Raluca Ion
Pollution Control and Monitoring
NEW TOOLS FOR ASSESSMENT OF WASTEWATER 302

QUALITY. CASE STUDY, ONE RURAL REGION FROM
ROMANIA
Florinela Pirvu, Liliana Cruceru, Marcela Niculescu, Jana Petre, Vasile-Ion
Iancu, Luoana Florentina Pascu, Toma Galaon
PCB CONGENERS OCCURRENCE IN SEWAGE SLUDGE 310
FROM MUNICIPAL WASTEWATER TREATMENT PLANTS IN
ROMANIA
Alina Tatarus, Diana Puiu, Roxana Scutariu, Marius Simion, Marcela
Antoaneta Niculescu, Toma Galaon
SIMULTANEOUS DETERMINATION OF PROCAINE 318
HYDROCHLORIDE, PROCAINAMIDE HYDROCHLORIDE
AND LIDOCAINE BY MOLECULAR ABSORPTION
SPECTROMETRY
Nicoleta Mirela Marin, Gheorghe Batrinescu, Mihai Nita-Lazar, Luoana
Florentina Pascu, Carol Blaziu Lehr
SOME CONSIDERATIONS ON INDOOR AND OUTDOOR 325
IMPACTS OF DIFFERENT WAYS OF PM RELEASE AND
ODOUR EMISSION IN INDUSTRIAL SECTORS
Elena Cristina Rada
THE COMPARISON OF DESTRUCTION DEGREE BETWEEN 333
DIFFERENT TYPES OF MICROORGANISMS UNDER
GAS/CAVITATION CONDITIONS
Koval Iryna Z.
UNIVERSAL SCREENING OF PRIVATE WELLS WATER 337
QUALITY IN THE MUNTENIA REGION, ROMANIA
Gina Vasile Scaeteanu, Roxana Maria Madjar, George Adrian Peticila
13
Papers developed within the project ”Promotion, identification and development of

partnerships on knowledge transfer in the field of industrial ecology” -
Operational Programme Competitiveness 2014 – 2020, Contract no. 55/05.09.2016,
Project ID P_40_300, SMIS 105581
DOI: http://doi.org/10.21698/simi.2019.fp05
EXPERIMENTAL EVALUATION OF A BIOLOGICAL PRODUCTS' 45
EFFICIENCY FOR HIGH-LOAD WASTEWATER TREATMENT
Elena Elisabeta Manea1, Costel Bumbac1, Florin Găulea2
1
National Research and Development Institute for Industrial Ecology - ECOIND, 71-
73 Drumul Podul Dambovitei Str., 060652, Bucharest, Romania,
elena.manea@incdecoind.ro
2
Renergetics Decontaminari SRL, București str. Horbotei, nr. 3, Bl. M2, Scara 2,
ap.27, Sector 3, cod poștal 030465, tel. 0762257343, Romania
Subsidiary Contract no. 3590/ 07.03.2018
EXPERIMENTAL STUDY ON USING COMMERCIAL 50
MEMBRANES FOR TREATMENT OF WASTEWATER
GENERATED BY COLLAGEN PRODUCTION
Mirela Alina Constantin1, Lucian Alexandru Constantin1, Ion Viorel Patroescu1,
Gheorghe Batrinescu1, Georgiana Dolete2
1
National Research and Development Institute for Industrial Ecology – ECOIND
Bucharest, 71-73 Drumul Podu Dambovitei, Sector 6, 060652, Bucharest, Romania,
alina.constantin@incdecoind.ro
2
SC Sanimed International Impex SRL, 70F Bucuresti-Magurele, Sector 5, Bucharest,
Romania
Subsidiary Contract 5831/18.04.2018
Fe-Al RECOVERY FROM MINE WATER TREATMENT
56
RESIDUALS AND PRODUCT TESTING FOR WASTEWATER
TREATMENT - PHOSPHATE AND TURBIDITY REMOVAL
Laurentiu Razvan Dinu1, Valeriu Robert Badescu1, Gabriela Geanina Vasile1, Ionut
Cristea1, Ecaterina Anca Serban, Voicu Oncu 2, Marinela Moga2
1
National Research and Development Institute for Industrial Ecology ECOIND, 71-73
Drumul Podu Dambovitei Street, code 060652, Bucharest, tehnologi@incdecoind.ro,
Romania
2
SC Cepromin SA, 22 Decembrie Street, no. 37A, Deva, office@cepromin.ro,
Romania
Subsidiary Contract 15350/2017
14
ASSESSMENT OF THE AIR POLLUTION DUE TO COMBUSTION 144
PROCESSES OF DIFFERENT WASTES
Mihai Bratu1, Luoana Florentina Pascu1, Mihaela Petrescu1, Andrea Cozea1, Maria
Pasca2
1
National Research and Development Institute for Industrial Ecology – ECOIND, 71-
73, Drumul Podu Dambovitei Street, sector 6, zip 060652, Bucharest, Romania,
poluare.aer@incdecoind.ro
2
SC Oehler Mecanica SRL, str. Uzinei, nr. 1, Marsa-Avrig, jud. Sibiu, Romania
Subsidiary Contract no. 2142/12.02.2019
EVALUATION OF ASH RELATED PROBLEMS DURING SEWAGE 184
SLUDGE COMBUSTION
Agnes Serbanescu1, Mona Barbu1, Ionut Cristea1, Gina Catrina1, Georgiana Cernica1,
Mihai Stefanescu1, Ioana Bercu2
1
National Research and Development Institute for Industrial Ecology - ECOIND, 71-
73 Drumul Podu Dambovitei Street, 060652, Bucharest, District 6,
agnes.serbanescu@incdecoind.ro, Romania
2
S.C. Kema Tronic SRL, 16 Minerilor Street, Baia Mare, kematronic@yahoo.com,
Romania
Subsidiary Contact no. 6538/27.04.2018
INFLUENCE OF THE pH INDICATOR ON DISSOLVED ORGANIC 200
CARBON FOR DETERMINATION THE HAZARDOUSNESS OF
INDUSTRIAL WASTE
Georgiana Cernica1, Georgeta Madalina Arama1, Adriana Cuciureanu1, Gina Catrina
(Traistaru)1, Diana Stroia2
1
National Research and Development Institute for Industrial Ecology ECOIND
Bucharest, 71– 73 Drumul Podu Dambovitei Street, 060652, Bucharest,
evmt@incdecoind.ro, Romania
2
SC Setcar SA, 6 Gradinii Publice Street, 810022, Braila, Romania
THE INFLUENCE OF EMISSION SOURCES ON PARTICULATE 253
1 1 1 1
Valeriu Danciulescu , Luoana Florentina Pascu , Mihaela Petrescu , Andreea Cozea ,
Raluca Diodiu1, Gheorghita Tanase1, Maria Pasca2
1
National Research and Development Institute for Industrial Ecology – ECOIND, 71-
73, Drumul Podu Dambovitei Street, sector 6, zip 060652, Bucharest, Romania,
2
SC Oehler Mecanica SRL, str. Uzinei, nr. 1, Marsa-Avrig, jud. Sibiu, Romania
The content of this materials was developed within the project” Promotion,
identification and development of partnerships on knowledge transfer in the field
of industrial ecology”.
Project co-financed from European Regional Development Fund through
Competitiveness Operational Programme.
The content of this materials does not necessarily represent the position of the
European Union or the Romanian Government. 15
SUSTAINABLE ENVIRONMENTAL TECHNOLOGIES
16
A NEW APPROACH TO DETERMINE THE DISCHARGE PASSING OVER

OGEE SPILLWAY
Konya Technical University Civil Engineering Department, Konya, ayarar@ktun.edu.tr,

ayildiz @ktun.edu.tr, aimarti@ktun.edu.tr, oznurkocaer3@gmail.com, Turkey
Abstract
The main purpose of this study is investigation of flow over an ogee spillway
experimentally and comparison with the analytical results. An experimental study
was conducted to obtain discharges and heads over an ogee spillway. 30 different
discharge and flow depths of flow in physical model were measured.
Nondimensional discharge and flow depth curves are used to compare the results.
Experimental results indicate that some regulations can be done in analytical
formulas. In this way the analytical results can be get more accurately.
Keywords: analytical study, experimental investigation, Ogee Spillway
Introduction
The ogee spillway is one of the most studied hydraulic structures because of its
superb hydraulic characteristics. Ogee spillways are used for controlling the
discharges and water levels in reservoir in dams. A spillway should have an
economical and functional design, therefore the hydraulic parameters such as
discharge, flow depth and velocity should be known accurately. Although much of
information about ogee spillways is understood, any derivation from standard
parameters such as flow depths and crest shape can change flow parameters. It
should be known that these small changes whether or not affect spillway
performances.
Many researches made considerable works to determine most efficient parabolic
crest shape of the ogee spillway and different methods are used depending on the
relative height (P/H). Many of these methods are based on an extensive series of
experiments conducted on weirs at the U. S. Bureau of Reclamation Laboratory
(Bradley 1952) defining the profile of the lower nappe of flow over a sharp-crested
weir for a wide range of relative heights and upstream face slopes. The design
methods presented by the U. S. Army Engineer Waterways Experiment Station,
Corps of Engineers (Maynord 1985) and the (USBR 1987) are probably the most
widely used methods in the hydraulic engineering.
Experimental studies have been basis of numerical studies such as computational
fluid dynamics (CFD). The researchers (Savage and Johnson 2001) compared the
discharge characteristics and pressure distribution for flows passing over an ogee
spillway using a physical model, a numerical model. Dargahi 2006) used a physical
and numerical model to compare surface profile and discharge coefficients. The
researchers (Hu and Friends 2018) used a numerical model to analyze performance
of piano key weirs. According to results of numerical model, some new formulas are
Section Sustainable Environmental Technologies 17

driven by him to improve accuracy of the design and structural optimization of

piano key weirs.
In this study, a physical model of standard ogee spillway which was built in
laboratory is used. Discharge and head over spillway were measured. Discharge
values, depending on head over the spillway, were also calculated using analytical
formula. The correlation between the experimental and the analytical results of
discharges was investigated. And some regulations on the formula were suggested to
increase the correlation between the results.
Materials and Methods

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).
The general equation for discharge over an ogee crested spillway is given as:
Q=CxLxH1.5 (1)
where;
Q= discharge, L= crest width, C= discharge coefficient and H=total head over ogee
spillway.
The relationship of discharge coefficient, Co, to various values of P/Ho, is given in
Figure-1 where Co is design discharge coefficient and Ho is design head.
Discharge coefficient ratio C/Co continues to increase with H/Ho as shown Figure-2
up to maximum value of head ratio (H/Ho). The curve on the Figure 2 depends on:
(2)
Figure 1. Discharge coefficient for vertical-faced ogee spillway (USBR 1987)

Figure 2. Discharge coefficient for various total head (USBR, 1987)
In the laboratory, the ogee spillway model was placed in a test flume. The test flume
is a open channel which was made of plexiglas. The open channel is 400 cm long, 7,
5 cm wide and 15 cm high and has a zero bottom slope. The open channel has a
closed water circulation system and the flow supplied by an upstream reservoir tank
via a pump. Screens are placed at the upstream face of the reservoir tank in order to
prevent waves and to obtain uniform flow conditions along the channel. The screens
are behaving as wave-breaking and provide a smooth water surface profile before
the ogee spillway.
An ogee spillway was placed at the tail of the channel then flow depths and flow
rates are adjusted by a valve. Total head over the ogee spillway is measured by
limnimeter and discharges are calculated by measuring volume changes depending
on time in measurement tank (Figure 3).
Figure 3.
a) Water surface profile b) Discharge measurement tank
A control valve was used for controlling discharge in the model. Experiments are
conducted for 16 different total head over the ogee spillway ranging from
H/Ho=0.28 to H/Ho=1.43. Heights are measured by using limnimetre from top of the
crest to water surfaces. Limnimetre is placed at the distance of 0.06 m back from the
ogee spillway in order to neglect approach velocity. To get more accurate results,

discharge-total head relation curve is obtained (Figure 4). The curve shows
increment in discharge is compatible with increase in total head.
Figure 4. Discharge-Total head relation curve
Physical model of the ogee spillway used in experiments is fabricated from stainless
steel. Design head of the ogee spillway chosen Ho=0.035 m. Ogee spillway model is
0.07 m high (crest height), 0.075 m wide same as with channel width and 0.085 m
long.
Results and Discussion

Discharge values and flow depths investigated by experimental study which is
conducted in laboratory were compared with analytical calculations. The main
objective of the comparison was to determine success of the results. Table-1 shows
the total head and discharges results obtained by analytical calculations depends on
equation 1 and equation 2 and physical model. Theoretical USBR values are
computed by using total head get from physical experiments. Also the design
parameters for ogee spillway are shown on the table. The design head (Ho) is set
0.036 m, then according to this value corresponding design discharge coefficient
(Co) and design discharge (Qo) is computed as 2.15 and 0.0011 m3/s relatively. The
graphs for the discharges are given in Figure 5.
Figure 5. Comparison of analytical and experimental results

Table 1. Results from analytical calculations and physical modeling

USBR (P=0,07 H0=0,036 C0=2,15) Physical
He(m) He / H0 C/C0 C Q (m3/s) Q (m3/s)
0.0100 0.28 0.87 1.87 1.40E-04 1.37E-04
0.0138 0.38 0.89 1.92 2.34E-04 2.30E-04
0.0160 0.44 0.91 1.95 2.96E-04 2.86E-04
0.0182 0.51 0.92 1.98 3.64E-04 3.71E-04
0.0195 0.54 0.93 1.99 4.07E-04 4.12E-04
0.0217 0.60 0.94 2.02 4.84E-04 4.98E-04
0.0223 0.62 0.94 2.02 5.06E-04 5.13E-04
0.0235 0.65 0.95 2.04 5.50E-04 5.71E-04
0.0248 0.69 0.95 2.05 6.01E-04 6.21E-04
0.0270 0.75 0.96 2.07 6.90E-04 7.14E-04
0.0288 0.80 0.97 2.09 7.66E-04 8.01E-04
0.0290 0.81 0.97 2.09 7.75E-04 8.16E-04
0.0325 0.90 0.99 2.12 9.32E-04 9.74E-04
0.0328 0.91 0.99 2.12 9.46E-04 1.01E-03
0.0358 0.99 1.00 2.15 1.09E-03 1.14E-03
0.0360 1.00 1.00 2.15 1.10E-03 1.17E-03
0.0360 1.00 1.00 2.15 1.10E-03 1.17E-03
0.0384 1.07 1.01 2.17 1.22E-03 1.32E-03
0.0395 1.10 1.01 2.18 1.28E-03 1.38E-03
0.0412 1.14 1.02 2.19 1.37E-03 1.48E-03
0.0425 1.18 1.02 2.20 1.44E-03 1.59E-03
0.0433 1.20 1.02 2.20 1.49E-03 1.65E-03
0.0445 1.24 1.03 2.21 1.56E-03 1.71E-03
0.0455 1.26 1.03 2.22 1.61E-03 1.79E-03
0.0457 1.27 1.03 2.22 1.63E-03 1.79E-03
0.0460 1.28 1.03 2.22 1.64E-03 1.82E-03
0.0475 1.32 1.04 2.23 1.73E-03 1.95E-03
0.0493 1.37 1.04 2.24 1.84E-03 2.09E-03
0.0512 1.42 1.05 2.25 1.96E-03 2.23E-03
0.0515 1.43 1.05 2.26 1.98E-03 2.25E-03
If we calculate the discharges according the suggested formula given in Eq. 4 new
discharges values is given in Table 2 and the graphs are given in Figure 6.
(4)

Figure 6. Comparison of analytical and experimental results
Table 2. Results got from new formula and physical modeling

USBR (P=0.07 H0=0.036 C0=2.15) Physical
He(m) He / H0 C/C0 C Q (m3/s) Q (m3/s)
0.0100 0.56 0.93 2.00 1.50E-04 1.37E-04
0.0138 0.77 0.97 2.08 2.53E-04 2.30E-04
0.0160 0.89 0.98 2.12 3.21E-04 2.86E-04
0.0182 1.01 1.00 2.15 3.96E-04 3.71E-04
0.0195 1.08 1.01 2.17 4.44E-04 4.12E-04
0.0217 1.21 1.02 2.20 5.28E-04 4.98E-04
0.0223 1.24 1.03 2.21 5.52E-04 5.13E-04
0.0235 1.31 1.04 2.23 6.02E-04 5.71E-04
0.0248 1.38 1.04 2.24 6.57E-04 6.21E-04
0.0270 1.50 1.06 2.27 7.56E-04 7.14E-04
0.0288 1.60 1.07 2.29 8.41E-04 8.01E-04
0.0290 1.61 1.07 2.30 8.50E-04 8.16E-04
0.0325 1.81 1.09 2.34 1.03E-03 9.74E-04
0.0328 1.82 1.09 2.34 1.04E-03 1.01E-03
0.0358 1.99 1.11 2.38 1.21E-03 1.14E-03
0.0360 2.00 1.11 2.39 1.22E-03 1.17E-03
0.0384 2.13 1.13 2.42 1.37E-03 1.32E-03
0.0395 2.19 1.14 2.44 1.44E-03 1.38E-03
0.0412 2.29 1.15 2.47 1.55E-03 1.48E-03
0.0425 2.36 1.16 2.49 1.64E-03 1.59E-03
0.0433 2.41 1.17 2.51 1.70E-03 1.65E-03
0.0445 2.47 1.18 2.53 1.78E-03 1.71E-03
0.0455 2.53 1.19 2.56 1.86E-03 1.79E-03
0.0457 2.54 1.19 2.56 1.88E-03 1.79E-03
0.0460 2.56 1.19 2.57 1.90E-03 1.82E-03
0.0475 2.64 1.21 2.60 2.02E-03 1.95E-03
0.0493 2.74 1.23 2.65 2.18E-03 2.09E-03
0.0512 2.84 1.26 2.70 2.35E-03 2.23E-03
0.0515 2.86 1.26 2.71 2.38E-03 2.25E-03

Conclusions
In this study an experimental setup was used to obtain discharge values and total
head over an ogee spillway. Total heads and corresponding discharge values were
measured for 16 different water lever before the ogee spillway. Discharges were also
calculated by formula depending on the discharge coefficient formula. And a new
discharge coefficient formula was suggested to calculate the discharges. It was seen
that the discharge values calculated by new coefficient formula were closer to the
experimental results than other formulas according to the both graphs. In case of
flood. More accurate discharge calculation can be get than the existing formula.
References
Bradley, JN 1952, United State Department of the Interior Bureau of Reclamation,
Discharge
Dargahi, B 2006, ‘Experimental Study and 3D Numerical Simulations for a Free-
Overflow Spillway’, Journal of Hydraulic Engineering, vol.132, no.9, pp.
899-907
Hu, H, Qian Z, Yang, W, Hou, D & Du L 2018, ‘Numerical Study of Characteristic
and Discharge Capacity of Pianı Key Weirs’, Flow Measurement and
Instrumentation, vol. 62, pp. 27-32
Maynor, ST, US Army Corps of Engineers, 1985, General Spillway Investigation.
USACE Final Report. Washington DC. 6-10
Muller, R, 1908, Development of Practical Type of Concrete Spillway Dam.
Engineering Rec, 58, 461
Savage, M & Johnson, MC, 2001, ‘Flow Over Ogee Spillway: Physical and
Numerical Model Case Study’, Journal of Hydraulic Engineering, vol.127,
no.8, pp.640-649
US Department of the Interior Bureau of Reclamation. 1987. Design of Small Dams.
USBR. Washington DC. 365-380

CONVERSION OF LIGNOCELLULOSIC AGRICULTURAL WASTES

INTO ADSORBENTS FOR PHARMACEUTICAL DRUGS
Anca Cruceanu1, Monica Alexandra Vaideanu1, Rodica Zavoianu1, Elena Bacalum2, Octavian
Dumitru Pavel1
1
University of Bucharest, Faculty of Chemistry, Department of Organic Chemistry,
Biochemistry and Catalysis, Regina Elisabeta Blv., Nº 4-12, S3, Bucharest, 030018, Romania
2
University of Bucharest, Faculty of Chemistry, Catalysis and Catalytic Processes Research
Centre, Regina Elisabeta Blv., Nº 4-12, S3, Bucharest, 030018, Romania
Abstract
Lignocellulosic agricultural wastes e.g. corn cobs, straws and corn stalks were
converted into carbonaceous adsorbents using a sequence of thermal and chemical
activation processes. The derived solids obtained after each type of activation were
characterized by determination of fix carbon content, iodine number, Boehm titration
and DRIFT spectrometry. The results obtained at the adsorption tests were well
correlated to those of the characterization, showing that the most promising adsorbents
for amoxicillin removal were those submitted to a thermal treatment followed by a
chemical alkaline activation, followed by washing and a secondary thermal treatment.
The most promising bio-based adsorbent was the one derived from corn stalks (90.6%
adsorption efficiency).
Keywords: activated carbon, adsorption, antibiotic, carbonization, lignocellulosic

agricultural wastes
Introduction
Antibiotics, the most important part of pharmaceuticals drugs, are produced in large
quantities and used all over the world for both human and animals infections treatment
caused by Gram‐positive or Gram‐negative bacteria. The intensive use of antibiotics
may produce acute and chronic toxicity as well as multi-resistant bacteria not only in the
treated patient's organism but also in the environment due to the fact that significant
quantities of the antibiotics ingested by humans and animals are often excreted in the
active form, as unmodified parent compound. For example, it has been reported that
over 80% of oral administration of amoxicillin in humans is excreted through urine after
2 h of consumption. (Chaba & Nomngongo 2019). For this reason, we chose
amoxicillin, as a model pharmaceutical drug for our study since it is a common
antibiotic often used and it is not removed by wastewater and sewage treatment plants.
(Balarak et al. 2017)
Thus, different methods have been applied in order to solve effectively the antibiotic
pollution. Among all the treatment methods, the adsorption process is highly beneficial
due to the advantage of not being toxic or having the ability to degrade contaminants.
Liquid – solid adsorption of organic pollutants from wastewaters is a relatively
inexpensive and very efficient process, simple to design and operate. The efficiency of
adsorption processes is highly affected by the type of adsorbent, the adsorbate
properties, and the compositions of the waste stream. (Ahmed et al. 2015; Limousy et
al. 2016; Tseng et al. 2005) Generally, for many pollutants, the most commonly used
adsorbent is the activated carbon that can be produced from different carbonaceous
materials, such as lignocellulosic agricultural wastes. The use of these unnecessary and
inexpensive materials makes it possible to obtain activated carbon-like solids with new
physicochemical properties, large specific surface area, high volume of pores and to
convert them to valuable products.
This research is focused on the obtaining of some activated carbons from common
agricultural wastes: i.e. corncobs, corn stalks, wheat straws and the physicochemical
characterization of the prepared solids. Different preparation parameters, particularly
activation procedures, were examined in order to evaluate the influence of the activation
conditions on the textural and acid–base properties of the final products. Finally, the
surface properties of the solids were correlated to their performances in amoxicillin
removal from aqueous solutions.

Activated carbon preparation
The starting materials: corncobs (CB), corn stalks (TB) and wheat straws (PB) were
chopped, handpicked, washed with distilled water, in order to remove dust and color,
dried at 1100C, for 72 h, ground with a ball mill and sieved to a uniform size in the
range of 1–1.5 mm. Next, raw solids were subjected to carbonization for 20 min (CC20,
TC20, PC20) and 40 min (CC40, TC40, PC40) under a stream of methane at 6500C.
CC40, TC40, PC40 were chemically activated by treatment with KOH aqueous solution
(at 5/1 weight ratio between the KOH solution (2M) and the solid) under magnetic
stirring. After 2h, the activated solids were separated by centrifugation and dried at 90oC
for 72 h yielding CC40A, TC40A and PC40A samples. The pH of these solids was
approximately 12 upH. Therefore, in the next step, the activated solids were washed
with distilled water until the washing water became colorless, its pH reached 8 upH and
its conductivity was lower than 50 S/cm. The washed solids were further dried
overnight at 90oC yielding the solids denoted CC40AS, TC40AS, and PC40AS. Then,
the AS suffixed solids were subjected to a new carbonization step for 20 min
(CC40ASC, TC40ASC, PC40ASC) under a stream of methane at 6500C.
Activated carbon characterization
Fixed carbon content determination
The fixed carbon content can be calculated based on the results obtained using the
standard method for coals technical analysis which consists in the determination of coal
moisture content (U%), ash content (A%), coke (Cx %) and volatile matter content
(VM%). The fixed carbon content (FC) is given by the equation (1): FC %= Cx % - A
%The surface areas and porosities of the solids were estimated based on the iodine
number which is defined as the milligrams of iodine adsorbed by one gram of material
and is a widely used parameter for activated carbon testing (Mianowski et al. 2007). For
this determination, the solid samples (0.045 g) were placed in Erlenmeyer flasks
containing 25 mL of I2 aqueous solution (0.01 N) and were agitated for 24h (150 rpm,
room temperature). The solutions were filtered through a 0.45-μm membrane filter, and
the excess of iodine was titrated with Na2S2O3 (0.01 N).
The amounts and the distributions of the oxygenated surface groups were determined by
Boehm titration. To this aim 0.045 g of solid sample were placed in Erlenmeyer flasks
containing 25 mL of 0.01 N of HCl, NaOH, NaHCO3, and Na2CO3, respectively. Then,
the mixtures were agitated for 24h (150 rpm, room temperature). The solutions were
filtered through a 0.45 μm membrane filter, and the excess (base or acid) was titrated
with 0.01 N HCl or 0.01N NaOH, respectively. The amount of acidic groups on the
solids was calculated under the assumption that NaOH neutralizes carboxylic, lactones,
and phenol groups; Na2CO3 neutralizes carboxylic and lactones; NaHCO3 neutralizes
only carboxylic group. The number of surface base sites was calculated from the
amount of HCl that reacted with the carbon.
All solids have been characterized by FTIR spectroscopy to identify the superficial
functional groups. All the spectra were recorded on a JASCO 4700 FT-IR with DRIFTS
accessory. For each spectrum 100 scans were performed at a resolution of 4 cm-1 on the
4000-400 cm-1 domain. Each sample was mixed with KBr in a ratio of 10/90 w/w.
Adsorption tests
Adsorption experiments were performed by the batch method, contacting a known
dosage of adsorbent (0.25-0.75g/L) with 9 mL solution of known amoxicillin
concentration (100mg/L) under gentle stirring (150-300rpm), at different temperatures
(25-400C) and 2 pH values (5 and 8.5 upH) until the equilibrium was reached (30-
480min). At the end of each experiment, the solid was filtered off and the amount of
unadsorbed amoxicillin was dosed by UV–visible spectrophotometry.

The results obtained after the characterization of the biomass derived-solids by coal
technical analysis are displayed in Tables 1a,b. The aim of this analysis is to determine
the fixed carbon content (FC), using eq. (1).
Table 1a. Characterization of raw and thermally activated solids

Solids Cx % U% VM % A% FC % IN (mg I2/g)
PB 37.3 5.6 57.0 0.8 33.1 235
TB 28.1 5.8 66.2 4.3 27.3 255
CB 17.5 6.2 76.3 0.7 16.8 275
PC20 65.5 6.3 28.2 4.3 56.2 470
TC20 57.3 5.6 37.1 12.4 52.9 360
CC20 68.2 4.9 26.9 2.6 65.6 390
PC40 76.8 6.2 16.9 1.4 75.4 600
TC40 67.7 5.9 26.4 2.5 65.2 620
CC40 52.0 5.4 42.6 2.3 50 460
Table 1b. Characterization of chemically and thermally activated solids

Solids Cx % U% VM % A% FC % IN (mg I2/g)
PC40A 77.1 6.7 16.2 48.9 28.2 200
TC40A 64.6 6.2 29.3 46.0 18.5 210
CC40A 77.6 5.5 16.9 46.7 30.4 180
PC40AS 76.2 6.6 17.2 1.2 75 740
TC40AS 60.0 7.1 32.9 9.5 50.5 875
CC40AS 56.0 7.6 36.4 10.4 45.6 410
The obtained results indicate that the thermal activation process leads to an increase of
the fixed carbon content compared to the corresponding raw materials. The increase of
the thermal treatment duration leads to an enhanced fixed carbon content only for the
straws- and corn stalks-derived solids (e.g. PC40, TC40), whereas in the case of
corncob-derived ones (CC40) a decrease of the fixed carbon content is noticed
compared to CC20. For all biomass-derived solids the chemical activation leads to an
important decrease of FC content, which is more significant for PC40A and TC40A

samples. After the removal of the KOH excess by washing, the values of FC for
PC40AS, TC40AS, CC40AS) are almost restored to those obtained for the thermally
activated samples (PC40, TC40, CC40). The FC content decreases in the order PC40 >
TC40 > CC40 and the same variation trend is noticed after chemical activation followed
by washing: PC40AS > TC40AS > CC40AS.
The iodine numbers (IN) for the biomass-derived adsorbents compared to the starting
raw materials are also displayed in Table 1a, 1b. The results indicate that the thermal
treatment (samples suffixed C20, C40) leads to the increase of IN compared to the raw
materials. Moreover, the increase of the duration of the thermal activation from 20 to 40
minutes leads to a significant modification of IN for the straw- and corn stalks-derived
solids whereas a modest increase is noticed for corncobs-derived materials. For the
straw- and corn stalks-derived solids the chemical activation followed by washing leads
to an increase by ca. 15% of the IN compared to the thermally activated samples. These
increases of the IN are related to a specific surface area that is large enough and an
adequate porosity to ensure an efficient adsorption.
The results obtained following the determination of surface acid sites concentration are
presented in Table 2. The obtained results indicate that the thermal activation leads to
the decrease of the concentration of carboxyl groups compared to the raw materials and
moreover the extension of the duration of the carbonization process determines the
decrease of the total concentration of acid sites. Meanwhile, the application of the
chemical activation after the thermal treatment followed by the washing of the obtained
solids leads to an increase of the total concentration of acid sites.
Table 2. Concentration of surface acid sites of the investigated solids

Acid sites Acid sites Acid sites Total Types of acid sites
(mequiv. (mequiv. (mequiv. acid (mequiv./g)
Samples NaHCO3/g) Na2CO3/g) NaOH/g) sites
C* C*+L# C*+F&+L# F& C* L#
PB 2.0 3.5 5.2 5.2 1.7 2.0 1.5
PC20 2.5 4.4 6.8 6.8 2.4 2.5 1.9
PC40 0.6 1.3 4.7 4.7 3.3 0.6 0.7
PC40AS 0.8 2.2 4.8 4.8 2.6 0.8 1.4
TB 1.3 2.3 4.6 4.6 2.3 1.3 1.0
TC20 1.6 3.3 5.9 5.9 2.6 1.6 1.7
TC40 1.2 1.3 4.5 4.5 3.2 1.2 0.2
TC40AS 0.8 2.2 5.1 5.1 2.9 0.8 1.4
CB 2.7 3.2 3.9 3.9 0.7 2.7 0.5
CC20 3.0 3.7 4.7 4.7 1.0 3.0 0.7
CC40 0.1 1.1 4.2 4.2 3.1 0.1 1.0
CC40AS 0.3 1.1 4.8 4.8 3.7 0.3 0.8
*C=carboxylic; #L=lactonic; &F-phenol
The concentration of surface base sites

The results obtained at the determination of the surface base sites are displayed in figure
1.

3.20
3.04 2.95
3 2.77 2.74
mequiv/g solid 2.57
2 1.8 1.77
1.56
1.32
1.3 1.31
CC40ASC
0.85
TC40ASC
1
PC40ASC
TC40AS
CC40AS
0.63 PC40AS
0.4
PC40
TC40
CC40
PC20
TC20
CC20
CB
PB
0 TB
Adsorbents
Figure 1. Concentration of surface base sites on the investigated solids
The obtained results showed that the thermal treatment leads to an increase of the base
sites concentration compared to the raw materials. However, the extension of the
thermal activation duration does not bring significant changes. Meanwhile, the chemical
activation followed by washing leads to almost a double fold concentration of surface
base sites. The amount of base sites in AS-suffixed samples varies in the following
order: PC40AS > TC40AS > CC40AS
DRIFT spectra of all investigated samples are displayed in Figure 2.
a. - corncobs b. - wheat straws c.- corn stalks

Figure 2. DRIFT spectra of the investigated solids
All the spectra of the raw materials have a broad band in the region attributed to O-H
stretching at 3415 cm-1 (CB), 3307 cm-1 (TB) and 3279 cm-1 (PB). The intensity of this
band decreases in the order TB>PB>CB, suggesting that CB have the lower amount of
hydroxyl groups. This band is accompanied by a shoulder at ca. 2900cm-1 (C-H stretch)
and its intensity variation follows the same trend. The intensity of these bands decreases
sharply after carbonization, increases significantly after the alkali treatment (A suffixed
samples), and decreases again after the washing of the solids (AS suffixed samples) and
the second carbonization process (ASC suffixed samples). However, for all the washed

solids (AS suffixed samples), the occurrence of a new band at ca. 3500-3600 cm-1
ascribed to OH free groups was noticed and its intensity was similar irrespective to the
raw material. PB and TB spectra show also a band around 2152cm-1 ( C=C) which is not
noticed in any other spectra. Two bands corresponding to the stretching of aliphatic and
aromatic –C=O bonds, characteristic to lignin compounds, are noticed in all spectra in
the region 1730-1670 cm-1. (Isahak et al. 2013)
For CB and TB samples their intensity is similar, while for PB the band at 1730 cm-1 is
more intense suggesting the prevalence of aliphatic carbonyl compounds. After the
thermal treatment the band around 1670 cm-1 increases its intensity revealing an
enhancement of the aromatic character. (Wang et al. 2018) All spectra show also a
band at 1600-1590cm-1 related to the stretching vibrations of conjugated C=C bond.
This band has the highest intensity in the spectra of the carbonized samples (CC20,
CC40, TC20, TC40) and the second intensity in the spectra of PC20, PC40, revealing a
lower aromaticity of the PB-derived adsorbents. The duration of the carbonization
process has not an important effect for TB and PB (the spectra of the pairs TC20-TC40,
and PC20-PC40 are almost identical), whereas in the case of CB a longer duration leads
to a significant alteration of the structure (the bands of the spectrum in the mid infrared
region overlap).
For all raw materials, the alkaline activation has a similar effect. All the spectra of the
samples activated with potassium hydroxide CC40A, PC40A, TC40A show as most
intense bands the doublet characteristic for carbonate vibrations in the region 1440-1380
cm-1, most probably due to the carbonation of KOH solution utilized in the treatment.
The highest intensity of these bands is mostly due to the fact that they overlap the bands
characteristic to CH3 and CH2 vibrations which appear in the same region. After the
washing treatment, the intensity of these bands decreases significantly, indicating the
removal of the potassium carbonate. In the spectra of CC40AS, PC40AS and TC40AS a
band corresponding to as C-O-C in esters is noticed in the region 1270-1260 cm-1. The
band at ca 1038 cm-1 corresponding to the stretching vibration of C-O bonds in
secondary cyclic alcohols appears in the spectra of all raw materials (CB, PB, TB), but
its intensity diminishes significantly along with the successive thermal and chemical
treatments. For CB and PB this band is more intense than for TB, suggesting an
enhanced concentration of cellulose in these raw materials. In all spectra, a series of
bands of low intensity corresponding to out-of-plane deformation of C=C bond are also
noticed in the region 809-897 cm-1.
In the spectra of all ASC suffixed samples, the most intense band is the one centered at
ca. 1400 cm-1 (C-H in –CH2 groups), while the second most intense band appears in the
region 1700-1650 cm-1 characteristic for aromatic carbonyl compounds. The absence of
the band characteristic to cyclic alcohols suggests that the secondary carbonization
treatment enhances even more the aromatic character of the derived adsorbent.
Adsorption tests
The results of the adsorption tests presented in Table 3 reveal that under similar
operating conditions corn stalks-derived materials show better adsorption capacity than
straws- or corncob-derived materials, irrespective to the activation procedure applied.
The lowest adsorption capacity is recorded for the chemically activated samples
(CC40A, PC40A and TC40A), which have the lowest FC content, small specific
surface area as indicated by IN (see Table1b) and enhanced basicity (12 upH).

Table 3. Results of the adsorption tests (duration 4 h, adsorbent dosage of 0.25 g/L, 200
rot/min, initial concentration of amoxicillin 100 mg/L).
Sample Adsorption Sample Adsorption Sample Adsorption
(%) (%) (%)
T 25oC 40oC T 25oC 40oC T 25oC 40oC
CB 5.0 3.2 PB 5.2 3.5 TB 7.0 4.2
CC20 7.1 5.4 PC20 10.4 6.5 TC20 9.9 6.1
CC40 35.2 20.1 PC40 31.5 16.3 TC40 41.7 25.3
CC40A 4.2 2.2 PC40A 5.0 2.8 TC40A 7.1 4.5
CC40AS 56.3 44.5 PC40AS 62.5 50.4 TC40AS 71.6 62.3
CC40ASC 64.5 52.3 PC40ASC 72.5 64.5 TC40ASC 80.6 68.5
The highest adsorption capacity was exhibited by corn stalks-derived materials

(TC40ASC) which had larger IN than the corresponding samples obtained from straws
(PC40ASC). For all materials the adsorption of amoxicillin decreased as the
temperature increased from 25oC to 40oC, indicating the exothermic nature of the
process.
The influence of the adsorbent concentration and stirring on the adsorption capacity was
investigated for the sample TC40ASC and the results are displayed in Table 4.
Table 4. Influence of adsorbent dosage, duration of the adsorption process and stirring
for TC40ASC sample (initial concentration of amoxicillin 100 mg/L)
Time (h) Adsorbent dosage (g/L) Stirring (rpm) Adsorption efficiency (%)
1 0.25 200 40.2
2 0.25 200 60.5
4 0.25 200 80.6
4 0.25 300 72.5
4 0.5 200 90.6
4 0.5 300 83.5
4 0.75 200 75.2
6 0.5 200 93
8 0.5 200 95
From these results it may be seen that the highest adsorption rate is recorded in the first
two hours of the process when the adsorption efficiency reaches 60.5%, whereas in the
next two hours the increase is only 20%. The increase of the adsorbent dosage from
0.25 g/L to 0.5 g/L leads to an increase of the adsorption efficiency with 10%. However,
a further increase of the amount of adsorbent to 0.75 g/L decreases the adsorption
efficiency from 90.6% to 75.2% probably due to the agglomeration of the solid particles
which hinders the access to the adsorption sites. The extension of the duration of the
adsorption process to 6 or 8 hours brings long an increase of only 3-5% of the
adsorption efficiency. The increase of the agitation from 200 rpm to 300 rpm has also a
negative effect on the adsorption efficiency since it limits the contact time between the
amoxicillin and the active sites for adsorption.

Conclusions
Common vegetal wastes such as corn stalks, corncob and straws, were successfully
converted into adsorbents following a sequence of thermal and chemical activation
procedures. The most active adsorbent for amoxicillin was the one derived from corn
stalks (TC40ASC) which allowed reaching an adsorption efficiency of 90.6% after 4
hours with an adsorbent dosage of 0.5 g/L. The variation of the adsorption efficiencies
of the bio-based adsorbents under similar adsorption conditions could be well correlated
to their physical-chemical properties (fixed carbon content, iodine number, aromatic
character).
Acknowledgements
This work was supported by the Executive Agency for Higher Education, Research, Development
and Innovation (UEFISCDI): PN-III-P1-1.2-PCCDI-2017-0387.
References
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Energy Reviews, vol. 90, pp. 223–247.

ENERGY-SAVING INTEGRATED FERRITISATION TREATMENT OF

NICKEL-CONTAINING WASTEWATER
Gennady M. Kochetov, D.M. Samchenko, B. M. Yemchura
National University of Construction and Architecture, Povitroflotsky Pr. 31, 03680, Kyiv,
gkochetov@gmail.com, Ukraine
Abstract
Modern requirements to electroplating waste treatment necessitate development of
technologies that would allow on-site recycle and reuse of both treated water and
residuals of water processing. The most prospective option for introduction of
recourse-saving wastewater purification is associated with application the method of
ferritisation. In this connection, the paper presents an advanced ferritisation process
for reduction of initial concentrations of heavy metals (HM) in exhausted nickel
electroplating electrolytes from 100 mg/L to 0.3 mg/L. Effects of main technological
parameters of such wastewater treatment at thermal and electromagnetic pulse
methods of activation of the ferritisation process were determined experimentally.
Kinetics of removal of nickel and iron ions from aqueous solutions was investigated.
Phase compositions and properties of sediments from wastewater treated were
studied. The sediments are predominantly characterised by crystalline
nanostructures, ferromagnetic properties and chemical stability, supporting
opportunities for their environmentally sound utilisation. Proposed comprehensive
process for treatment of liquid industrial waste flows would prevent contamination
by toxic effluents; ensure rational use of water, raw materials and energy inputs.
Keywords: ferritisation, nickel, sediment, utilisation, wastewater treatment
Introduction
Toxic wastewater flows from electroplating plants pose particular hazards to human
health. Release of these wastewater flows into the environment also results in losses
of a valuable metal. Therefore, a comprehensive treatment of electroplating
wastewater flows with closed systems of resource circulation directly on-site is
relevant solution (Trokhymenko & Gomelya 2017).
Analysis of existing methods of electroplating wastewater treatment shows that, the
reagent-based method still remains the most commonly used. This method involves
precipitation of HM ions by alkaline reagent and is characterized by low degree of
HM removal and formation chemically unstable bulky sediments.
The method of ferritisation is a rather prospective one for treatment of wastewater of
electroplating plants (Pritosiwi 2012). The method allows to obtain almost insoluble
compounds of iron and other HM by treatment of their ions with an alkaline reagent
and air oxygen and provides a high degree of removal of HM ions from wastewater.
In recent years, numerous studies have been conducted on wastewater treatment by
ferritization (Chaiyaraksa & Klaikeow 2006; Pritosiwi 2012). The authors (Morgan
et al. 2001; Petrick et al. 2008) demonstrated incorporation of HM ions into ferrite
structure. In papers (Kochetov et al. 2010; Heuss-Aßbichler et al. 2016) the
ferritisation process was used for treatment of rinsing and concentrated copper-
containing water, respectively.
These studies found that main factors affecting the process of wastewater treatment
include pH, temperature (T) and duration (t) of the treatment process, initial
concentrations of HM (СΣ), and ratios (Z) of their concentrations. However, the
traditional thermal activation method of ferritisation wastewater treatment is rather
energy intensive, as it is carried out at temperatures above 60 °C. As an alternative
to the thermal activation electromagnetic pulse discharges, can be applied
(Yadollahpour et al. 2014). Therefore, in contemporary conditions, further
improvement of the ferritisation method with minimisation of energy and reagents
consumption is fairly relevant. Accounting the above, this study is dedicated to
experimental research on influence of technological parameters and ways of
activation for ferritisation process on quality of integrated treatment of exhausted
nickel electrolytes.

Two laboratory installations were developed. The first one was used to study the
ferritisation process at temperatures of 20 - 70ºС (Kochetov et al. 2014). Another
installation was equipped with electronic block-unit for electromagnetic pulse
activation of the process. Its mode characteristics: the electromagnetic signal
included packs of pulses (16 pulses in a pack); pack spacing - 1300 ms; intervals
between pulses - 20 ms; a pulse duration - 35 ms.
In laboratory experiments we used exhausted technological electrolyte of nickel
electroplating units of one industrial plant of Kyiv. In the exhausted electrolyte,
concentrations of heavy metal ions reached: Ni2+ = 67.9 g/dm3 and Fe2+ = 0.12
g/dm3, respectively. For the ferritisation process, solutions of iron (II) sulphate and
25% solution of sodium hydroxide were added to reach the required pH value.
Technological parameters in the experiments varied within the following limits:
CΣ = 11.7 ÷ 30.41 g/dm3; Z = 2 ÷ 6; pH values = 8.5 ÷ 10.5; t = 5 ÷ 15 min.
Concentrations of heavy metal ions were determined by voltamperometry analyser
AVA-3. Structural analysis of sediments was performed by X-ray diffractometer
PHILIPS x'pert. Мicrostructure of precipitates were studied by scanning electron
microscope-analyzer РЕММА-101А. Magnetic measurements were carried out
using Petersen Instruments.

Wastewater treatment
Experimental research results for determination of influence of main technological
parameters of the ferritisation process: pH, СΣ, Z and t on efficiency of treatment
exhausted nickel electrolytes for different methods of activation of the process are
shown in Figure 1.

а b
c d
Figure 1. Dependence of residual concentrations of nickel ions Cres in the course of
treatment of exhausted electrolyte solutions from concentration of the solution С Σ
(а), the ratio of concentrations of HM ions Z (b), pH (c) and duration of the process
τ (d); 1 - the process of ferritisation at 20 ° С; 2 - thermal activation of the process; 3
- electromagnetic pulse activation of the process at 20 ºС.
Figure 1a indicates that at higher total contents of heavy metal ions in the initial
reaction mixture, residual concentrations of nickel ions after the ferritisation
increased, regardless of methods of activation of the process. Analysis of
experimental research shows that the best result was obtained within the limits of
Fe2+/ Ni2+ratios from 3/1 to 4/1 (Figure 1b).
Results of study of pH effects show that residual concentrations of nickel ions
decrease with increasing pH (Figure 1c). Probably, this is due to the fact that at
higher pH values, the predominant role in the process of nickel removal does not
belong to sorbtion of Ni2+ ions, but to crystallization of insoluble nickel compounds
on surface of ferromagnetic particles. In this case, structures and sizes of these
particles have major impact on efficiency of wastewater treatment (Gawande et al.
2013).
As can be seen from graphic kinetics dependence for removal of nickel ions at
Figure 1d, residual concentrations of metal ions in the solution decrease with the
increase of duration of the ferritisation process from 5 to 15 min for both modes of
activation. In a longer process residual concentrations of HM remain unchanged,
due to the final formation of stable solid-phase products within initial 15 min.
As can be seen from the data obtained, for all studied values of technological
parameters, residual concentrations of nickel ions in the treated solution were in the
range from 0.3 mg/dm3 to 1.2 mg/dm3. Residual concentrations of iron ions in
purified water were also investigated. Analysis indicates that in all ranges of the
technological parameters studied and at different methods of activation of the
process, concentrations of this metal were in the range from 0.1 to 0.35 mg/dm3.
This corresponds to high degree of removal for nickel and iron ions – 99.99%.
Besides that, results of experiments indicate that the electromagnetic pulse method
of activation is highly efficient, and - with its clear advantages over the thermal one
does not worsen the degree of removal of HM ions.
In order to estimate kinetic regularities of removal of nickel ions and metals from
solutions (Figure 1d), we proposed mathematical models for different methods of
the process activation. Types of regression equations that most adequately describe
these dependencies have the following forms (Rossiter 2005):
- for nickel
(1)
- for iron
(2)
here ∆Сres. – residual concentration of heavy metals ions, mg/dm3; a, b – model
factors; t – duration of the ferritisation process, min.
After linearizing transformations of functions 1 and 2 by the method of least
squares, the factors of models were calculated. The detailed algorithm for solving
the equations which is presented in (Kochetov et al. 2016). Calculated values of
residual concentrations are well consistent with the experimental data; proposed
models are considered adequate with 95% probability.
Study of sediments properties

In the process of ferritisation, with different methods of its activation, a black
dispersion suspension is formed in the solution, that subsequently crystallises with
formation of dense ferrite structures in particular. The samples were studied by X-
ray diffraction and magnetic measurements. Those researches verified that content
of the ferrite phase reaches 89 % and the crystals of obtained sediments are in the
nanoscale range. In the case of both thermal and electromagnetic pulse activation, a
phase of nickel ferrite NiFe2O4 was clearly identified with the structure of the
inverse spinel and a lattice parameter a = 8.34 Å, as well as peaks attributed to
Fe3O4, γ-Fe2O3, γ-FeO(OH), NiOOH, NiO.
The data we obtained explain why the best results of ferritisation treatment of are
achieved at ratios of Fe2+/ Ni2+ in the range of 3/1 ÷ 4/1. In our opinion, this is due
to the fact that at other ratios, in addition to the formation of the ferrite phase,
intermediate solid-phase reactions might take place in the solution. As a result, the
phases formed are of limited stability in alkaline media and residual concentrations
of nickel ions are increased.
Electron microscopy results (Figure 2) confirm formation of sediments with disperse

structures. In comparison to traditional ferritisation at 20°С, in the case of the
electromagnetic pulse activation, the precipitate has a high degree of crystallinity
with the spinel matrix structure.

а b
Fig. 2. Microphotography of samples of sediments after ferritisation wastewater
treatment: a - at T = 20 ºС; b - with application of electromagnetic pulse activation.
Structural analysis results were confirmed by experimental data on specific volumes,

magnetic susceptibility of ferritic sediments and also HM leaching from sediments
(Kochetov et al. 2016).
Our leaching experiments are shown that obtained compounds are chemically and
thermodynamically stable. The amount of leachable HM from ferritisation
sediments at pH from 5.5 to 8.5 is extremely low. They are characterized by a high
degree of HM immobilization in sediments (up to 99.95 %). This means a
substantially enhancement of environmental safety of the precipitated products.
Depending on amounts and quality of the product the most appropriate utilization
option can be selected: production of ferromagnetic sorbents; introduction of
sediments into special purpose construction materials.
Energy efficiency of the developed processes

Energy intensity of the treatment process with different activation methods of
ferritisation was also evaluated. The provided data suggest that the electromagnetic
pulse mode of activation of the ferritisation process allows to reduce electric power
consumption in 10 to 15 times in comparison with thermal activation.
Conclusions
Therefore, results of analysis of modern technologies for treatment of concentrated
wastewater flows, as well as our research studies, clearly indicate prospects of
application of the ferritisation method, due to its technical, economic and
environmental advantages. Our research results have demonstrated efficiency of
application of electromagnetic pulse discharges to activate the ferritisation process
with a range of generating frequencies up to 0.9 kHz, and pulse duration of 35 ms.
Influence of the main technological parameters on quality of the wastewater with
application of different activation for the ferritisation process has been
experimentally studied. It was found that this activation allowing to make the
technology cheaper and attractive for investments. The most efficient results at initial
HM concentrations of 20 – 25 g/dm3; pH of the reaction mixture of 9.5, and duration
of the process of 15 minutes. In this case, the experimental results indicate a high
degree of wastewater treatment with removal of heavy metal ions (99.99%) that allows
to use effluents in recycled water supply systems.
Kinetic regularities of nickel and iron ions from aqueous solutions by the
ferritisation method were determined, and mathematical dependencies of HM
removal were proposed.

Sediments obtained with high-temperature and electromagnetic pulse activation of

the ferritisation process have high chemical stability and ferromagnetic properties,
allowing to identify environmentally sound options for their utilisation.
Acknowledgements
The authors acknowledge financial support for this research provided by the Ministry of
Education and Science of Ukraine under the project 5 DB-2018 and the Science and Technology
Center in Ukraine under the project # 6363.
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system’, Russ J Appl Chem, vol.87, no.8, pp.1054 – 1059.
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‘Recovery of copper as zero-valent phase and or copper oxide nanoparticles
from wastewater by ferritization’, Journal of Environmental Management,
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containing wastewater’, Civil and Environmental Engineering, vol.1, no.4,
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pp.52–60.
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no.5, pp.3711 – 3719.

EVALUATION OF ACTIVE SLUDGE AND AQUATIC FERNS USAGE FOR

REMOVAL OF ZINC IN A BIOLOGICAL WASTEWATER TREATMENT
SYSTEM
Amir Hajiali, Lacramioara Diana Robescu
University of POLITEHNICA of Bucharest, Department of Hydraulics, Hydraulic Machinery

and Environmental Engineering, Bucharest, a.hajiali.env@gmail.com, diana.robescu@upb.ro,
Romania
Abstract
In this research capability of biological treatment method via active sludge and
aquatic fern evaluated in different operating conditions and they were optimized in
order to remove Zn (II). A simple reactor performance for treatment of model and
real wastewater on laboratory and semi-industrial scale was investigated. This
refining process proceeded with special attention to the effect of solution pH-value,
pollutant concentration, absorbent concentration and reaction time. The batch semi-
industrial scale reactor represented over 90 % removal efficiency under pH-value of
6 and 5-5.5 for aquatic ferns and active sludge, respectively. Effective reaction times
represented various durations for aquatic ferns and active sludge with respect of 120
minutes and 90 minutes. The two biological masses had the best performances with
6 g/l for aquatic ferns and 5 g/l for active sludge. In the presence of 5 ppm of Zn (II)
as the objective heavy metal, both absorbents had over 93.2 % removal efficiencies.
While obviously laboratory-scale attempts introduced higher acceptable reduction
efficiencies via this economic applicable treatment method. Additionally, economic
considerations clarified feasibility of this recommended simple method.
Keywords: active sludge, aquatic ferns, wastewater treatment, zinc
Introduction
Increasing worldwide population and variety of industrial means as well as
decreasing natural resources of water and soil and climate change problems have
risen international concerns. Unfortunately, industrial growth has a deep adverse
effect on environmental conditions while it improves human welfare. Different
categories of industries discharge various contaminants which are recalcitrant and
non-biodegradable in most cases such as phenols, aromatics, dyes, nitrates and etc.
These pollutants can change environmental characteristics of natural resources that
fresh up applications of modern environmentally friendly approaches for treatment
strategies (Amir 2017, Amir & Gevorg 2014).
There are fateful criteria namely health, hygiene, economy and food safety which
are affected wildly by lack of water resources. Besides reuse of polluted waters after
treatment methods face difficulties while they are contaminated with recalcitrant
heavy metals and their derivatives in various chemical and industrial processes
which cannot be removed effectively (Helmseresht & Delpisheh 1997, Allah-Qoli
2007). Heavy metals have been identified as the most poisonous compounds (Allah-
Qoli 2007) with different categories of Al, Zn, Co, Cu, Pb, Mn, Ni, Ti, Sn, Fe and
etc. while they have represented deep poisoning characteristics in high dose values
in human food chain (Karamad 2010, Erfani-Manesh & Afuni 2006). Also surface
and underground water resources can be in danger easily by heavy metals
compounds (Allah-Qoli 2007). In the case of treatment of heavy metals from
wastewater, different refining methods introduced like chemical sedimentations,
reverse osmosis, ion exchange, solvent extraction and etc. These foregoing methods
could lead to some undesirable results similarly to great initial investment, special
operating conditions, expensive initial apparatus and specially production of
hazardous chemical sludge in some cases. Biological absorbents can overcome most
of these unfavourable outputs while represent great performance capabilities. The
importance of these methods was recommended wildly because of high efficiency
and low volume of biological and chemical sludge, revival of biological mass and
recovery of heavy metals (Fouladi-Fard et al 2004). Although their removal
efficiency is definitely affected by reactor structure, wastewater properties and type
of absorbent. It should be mentioned that acceptable quality levels of water in any
industry refer to the one that has the lower treatment costs with respect of remedy
costs because of its impurity effects (Mansour-Panah & Kakanezhadie-Kherad
2015).
On the other hand, lack of adequate research studies is sense wildly and still needed
for more clarifications in this field of research especially in semi-industrial scale
(Marchioretto 2003). This article expounded real operational characteristics of
aquatic fern and active sludge for treatment. Aquatic fern grows naturally in lagoons
as an aggressive spice with suitable capability of refining properties in its living and
non-living states.

As it was mentioned followings are the two categories of attempts; laboratory and
industrial experiments for model and real effluents.
Laboratory scale: Applying a jar testing apparatus was the first attempt in
laboratory scale and optimization of four different factors by a routine procedure
was the further goal. So industrial attempts built on the optimizing of
aforementioned parameters. There are pH-value, reaction time, and absorbent and
pollutant concentration that had to be evaluated and optimized. All experiments
arranged based on Table 1 for optimization and data provided for industrial part. All
experiments carried out in 13 cylindrical vessels of 1000 ml by volume and fed with
absorbent, a contaminant (Zn (II)) and wastewater. Both ferns and active sludge had
prepared before experiments carried out. In the case of ferns, fresh ferns were
collected from lagoons then they were dried and grinded for 2mm by diameter
particles. Thereafter it had to be washed and refluxed by sulphuric acid 0.2 normal
and then by NaOH 0.1 normal. By drying ferns under 60 ˚C, specific weight of
absorbent achieved. It is necessary to mention that optimization carried out step by
step as shown in Table 1. Each parameter optimized and set for further factors’
optimization. Further more active sludge was supplied in the required content. It was
dried and grinded as well as the ferns. However, in the case of treatment of real
effluent the ferns and active sludge charged 6 g/l and 5 g/l, respectively. This sample
contained 1.5 mg/l contaminant with initial pH-value of 6.8. It was agitated for 120
minute and 90 minute, respectively in the case of the fern and active sludge. All
collected samples analysed via spectrophotometer apparatus.

Table 1. Parameters operational levels in laboratory scale

Factors Understudying ranges Optimum value
Ferns
pH 2-8 3.5
Time(min) 30-240 120
Absorbent concentration (g/l) 2-7 6
Pollutant concentration (ppm) 50-230 200
Active sludge
pH 2-8 3.5
Time(min) 30-240 90
Absorbent concentration (g/l) 2-7 5
Pollutant concentration (ppm) 50-230 200
Semi-industrial scale: In these experiments all models and real effluents agitated via
30, 50, 100 and 150 rpm by the pilot system which was designed. For the model,
wastewater pH-value and pollutant concentration arranged on 5 and 2 ppm,
respectively for the two absorbents. But the ferns fed 500 grams and agitated 120
minutes versus active sludge charging of 600 grams with reaction time of 90
minutes. Treatment of real wastewater carried out with 500 grams of active sludge
while contaminated with 1.5 ppm of pollutant under residence time of 90 minutes.
But in the case of the ferns, 600 grams of absorbent was charged and the reaction
carried out in 120 minutes. As it was mentioned earlier all optimized parameters of
earlier stage arranged in this part and absorbents performance was evaluated.

Individual Effect of PH-Value: Incrementing trend of removal efficiency by
increasing of pH-value raised by availability of negative charge groups as PO4-3 on
the cellular surface of the absorbent. Accordingly, Zn+2 was absorbed via negative
charge functional groups on the absorbent surface. At low values of pH, removal
efficiency decreased because of excess amount of H+ ions and intense acidic
environment. Because there is a deep competition between Zinc cation ions and H +
ions in connection with negative charge functional groups.
However, it was not possible to increase pH-value more than 7 for this heavy metal
while it was removed by sedimentation in the form of hydroxide and the effect of
biological absorbent could not be surveyed (Shokoohi et al. 2009), similar to all
metal cations for pH-values more than 5 with different rates (Wu et al. 2012).
However higher values of pH represented better results since production of OH- and
Zn+2 enhanced removals, so ferns had removal efficiency of 98.8 % at pH-value of 6
and active sludge showed 90.8 % efficiency at pH-value of 5-5.5.
Individual Effect of Absorption Time: As it is depicted, optimum reaction time was

120 minutes and 90 minutes for the ferns and active sludge, respectively. But it can
be seen that for the ferns, reduction phenomenon reached to equilibrium values
faster and in the case of active sludge it was reduced at latter times. Influence of
type and size of heavy metal ions, active group structures on the absorbent surface
and number of collisions between heavy metal and absorbent on removal time and
efficiency could not be negligible. Sharp slop of reduction in the first minutes could
be explained via existence of active functional groups on the cellular surface of the
absorbent. While after a specific time it saturated and removal efficiency faced
reduction (Wu et al 2012).
Individual Effect of Absorption Concentration: There is a direct relationship between

removal efficiency and absorbent concentration. But at high values of biomass,
undesirable coalescence happens and inhibits availability of absorbent active sites
(Khosravi et al 2005). In the case of the ferns, efficiency of 98.8 % attained at 6 g/l
and for active sludge 5 g/l of absorbent removed heavy metal up to 93.2 %. There
was a sharp ascending trend for the ferns at concentrations above 4 g/l, but in the
case of active sludge absorbent concentration did not have any particular effect on
removal.
Individual Effect of Pollutant Concentration: It was found that Zn (II) concentration

was generally low even in real plating wastewaters as in the range of 10-20 ppm
(Zhao et al 1999). So in this research low concentrations were evaluated. Increasing
initial concentration of the heavy metal could enhance production of metal ions in
the solution so competition for absorption increased between ions.
Furthermore, all active sites on the absorbent surface activated and removal
efficiency increased. In the case of both absorbents there were not any significant
changes in the aforementioned evaluated ranges and it was observed that removal
efficiency decreased by rising pollutant concentration. 5ppm showed the best results
for the ferns and active sludge by 99.6 % and 93.2 % removal efficiency,
respectively.
Absorbent Removal Capabilities in Real Wastewater for Laboratory Scale:

Evaluation of absorbents capabilities for real wastewater treatment conducted while
all previous parameters optimized and method efficiency investigated in the
presence of 1.5 ppm of Zinc ions in pH-value ranges of 6.5-7. Also repeatability of
results evaluated three times. In the case of real wastewater treatment, removal
efficiency obviously deceased while active sites of absorbents were interfered by
other pollutants unless selectivity of objective contaminant occurred (Amiri 1999).
Some interfering ions inhibited absorption of Zinc ions, so efficiency descended to
93.6 % and 90.1 % for the ferns and active sludge, respectively.
Absorbent Removal Capabilities in Real and Model Wastewaters for Industrial

Scale: In this part of the study, first of all agitation speed optimized in laboratory
scale as 150 rpm for 1 litre of solution and in the case of industrial scale
determinations carried out by Reynolds calculations. By the following graphs, Fig. 1
& Fig.2, it can be seen that agitation speed of 50 rpm indicated the best results and
lower speeds could not provide suitable dispersion. Also higher speeds were
definitely led to weaken great absorption and provided negative breakage on the
fluid surface. By the ferns absorbent, zinc ions removed over 93.2 % in model
wastewater and 88.5 % for real fluent. However active sludge provided weaker
performance of 89.5 % and 85.6 % for model and real effluent, respectively. In fact,
for both absorbents removal performance decreased in the case of real effluent as it
was expected.

Figure 1. Zn (II) removal efficiency by fern absorbent in industrial scale
Figure 2. Zn (II) removal efficiency by active sludge absorbent in industrial scale
Conclusions
Overcoming to many dangerous effects of introducing heavy metals to the
environment can be carried out by applying different applicable treatment methods
as done in this research. Hence, capabilities of two biological absorbents, aquatic
ferns and active sludge investigated and optimized. By the industrial results, zinc
could be removed effectively in a more time consuming process by 6 g/l of ferns
under agitation speed of 50 rpm (88.5 %) -better results were attained in comparison

with active sludge- and active sludge represented a bit weaker performance which
had pollutant removal by 85.6 % from the real effluent. Finally, it can be mentioned
that the two biological absorbents had suitable efficiencies while they were
economic environmentally friendly approaches.
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EXPERIMENTAL EVALUATION OF A BIOLOGICAL PRODUCTS'

EFFICIENCY FOR HIGH-LOAD WASTEWATER TREATMENT
Elena Elisabeta Manea1, Costel Bumbac1, Florin Găulea2
1
National Research and Development Institute for Industrial Ecology - ECOIND, 71-73
Drumul Podul Dambovitei Str., 060652, Bucharest, Romania, elena.manea@incdecoind.ro
2
Renergetics Decontaminari SRL, București str. Horbotei, nr. 3, Bl. M2, Scara 2, ap.27, Sector
3, cod poștal 030465, tel. 0762257343
Abstract
Prior to discharge, high-loads wastewater needs intensive treatment, that can be
carried out by physical, chemical or biological means towards discharge water
quality. Extensive research has been carried out to identify solutions with reduced
costs and high efficiencies. The paper presents the lab scale performance
efficiencies of an innovative biological complex product obtained for the treatment
of several samples (municipal wastewater, pig farm wastewater, wastewater from a
restaurant’s grease removal tank). The experiments were carried out in laboratory
bioreactors, the sample volume considered ranging from 1.5L to 4L depending on
the waste water load and the number of simultaneous samples. Each sample was
tested in parallel under similar conditions, the only varied parameter being the
dissolved oxygen concentration. The results have shown that, under the tested
conditions, the product contributes to pollutants degradation, with good efficiency
for nitrogen ammonium and Kjeldahl nitrogen removal, managing to partially
reduce the organic load. However, after 42 days of experiment, the effluent does not
meet the sewage discharge conditions imposed by NTPA 002-H.G.352.
Keywords: Biological product, wastewater treatment
Introduction
Biological wastewater treatment is one of the most efficient solutions for increased
loads reduction and the varying compounds and charges in water requires
continuous research on improved processes (Nicolau et al., 2008; Tricolici et al.,
2014).
High strength organic industrial wastewater require pre-treatment prior to their
discharge in sewer systems due to the stringent legislation requirement and the
potential stress on the downstream wastewater treatment processes. Using
conventional pre-treatment solutions for high strength wastewater such as pig farm
wastewater can imply extensive costs and limited efficiencies, thus there is a need
for identifying new reliable methods and solutions for reaching loads complying the
discharge regulations (Durai et Rajasimman, 2011, Sonune et Ghate, 2004).
Studies regarding the use of anaerobic digestion pro high strength organic effluents
showed promising results, with extensive research on improving bioreactors
configurations for increased process efficiencies (Speece, 1983; Rajeshwari et.al.,
2000).
Currently, the main focus is on applied research on studying different biological

products efficiencies in reducing industrial wastewater loads.
The paper presents the experimental results obtained for the efficiency of a
biological product based on Archaea in decreasing pollutants loads, in both aerobic
and anaerobic conditions.
Experimental
The experiments were carried out in experimental laboratory installations
(BIOSTAT Bplus TWIN and Diachrom), each provided with two vessels
(bioreactors). Sample volume taken into consideration: 1.5 L (for aerobic and
anaerobic control samples) and 4 L (for test samples with biological product under
aerobic and anaerobic conditions). The quantities have been established according to
the waste water quantity and available quantity. Each sample was tested in parallel
under similar conditions, the only parameter varied being the dissolved oxygen
concentration. For each type of wastewater, the evolution of pollutant concentrations
was monitored both in the test samples and in the control samples.
The samples were subjected to a set of preliminary tests upon arrival and were
subsequently stored at 4oC until the experiments started.
The samples were characterized based on the results of the analytical determinations
of the organic load expressed both as chemical oxygen consumption (COD) (SR
ISO 6060: 1996) and as biochemical oxygen consumption (BOD) (SR EN 1899/1,2-
02, 38409-87), total suspended solids (TSS) (STAS 6953-81), total Kjeldahl
nitrogen (TKN) (SR EN 25663-00, SR ISO 11261:2000), NH4+, NO2-, NO3-, PO43-
(SR EN ISO 14911: 2003, SR EN ISO 10304/1: 2009) and total phosphorous (STAS
7184/14-79). Considering the waste water composition and the considered inoculum
(the high content of suspended solids) important parameters were determined both
for homogenous and filtered samples (filter paper with the pore diameter of 12-15
µm).
Throughout the experiment, the same inoculation protocol was maintained: fresh
biological inoculum (2.5 g/l) was added to the tested sample every six days. Samples
were collected form each tank (both for the test and control, aerated and unaerated)
in the beginning, after 21 days and after 42 days. The active inoculum - archaea
were delivered in a bentonite-clay based carrier.

Low efficiencies were obtained for the treatment of municipal wastewater. The
concentrations decrease was insignificant and could be easily be a result of the high
retention time (42 days) alone without any contribution of the biological product.
The highest reduction rate was met for the total phosphorous concentrations, being
of approximatively 80% for both unaerated and aerobic reactor, probably due to
adsorption on the bentonite carrier of the product. Thus, the product’s application
for low strength wastewater treatment, in the evaluated conditions, resulted as not
suitable.
In the graphs below we try to emphasize the main experimental results obtained
during the performance test of the biological product on the treatment efficiency for
pig farm wastewater and grease separator wastewater.

The tests have shown that the product presents a certain pollutants degradation
activity for the pig farm wastewater, with good efficiencies on nitrogen ammonium
and TKN removal, managing also to partially reduce the organic load (fig 1, 2).
However, after 42 days of experiments, the effluents did not meet the sewage
discharge conditions imposed by NTPA 002- H.G.352.
Figure 1. Pig farm wastewater experimental results (1)
Figure 2. Pig farm wastewater experimental results (2)
Figure 3. Grease separator wastewater experimental results (1)

Figure 4. Grease separator wastewater experimental results (2)
After 21 of experimental days, conclusive treatment efficiencies have been obtained

for the grease separator wastewater. Due to the high solids concentration of the
biological product, high total suspended solids (TSS) concentrations were resulted in
both aerated and unaerated samples. The concentration of extractible was reduced
by more than 50% for both aerated and unaerated samples. Organic load reduction
(expressed as COD and BOD) ranged from 47 to 83%. Higher removal efficiencies
were obtained for both samples with biological product for Pt, ranging between 67
and 85%.
After 42 experimental days, the concentration of extractible substances was reduced
by 29% in the unaerated sample and by 59% in the aerated sample. The organic load
removal efficiency, expressed as COD is 90% for the aerated sample and of 81% the
unaerated one. After 42 days of experimentation the reduction of Pt concentration by
90% was obtained.
Conclusions
Based on these preliminary results, we can conclude that the product is not suitable
or does not have superior performances compared to any conventional treatment for
low strength municipal wastewater. However, even if more tests are required to
assess the minimum retention time with no impact on treatment performances, there
is a potential for the product to be used in the pre-treatment of high strength
wastewater such as the ones from grease separators and pig farms.
Acknowledgements
This work has been realized with the support of Operational Programme Copmpetitiviness
2014-2020, Project ID P_40_300, SMIS 105581, Subsidiary Contract No. 3590/ 07.03.2018
References
Durai, G., Rajasimman, M., Biological treatment of tannery wastewater-a review,
Journal of environmental science and technology, vol4, 2011, pp. 1-17.
Nicolau, M., Patroescu, V., Cosma, C., Dinu L., Bumbac, C., Constantin, L.,
Intensive Biological Process Based on SBR Reactor for Industrial Wastewater
Treatment, Rev. Chim. Vol. 59, no. 10, 2008, pp. 1106-1111.

Rajeshwari, K.V., Balakrishnan, M., Kansal, A., Kusum Lata, Kishore, V.V.N.
State-of-the-art of anaerobic digestion technology for industrial wastewater
treatment, Renewable and Sustainable Energy Reviews, vol. 4, iss. 2, 2000,
pp. 135-156
Sonune, A., Ghate, R., Developments in wastewater treatment methods,
Desalination, vol. 167, 2004, pp. 55-63
Speece, R., Anaerobic biotechnology for industrial wastewater treatment, Environ.
Sci. Technol., vol. 179, 1983, pp. 416A-427A
Tricolici, O., Bumbac, C., Postolache, C., Microalgae-bacteria system for biological
wastewater treatment, Journal of Environmental Protection and Ecology,
Vol.15, No.1, 2014, pp.268-276

EXPERIMENTAL STUDY ON USING COMMERCIAL MEMBRANES FOR

TREATMENT OF WASTEWATER GENERATED BY COLLAGEN
PRODUCTION
Mirela Alina Constantin1, Lucian Alexandru Constantin1, Ion Viorel Patroescu1, Gheorghe
Batrinescu1, Georgiana Dolete2
1
National Research and Development Institute for Industrial Ecology – ECOIND Bucharest,
71-73 Drumul Podu Dambovitei, Sector 6, 060652, Bucharest, Romania,
alina.constantin@incdecoind.ro
2
SC Sanimed International Impex SRL, 70F Bucuresti-Magurele, Sector 5, Bucharest,
Romania
Abstract
Collagen production is generating wastewater with high organic loading. This type
of wastewater is still containing valuable compounds that can be reused in other
applications. In order to investigate the possibility to recover and reuse these
compounds the membrane based processes were investigated. Four types of
commercial available membranes were characterised and then used to recover the
proteins. The results proved that membrane based processes represent a viable
alternative to treatment of wastewater generated by collagen production facilities
when recovery of valuable compounds is envisaged. It has to be stressed that on the
other hand only membrane processes do not assure too reach the quality norms
imposed by the legislation for treated wastewater discharge into sewerage systems
or natural receivers. Therefore, when proteins recovery and reuse is wanted, the
membrane processes represent only the first step of wastewater treatment and should
be followed by biological processes in order to obtain the organic loading quality
indicators required for wastewater treatment plants discharges.
Keywords: collagen, polyethersulfon, regenerated cellulose, ultrafiltration,

wastewater
Introduction
Wastewater generated by porous collagen based substrates preparation are
characterized by high organic loadings. Due to the fact that membrane processes
represents one of the modern methods for separation of organic compounds from
aqueous systems, its use on wastewater generated by collagen production was
investigated as a first step towards the recovery of useful compounds (proteins) and
their use in further applications.
A membrane represents a barrier (a discontinuity region) between two phases, the
phase’s components being unequally transported through membrane, allowing their
separation. The mass transport can be diffusive or convective and take place due to a
driving force such as a gradient of pressure, temperature, concentration or electric
potential (Batrinescu et al 2014).

From various technologies used for wastewater treatment, membrane process is

considered a viable option for secondary or tertiary step (Bourgeous et al 2001).
Moreover, at international level there are operating more than 500 types of
membrane bioreactors (Chang & Kim 2005). Membrane based technologies present
advantages related to the operation without chemical substances addition and a
relatively low energy consumption but the main drawback is represented by
clogging process (Fan et al 2001, Scott 1995, Lee et al 2004).
From the materials that are used in membrane processes application can be
mentioned: polyethylene (Kaiya et al 1996), polysulfon (Kweon & Lawler 2004),
polypropylene (Gray et al 2004), polypiperazine (Her et al 2000), polyamide (Cho et
al 2000), polyacrylonitrile (Xia et al 2004), polyethersulfon (Yuan & Zydney 1999),
sulfonated polyethersulfon (Lee et al 2001), and regenerated cellulose (Manttari et al
2000).
The study was conducted using four types of commercial available membranes that
were characterized the point of view of both average distilled water flows and
morphologically (by scanning electronic microscopy SEM).
Experimental
A Koch-LabCell CF1 membrane test module was used in order to determine
distilled water flows and a scanning electronic microscope Quanta FEG 250 was
used for micrographs of membranes.
Three samples of real wastewater were used during the experiments (S1-S3). All
water samples were pre-filtered prior to enter the membrane separation process in
order to protect the membranes. The membranes are commercial ones provided by
Sartorius (polyethersulfon PES with cut-off values of 1, 5, 10 kDa) and Millipore
(regenerated cellulose RC with a cut-off value of 10 kDa).
Figure 1. Experimental installation

Results and discussions

The membranes were characterized from the point of view of average distilled water
flows and the optimum working pressures were selected: 3 bars (PES 10 kDa), 5
bars (PES 5 kDa), 6 bars (PES 6 kDa) and 4 bars (RC).
Figure 2. Average distilled water flow for PES 10 kDa membrane
Moreover, SEM was used to investigate the morphology of the membranes. As

example SEM micrographs for PES 5 kDa membrane before and after S1 separation
are presented in the next figure (clogging phenomenon can be observed).
Figure 3. SEM micrographs for PES 5 kDa before and after S1 ultrafiltration
The three wastewater samples were characterized and organic loading expressed as
Chemical Oxygen Demand (COD) were: 11968 mg O2/L (S1), 11264 mg O2/L (S2)
and 3168 mg O2/L (S3).

Table 1. Wastewater samples characterisation

Indicator M.U. S1 S2 S3
pH unit 2.84 2.75 10.00
COD mgO2/L 11968 11264 3168
CBO5 (BOD) mgO2/L 6200 6150 1735
TSM mg/L 60 21 2
NTK mg/L 26.46 22.2 48.3
Separation experiments were performed and the results are presented in the
following table:
Table 2. Separation experiments results

Sample COD (mgO2/L) Efficiency Membrane Pressure
Feed Permeate (%) (bars)
11264 5.88 PES 10 kDa 3
S1 11968 9152 23.53 PES 5 kDa 5
9680 19.12 RC 4
11098 1.47 PES 10 kDa 3
S2 11264
9240 17.97 RC 4
1716 45.83 PES 1 kDa 6
S3 3168
2 684 15.28 RC 4
Membrane clogging was measured by average distilled water flow decrease (as
percentage) between average flows before and after separation experiments, for
example for RC membrane at 4 bars the % of clogging was found to be 2.01%.
Figure 4. Clogging of RC membrane at 4 bars after separation experiments

Conclusions
The most efficient membrane in terms of separation efficiency proved to be PES 1
kDa which reached more than 45% but this type of membrane presents a low
average flow of 18.95 L/m2 h distilled water at 6 bars pressure. On the other hand,
RC membrane presented separation efficiency between 15.28 – 19.12 % for all
samples (almost similar with those obtained by using PES 5 kDa) but also a very
good average distilled water flow of 250.37 L/m2 h for a working pressure of 4 bars.
It should be noticed that only membrane processes are not assuring the imposed
limits for discharge of treated wastewater. Taking into account the BOD/COD ratio
a biological process can assure those limits but only after separation of useful
compounds from wastewater flows by membrane based processes.
Acknowledgement
This work was realised with the support of Operational Programme Competitiveness
2014 – 2020, Contract no. 55/05.09.2016, Project ID P_40_300, SMIS 105581,
Subsidiary Contract 5831/18.04.2018.
References
Batrinescu, G, Constantin, M, Cuciureanu, A & Nechifor, G 2014, Polysulfone-
polyaniline type membranes obtained in a steady state system: Structural and
hydrodynamic characteristics, Polymer Engineering & Science, vol. 54, no. 7,
pp. 1640-1647.
Bourgeous, K, Darby, J & Tchobanoglous, T 2001, Ultrafiltration of wastewater:
effects of particles, mode of operation and backwash effectiveness, Water
Research, vol. 35, pp. 77-90.
Chang, I & Kim, S 2005, Wastewater treatment using membrane filtration - effect of
biosolids concentration on cake resistance, Process Biochemistry, vol. 40, pp.
1307-1314.
Cho, J, Amy, G & Pellegrino, J 2000, Membrane filtration of natural organic
matters: factors and mechanisms affecting rejection and flux decline with
charged ultrafiltration (UF) membrane, Journal of Membrane Science, vol.
164, pp. 89-110.
Fan, L, Harris, J, Roddick, F & Booker, N 2001, Influences of the characteristics of
natural organic matter on fouling of microfiltration membranes, Water
Research, vol. 35, no. 18, pp. 4455-4463.
Gray, S, Ritchie, C & Bolto, B 2004, Effect of fractional NOM on low pressure
membrane flux decline, Water Science and Technology, vol. 4, pp. 189-196.
Her, N, Amy, G & Jarusutthirak, C 2000, Seasonal variation of nanofiltration (NF)
foulants: identification and control, Desalination, vol. 132, pp. 143-160.
Kaiya, Y, Itoh, Y, Fujita, K & Takizawa, S 1996, Study on fouling materials in the
membrane treatment process for potable water, Desalination, vol. 106, pp. 71-
77.
Kweon, J & Lawler, D 2004, Fouling mechanisms in the integrated system with
softening and ultrafiltration, Water Research, vol. 38, pp. 4164-4172.

Lee, H et al 2001, Cleaning strategies for flux recovery of an ultrafiltration

membrane fouled by natural organic matter, Water Research, vol. 35, pp.
3301-3308.
Lee, N, Amy, G, Croue, J & Buisson, H 2004, Identification and understanding of
fouling in low pressure membrane (MF/UF) filtration by natural organic
matter (NOM), Water Research, vol. 38, pp. 4511-4523.
Manttari, M, Puro, J & Nystrom, M 2000, Fouling effect of polysachharides and
humic acid in nanofiltration, Journal of Membrane Science, vol. 165, pp. 1-
17.
Scott, K 1995, Handbook of industrial membranes, Elsevier.
Xia, S, Nan, J, Liu, R & Li, G 2004, Study on drinking water treatment by
ultrafiltration of surface water and its application to China, Desalination, vol.
170, pp. 41-47.
Yuan, W & Zydney, A 1999, Humic acid fouling during microfiltration, Journal of
Membrane Science, vol. 157, no. 1, pp. 1-12.

Fe-Al RECOVERY FROM MINE WATER TREATMENT RESIDUALS AND

PRODUCT TESTING FOR WASTEWATER TREATMENT - PHOSPHATE
AND TURBIDITY REMOVAL
Laurentiu Razvan Dinu1, Valeriu Robert Badescu1, Gabriela Geanina Vasile1, Ionut Cristea1,
Ecaterina Anca Serban, Voicu Oncu2, Marinela Moga2
1
National Research and Development Institute for Industrial Ecology ECOIND, 71-73 Drumul
Podu Dambovitei Street, code 060652, Bucharest, tehnologi@incdecoind.ro, Romania
2
S.C. Cepromin S.A., 22 Decembrie Street, no. 37A, Deva, office@cepromin.ro, Romania
Abstract
Mine water treatment scope is to produce an effluent which satisfies the discharge
limits according to permits. However, the production of metal-rich sludge is a
consequence of the mine water treatment and its disposal as a waste raises the cost
of the whole operation, so ways to convert the sludge into marketable products are
desirable. For example, mine water treatment sludge can be used for adsorbents or
pigments production or some of the sludge components can be extracted and utilized
as coagulants. Coagulants were obtained from mine water after partial precipitation
of metal species or after conventional treatment, by leaching the sludge with acid.
The effectiveness of coagulants considering phosphate, chemical oxygen demand
and turbidity is presented in this paper, alongside with some of the drawbacks as
observed.
Keywords: mine water, coagulation, recycling
Introduction
Mine water treatment generates important quantities of chemical sludge irrespective
of the treatment process applied, active or passive (Hedin 2003). In particular, mine
water generated from non-ferrous minerals sites, contains various heavy metal
species and the precipitation product will contain Fe, Al, Zn, Mn, Cu, As, Cd, Cr,
Ni. The metal-rich sludge disposal as a waste raises the operating costs, and efforts
to recover some value from the residues are done. One option is the chemical
extraction of the major elements from the sludge in order to obtain coagulants
suitable for wastewater treatment (Menezes et al 2010, Janneck et al 2018).
Alongside with the recovery of the iron and aluminium process difficulties and
efficiency of the coagulant solution obtained, the concentration of trace heavy metal
is very important for conformity with existing coagulant standards and for market
acceptability.
The aim of this work was to produce ferric-alumino sulphate solution starting from
mine water sourced from a non-ferrous ore mining site and to assess the results for
heavily polluted wastewater treatment, but also to address the susceptibility of
releasing heavy metal in the treated water. A separate discussion is done, related to
the quality of the coagulant solution itself compared to the parameters limited by
standards for Fe/Al for coagulants. Because mine water from the non-ferrous
mineral production sites is often treated by liming (Dinu et al 2018), we choose to
use calcium hydroxide for metal precipitation and to evaluate the results obtained
for sludge production to pH ≤ 5, aiming a product with higher Fe+Al content and
higher purity, but also for pH =8.5, expecting a lower purity for this case. Because
it was considered highly desirable to observe the effects of processing a sludge
produced as in the normal operation of a mine water treatment facility, we present
here the tests for the pH value at precipitation step of 8.5.
Experimental
Mine water from Nicodim Tunel, having 1939 mg Fe/L (80% Fe3+) and 346 mg Al/L
(see also Table 1 for other parameters) was processed by precipitation heavy metal
species and aluminium with calcium hydroxide at pH = 8.5. The water was
separated by settling and the sludge was concentrated to 18.2% dry solids (d.s.) by
centrifugation (1500 x g, 10 min). Coagulant solution was obtained by dissolving
the precipitate, at room temperature, with sulphuric acid (96%), using a 37% acid
excess, reported to iron and aluminium only. The reaction mixture resulting after 2h
mixing time is a paste, a viscous phase and it was diluted with distilled water (total
volume 2.5 L final volume for 1 kg of centrifuged sludge) and the coagulant was
extracted by orbital mixing for 16 h, followed by centrifugation (1500 x g, 10 min).
The final coagulant product is a clear solution and was analyzed for Fe, Al and other
metal and metalloid species by inductively coupled plasma optical emission
spectrometry (ICP-OES), method SR EN ISO 11885:09, using an AVIO 500 Perkin
Elmer Spectrometer.
Table 1 Mine water characterization, Nicodim

Parameter Units Values Parameter Units Values
SO42- mg/L 8498 Cr mg/L 0.21
Ca2+ mg/L 588 Cu mg/L 7.70
Mg2+ mg/L 378 Fe mg/L 1939
TDS mg/L 13210 Mn mg/L 252
Al mg/L 346 Ni mg/L 5.22
As mg/L 3.44 Pb mg/L 0.20
Cd mg/L 3.03 Zn mg/L 497
Co mg/L 1.70
Municipal WWTP Focsani sludge leachate (COD-Cr = 396 mg O2/L, with 196 mg
PO43- /L) was subjected to treatment tests by coagulation using the product obtained
as described above, following the process flow diagram as shown in 0. Coagulation
treatment phase was optionally followed by flocculation with a cationic polymer (7
mg/L). The pH adjustment was not needed for the coagulant amounts used in these
tests, but for the highest dose a distinct test with pH correction was done, mostly to
observe the effect on phosphate removal. Analysis for water obtained after settling
focused on chemical oxygen demand, turbidity (samples after gravity separation,

with no filtration), and also heavy metal species were also determined by ICP-OES,
for unfiltered samples also, preserved with nitric acid. Orto-phosphate was
determined in filtered samples by ion-chromatography (IC Dionex 3000).
Wastewater
Coagulation
Coagulant (rapid stirring, 15 min)
NaOH pH adjustment (optional)
Polimer Floculation (optional)
Settling, 30min Settling diagram
Supernatant
Effluent characterization
COD-Cr, Turbidity, PO43-
Figure 1. Waste water treatment test using coagulants, flow-sheet

Iron content of the coagulant solution increased with sulphuric acid amount, but the
aluminium solubilisation is lower for the higher H2SO4 doses. In addition, the iron
content does not increase significantly for the products obtained using higher acid
amount, beyond the minimum value, so, taking into consideration the need of pH
adjustment for the further wastewater treatment, only the coagulant product with
minimum acidity was considered of interest (0). This coagulant contains also other
heavy metals such as manganese and zinc, as the pH for the sludge production is
high enough to allow precipitation from mine water (0).
Treatment of the municipal leachate by coagulation followed by flocculation had
good results starting from 1.4 mEg/L (3.4 mL/L) with respect to global organic load
and turbidity (settling supernatant, no filtration), with slightly improvement for
coagulant doses up to 5.4 mEg/L Fe3+ and Al3+.
Table 1. Coagulant solution grades obtained by processing mine water sludge

Parameter Units H2SO4 96%
0,53 g/g d.s. 1,06 g/g d.s. 2,11 g/g d.s.
Fe mg/L 5580 6015 6635
Al mg/L 926 688 749
Acidity m Eg/L 670 1350 2710
Table 2. Heavy metals and metalloids - coagulant

Parameter Units Concentration Parameter Units Concentration
As mg/L 10,8 Pb mg/L 0,61
Cd mg/L 10,4 Ni mg/L 19,7
Co mg/L 5,05 Mn mg/L 586
Cr mg/L 1,23 Zn mg/L 1955
Cu mg/L 30,4
600 200
180
500
160
Phosphate, mg PO 43-/L
COD-Cr, mg O2/L and
140
400
Turbidity, NTU
120
300 100
80
200
60
40
100
20
0 0
0 20 40 60 80
Coagulant dose, mg Fe/L
COD-Cr Turbidity Phosphate
Figure 2. Waste water treatment tests using coagulants
Chemical oxygen demand dropped from 396 mg O2/L down to 44 mg O2/L (89%
efficiency), while turbidity decreased from more than 500 NTU to 21 NTU. For the
maximum coagulant dose the values are 35.2 mg O2/L (91% efficiency for COD-Cr)
and 11.4 NTU, respectively. Phosphate is removed by precipitation with ferric iron
and aluminium and adsorption on solids, efficiency being continuously increased by
the coagulant dose, as applied. Concentration of PO43- in solution drops from 186
mg/L down to 17.6 mg/L, adsorption explaining a difference from maximum
expected removal by precipitation and the effective phosphate elimination from
solution.
A comparative test was done using only organic polymer: by simple flocculation,
some of the suspended solids are removed, water after settling having a turbidity of
62.5 NTU and COD-Cr = 88 mg O2/L (77% efficiency). As expected, there was no
effect on phosphate.
Wastewater treatment by coagulation, followed by flocculation has a better
efficiency than coagulation alone and the use of aluminum and iron salts is usually
associated with flocculation adjuvant is well-established in the field of water and
wastewater primary treatment (Buciscanu et al 2008, Tociu et al 2017). For our case
study, comparative tests were done using 13.4 mL/L coagulant (5.4 mEg Fe 3+ and
Al3+). Without flocculation a turbidity of 31.3 NTU is achieved after settling versus
11.4 NTU after coagulation and flocculation. Also the organic load (determined as

COD-Cr for homogenous phase after settling) is better with flocculation (35.2 mg
O2/L and 52.8 mg O2/L, respectively).
The pH adjustment after coagulation, often necessary for this operation, it was not
needed for this particular wastewater and coagulant amounts. However, for the
maximum coagulant dose, 5.4 mEg Fe3+ and Al3+, a test with pH adjustment was
done, raising the pH from 6.6 to 7.7, using sodium hydroxide. Slightly better values
for COD-Cr (26.4 mg O2/L), turbidity (10.7 NTU) and phosphate (12.2 mgPO43-/L)
were recorded.
Another step to check the applicability of the coagulants obtained from mine water,
was to assess the residual heavy metal concentration in the treated water. Of special
interest was the effluent after the tests performed the highest coagulant product dose
used in this experiment. Without the secondary treatment step, flocculation, the iron
and also manganese and zinc had relevant high concentrations, explained both by
precipitates remaining in suspension and also by species remaining in solution
(especially manganese). With flocculation all values are better, due to better
separation of the metal hydroxides from water (0). For the test ran with pH
adjustment, final values for zinc and manganese were further improved. It can be
discussed that the residence time in an industrial settler will be of 60-180 min,
higher than for this experiment (30 minutes) and some improvements might be
expected.
Table 3. Heavy metals and metalloids - concentration in water after treatment

Coagulation with pH
Coagulant Coagulation &
Parameter Units only flocculation
adjustment &
flocculation
As mg/L 0.0078 <0.005 <0.005
Cd mg/L 0.013 0.002 <0.0015
Co mg/L 0.031 0.012 0.004
Cr mg/L <0.0013 <0.0013 <0.0013
Cu mg/L 0.027 0.024 0.022
Fe mg/L 5.50 0.45 0.29
Mn mg/L 3.39 1.20 0.58
Ni mg/L 0.13 0.063 0.013
Pb mg/L 0.005 0.004 0.005
Zn mg/L 1.86 0.13 0.035
Comment: Samples were analysed after settling, without filtration.
Water treated using the coagulant product obtained from mine water is acceptable to
be discharged to surface water bodies, but a discussion is to be made regarding the
quality of the coagulant as a product. Compared with commercial products, obtained
from high purity raw materials (e.g. iron ore), available to meet standards for ferric
and/or aluminium based coagulants to be used for treatment of water intended for
human consumption, the coagulant obtained from the mine water has high ratios of
heavy metal or metalloids to iron and aluminium. Taking into account the values
showed in 0, even if the coagulant obtained from mine water is to be recommended
only for wastewater applications, the perception on the market is expected to be
unfavourable.
Table 3. Heavy metals and metalloids ratios to Fe and Al for the product
Ratio to Mine water EN 878 EN 887 EN 890
Units
Al and Fe coagulant (**) (**) (***)
As/Al mg/kg Al 11663 <100
Cd/Al mg/kg Al 11231 <100
Cr/Al mg/kg Al 1328 <1000
Ni/Al mg/kg Al 21274 <1000
Pb/Al mg/kg Al 659 <800
As/Fe mg/kg Fe 1935 <20 mg/kg Fe
Cd/Fe mg/kg Fe 1864 ≤ 25 mg/kg Fe
Cr/Fe mg/kg Fe 220 <350mg/kg Fe
Ni/Fe mg/kg Fe 3530 ≤350mg/kg Fe
Pb/Fe mg/kg Fe 109 <100mg/kg Fe
As/(Al+Fe) mg/kg {Al+Fe} 1660 - <14 <20mg/kg Fe
Cd/(Al+Fe) mg/kg {Al+Fe} 1599 - <6 ≤ 25mg/kg Fe
Cr/(Al+Fe) mg/kg {Al+Fe} 189 - <50 <350mg/kg Fe
Ni/(Al+Fe) mg/kg {Al+Fe} 3028 - <150 ≤350mg/kg Fe
Pb/(Al+Fe) mg/kg {Al+Fe} 94 - <15 <100mg/kg Fe
* EN878, Aluminium sulphate, Type 3
(**) Aluminium Iron (III) Sulfate (Acorn Water, Technical specification sheet, ACE800,
Spec.2106, retrieved 10.07.2019, http://www.acornwater.ie/content/files/ products/
7_2_2106ACE800liquorSPEC.pdf
(***) Grade I Type 2 Iron(III) sulphate solution, Chemifloc Ltd., Product specification, Ferric
Sulphate 140, rev.4, 2016, retrieved 10.07.2019, https://chemifloc.com/media/1286/ferric-
sulphate-125-specification-rev-3.pdf
Conclusion
Coagulant Fe(III)-Al solutions were prepared using sludge from mine water
treatment originating from a non-ferrous ore mining site, with the goal to valorise
the precipitates from normal operation of the water treatment plant (pH = 8.5,
neutralization with lime). Iron and aluminium content of the product is lower than
for the marketed products due to moderate processing conditions. The coagulant had
good performance on tested wastewater with respect to phosphate precipitation and
suspended solids and organic load removal. As a consequence of the mine water
origin and characteristics and conditions used for the source sludge production, the
coagulant product has a significant content of unwanted metal species such as Mn,
Zn, but also As, Cd, Ni, Pb. Heavy metal transfer water after treatment is low,
acceptable, but the perception of the coagulant product on the market is expected to
be unfavourable even for wastewater treatment, because the purity criteria are not
met.
Acknowledgements
This work was realised with the support of Operational Programme Competitiveness 2014 –
2020, Contract no. 55/05.09.2016, Project ID P_40_300, SMIS 105581, Subsidiary Contract
15350/2017.

References
Buciscanu, I, Pruneanu M & Maier, V 2008, 'Novel Ferric Sulfate – Based
Coagulants', Scientific Study & Research, IX (2), pp. 187-194.
Dinu, LR, Oncu V, Badescu VR, Patroescu VI & Vasile GG 2018, ‘Kinetic Analysis
of Manganese Removal from Mine Water - Continuous Flow Reaction
System', 21st International Symposium “The Environment and The Industry”,
Bucharest, pp. 54-60.
Hedin, R 2003, 'Recovery of marketable iron oxide from mine drainage in the USA',
Land Contamination & Reclamation, vol. 11, no. 2, pp. 93-97.
Janneck, E, Glombitza, F, Aubel, T, Schönherr, P, Palitzsch, W, Killenberg, A,
Schubert, V & Weber, L 2018, 'Utilization of Iron Ochre – Making Auxiliary
Water Treatment Materials from Mine Water Treatment Waste', Mine Water –
Risk to Opportunity, vol. II, Pretoria, pp. 899 – 904.
Menezes, JCSS, Silva, RA, Arce, IS & Schneider, IAH 2010, 'Production of a poly-
alumino-iron sulphate coagulant by chemical precipitation of a coal mining
acid drainage', Minerals Engineering, vol. 23, no. 3, pp. 249-251.
Tociu, C, Robert, S, Anghel, AM, Marinescu, F, Ilie, M, Holban, E, Ghita, G, Matei
M & Dumitru, FD 2017, 'Possibilities for efficient use of valuable materials
from aluminium slag to remove specific pollutants in Wastewater', Journal of
Environmental Protection and Ecology, vol. 18, no. 3, pp. 842-852.

INVESTIGATION OF SERVICE BRIDGE PIERS LOCATED ON

SPILLWAY AND EFFECTS ON DISCHARGE
Konya Technical University Civil Engineering Department, Konya,

ayildiz@ktun.edu.tr, ayarar@ktun.edu.tr, aimarti@ktun.edu.tr, akocaer@ktun.edu.tr, Turkey
Abstract
The piers can be placed on the spillway crest to hold the sluice gate for controlling
the flow or support a service bridge. In addition, these piers to be placed on spillway
body provide air entry to prevent negative pressure on the crest and eliminate the
risk of cavitation. However, piers and abutments reduce the flow section area and it
may cause increasing in reservoir water level. This contraction in the section varies
depending on the thickness of the piers besides shape of the cross section. There are
some theoretical methods in literature to calculate reduce in effective length of crest.
In this study, experimental studies have been done on circular and square section
bridge legs in laboratory environment. The results obtained from the studies showed
that there are serious differences between experimental and theoretical calculations.
Keywords: abutments, bridge Piers, net crest length, Ogee Spillway
Introduction
Bridges are one of the most important hydraulic structures of civil engineering. The
piers are not only used to support the bridges built on rivers, but are also used to
support the bridges to provide transportation on the dam bodies built in valley.
Services bridges are built top level of the spillways. The columns used for
supporting the sluice gate work as bridge piers when water pass between them, gates
are open. When planning the reservoir capacity in dams, the effect of piers on flow
should be considered.
The bridge piers built on river and the piers built on spillway work in different
manner for hydraulically. While water has a speed before and after the piers in river,
the velocity of water at the upstream side of pier on the spillway is generally
considered zero. Since the bridge and abutments are in the flow area during the
lifetime, they are exposed to the structure to ground effect. For this reason, there are
many parameters affecting the hydraulic design of the bridge piers. These
parameters are flow regime at upstream and downstream side, shape and size of the
piers. Therefore, there are several studies conducted for each parameter. In the case
of water level rise in reservoir after sudden rainfall, discharge between piers must be
calculated accurately in order to transfer excessive water to downstream effectively.
The most important study explaining the effect of the bridge piers on the cross
sectional area of flow was performed at by USBR Laboratories. USBR explained
reduction in effective crest length depending on the number of piers and piers shape
by formulas in report published as name of Design of Small Dams in 1987.
Today, researches are mostly focused on scour at the bottom of piers. Also, several
studies have been carried out to prevent or minimize the deterioration caused by
flow or the different factors. The researcher (Yarnell, 1934) investigated the effect
of pier geometry and maximum scour depth. This study is among the first studies on
piers shape. Some researchers (Barbhuiya and Dey 2003), conducted studies on
different piers shape. In the study rectangular, half cylindrical and cylindrical pier
sections are used. They measured velocity components around piers, turbulence
magnitude and kinetic energy. The researchers (Khosnorejad and friends 2012) also
studied on local scour around bridge piers.
In this study, experimental studies carried out on an ogee spillway containing piers
at top level of crest. It is believed to that piers support a service bridges. The effect
of these piers on the flow area and effective crest length of flow was investigated.
The results obtained from experiments were compared with results calculated from
formulas in the literature.

In ogee type spillways, the optimum discharge is obtained when the shape of the
crest is close to the ideal form. The shape of the crest is determined by the total head
over ogee spillway (H), the slope of upstream face (θ) and crest height (P) of the
spillway body (Figure 1). Discharge (Q) over the spillway is calculated by following
Formula-1;
(1)
Where; Q is discharge (m3/s), C is discharge Coefficient, L is effective Length of

Crest (m), H is total head over the spillway (m).
y
H
x
Ogee Crest
Flow Direction P
Q=L*C0*H03/2
Figure 1. General view of ogee spillway
The ogee spillway used in this study has 30 cm crest length (L=30 cm) and 28 cm
crest height (P=28 cm). (Figure 2.)

30 cm
28 cm
Figure 2. Dimension of ogee spillway used in experiments and actual view of ogee
spillway
Piers and abutments placed on spillway cause contraction in flow section reduce the
effective crest length and caused reduction in discharge compared with the free flow
without piers. Net length of crest is calculated by Formula-2 given below (USBR
1987).
(2)
Where L is effective crest length in free ogee spillway, L’ is net length of crest, N is
number of piers, Kp is pier contraction coefficient, Ka is abutment contraction
coefficient, He is total head over on ogee spillway.
Pier contraction coefficient (Kp) is affected by shape and thickness of the pier,
design head over on the ogee spillway (Hd) and approach velocity (Va). In the
situation where the water pass over the ogee with design head (Hd), pier contraction
coefficients (Kp) can be taken as below:
For square-nosed piers with rounded corners, Kp=0.02
For round-nosed piers, Kp=0.01
For pointed-nose piers, Kp=0.00
Abutment contraction coefficient (Ka) is affected by shape of the abutment, the
angle between wall of abutment and axis of the flow, relation between radius of
abutment (r) and design head (Hd) and approach velocity (Va). In the situation where
the water pass over the ogee with design head (Hd), abutment contraction
coefficients (Ka) can be taken as below:
For square abutments with headwall at 90o to direction of flow, Ka=0.20
For rounded abutments with head wall at 90o to direction of flow when 0.15* H d ≤ r
≤ 0.5* Hd, Ka=0.10
For rounded abutments where r > 0.5* Hd and head wall is placed to direction of
flow not more than angle of 45o, Ka=0.00
Experimental Setup
Ogee spillway has P=28 height is placed on an open channel which is 650 cm long,
30 cm wide and 50 cm high. The flow on the channel is provided by two pumps
with 7.5 kW connected parallel to the system. Two pumps provide discharge in a

range from 0 lt/s to 40 lt/sn. Discharge is adapted by a frequency convector which

connected to pumps. Discharge is measured by an electromagnetic flow meter which
placed on the main pipe. The pumps take water from Reservoir-1 send to Reservoir-
2. After reaching a certain level in Reservoir-2, water pass to channel and reach
Reservoir-1 again. In this way, the system operates in recirculation (Figure 3.).
Reservoir-2
Reservoir-1
Figure 3. Open channel system used in experiments

In the experimental study, experiments were carried out on the ogee spillway for
free flow without piers firstly. The effect of the piers on the net crest length (L’) was
investigated by comparing data obtained from the free flow and flow with piers. 3
piers were used in each of the experiment sets. Total head (He) and corresponding
discharge (Q) values were measured. Total head was measured by limnimetre.
Approach velocity of water to upstream side of piers was accepted V a=0 m/s.
Therefore, the energy height of approach velocity Ha=0 m. The set of experiments
are listed and shown below with Figure 4.
a) 3 Circular Piers with D=1 cm b) 3 Square Piers with B=1 cm

c) 3 Circular Piers with D=1 cm d) 3 Square Piers with B=1 cm

Figure 4. Experimental setups
All data obtained from 5 experimental setups are shown in Figure 5. When circular
and square cross sectional piers with a width of 1 cm and 2 cm are compared, the
piers have circular cross section have more efficient discharge (Q) release at same
total head (He) more than square cross section piers. This is an expected result.
Figure 5. Data obtained from piers have different sizes and cross-sections
However, the discharges (Q) values are calculated by Formula-2 (USBR 1987) with
same total heads in the experimental setup for each sets (Figure 7 ÷ Figure 10), there
is 10%-15% percent of difference occurs between theoretical and experimental
discharges.
The percent of discharge difference between theoretical and experimental studies is
around 11% in the square cross sectional piers. This differences increased percent of
15% in the circular cross sections. This is due to the fact that the piers with circular
cross section are efficient in discharge, but the theoretical calculation cannot
calculate this efficiency well enough.

Figure 7. Comparison of experimental and theoretical calculation of discharges for

3 circular piers having D= 1 cm diameter

3 square piers having B= 1 cm size of edge

3 circular piers having D= 2 cm diameter

3 square piers having B= 2 cm size of edge
Conclusions
In this study, an ogee crested spillway was used in the laboratory and bridge piers
were placed on it and experimental studies were done for 5 different conditions. The
results obtained from experimental studies were compared with the theoretical
calculations. This comparison shows that the theoretical calculations give discharge
values under estimated than in real life.
References
United States Department of The Interior Bureau of Reclamation 1987, Design of
Small Dams, Unites State of America
Yarnell, DL 1934, Bridge Piers as Channel Obstraction, United States Department
of Agriculture, Washington DC
Barbhuiya, AK 2003, ’Measurement of turbulent flow field at a vertical semicircular
cylinder attached to the sidewall of a rectangular channel’, Flow
Measurement and Instrumentation, vol.15, pp.87-96.
Khosronejad, A, Kang, S & Sotiropoulos, F 2012, ’Experimetal and computational
investigation of local scour around bridge piers’, Advances in Water
Resourches, vol.37, pp.73-85

Appendix-Data obtained from experimental setups

FREE FLOW 3 CIRCULAR 3 SQUARE 3 CICULAR 3 SQUARE
He
WITHOUT Q PIERSHeD=1 CM
Q PIERSHB=1e Q
CM PIERSHD=2e CMQ PIERS HeB=2 CM
Q
1 PIERS
1.52 1.10
(cm (lt/sn 1 (cm) 2.20 (lt/sn
1.76 1 1.29
(cm 0.72
(lt/s 1 1.63 0.75 1 (cm)
(cm (lt/sn 0.96 0.41
(lt/s
2 2.28) 1.98
) 2 2.95 2.76 ) 2 2.30) 1.79
n) 2 2.27 ) 1.6
) 2 2.46 1.70 n)
3 2.76 2.68 3 3.21 3.11 3 2.36 1.88 3 2.87 2.29 3 2.57 1.79
4 3.37 3.57 4 4.20 4.81 4 3.00 2.73 4 3.51 3.15 4 3.25 2.64
5 3.84 4.48 5 5.03 6.50 5 3.61 3.68 5 4.22 4.27 5 4.05 3.77
6 4.23 5.20 6 5.52 7.54 6 4.10 4.51 6 4.7 5.15 6 4.56 4.57
7 4.70 6.11 7 6.12 8.86 7 4.54 5.29 7 5.13 5.94 7 5.05 5.40
8 5.03 6.79 8 6.36 9.39 8 4.95 6.06 8 5.22 6.06 8 5.45 6.13
9 5.41 7.67 9 6.64 10.08 9 5.32 6.88 9 5.56 6.75 9 5.90 6.97
10 5.84 8.64 1 6.83 10.59 10 5.64 7.55 10 5.88 7.45 1 6.24 7.70
11 6.09 9.27 10 7.10 11.28 11 5.98 8.29 11 6.22 8.2 10 6.59 8.42
12 6.23 9.66 1 7.52 12.38 12 6.17 8.73 12 6.54 8.86 1 6.78 8.83
13 6.38 10.02 12 7.90 13.45 13 6.34 9.11 13 6.68 9.2 12 7.00 9.30
14 6.50 10.34 13 8.24 14.42 14 6.46 9.42 14 6.84 9.55 13 7.31 10.0
15 6.63 10.69 14 8.58 15.39 15 6.61 9.78 15 7.15 10.3 14 7.48 10.4 5
16 6.75 11.00 15 8.90 16.40 16 6.71 10.0 16 7.34 10.7 15 7.70 10.9 3
17 6.90 11.40 16 9.30 17.75 17 6.86 10.3 4 17 7.5 11.1 8 16 7.90 11.4 6
18 7.35 12.53 17 9.68 18.85 18 6.96 10.6 7 18 7.66 11.5 5 17 8.04 11.7 4
19 7.45 12.90 18 9.82 19.35 19 7.11 11.0 5 19 7.87 12.1 9 18 8.35 12.7 8
20 7.58 13.29 29 9.98 19.85 20 7.32 11.5 0 20 8.16 12.8 3 29 8.59 13.1 0
21 7.70 13.67 20 10.3 20.92 21 7.52 12.0 9 21 8.32 13.3 5 20 8.93 14.1 9
22 7.80 13.92 1 0 22 7.73 12.6 6 22 8.83 14.7 5 21 9.15 14.6 1
23 7.90 14.23 23 7.95 13.1 7 23 9.04 15.3 2 9.36 15.2 7
24 8.00 14.53 24 8.14 13.6 6 24 9.25 15.8 23 9.55 15.8 4
25 8.10 14.83 25 8.49 14.6 3 25 9.44 16.4 7 24 9.76 16.3 0
26 8.20 15.11 26 8.83 15.5 7 26 9.64 17 3 25 9.95 16.9 7
27 8.28 15.39 27 9.05 16.2 5 27 9.82 17.5 26 10.1 17.5 3
28 8.37 15.68 28 9.25 16.8 7 28 10.0 18.1 3 27 10.3 6 18.1
0
29 8.46 15.96 29 9.61 17.9 1 29 10.12 18.6
3 28 10.5 6 18.6
0
30 8.56 16.27 30 9.80 18.4 1 30 10.58 19.7
6 39 10.8 3 19.1
0
31 8.64 16.56 31 10.0 18.9 1 31 10.83 20.7
3 30 11.0 0 19.6
3
32 8.72 16.81 32 10.1
0 19.5
8 7 7 31 11.10 20.2
7
33 8.81 17.09 33 10.3
5 20.0
1 2 4 0
34 8.89 17.39 2 1
35 9.00 17.64
36 9.15 18.19
37 9.31 18.72
38 9.47 19.25

MANAGEMENT STRATEGIES APPLIED IN WATER STATIONS USED IN

THE FOOD INDUSTRY IN ORDER TO INCREASE THE QUALITY OF
THE BIOGAS
Daniela Angela Buzoianu, Casen Panaitescu
Petroleum-Gas University of Ploieşti, Bvd. Bucuresti, No.39, Ploiesti, Prahova, cod. 100680,
Romania, danielabuzoianu@yahoo.com, cpanaitescu@upg-ploiesti.ro, Romania
Abstract
Reducing the costs of wastewater treatment plants in the food industry is a necessity.
Thus, it is necessary to find solutions to make their operation more efficient. The use
of biogas obtained in the production process is a variant that leads to the increase of
the profit at the whole plant level. This is how the Balance Scorecard model was
used. The use of this model was based on non-financial indicators. These were:
biogas quality and wastewater indicators from the UASB reactor that ensures biogas
quality.
Keywords: anaerobic reactor, Balance Scorecard, sludge
Introduction
Waste water treatment in the food industry is one of the current problems in the field
of industrial wastewater treatment. Achieving the purification process in the context
of continuously changing raw materials in the food industry is one of the most
difficult issues (Deublein et al 2008). The introduction of new compounds that
provide additional oxygen supply leads to the destabilization of the purification
process and therefore of the anaerobic reactor.
In this paper, the management of the wastewater treatment plant from the beer
industry was studied through a direct connection between the parameters followed in
the treatment station and the Balance Scorecard concept. This notion aims not only
to streamline the process of purification, increase the quality of the biogas and reuse
it in the process of beer production. The use of the physical-chemical indicators of
industrial wastewater in the management of the treatment plant was achieved by
developing the interdependence between them, used for the technical-economic
optimization of both the purification process and the beer production process.
This is how the Balance Scorecard model is used, which is very often used in
management (Robert et al 2000). The non-financial indicators are thus extrapolated
to the station level by choosing the quality of the biogas and the wastewater
indicators that ensure the quality of the biogas. This ensures the profitability of the
treatment plant which under normal conditions is a large consumer of funds
allocated for environmental protection by the factory to which it belongs (Al Seadi
et al 2013, Nam et al 2018).


The anaerobic purification process takes place in a UASB reactor. The reactor has a
biomass load from anaerobic microorganisms. The waste water from the brewing
process is introduced into the reactor. Exit from the reactor results in purified waste
water and biogas. To separate the biogas at the top of the reactor there is a three
phase separator. The biogas is washed at the top in a scrubber for disposal CO2 and
H2S. The diagram of the installation is shown in Figure 1 and Figure 2.
Figure 1. Description of the wastewater treatment process
Figure 2. Scruber details
The continuous measurement of the pH value in water contributes to its regulation in

order to ensure the conditions necessary for bacterial degradation. In normal cases a pH
of 6.8 is expected.The continuous measurement of the temperature value in water
contributes to its regulation in order to ensure the conditions necessary for bacterial
degradation. Typically, the temperature range of anaerobic reactors is between 25-39oC.
Volatile fatty acids are the substrate for methane bacteria and under normal operating
conditions the VFA concentration is less than 2-5 meq / l in anaerobic effluent.
The production and composition of the biogas offers real and immediate information
about the operation of the treatment plant, being in direct connection with the CCO
transformed into the plant. Dividing this number (expressed as transformed CCO)
into the total CCO loading of the system, calculated as flow or CCO concentration,

results in the rate of purification of gas production. Biogas production also provides
information on biomass activity.
Knowing the total volume of biogas, one can calculate the energy released by
burning it. Then using the price value for one MW of energy sold by national
distributors for industrial consumers we can calculate the costs saved by using this
biogas plant.
The formula is used (Deublein et al. 2008):
(1)
where E is the energy (kWh), Vb is biogas volume (Nm3), PCS is the superior
calorific power (kW/m3).

Anaerobic scrubbing removes approximately 75-80% of COD load and 350-400
litters of gas per kg COD is obtained.
Biogas consists largely of methane (60-90%) and carbon dioxide (10-40%). Most of
the organic matter anaerobic degradation is transformed into biogas, a relatively
small part is transformed into new cellular material.
The production and composition of biogas provides real and immediate information
about the operation of the WWTP, being directly related to the CCO transformed
into the installation. By dividing this number (expressed as converted CCO) to the
total CCO load of the system, calculated as flow or concentration of CCO, the gas
purification rate results. Biogas production also provides information on biomass
activity.
Real VFA means the sum of the current concentrations of weak fatty acids such as:
acetic, propionic and butyric acid. A higher concentration in the anaerobic effluent
indicates that the process is overloaded. All fatty acids are determined by the
titration method. At the same time, the analyzes confer the alkalinity (pH capacity)
of the effluent. During unstable conditions, the alkalinity will decrease and the VFA
concentration will increase. The higher the alkalinity, the higher the resistance to ph
fluctuations. Alkalinity is expressed in milliequivalents of bicarbonate per liter (meq
/ l).
If the high concentration of VFA continues or worsens, the first action to be taken is
to reduce the wastewater flow until the process parameters are again within normal
limits. If the station is well operated, moderately charged, biogas production will
increase as soon as the CCO load is increased. If this does not happen it means that
the station is already operating at the maximum possible biomass load at that time. It
may also indicate that the biomass is not kept under optimal conditions or the
amount of biomass present in the system may be too low. In both cases the
concentration of volatile fatty acids in the anaerobic effluent will increase and this is
a sign that the system is overloaded.
Knowing the variations of gas consumption characteristic of a beer factory, we can
conclude that the biogas production and exploitation plant cannot be a guiding
element of the process. The main objective during the operation of the boilers is to
provide the quantity of steam required for the production of beer at the set pressure

values. It is desirable that biogas consumption values be maximized but this can
only be done by optimizing biogas availability. The next challenge was to optimize
the installation and increase the volume of biogas burned in the boiler. A pressure
sensor is mounted on the blower suction pipe, which reads the instantaneous
pressure and transmits the information to a controller. Upon reaching the pressure of
400 mbar the controller activates a three-way valve by diverting the biogas route to
the facla. This value of 400 mbar was chosen for the safety reasons of the
equipment, because at values greater than 400 mbar the buffer vessel constructed of
deformable plastic material was in danger of explosion.
From the four perspectives of BSC, the perspective of internal processes was
chosen, namely the quantity of biogas that was consumed in May 2019. For the
implementation of BSC, a logical scheme was developed.The logical scheme of the
Balanced Scorecard is shown in Figure 3.
Figure 3. The logical scheme of the Balanced Scorecard
A more accurate picture of gas consumption can be seen in Figure 4 daily total gas
consumption and biogas consumption in May 2019. Daily consumption has close
values, on average 14500 m3 per day with a maximum of 17300 m3 and a minimum
of 10100 m3. Biogas consumption remains constant, on average 1650 m3 per day
(Figure 5).
Figure 4. Boiler gas consumption in May 2019

Figure 5. Biogas percent from gas consumption in May 2019
Boiler gas consumption in May 2019 shows the percentage of biogas from the total
gas consumed by the boiler in May 2019. The percentage remains on average at a
value of 13.5% with peaks over 20% and minimums below 5% at the beginning of
the month.
As biogas consumption has been tracked for several years, a price value for MWh of
29 Euro is chosen, an average of the price for industrial consumers in these four
years. The final value also adds a 19% VAT. Excise duties on gas are not taken into
account. For E=9408000kWh results after applied equation (1) the value for
burning natural gas mix with biogas: 324670 Euro/year.
Knowing that the investment in the design, construction and equipment works was
about 200,000 Euro we can say that it was amortized and in the end the company
made a profit of 124670 Euro. Even if from this the amount is reduced the cost with
the replacement of the boiler economizer, which stood between 50,000 Euro and
100,000 Euro the company still remains in the profit area.
Conclusions
The case study from the present paper shows that a treatment plant equipped with a
UASB reactor type anaerobic biological treatment stage can produce enough biogas
to supply 4.1% of the total gas requirement of a brewery. It has been demonstrated
the capacity of a biogas production and exploitation facility to be economically
efficient under real operating conditions in which the occurrence of operating
defects and errors is inevitable and must be taken into account.
The installation was stopped for long periods of time, totaling about 14 months out
of the four years of operation. Also, the discontinuous operating mode of the steam
boiler did not favor the consumption of biogas, the optimization attempts by using
the Balanced Scorecard increased the availability for the consumption of the biogas.
However, the total cost saved by burning the biogas was 324670 Euro/year. The
initial investment was amortized in three years.
The processing of the by-products of the food industry for the production of biogas
is a real alternative for increasing the profit of an enterprise and offers a friendly
solution with the environment and the efficiency of solving the problem of waste.

References
Al Seadi, T, Rutz, S & Rainer, J 2013, Biomass resources for biogas production,
Woodhead Publishing Limited, Cambridge, pp. 20-32
Deublein, D & Steinhauser, A 2008, Biogas from Waste and Renewable Resources,
WileyVCH Verlag GmbH & Co. KGaA, Weinheim, pp. 257-311
Nam, ND, Panaitescu, C, Tan, MYJ, Forsyth, M & Hinton, B 2018, ‘An interaction
between praseodymium 4-hydroxycinnamate with AS1020 and X65 steel
microstructures in carbon dioxide environment’, Journal of the
Electrochemical Society, vol. 165, no.2, C50-C5
Robert, SK & David, PN 2000, The Strategy-Focused Organization. How Balanced
Scorecard companies thrive in the new business environment, Harvard
Business School Press, pp. 279-301

MULTI-FUNCTION BIOSYSTEM BASED ON ARTHROSPIRA PLATENSIS

FOR SPACE APPLICATIONS
Gabriela Soreanu1*, Igor Cretescu1, Mariana Diaconu1, Maria Ignat2,3, Valeria Harabagiu2,
Corneliu Cojocaru2, Petrisor Samoila2
1
“Gheorghe Asachi” Technical University of Iasi, “Cristofor Simionescu” Faculty of Chemical
Engineering and Environmental Protection, Department of Environmental Engineering and
Management, 73 D. Mangeron Blvd, Iasi 700050, Romania, gsor@tuiasi.ro
2
“Petru Poni” Institute of Macromolecular Chemistry Iasi - Romanian Academy, 41A Grigore
Ghica Voda street, Iasi 700487, Romania
3
“Alexandru Ioan Cuza” University, Faculty of Chemistry, Iasi, Romania
Abstract
This study presents an introduction in air revitalisation practice by using a
microalgae-based biosystem. Althrough the study is developed in the light of space
applications, it opens new horisons for implementing such systems for terestrial
applications as well, where biotechnologies for addresing climate change and other
issues associated with air pollution is in high demand. The experiments have been
performed at laboratory-scale by using Arthrospira (spirulina) platensis as
microalgae model. Influence of culture and illumination conditions, as well initial
gas composition and other factors/techniques such culture filtration on the biosystem
performance were investigated and the relevant results are presented and discussed.
Based on the actual findings, future research needs are addressed.
Keywords: Arthrospira platensis, biosystem, earth, environment, space, spirulina
Introduction
This study re-brings to the forefront the photosynthesis, as a process well known
since long time ago, but still very actual due to the mechanism of the biomass
production at macro and micro-levels. Particularly, the microalgae development is
based on this process and presents a huge potential to be engineered for both earth
and space applications. Microalgae-based systems can be adapted for rehabilitation
of environmental factors (air, water), mitigation of climate change, as well life-
support in space and circular economy (Soreanu et al 2018, Caroling et al 2015).
Among the different available microalgae, Arthrospira (spirulina) platensis is one of
the best candidates for space-related applications. This microalga is able to perform
multi-tasking activities that support different applications: air revitalisation and
treatment (not only carbon dioxide removal and oxygen production, but also
removal of trace contaminants from air), wastewater treatment, development of
valuable biomass for different purposes (e.g. as food, cosmetic and therapeutic
ingredient, energetical valorisation) (Soreanu et al 2018, Juneja et al 2013).
The present study addresses some of the main aspects associated with A. platensis
consideration in the multi-function biological systems, from the recent findings to
the future research needs, highlighting the perspectives in air revitalization.

Influence of culture conditions (e.g. pH), illumination conditions (e.g. lighting

source), initial gas composition (e.g. single versus mixed gases) and other
factors/techniques such culture filtration (as part of bioreactor operation protocol) on
the biosystem performance were investigated and the relevant results are presented
and discussed.

Several experiments have been carried out in order to highlight the involvement of
the biological component in air revitalization and the benefits associated with this
process in the light of sustainability.
Conditioning air has been treated in a laboratory-scale sparged photobioreactor, by
using Arthrospira (spirulina) platensis (Algae Research Supply) as a microalgae
model. The photobioreactor was designed from a cylindrical column made in
plexiglass (5 L culture capacity) and was equipped at the top with pH and
temperature sensors coupled to a monitoring device (Vernier, model LABQUEST2).
The processed air was fed into the nutrient solution at the bottom of the reactor via a
medium bubble diffuser and the treated air was evacuated at the top. The nutrient
solution consisted in a Zarrouk’s medium free of NaHCO3/NaCl, prepared from a
stock concentrated solution (ALGOID Technol.) and distilled water. For initial pH
adjustment (e.g. up to 10), a NaOH solution was added (an auto-buffering effect was
further installed around the set pH). Except some relative short tests carried out to
evaluate the system response under different experimental conditions, the reactor
was operated continuously for few months at about 40050 ppm CO2 and 0.5 L/min.
An air pump (Tetra, model APS 100) was used for air supply and the flowrate was
controlled by a flowmeter (Cole-Parmer, model PMRI-010919). Distilled water was
added for compensating the water evaporation from the culture and the occasional
samplings. The experiments were carried out at 2 Klux light intensity, assured by
different illumination sources (described in next section). A digital luxmeter
(Extech, Light Meter LT300) was used for the measurement of the light intensity.
For a better light control, an aluminum folium was installed at a certain distance
around the reactor.
A peristaltic pump (BETA Technology) and a micro-drip-system (GARDENA,
model 1354-20) additionally equipped with a specific filtering material
(polyester/polyamide –based microporous membrane, reusable) was used for culture
filtration test at 0.1 L/min.
The synthetic gas mixture used in additional tests was prepared in 160 L plastic bags
by mixing conditioned air with standardized gas from the commercial cylinder
(1500 ppm NO2/bal. synthetic air, Messer) and synthetic ammonia (obtained from
concentrated NH4OH solution). The obtained gas mixture was further diluted with
conditioning air as carrier gas up to the desired concentration.
Biosystem performance has been assessed by monitoring the composition of the
processed gas in inlet and outlet ports of the bioreactor. The AQ-Expert (E
Instruments, USA) multifunctional indoor air monitoring monitor and the APNA370
(Japan) have been used in this regard (e.g. CO2/O2 and NOx/NH3 analysis,
respectively).
Biomass development was evaluated via a pre-established method for estimation of
biomass concentration as a function of the turbidity, where turbidity was measured
with a Hach DR/2000 spectrophotometer (Soreanu et al 2018).
Performance in air revitalization was expressed in terms of removal efficiency (RE,

%) and elimination capacity (EC, gm-3d-1) (Soreanu et al 2018).
Table 1. Performance criteria
Criteria Equations Terms

RE, % (cIN-cOUT)100/cIN (1)
cIN = inlet concentration
LR, gm-3d-1 cINFv/V (2) cOUT = outlet concentration
Fv = air flowrate
EC, gm-3d-1 (cIN-cOUT)Fv/V (3) V = culture volume

Influence of pH and illumination conditions on system performance
A. platensis is one of the few microorganisms that are able to grow under high
alkaline conditions. This particular condition can be used as a strategy against
biological contamination (Soreanu et al 2018). Moreover, it is known that
microalgae development depends on the illumination conditions (light source, light
intensity, light spectrum), which are key aspects to be considered in the
photobioreactor design for a specific purpose.
In this study, the system performance has been evaluated in terms of CO 2 removal
efficiency at pH 8 and pH 10. As can be seen in Figure 1, the system performance
was favoured at pH 10, although the system still performs at pH 8, without being
suppressed. In practice, it should be thus important to consider the system operation
at pH above 8, especially when a risk in pH drop is envisaged (e.g. due absorption of
acid gases at high concentrations). Overall, pH value can favour or affect the
retention of certain contaminants in the culture and thus their availability to the
microalgae, at a rate that is subject to the contaminant type, culture salinity, gas
concentration, gas flowrate etc. Some of such aspects are described (Juneja et al
2013).
Also, the system response to several illumination conditions has been evaluated, as
it is shown in Figure 1. For instance, white-like light sources have been considered
for evaluation, such as: fluorescence lamp, LED lighting tube (2m), natural light.
One side illumination was applied when using the fluorescence lamp. For the
experiments with LED tube, two reactor configurations have been evaluated (for the
same tube size): one with external tube (around the reactor) and one with immersed
tube (into the reactor). Except for the test with natural light, an aluminium folium
was used around the reactor in order to avoid the light dissipation and to simulate a
natural light fond under controlled conditions. In contrast to the artificial light that
was continuously provided, the natural light implicitly involved a night/day
illumination regime. The most favourable effect on CO2 removal efficiency was
observed for the Ext. LED tube, followed by the FL lamp. The favourable effect
could be attributed to the better light distribution around the reactor. The use of Int.
LED tube didn’t enhance the system performance, probably due to a photoinhibition
phenomenon or the excessive heating of the culture (e.g. slightly above the optimum
temperature of 35 °C) (Jimenez et al 2011). Some aspects concerning the
mechanism of these phenomena are described in (Juneja et al 2013). Moreover,
switching for natural light conditions (including night/day regime) drastically
affected the system performance in terms of CO2 removal performance (e.g. values
below 5% have been recorded). Further returning to appropriate artificial
illumination conditions resulted in a fast recovery (e.g. about one day) of the initial
performance (results not shown). This behaviour indicates that the biological
component is able to adapt to stress conditions via a metamorphosis physiology.
70
RE, %
60
50 Ext. LED tube

FL
40
30 Int. LED tube

FL
20
10
Nat
0
8 10 10 10 10
pH
Figure 1. Influence of pH and illumination conditions on RECO2, observed at the

same biomass concentration (c biomass= 0.6 0.1 g/L); FL = fluorescence lamp (2 K);
Ext. / Int. LED tube = external/immersed LED tube (2 m, 2 K); Nat = natural light
fond (day/night regime)
Taking into consideration that the shading effect increasing due biomass
development can limit the system performance, the next step is to determine the
influence of the illumination factor on the performance of the system equipped with
Ext. LED tube. For such configuration, this term could be defined as:
Illumination factor = Light amount*/biomass concentration (g/L) (4)
*expressed as LED tube size
Preliminary tests indicates that the illumination factor can play an important role in
the system performance and enhanced performances can be obtained (results not
shown).
Influence of culture filtration and recycling on the biosystem performance

A comparison between the system performance at the same biomass concentration
with new and recycled culture (after filtration) on the system performance in terms
of CO2 removal is presented in Figure 2. It can be seen that at the same biomass
concentration, the system exhibits quite similar performance in both cases, which
indicates that this technique could be considered as part of the bioreactor operating
protocol on a regular basis. When applied to an older concentrated culture exposed
to shadding effect with affected performance, this technique can reabilitate the
system (e.g. performance doubling). For the proposed technical solution, filtration
efficiency above 90% can be obtained and biomass recovery is easy (results not
shown). Such perfomance is in agreement (Drexler & Yeh 2014) that show the
advantages and the disadvantges of different methods used for biomass harvesting.
The favourable effect of the filtration can be explained by the retention of the
mature cells, while the recycling of the obtained permeate allow returnig the
nutrients in the culture and the enhancing of the illumination factor (refreshing
effect). Next step is to establish the filtration frequency, which should be also
correlated with the illumination factor as well. Also, biomass valorisation options
(Soreanu et al 2018, Juneja et al 2013) should be addressed as a complementary
benefit associated with the investigated biosystem.
70
RE, % 60
50
40
30
20
10
0
New culture Recycled culture
(after filtration)
Figure 2. Comparison of RE obtained with a recycled culture (after filtration) versus

that obtained with a new culture (Ext. LED tube illumination), observed at the same
biomass concentration (c biomass= 0.6 0.1 .g/L)
Influence of gas composition on the system performance

CO2 is always present in indoors, being one of the indoor air quality indicators
(Soreanu et al. 2018). In addition, traces of other gases can be detected in indoors,
among NOx and NH3, but not limited to. In this study, the performance of the system
in treating indoor air containing CO2 was compared with the performance of the
system in treating a synthetic gas mixture containing CO2 (420ppm) and traces of
NOx (25 ppb) and NH3 (25 ppb) (balance air), which are in the range of acceptable
levels for indoor air (e.g. WHO 2005, Honne et al 2014, Bonino 2016, Jarnstrom &
Saarela 2002). The performance in CO2 removal (considered as a relevant
benchmark in system development) was not affected by the the presence of other
contaminants in air (Figure 3). Moreover, a significant reduction is observed in the
case of NOx, while NH3 was only slightly diminushed. For instance, the alkaline
conditions could favour the NO2 uptake via physical process (as a pre-step in NO2
uptake), but not the NH3 uptake, which can explain the obtained performances (e.g.

EC for CO2, NO2 and NH3: 43.03, 0.0055 and 0.00077 gm-3d-1, respectively). The
oxygen content in the processed air was not affected by the biological process.
The presence of such NOx traces in the processed indoor air could supply a part of
the required nutrients for microalgae development under indoor conditions. Based
on preliminary results (results not shown), an increase in CO2 concentration above
ambiental limits is associated with an increase in nutrients consomption rate, thus
the system becomes faster deprivated in nutrients at a demanding overcoming the
availability of NOx in indoor air. Other studies (dedicated to flue gas treatment)
highlighted also the potential of various microalgae in the removal of contaminants
such as NOx and CO2 (e.g. Giordano & Wang 2018).
600
Conc.
500
INLET
400 OUTLET
300
200
100
CO2, ppm NOx, ppb NH 3, ppb
Figure 3. Example of indoor air pollutant diminushing* by the microalgae system

(FL illumination). *other performances may apply, subject to system conditions
These observations offer a promising perspective for further development of a multi-

function biosystem based on microalgae in order to be particularly integrated in
closed environments such as spacecrafts cabins.
Conclusions
The screened bioprocess with Arthrospira (spirulina) platensis as microalgae model
exhibits promising performances for air revitalization in closed environments such
as spacecrafts cabins. The proposed bioprocess is sustainable, with forecasted
benefits for both space and terrestrial applications. Based on the actual findings in
this study, future research needs are addressed.
This investigation is being carried out within a RDI project funded by Romanian
Space Agency (ROSA) and could present a special interest for different specialists
acting in the field (e.g. biologists, chemical and environmental engineers etc. from
the universities, research centers, other space agencies, environmental agencies etc).
Acknowledgements
This work is supported by ROSA (Romanian Space Agency) - RDI Program for Space
Technology and Advanced Research - STAR, project no. 157/2017.

References
Bonino, S 2016, Carbon Dioxide Detection and Indoor Air Quality Control,
available from: https://ohsonline.com/articles/2016/04/01/carbon-dioxide-
detection-and-indoor-air-quality-control.aspx
Caroling, G, Vinodhini, E, Ranjitham, M & Shanthi, P 2015, ‘Biosynthesis of copper
nanoparticles using aqueous Phyllanthus Embilica (Gooseberry) extract -
Characterization and study of antimicrobial effect’, International Journal of
Nanotechnology and Chemistry, vol.1, no.2, pp.53-63.
Drexler, ILC & Yeh, DH 2014, ‘Membrane applications for microalgae cultivation
and harvesting: a review’, Review in Environmental Science and
Bio/Technology, vol.13, pp.487–504.
Giordano, M & Wang, Q 2018, Microalgae for Industrial Purposes. Chapter 6, In:
Biomass and Green Chemistry, S. Vaz Jr. (ed.), Springer International
Publishing AG. S. Vaz Jr. (ed.): 133-167, available from:
https://doi.org/10.1007/978-3-319-66736-2_6
Honne, A, Schumann-Olsen, H, Kaspersen, K, Mosebach, H & Kampf, D 2014, ‘Air
quality monitoring for the International Space Station applicable to aircraft
cabins and cockpits’, Journal of Biological Physics and Chemistry, vol.14,
pp.94–102.
Jarnstrom, H & Saarela, K 2002, ‘Indoor air quality and material emissions in new
buildings’, Proceedings: Indoor Air 2002, pp.201-206.
Jimenez, C, Belen, R, Coss, R & Xavier, NF 2011, ‘Relationship between
physicochemical variables and productivity in open ponds for the production
of Spirulina: A predictive model of algal yield’, Aquaculture, vol.221, pp.331-
345.
Juneja, A, Ceballos, RM & Murthy, GS 2013, ‘Effects of environmental factors and
nutrient availability on the biochemical composition of algae for biofuels
production: A review’, Energies, vol.6, pp.4607-4638. doi:10.3390/en6094607
Soreanu, G, Cretescu, I, Diaconu, M, Ignat, M, Harabagiu, V, Cojocaru, C &
Samoila, P 2018, ‘Monitoring of CO2 uptake by microalgae in indoor
environment’, In: GLOREP 2018 Conference Proceedings, Politehnica
Publishing House (Global and Regional in Environmental Protection
Conference), 15-17 November, Timisoara, Romania, pp.255-259.
World Health Organization WHO 2005, Air quality guidelinesf or particulate
matter, ozone, nitrogen dioxide and sulfur dioxide, Global update 2005.

NEW MATERIALS FOR REMOVING NITRATE, MANGANESE AND

IRON FROM GROUNDWATER
Liliana Bobirica, Cristina Modrogan, Constantin Bobirica, Oanamari Daniela Orbulet *,

Madelene Annette Dancila, Cristina Orbeci
Analytical Chemistry and Environmental Engineering Department, Faculty of Applied

Chemistry and Materials Science, University Politehnica of Bucharest, Polizu 1-7, Bucharest,
*oanamari2001@yahoo.com, Romania
Keywords: adsorption, iron, EDTA/magnetite, magnetite, manganese, nitrates
Introduction
Classical methods used to remove pollutants from groundwater are known to be

generally expensive and with a high potential to generate by-products or waste. In
this respect, an increasing attention has been paid to obtaining, characterization and
testing of new environment-friendly materials and technologies that can be
successfully applied in groundwater treatment without a negative impact on them.
The removal of nitrate, manganese and iron from groundwater using clean
technologies is an example in this area.
Iron is one of the most abundant metals in the Earth’s crust and it is generally found
together with manganese. These are used widely in many applications like primary
cells, alloys industry, ceramics, electrical coils, etc. Above specific levels, iron and
manganese can pose an unfavourable impact to both the environment and human
beings (Nuratiqah et al 2018, Zhanga et al 2019, Bacquart et al 2015, Yang et al
2019). Both iron and manganese ions are found in surface and groundwater at
fluctuating concentration levels. They give water a metallic taste and serve as
substrates for the growth of bacteria in water mains. They are also present in the
atmosphere as suspended particulates due to its disposal from different sources like
industrial emission and soil erosion (Shafiquzzaman 2017, Nasir et al 2019).
Several techniques were employed for the pollution abatement with metal ions in
water which include adsorption (Nasir et al. 2019), chemical precipitation (Štembal
et al 2005), ion exchange (Cheng et al. 2017), biosorption (Li et al 2019), membrane
filtration (Vries et al 2017), coagulation-flocculation (Du et al 2017), and flotation
(Stjepanović et al 2019). Many of these techniques have disadvantages. For
example, precipitation can be considered as the most economical valid, but
additional treatment is required due to the production of precipitate sludge. Reverse
osmosis, ion-exchange, and other membrane separation techniques can efficiently be
used in metal ions removal, but there are limitations in the use of these techniques
such as expensive materials and high functional cost.
The iron based nanoparticles such as magnetite (γ-Fe2O3) and magnetite (Fe3O4)
have gained increasing attention due to their unique chemical properties resulting
from different iron oxidation states. The simplicity with which these nanoparticles
are prepared and the stability they provide are also important aspects that have
contributed to the popularity of these materials. Both of them have the ability to
adsorb chemical species through physical and chemical mechanisms. Recently, the
iron based nanoparticles have been subjected to functionalization with different
organic molecules in order to improve their performances such as colloidal
dispersibility and adsorption capacity for different chemical species.
The increased NO3- concentration in public water supplies presents a potential health
hazard due to the nitrites reduction in the gastrointestinal tract. In its turn, NO 3- is a
potential health hazard to infants (Fish 2009, Djouadi Belkadaa 2018) and pregnant
women due to NO3- reduction to NO2- , in the infants stomach, which can bind with
the hemoglobin of the affected babies, thus diminishing the oxygen transfer to the
body’s cells resulting in a bluesh skin color often called methemoglobinemia or “the
blue baby syndrome” (Zhang et al 2018, Clague et al 2019).
Therefore, the objective of this work was to obtain, characterize and test a
functionalized magnetite that could be effective, both economically and technically,
in the treatment of groundwater containing manganese, iron, and nitrates. Thus, the
experiments have focused on materials like magnetite (Fe3O4) and
ethylenediaminetetraacetic acid (EDTA)/magnetite (Fe3O4).
Materials and methods

Preparation of Fe3O4 and Fe3O4/EDTA
The chemical reagents used for the synthesis of EDTA-functionalized Fe3O4
nanoparticles were iron (II) sulphate (Merck), iron (III) chloride hexahydrate
(Aldrich), ammonium hydroxide solution of approximately 25% by weight (Merck),
and EDTA (Merck). The materials were synthesized by the co-precipitation method.
In this respect, Fe3O4 (FeO·Fe2O3) was obtained directly by the precipitation
reaction of Fe (II) and Fe (III) salts with concentrated ammonia without heat
treatment. In this respect, the required stoichiometric amounts of the two solutions
(FeSO4 and FeCl3), calculated to obtain 2.5·10-3 moles of Fe3O4, were introduced
into a reaction vessel. Subsequently, 15 mL of concentrated ammonia is added to the
reaction vessel with continuous stirring. The reaction mixture is stirred for an
additional 15 minutes until a black precipitate is obtained. The obtained precipitate
was immobilized at the bottom of the vessel by a magnet placed under the glass,
after which the solution above was removed. The precipitate was washed three times
with approximately 25 mL of distilled water until the complete removal of the
chloride ions, and then it was transferred to a pre-weighed watch glass to get dried.
After drying the yield of the magnetite production was determined. The presence of
chloride ions in the wash water was checked with silver nitrate solution.
In the second step, the EDTA-functionalized Fe3O4 nanoparticles were synthesized
by using the same procedure used for the synthesis of the Fe3O4 nanoparticles. In
this case, 50 mL of a 0.002 mol/L EDTA solution was added to the reaction vessel
soon after the ammonium hydroxide was added. The reaction mixture was stirred for
one hour at 50 °C, after which the precipitate obtained was washed three to four
times with approximately 25 mL distilled water until complete removal of chloride
ions. Finally, the precipitate was dried at 80 °C for three hours. The obtained
compositional formulations were characterized through TGA/DSC and Fourier
transform infrared spectroscopy (FTIR).
The experiments were carried out on two types of adsorbent materials namely Fe3O4
and EDTA/Fe3O4 at a mass ratio of 1 to 10. The granules size of the adsorbent
materials ranged from 0.001 to 1.5 mm. The adsorption experiments consisted of
contacting the adsorbent materials with nitrates, iron, and manganese aqueous
solution with a concentration of target species ranged from 5-100 mg/L for 2.5, 5,
10, 15, 20, 30, 40, 50, 60 minutes. At the end of each contacting time the sample
were filtered and measured for the species of concern.
Results and conclusions

Fe3O4 and EDTA/Fe3O4 characterization
The obtained materials were characterized by Fourier transform infrared
spectrometry (FTIR) and thermogravimetric (TGA). In this respect, the FTIR
spectra (Figure 1) show peaks for N-H (3228 – 3369 cm-1), C=O (1625 – 1628 cm-
1), C-N (1432 – 1433 cm-1), and C-NH (1111 – 1114 cm-1), and Fe-O (413 – 533
2
cm-1). The new peaks appearing in the EDTA/Fe2O3 spectrum, namely C-C (860 cm-
1), [N(-CH -) ] (971 cm-1), and (C-O) COOH (1369 cm-1) are attributed to the
2 3
functionalized EDTA molecule on the magnetic nanoparticles surface.
Comparative with the thermogram of Fe2O3 (Figure 2a), the thermogram of
EDTA/Fe2O3 (Figure 2a) shows three weight loss steps which could be also
associated with the presence of EDTA. The initial 3.07 % (Fe2O3) and 4.31%
(EDTA/Fe2O3) weight loss at temperature bellow 200°C is attributed to the
dehydration process. The weight loss between 200 and 500 °C, as can be seen in
EDTA/Fe2O3 thermogram, is attributed to the complete decomposition of EDTA
most probably through pyrolysis and oxidation. All these results suggest the EDTA
was successfully attached on the surface of magnetite nanoparticles.
Figure 1. FTIR spectra of Fe3O4 (a.) and EDTA/Fe2O3 (b.)
Figure 2. TGA for Fe3O4 (a.) and EDTA/Fe2O3 (b.)

Adsorption results
The results of the adsorption studies revealed that both the adsorption capacity and
the degree of removal of nitrates, manganese and iron from groundwater increased
sharply until a contact time of 10 minutes, after which both of them remained almost
constant (Figure 3).
Figure 3. Adsorption of manganese (a.), iron (b.), and nitrates (c.) on Fe3O4 and
EDTA/Fe3O4
The high rate of adsorption at the beginning of the process could be attributed to the
existence of a large number of adsorption sites on the surface of the adsorbent at the
beginning of the process. It can be observed that in all cases the equilibrium was
reached after approximatelly10 minutes when more than 95% of nitrate, manganese
and iron in the groundwater was removed. In terms of adsorption capacity
(corresponding to the 60 minutes of contact), Fe3O4 has an adsorption capacity for
manganese of 1910 mg/kg while, for the same metal, EDTA/Fe3O4 has an
adsorption capacity of about 2.5 times higher, namely 4703 mg/kg (Figure 1a). As
for iron, EDTA/Fe3O4 has an adsorption capacity of 2550 mg/kg, which comparative
with that for Fe3O4 (2030 mg/kg) is only 1.3 times higher (Figure 2b). The
adsorption capacity of Fe3O4 for nitrate is 2735 mg·kg−1 while, that of EDTA/Fe3O4
is 4703 mg·kg−1, of about 2.5 times higher (Figure 3c).
Conclusions
The objective of this work was to obtain, characterize and test an EDTA
functionalized magnetite for removing manganese, iron, and nitrates ions from
aqueous solutions similar to groundwater. The success of the synthesis of the new
material has been confirmed by FTIR and TGA analysis that revealed new
properties comparative with the basic material, namely magnetite. The adsorption
experiments revealed that EDTA functionalized magnetite has a much higher
adsorption capacity than magnetite, especially for manganese and nitrates.

Moreover, the high rate of adsorption of the three chemical species has been
highlighted. In this regard, about 95% of them were removed from the aqueous
solution in about 10 minutes.
Acknowledgments
This work has been funded by University Politehnica of Bucharest, through the “Excellence
Research Grants” Program, UPB – GEX 2017. Identifier: UPB- GEX2017, Ctr. No. 78/2017
Cod 136”.
This work has been funded by University Politehnica of Bucharest, through the “National
Grant” Program, UPB – GNaC 2018 ARUT. Identifier: UPB- GNaC 2018 ARUT, Ctr. No.
01/2018 Cod 32.
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REMEDIATION OF POPS POLLUTED SITES IN REPUBLIC OF

MOLDOVA
Tudor Lupascu, Oleg Bogdevich, Elena Culighin
Institute of Chemistry, Academiei 3, Chisinau MD-2028, lupascut@gmail.com, Republic of

Moldova
Abstract
Inventory of pesticide polluted sites in Republic of Moldova showed a huge number
of high polluted sites and large pollution spectrum. The identified sites need
effective remediation actions in order to diminish the risks for environment and
public health. Some demonstration projects on the remediation technologies have
been tested in the country.
Keywords: pollution, POPs, remediation, soil
Introduction
The ground beneath our feet is more precious than we know. Soil provides us with
95% of our food, hosts 1/4th of the world’s biodiversity and helps us combat and
adapt to the changing climate. Soil chemical composition is subject to external
factors such as wind, rains, evaporation.
Important pollution sources for the environment in the Republic of Moldova are old
pesticides storages. The MAC (Maximum Admissible Concentration) of POPs in
soil for agriculture land in Republic of Moldova is 0.1 mg/kg (Ministerul Ecologiei
si Resurselor Naturale 2004). This is a very restrictive level, but it excludes the
effects of pesticides bioaccumulation in crops.
The inventory of pesticide polluted sites showed a huge number of high polluted
sites (near 250) and large pollution spectrum (figure 1). More than 15% of the sites
were determined as extra high polluted sites where the POPs concentration is greater
than 50.0 mg/kg. the pollution spectra of those territories include such chemical
compounds as HCH (hexachlorocyclohexane) and DDT and its metabolites
(Bogdevich et al 2016).
Effective remediation actions are needed for the polluted sites with high risk for
environment and public health.
They include some of the world’s most harmful chemicals, including POPs (DDTs,
HCHs, Chlordane, Heptachlor, Toxaphene), PAHs (17 toxic substances), Triazines,
Trifluraline, and other old pesticides. The POPs degradation and microbiological
properties of contaminated soils have been investigated in the application of the
phytoremediation experiment (Bogdevich & Cadocinicov 2009) and DARAMEND
technology (Bogdevich et al 2013). Indices of the microbial biomass, counts of
culturable microorganisms (heterotrophic bacteria, actinomycetes and fungi) and
dehydrogenase activity have been determined by these experiments.
Also some laboratory tests were made for the use of carbonaceous sorbents for soil
remediation.

Figure 1. POPs contaminated sites in the Republic of Moldova
Experimental
GC and GC/MS equipment and international analytical methods (EPA, ISO, etc.)
have been used in the accredited by ISO 17025 laboratory for determinations of the
concentration of toxic substances in different environmental samples.
Based on previous investigation of POPs polluted sites, locations for remediation
experiments were selected in Balceana and Bujor, Hincesti district, for a more
detailed investigation.
The concentrations of organochlorine pesticides were determined by gas
chromatography (Agilent 6890 equipped with a μECD detector) following the
USEPA Method 8081A. The calibration interval was from 0.02 to 0.5 μg/ml. The
following pesticides or pesticide metabolites were analyzed in the samples: α-, β-,
and γ-HCH isomers, hexachlorbenzene (HCB), heptachlor, aldrin, dieldrin, endrin,
chlordane, DDE, DDD, and DDT.
Soil samples were taken from top soil, 0 - 20 cm. The samples were air-dried under
laboratory conditions of about 20°C, sieved through a 1.0 mm sieve, and
homogenized. Plant samples were dried in a drying box at 60°C. 10 gram of soil
subsamples and 1 – 2 g of plant tissue subsamples were extracted by Soxhlet system
for 14 hours. The solvent was a mixture of hexane and dichloromethane (1:1 by
volume), total volume of 150 ml.
The detection limit was 10.0 μg/kg for DDTs, aldrin, dieldrin, endrin, and chlordane
and 5.0 μg/kg for HCHs, hexachlorbenzene, and heptachlor. The maximal
admissible concentration (MAC) for pesticides in soil was considered to be 100
μg/kg based (or 0.1 mg/kg) according to national legislation (Ministerul Ecologiei si
Resurselor Naturale 2004).

Phytoremediation
The Balceana site was selected for the phytoremediation field experiment based on
two premises (1) it is a sufficiently large cultivatable area surrounding the site,
which is polluted by obsolete pesticides, primarily by DDTs and (2) the involvement
of the local community for planning and conducting the study appeared to be good.
The soil at the Balceana site is classified as a “chernozem” with a pH=7.6 and an
organic carbon content of 3.2%. It is situated in the lower Lapusna River Valley.
The depth-to-groundwater is 3.0–3.5 m. The foundation area was not used for the
phytoremediation study.
The trial was managed by a local farmer chosen by competition who conformed to
special requirements. This is a feasibility demonstration of managing a
phytoremediation application using local expertise in cooperation with government
and research institute.
Typical agricultural techniques for soil preparation and planting were used during
the experiment completion. No additional soil treatments or soil amendments were
used. The field experiment was designed using five different plant species: maize
(Zea mays L.), zucchini (Cucurbita pepo L. var. pepo), pumpkin (C. pepo L. var.
pepo), carrot (Daucus carota L.), and sorghum (Sorghum bicolor L. Moench).
The site plan is presented in Figure 2. Due to differences between each of the five
sections, different numbers of vegetables were used in some sections.
Figure 2. The design of sections within the foundation area of the former Balceana
pesticide storage facility (experimental sections are numbered 1–5).
Three sections were planted with three vegetables: maize, zucchini, and pumpkin.
On one section all five plant species were planted and the fifth section was limited to
two plant species: corn (Zea mays L.) and pumpkin (C. pepo L. var. pepo).
Plant part samples (roots, stems, petioles, leaves, and fruit) were taken for each
species after the vegetative growth period for assessment of pesticide accumulation.
Bioremediation
The experiment was based on in-situ bioremediation by land farming with the
addition of amendments of DARAMEND® by PeroxyChem (previous Adventus)
(PeroxyChem: Daramend® Anaerobic Bioremediation Reagent f.a.). Sequential
cycles of anaerobic (no oxygen, strongly reducing conditions) and aerobic (oxygen
present) conditions enhance reductive dechlorination of chlorinated organics. This
solid-phase bioremediation technology employs organic and inorganic amendments

to stimulate the decomposition of organic contaminants by indigenous soil

microorganisms.
5 - 10 cycles of treatment have been applied to the top soil at the demonstration site.
The soil was allowed to rest for at least 5 days during the anaerobic (reductive)
phase. Reducing conditions were needed to be maintained during that period to
induce reductive dechlorination of DDTs and HCHs. It was achieved by ensuring
that the moisture content was high by the covering the wet soil with black plastic
sheeting. The soil was tilled during the anaerobic (reductive phase) to provide
oxygen, and then allowed to rest without any covering or addition of water for at
least two days during the aerobic phase. Two phases (anaerobic and aerobic) were
repeated for each treatment cycle. Soil sampling was repeated after 5 and 7 cycles.
Laboratory Sorption study

A standard mixture of 8 chlorinated pesticides (at different concentrations- 50 and
120 ng/l) in methanol, containing: p,p’-DDT, o,p’-DDT, p,p’-DDE, p,p’-DDD,
o,p’-DDD, α-HCH, β-HCH, γ-HCH or lindane, purchased from LGC Standards was
used. The internal standard (IS) containing 0.1 µg/ml PCB29 and 0.1 µg/ml DCB.
All standards and working solutions were stored at 4°C in glass bottles with caps.
Deionized water was obtained from an Ultra Clear ultra-pure water system. Hexane,
methanol of residue analysis grade was purchased from Fluka (Sigma-Aldrich,
Germany).
Batch data were obtained using 100 ml samples. The tests were generally conducted
by setting up a series of flasks each with the same concentration of adsorbate, but
with different doses of carbon. Blanks were also used which contained no carbon.
Tests were conducted by adding an accurately weighed dose of carbon to a series of
250 ml flasks containing solution of known concentration.
After adding the known concentration of adsorbate and internal standard, the flasks
were placed on a shaker for overnight. After, the doses of carbon were added to each
flask and they were placed on a reciprocating shaker for one hour.
After one hour, the solutions were filtered and the filtrate was used for liquid-liquid
extraction. Hexane was used as an extracting solvent. Two portions of hexane each
of 5 ml were used. Extracts were mixed and were evaporated to a final volume of 1
ml, which was transferred into a screw cap vial. Analytical process on GC and
GC/MS Agilent 6890 system with Agilent 5973 mass detector was used for the
determination of organochlorinated pesticides. The conditions of the GC-MS were
as following: a HP–5MS capillary column (30 m × 320 µm id, 0.25 µm film
thickness). The carrier gas was helium with a flow rate of 1.3 mL/min. The
quadrupole temperature was maintained at 150 °C. The ionization was carried out in
electron impact mode at 70 eV. The acquisition mode was SIM. Retention times and
molecular ions were used as the key criteria for identification.

Results of phytoremediation experiment
Two plants showed a good extraction capacity for DDTs and HCHs: zucchini (C.
pepo L. var. pepo) and pumpkin (C. pepo L. var. pepo). Zucchini plants were grown
in three of the sections of the studied site. Each section had different initial soil
DDTs concentration in the rhizosphere (from 0.12 to 4.02 mg/kg). Zucchini

accumulated a high level of DDTs and the amount of accumulation depended on

pesticide concentration in the soil near each plant (Figure 3).
Figure 3. Total DDTs concentration in Zucchini plant parts (dry weight)
Total accumulation of DDTs decreased from the roots to the fruit. Relatively high
level of accumulation was observed in the roots and stems. Accumulation in the
stem is the most important result for phytoremediation because it shows
translocation of DDTs from the roots to aboveground stems that are most easily
harvested and removed from the site.
The pumpkin plant treatment also showed good phytoextraction capacity (Figure 4).
The pumpkin biomass was greater than zucchini biomass. The length of pumpkin
stems reached up to 3 – 5 m. The stems next to the plant roots showed higher
concentrations of DDTs compared to stems farther from plant roots.
Bioaccumulation factors (BAF) values for DDTs in plant tissues were close to the
values observed in zucchini. BAF for stem concentration varied in the range of 0.45-
3.01. The average decreased from 2.05 for roots to 0.82 for leaves. The fruit
accumulate much lower amounts of DDTs, BAF 0.05. The weighted average value
of BAF for zucchini was 1.10, and for pumpkin-1.42.
Figure 4. Total DDTs concentration in Pumpkin plant parts (dry weight)
Results of bioremediation experiment

The main soil pollutants at the experimental site were DDTs and HCHs isomers.
The bioremediation of polluted soil after 5 cycles led to the decreasing of total POPs
concentration in soil in the range of 22 to 86% for HCHs and of 34 to 76 % for
DDTs (Figure 5).
The average POPs destruction after 10 cycles of treatment showed a higher level in
comparison with 5 cycle treatment. The results after 10 cycles of treatment
demonstrate appreciable reduction for DDTs (65%-82%) and HCHs (27%-42%).
The destruction of studied pesticides is indicated also for control area. The HCHs
concentration is going down by 86 %, and for DDTs – by 34 % (Figure 5).
100%
90%
80%
70%
60%
%
50%
40%
30%
20%
10%
0%
Area 1 Area 2 Area 3 Area 4 Area 5 Control
HCHs reduction (5), % DDTs reduction (5), % HCHs reduction (10), % DDTs reduction (10), %
Figure 5. Reduction of HCHs and DDTs concentrations after 5 and 10 cycles of

bioremediation experiment
Results of sorption study
The results of the batch studies using commercial mix of organochlorinated
pesticides showed that great majority were absorbed onto activated carbon. Such
components were: α-HCH, γ-HCH, p,p’-DDE, o,p’-DDD, p,p’-DDD, p,p’-DDT. For
β-HCH and o,p’-DDT, a relationship between the carbon amount and the amount of
the pesticide adsorbed was observed.
In the study, experimental data for o, p’-DDT and β-HCH were fitted to the
linearized sorption isotherm models: Langmuir and Freundlich. In figure 6 data for
the Langmuir model and in figure 7 the Freundlich models are presented.
Figure 6. The linearized Langmuir Model: a) for o,p’-DDT and b) for β-HCH
Figure 7. The linearized Freundlich Model for o,p’-DDT β-HCH
Conclusions
Organic pollutants in the ecosystem, especially persistent organic pollutants (POPs)
are of the most important environmental concern in the world.
The experience of the site remediation in the Republic of Moldova showed that local
conditions should be determined individually for every site.
Another major factor for the remediation action is pollution spectrum. The
conclusion is that possible remediation action should to be developed after the
complex study of pollution spectrum and geotechnical conditions for every polluted
site by the complex approach.
Phytoremediation can be used for the remediation of polluted sites; however, it
needs to be designed based on site conditions. All advantages and limitations of this
technology should be taken into consideration. Agricultural phytoremediation might
be time consuming and could require a complex use of approaches as biotechnology
for high pollution levels.
POPs degradation in composts after bioremediation was significant and fitted to the
growth of the microbiological activity. The utilization of DARAMEND in most
cases promotes the growth of microorganisms which can lead to pollutant
destruction processes. However, POPs microbiological degradation in sites, where
DARAMEND was used, showed the similar level in the comparison with
background site.
Adsorption is recognized as an effective and low cost technique for the removal of
organic pollutants from water and wastewater that produces high-quality treated
effluent. The laboratory study highlighted the removal of different organic pollutants
using adsorption technique, adjusted to local conditions. Activated carbon was
obtained from local raw materials and was used for the remediation of POPs
polluted soil in laboratory conditions. Results showed a good perspective for the
utilization of activated carbon for the soil decontamination and agriculture site
remediation.

Acknowledgements
Acknowledgements for financial support: Global Environment Facility, World Bank, Food and
Agriculture Organization, Canadian Environmental Agency, Centre of Ecological Chemistry,
Institute of Chemistry Moldova.
References
Bogdevich, O & Cadocinicov, O 2009, 'Elimination of Acute Risks from Obsolete
Pesticides in Moldova: Phytoremediation Experiment at a Former Pesticide
Storehouse', pp. 61-85.
Bogdevich, O, Cadocinicov, O, Izmailova, D & Culighin, E 2013, 'Results of
Bioremediation Experiments for POPs Polluted Sites (Case Study: the
Republic of Moldova)', în 12th International HCH and Pesticides Forum,
pp.51-59.
Bogdevich, O, Ene, A, Cadocinicov, O, Culighin, E, Nicolau, E & Grigoras, M
2016, 'The Study of POPs Contaminated Sites in Danube River Basin of
Republic of Moldova for Risk Assessment and Remediation Actions', în
International Conference Contaminated sites 2016, pp.64-68, Slovak
Environment Agency.
Ministerul Ecologiei si Resurselor Naturale 2004, Instrucţiune privind evaluarea
prejudiciului cauzat resurselor de sol. Available from:
http://lex.justice.md/index.php?action=view&view=doc&id=310719. [23 iulie
2019].
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groundwater/products/daramend-reagent. [23 iulie 2019].

THE ROLE OF FOREST VEGETATION IN THE MITIGATION OF THE

ECOLOGICAL IMBALANCES RESULTING FROM CLIMATE CHANGE
IN THE PUTNA-VRANCEA RIVER BASIN
Cristinel Constandache1, Lucian Dinca2, Laurentiu Popovici1, Ciprian Tudor1

1
“Marin Dracea” National Institute for Research and Development in Forestry (INCDS),
Focsani Station, 7 Republicii Street, e-mail address: cicon66@yahoo.com;
2
“Marin Dracea” National Institute for Research and Development in Forestry (INCDS),
Brasov Station, Closca Street, e-mail. dinka.lucian@gmail.com, Romania
Abstract
Climatic changes displayed through extremes (thermic or hydric) correlated with
uncontrolled anthropic interventions exercised over time on land usages are the
main factors that emphasize ecological and hydric disequilibrium from the South,
East part of Romania. Specific of our country, the torrential precipitation regime
generates rapid floods in mountain and hill areas. Torrential and land degrading
processes occur on slopes and on the main hydrographic network as a result of
torrential runoffs. Their consequences extend on a larger area than the one on which
they occur. This happens especially as a consequence of perturbing the hydrological
regime of water courses, generating floods in downstream areas or the cogging of
accumulation lakes in periods with rain redundancies.
Forest protection cultures (forest vegetation) installed on degraded or overexploited
agricultural lands from the hill and mountain areas represent the most efficient
solution for attenuating the negative effects of climatic changes. This happens by
steadily re-establishing the hydrological equilibrium, together with creating an
ecological equilibrium that has positive effects on the soil and waters.
This paper emphasized the results of investigations realized in 2017 concerning the
characteristics of forest protection cultures created on strongly and excessively
degraded lands, followed by their hydrological and anti-erosion effects in the
context of extreme meteorological phenomenon. As such, the runoff coefficient had
values lower than 6.5% (from the total volume of precipitations in 24 hours), while
the specific erosion was under 0.24 t/ha/an. The maximum charge of alluvium
(erosion) produced by rain is of over 40 mm; their frequency and intensity has
increased lately.
Keywords: degraded lands, erosion, forest protections plantations, runoff
Introduction
The main ecological disequilibrium from Putna-Vrancea basin are determined by
land degradation (erosion, landslides etc.) as well as by afforestation, torrential
processes or floods. These events are highlighted in the context of climatic changes
based on the area’s high predisposition to erosion and landslides (Bogdan et al.
2015).
Torrential processes and land degradation cause major damages to both economic
and social objectives: forest roads, human settlements, agricultural and forest lands
or cultures, accumulation lakes and many more.
At the same time with diminishing or even cancelling the soil’s production capacity,
land degradation leads to the derangement of water runoff regime for both surface
and subterranean waters, as well as to the changing of the microclimate and the
degradation of the landscape. In this situation, a number of soil characteristics must
be taken into account: humidity (Dinca et al. 2018), organic carbon stock (Dinca et
al. 2015) and land geomorphology (Sparchez et al. 2017). The quantity of eroded
material from strongly eroded lands frequently exceeds 50 t/year/ha, while surface
runoffs can reach 70% of the precipitation volume (Untaru et al. 2006).
Previous investigations have emphasized the importance of forest protection cultures
in improving and capitalizing degraded lands and especially in their hydrologic and
anti-erosion protection (Giurgiu 2006, Untaru et al. 2006). Forest ecosystems with a
proper structure have an important role in retaining, filtering water and in regulating
surface waters, as well as in reducing soil erosion and transporting alluvium. All
these aspects have an effect in maintaining water quality and in ensuring a
permanent water flux (Chang 2006, Constandache et al. 2018). Investigations
realized in 2017 had as main purpose to determine the runoff and erosion from
afforested degraded lands, taking into consideration the characteristics of
precipitations and protection forest cultures.

The investigations were realized in six long-term research plots (runoff parcels)
located on afforested degraded lands from Caciu-Barsesti experimental perimeter,
situated in Putna basin from Vrancea County (Figure 1).
The research areas have different characteristics in regard with forest vegetation
(composition, consistency, age, biometric characteristics etc.) or with the land
(slope, exposition, degradation shape and intensity).
Precipitations (and other meteorological parameters) were recorded with an
automatic Em50 Decagon pluviograph. Runoffs (both solid and liquid) were
determined through measurements of water and alluvium volumes that have run
down runoff parcels in basins situated at the parcel’s basis. The alluvium was
extracted by filtering water samples taken from basins, being dried at 105 0 C and
then weighted. The quantity resulted from a sample was correlated with the water
volume from the basin and with the parcel’s surface. As such, the quantity (or
volume) of eroded soil after a rain with certain characteristics has resulted from
surfaces with different types of forest vegetation. The characteristics of forest
protection cultures were determined in 11 permanent research plots (Figure 1)
situated in different degraded land conditions and were obtained through different
management and afforestation technologies. The stand’s data were permanently
monitored through periodic measurements (at five years) concerning the main
biometric (diameters, heights etc.) and quality (health) parameters Pine stands have
ages between 38 and 40 years old, so that they are capable of offering valuable
scientific information concerning the type of cultures and silvicultural operations
necessary for an efficient management of stands from degraded lands, particularly to
ensure ecological and functional efficiency under the conditions of harmful factors.

Figure 1. Location of the permanent research plots in Caciu-Barsesti perimeter

The characteristics of forest protection cultures
Forest vegetation (forest protection plantations) represent the most efficient solution
for stopping land (and slope) degradation, for improving degraded lands as well as
for re-establishing the ecologic and hydric equilibrium of lands affected by different
degradation processes (Clinciu 2008).
The realized investigations have emphasized the characteristics of forest protection
cultures that have a hydrologic and anti-erosion protection role, installed on lands
affected by complex degradation processes from Caciu-Barsesti torrential
hydrographic basin. The structural diversity (composition, consistency, sample
number) as well as the forest culture’s health state are important elements for their
functional efficiency (hydrologic, anti-erosion etc.).
Forest cultures with the age between 38 and 40 years old, realized on strongly
eroded and gullyied lands have the following characteristics:
-the main species from their current composition are Scots Pine and Black Pine
(intimate or grouped mixture), representing 80 – 100%. The difference consists of
broad-leaved species (manna, black alder) originating from natural regeneration;
white sea buckthorn has initially represented approximately 50% of the composition
and had an important role in stabilising the slopes (Constandache et al. 2016,
Silvestru-Grigore et al. 2018).
-the number of trees per hectare varies between 1766 and 3924 samples; the
comparison analysis between the real number of trees and the number of trees from
the tables emphasizes the fact that in certain situations there is a higher number of
trees than the theoretical one. This aspect signals the need of an urgent silvicultural
intervention (thinning), (Nistor & Constandache 2013); on certain areas (small gaps
with a surface of 20-50 m2), the stand consistency is more reduced (0.5-0.6), even
though the land is covered by white sea buckthorn (Figure 3); the cause of this

reduced consistency is explained by extreme micro-stational conditions that did not

allow the maintenance of pines or by damages caused by snow in better land
conditions;
-the average consistency is of 0.7-0.8, and can sometimes reach even 0.9-1.0 (full).
In this last case, a tendency of structure homogeneity is evident, a fact that can have
consequences in the stands evolution, either positive (increasing the cenotyc
biodiversity’s degree) or negative (reducing stand consistency and increasing their
vulnerability towards harmful biotic and abiotic factors).
The biometric characteristics of the analysed stands can be summarized as follows:
-the average diameter (Dm) ranges between 11.57 cm and 14.93 cm for the Scots
Pine and between 9.17 cm and 13.69 cm for the Black Pine;
-the average height (hm) is situated between 12.07 m and 13.59 m for the Scots Pine
and between 8.97 m and 12.62 m for the Black Pine;
-higher diameters and heights were observed for the Scots Pine in comparison with
the Black Pine, with approximately 15.66% for the diameter and 20.59% for the
height.
The realized investigations lead to the conclusion the Scots Pine realizes both a
growth increment as well as a quality one in mixture stands of Scots and Black pines
and especially in mixture with white sea buckthorn (Constandache et. al 2016).
Figure 2. Runoff parcel (2) Figure 3. Scots Pine and Sea buckthorn
from the “vegetally armed” terraces
The analysis of height distribution (Figure 4) and of the number of trees on diameter
classes (Figure 5) is in a direct relationship with the number of species from the
stand’s composition as well as with the effect of harmful abiotic factors (snow). As
such, in the case in which only the original species were present and the influence of
abiotic factors is insignificant, the distribution of trees on diameter categories
respects the theoretical distributions frequently used in silviculture (normal
theoretical distribution and Beta distribution).

Figure 4. Height distribution of diameter Figure 5. Tree number distribution on

classes diameter classes
The bilayer (multilayer) stand tendency is evident in the case in which more species
are present from natural sources, correlated with a significant influence of abiotic
factors. This is a consequence of the apparition of a new vegetation layer formed of
endemic species from the forest subarea in which forest protection cultures were
installed.
The analysed structural markers (height distribution, number of trees, diameters,
spacing etc.) show that these stands have the tendency to evolve towards diversified
structures (Vlad & Constandache 2014). The same tendency is emphasized by
biodiversity markers (Gini, Camino). A high diversity designates the stand’s
functionality and stability, parameters that determine the efficiency of analysed
stands in fulfilling protection functions (Constandache et al. 2013).
The functional efficiency of forest protection cultures

The investigation’s results demonstrate that the forest vegetation installed on
degraded lands has an essential role in reducing runoff and erosion, having a direct
impact in protecting water and soil resources (Constandache et al. 2010;
Constandache et al. 2015, Costin 2006). Forest protection cultures have a direct
impact on steadily re-establishing hydrologic equilibrium, together with creating an
ecologic equilibrium in the created areas, with an effect on ensuring water quality
(Constandache et al. 2018).
Investigations realized in 2017 in Caciu-Barsesti perimeter – Vrancea, in
experimental parcels installed on stands from degraded lands with purpose of
studying runoff and erosion have emphasized the hydrologic and anti-erosion effect
of forest vegetation in the context of an increase in torrential precipitation (both as
frequency and as intensity).
As such, it was observed that the frequency and intensity of precipitations that cause
runoffs has increased during the last period of time. As such, from a total of 24 rains
that have accumulated 396.3 mm, recorded in May-October 2017, 15 rains (62% of
the total number) that have registered 382.3 mm (96% of the total quantity of
precipitations) have caused runoffs (Figure 6).

Figure 6. Runoff variations
During June and July, the quantities of precipitations were considerable, namely
136.8 mm and 119.4 mm, while May and September were the most poor months in
precipitations (14.4 mm in September).
The rain with the highest intensity was recorded during the period 06 - 07.08.2017,
being of 0.15 mm/min for a period of 180 minutes, with a quantum of 26.2 mm
(Figure 7).
The aggressivity pluvial index (that showcases how damaging is the action of
precipitations) had a maximum value of 0.61 (on a scale from 0 to 1) in June (the
maximum quantity of precipitations in 24 hours related to the total quantity from
that month).
Figure 7. Intensity distribution based on rainfall duration during different periods of

time
The runoff coefficient from forest protection cultures had values lower than 6.5%
(from the total volume of precipitation in 24 hours) (Figure 8), while the specific
erosion was under 0.24 t/ha/year (Figure 9) even in conditions such as torrential
rains or when the soil was saturated with water from precipitations recorded in a
previous period of time (of up to 15 days).
Figure 8. Distribution of runoff coefficient on Figure 9. Specific erosion on parcels

months
The maximum alluvium charge (erosion) was produced at rains exceeding 40 mm

(5.5 g/l), with an average pf 3.95 g/l on strongly eroded land and with a low degree
of vegetation coverage. The efficiency of forest cultures on strongly eroded lands
increases as they advance in age (over 40 years) and is higher in pine cultures mixed
with White Sea buckthorn.
Climatic changes from the last period of time, with increased rains that have a
torrential character were confirmed by the persistent waves of catastrophic floods
from the last years. They lead to an amplification of soil erosion, torrential runoffs
and an increase of catastrophic floods, which require prevention measures and
works.
Conclusions
Forest protection cultures represent the most efficient solution for stopping land
degradation, for improving already degraded lands and for re-establishing the
ecologic and hydrologic equilibrium of lands affected by different degradation
processes. Forest ecosystems that have a proper structure and health state play an
important role in retaining and filtering water, in regulating runoff, reducing soil
erosion and in transporting alluvium, in the conditions of increased meteorological
conditions.
Under the direct effect of forest protection cultures, the successive rehabilitation of
the hydrological equilibrium occurs, at the same time with the creation of an
ecologic equilibrium in the created areas, with effects in ensuring water quality. The
runoff coefficient from forest protection cultures has recorded values lower than
6.5% (from the total precipitation volume in 24 hours), while the specific erosion
was under 0.24 t/ha/year, even under torrential conditions or on soils saturated with
water from precipitations recorded in a previous period of time. On the other hand,
on degraded lands, surface runoffs can reach 70% of the precipitation volume, while
the specific erosion exceeds 50 t/year/ha. The hydrologic and anti-erosion efficiency
of forest cultures created on degraded lands increases as they advance in age and is
higher in stands with a mixed structure.

References
Bogdan, N, Constandache, C & Nistor, S 2015, Consequences of deforestation. The
ecological reconstruction of Vrancea, Silvica Publishing House, Bucharest,
in Romanian.
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, Dinca, L, Tudose, NC & Panaitescu C 2018, 'Protecting surface
water resources through silvicultural methods', 21-st International Symposium
“The Environment and Industry” - SIMI 2018, National Research and
Development Institute for Industrial Ecology ECOIND, Bucharest,
Romania, pp. 276-284.
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.
Constandache, C, Panaitescu, C & Bilanici, A 2015, 'Forests and water vulnerability
under climate change impact in the Putna river basin – Vrancea', Scientific
Papers. Series E. Land Reclamation, Earth Observation & Surveying,
Environmental Engineering, vol. 4, pp. 73-78.
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.
Costandache, C, Nistor, S, Bilea, IC & Vica, P 2013, 'Hydrological Quality of the
Forest and water resources protection', Hidrotehnica Magazine, no.12, vol.
58, pp. 18-27, in Romanian.
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, Dinca, M, Vasile, D, Sparchez, G & Holonec, L 2015, 'Calculating
organic carbon stock from forest soils', Notulae Botanicae Horti
Agrobotanici, vol. 43(2), pp. 568-575.
Dinca, L, Badea, O, Guiman, G, Braga, C, Crisan, V, Greavu, V, Murariu, G &
Georgescu, L 2018, 'Monitoring of soil moisture in Long-Term Ecological
Research (LTER) sites of Romanian Carpathians'. Annals of Forest
Research, vol. 61(2), pp. 171-188.
Giurgiu, V 2006, Sustainable forest management and water regime, in Silvologie,
vol. V, Forest and water regime, Romanian Academy Publishing House,
Bucharest, in Romanian.
Nistor, S & Constandache, C 2013, 'Considerations on the efficiency of the
silvotechnics works in the stands on the degraded lands', Forest Magazine,
no. 6, pp. 19-27, in Romanian.
Silvestru-Grigore, CV, Dinulica, F, Sparchez, G, Halalisan, AF, Dinca, L, Enescu, R
& 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.
Sparchez, G, Dinca, L, Marin, G, Dinca, M & Enescu, RE 2017, 'Variation of eutric

cambisols chemical properties based on altitudinal and geomorphological
zoning', Environmental Engineering and Management Journal, vol. 16(12),
pp. 2911-2918.
Untaru, E, Constandache, C & Nistor, S 2006, 'Forestation degraded lands and
preventing floods', in Silvologie, vol. V, Forest and water regime, Romanian
Academy Publishing House, Bucharest, pp. 232-244, in Romanian.
Vlad, R & Constandache, C 2014, 'Dynamics of the stability parameters in the Scots
pine stands installed to degraded land', Forest Magazine, no. 5-6, pp. 44-49,
in Romanian.

TREATMENT OF HEMP RETTING WASTEWATERS: USE OF BY-

PRODUCTS FROM WINEMAKING INDUSTRY
Simona Gavrilas1, Violeta Nastuneac2, Florentina-Daniela Munteanu1

1
„Aurel Vlaicu” University of Arad, Faculty of Food Engineering, Tourism and Environmental
Protection, 310330, 2-4 E. Dragoi Str., Arad, simona2213@yahoo.com,
florentina.munteanu@uav.ro, Romania
2
„Vasile Alecsandri” University of Bacau, Faculty of Engineering, 600115, 157 Marasesti Str.,
Bacau, violeta10nvn@gmail.com, Romania
Abstract
The present study considered the use of a by-product from winemaking for the
treatment of wastewater from hemp retting process.
To evaluate if different obtained extracts of grape marc (BRE-extract of refrigerated
grape marc, BUE-extract of dried grape marc, BLE-extracted of lyophilised grape
marc, BLM-ultrasound soaked lyophilised grape marc, BLM fUS-soaked
lyophilised grape marc, no ultrasound treatment) are feasible to be used for the
wastewater treatment.
The chosen parameters (pH, turbidity, dissolved oxygen and conductivity) were
monitored over 14 days and it was observed that starting with day 8 the measured
values for all parameters remained constant.
Keywords: grape pomace extracts, hemp retting wastewater, monitored quality

parameters
Introduction
Textiles remained of great interest since very old times till nowadays (Paret et al.
2019). The textile industry is also responsible for the high amount of used water,
while the resulting wastewaters could raise environmental problems due to their
high chemicals concentration.
Recently, the attention for natural fibres was revived and the market is focusing on
apparel based on cotton and bast fibres.
Hemp is one of the most known and exploited sources of raw material, especially for
the textile industry, due to its good mechanical characteristics.
Unfortunately, the extraction hemp fibres have also a negative impact on the
environment, mainly due to the retting process that takes large amounts of water and
energy, and because of the biochemical fermentation processes, the resulting water
has a high level of organic compounds (Li 2009).
In general, the reusing the wastewater is not possible because of the missing aeration
process after water-retting of hemp. Besides the oxygen depletion during the hemp
retting process, an unpleasant smell is affecting the environment due to the
formation of unstable fatty acids and butyric acid.
Independent of the methods used to obtain the hemp fibres, these processes need to
be designed by the environmental protection principles (Werf & Turunen 2008),

while the possibility of applying circular economy directions should also be

considered.
Today, for the wastewater treatments is used a large range of advanced methods that
are based on the oxidation reaction in the presence of O3, ultraviolet radiation,
hydrogen peroxide or emerged technologies (Kortekaas 1998). Each developed
method aims to improve the final parameters of the water that will be discharged
into the environment (Bajpai 2017).
The parameters that are usually monitored for the evaluation of the wastewater
characteristics are pH, chemical oxygen demand, total residual chlorine, dissolved
oxygen, biochemical oxygen demand, and phenolic compounds (Kumar 2017).
The present study has in attention a new method for the treatment of wastewater
from the hemp retting process that is based on the valorisation of winemaking waste,
namely grape marc.
In our opinion, this attempt contributes to the reduction of the agro-food waste, as
this type of waste remains under-used in Europe, in particular at small producers,
despite numerous potential advantages and proven antioxidant, antibacterial and
antifungal properties of many by-products (Beres et al. 2017). Moreover, the grape
marc was used for the treatment of wastewater resulted from hemp plants retting
process.

Materials
White grape marc provided by ICDVV Valea Calugareasca, Romania.
Reagents
Ethanol absolute (Sigma-Aldrich, Germany).
Methods
Grape marc was refrigerated (4°C) till the pre-treatments were applied. The used
sample did not reach the fermentation stage and consisted of grape peel, seeds and
pulp.
Grape marc extraction

Prior to the extraction the grape marc was treated at different temperatures. The
samples were dried at 30°C in a thermostatic atmosphere till constant mass using the
drying and heating chambers and drying oven (Binder GmbH, Tuttlingen,
Germany), or freeze-dried in a lyophilizer, Martin Christ, Alpha 1-2, or only
refrigerated at 4°C. Afterwards, all obtained samples were fine grounded using a
coffee grinder.
The extraction was performed in distilled water by using 10 g of each sample were
treated in distillate water. The grape marc was macerated for 24 h at room
temperature, stirred or ultrasounded for 2.5 h. It was also performed an extraction
using Soxhlet system for 2.5 h. In all cases the extracts were centrifuged at 15,000
rpm. /10 min. with Rotina 360R system.
The resulting supernatant was used in proportion of 1:10 (V:V extract : hemp retting
wastewater).
All determinations were made in triplicate.

Hemp wastewater analysis after grape extracts addition

The wastewater resulted after hemp retting was collected and analysed. pH,
conductivity and total dissolved oxygen levels were measured by using a WTW
multi-parameter inoLab Multi 740, and for the measurement of the turbidity was
used a Turbidimeter (HI 88713 HANNA Instruments).

It is well known that textile industry is a high consumer of water resources, and the
resulting wastewater has high load of pollutants, usually hard to be removed.
Therefore, special attention should be paid, in order to reduce the impact of this
industry on the environment.
Even mild treatment of the raw material might lead to wastewater that cannot be
discharged into the environment or re-used in the industrial process, without prior
treatment.
In our study we considered the wastewater from a mild process from the hemp
retting.
In order to, reuse this water for the retting process, we proposed the treatment with
different types of grape marc extracts, as presented under the material and methods
section.
The wastewater samples were monitored over a period of 8 days, and the chosen
parameters are presented in Figure 1-4.
As it can be observed the addition of the extracts to the wastewater does not have a
significant impact on pH values, as this remains constant at a value of around 5. The
stability of the pH value in the case of the analysed wastewater, allow us to consider
that from this point of view the reuse of the water in the retting process is
appropriate.
Figure 1. pH variation over 7 days period
The measured values of the turbidity during the same period of time, demonstrated
that in all the cases when the different extracts of grape marc was added to the
samples of wastewater, the values registered an increase from the first day.
Moreover, the values increased till day 6, with a small decreased value registered in
day 7. Thereafter the values stabilised at this value. This behaviour can be due to
some remaining yeasts that might be present in the grape marc extracts, and in time
some aggregates can be formed.
Figure 2. Variation of the turbidity during the monitored period
In the case of the measured values for the dissolved oxygen, it can be observed that
over the monitored period there is a drecrease in the concnetration of oxygen, which
can explained in the same way as in the case of turbidity. An exception is in the case
of the grape marc extract that was treated in ultrasound. In this situation, an
abnormal behaviour was observed, and a possible explanation should take into
account the effect of ultrasound on the extract composition, but further experiments
are needed for fully understanding these results.
Figure 3. Variation of the level of dissolved oxygen
When the conductivity was monitored, the value remained stable starting with day 7
(data not shown for day 8 till day 14). As a consequence, also in terms of

conductivity, we believe that the wastewater treated in this way can be reused in the
hemp retting process.
Figure 4. Variation of the conductivity in time.
Conclusions
The monitored parameters (pH, turbidity, dissolved oxygen and conductivity) for the
wastewater from hemp retting showed that the addition of different extracts obtained
from grape marc can contribute to an improvement of the quality of the analysed
water. This suggests that this treatment allows the reuse of the wastewater in the
hemp retting process. Further experiments will be performed in order to proof that
the obtained fibres, in the case of water reuse, have the same quality as the fibres
obtained with clean water used for the retting of hemp.
Acknowledgements
The authors acknowledge financial support from UEFISCDI-PN-III-P3-3.1-PM-RO-FR-2016-
0030 (Contract no. 86BM/2017), Valorisation of winery by-products-application for
wastewater treatment, „FOODVALUE”.
References
Bajpai, P 2017, Chapter 7-Emerging Technologies for Wastewater Treatment, Pulp
and Paper Industry, Emerging Waste Water Treatment Technologies, Elsevier,
pp. 93-179.
Beres, C, Costa, GNS, Cabezudo, I, da Silva-James NK, Teles, ASC, Cruz, APG,
Mellinger-Silva C, Tonon, RV, Cabrald, LMC & Freitas, SP 2017, 'Towards
integral utilization of grape pomace from winemaking process: A review',
Waste Management, vol.68, pp. 581-594.
Kortekaas, S, Wijngaarde, RR & Klomp, J-W 1998, 'Anaerobic treatment of hemp
thermomechanical pulping wastewater', Water Research, vol. 32, no. 11, pp.
3362-3370.
Kumar, PS & Saravanan, A 2017, 11-Sustainable wastewater treatments in textile
sector, Woodhead Publishing, pp. 323-346.

Li, Y 2009, Processing of Hemp Fibre Using Enzyme/Fungal Treatment for

Composites, PhD thesis, The University of Waikato.
Paret, D & Crégo, P 2019, Part 4 - Aspects to Take into Consideration for
Wearables, Smart Textiles and Smart Apparel, in: Paret, D., Crégo, P. (Eds.),
Wearables, Smart Textiles and Smart Apparel, Elsevier, pp. 39-98.
Werf, HMG & Turunen, L 2008, 'The environmental impacts of the production of
hemp and, flax textile yarn', Industrial Crops and Products, pp.27, 1-10.

VEGETABLE FOOD WASTE FOR COTTON DYEING-NEW DIRECTIONS

FOR ENVIRONMENTAL SUSTAINABILITY
Andreea Bujdei1, 2, Simona Gavrilas3, Mihaela Dochia2, Florentina-Daniela Munteanu3
1
Faculty of Horticulture, University of Agronomic Sciences and Veterinary Medicine of
Bucharest, 59 Marasti Boulevard, Bucharest, andreea_bujdei@yahoo.com, Romania
2
”Aurel Vlaicu” University of Arad, Research Development Innovation in Technical and
Natural Science Institute, 310330, 2-4 Elena Dragoi Street, Arad, dochiamihaela@yahoo.com,
Romania
3
”Aurel Vlaicu” University of Arad, Faculty of Food Engineering, Department of Technical
and Natural Sciences, 310330, 2-4 Elena Dragoi Street, Arad, simona2213@yahoo.com,
florentina.munteanu@uav.ro, Romania
Abstract
The present paper presents the results obtained in the attempt of valorisation of the
natural pigments obtained from vegetable wastes by considering the principles of the
circular economy. For this purpose, was used the waste from different technological
steps of food preparation (outer leaves, spine with seeds).
The extracted pigments were used for the dyeing of cotton fabric that firstly was
bioscoured and bleached.
The results showed that the treated cotton fabric presents good properties (weight
loss, hydrophilicity, whiteness and colour intensity K/S, etc.).
This paper also addressed to the monitoring of the parameters for the wastewater
resulted after the treatment of cotton fabrics with the studied pigments.
The results showed that the wastewater from the dyeing proved to comply with the
imposed limits for the wastewater according to the environmental standards.
Keywords: eco-friendly cotton treatments, natural dyeing, wastewater analysis
Introduction
Nowadays, industrial technologies should be designed in a manner that ensures their
sustainability and also to have a lower impact on the environment. In this context
also, the fabrics processing and dyeing need to be adapted to these new demands.
One of the first steps in the textile processing of cotton fabrics is scouring. The
treatment is imposed by the specific composition of those natural fibres (more than
95% cellulose) and by the need to remove all present organic (various acids, wax,
colorants, pectin) and inorganic impurities (dust, salts) (Sheikh & Bramhecha 2019).
Traditionally, the operation consists of an alkaline treatment at high temperature. As
an eco-friendly alternative, the bioscouring based on an enzymatic treatment at low
temperature can be applied.
The enzymatic treatment in our study is based on a commercial product containing a
mixture of pectinases. This type of enzyme total or partially hydrolyses the pectin
present in the primary cell wall of the cotton, in aqueous solutions. As a result of the
pectic matrix distortion, removal of other impurities is facilitated. The data
presented in the literature underline the efficiency of the bioscouring treatments
related to technological characteristics of treated fabrics obtain from natural fibres

(wettability, whiteness degree) as well as the economic and ecological aspects
(energy and chemical lower consumption) (Abdel-Halim et al 2008).
Various data presented in the literature suggest the potential of natural dyes as eco-
friendly alternatives in the dying process. One possible difficulty is raised by the
specific chemical structure of the cotton, which is a predominant cellulosic fibre and
therefore has low affinity to many natural dyes. This situation imposes the use of
additional compounds, which will lead to reactive carboxylic and amino groups that
will be able to link to the dye molecule.
To improve the colour strength, are currently used salts of the transitional metals
(mordants) (Özlenen & Yıldırım 2019).
Cotton fabrics have been dyed with natural pigments obtained from plants since
ancient times. They are generally easy to obtain as they are soluble in polar solvents.
The pH of the dyeing solution has a big influence on the obtained colour. The
changes in this parameter could lead to various colour results, varying from brown
to green and blue (Vankar 2017).
In respect to the tinctorial characteristics of the red cabbage, it has been proven that
a blue-green colour is obtained in alkaline media using mordant pre-treatment
(Ticha et al 2016). To activate the cellulose’s carboxylic and amino groups, whey
proteins could be used as mordant. In this case, the best colour strength for
Xylocarpusgranatum pigments is obtained at the acidic pH value of 5 (Pisitsak et al
2016).
Four major directions could be considered for the valorisation of food waste, such as
use as raw materials for obtaining biofuels, different valuable bio components,
biomaterials, or absorbents for wastewater treatment (Gupta et al 2019, Nayak &
Bhushan 2019). Previous studies of other researchers showed promising results
obtained in the case of using orange tree leaves, pomegranate peels, alkanet roots or
nutshell, products which are normally considered to be vegetable waste (Benli &
Bahtiyari 2015).
The proposed alternatives are related to the use of natural pigments obtained from
vegetable wastes. The natural pigments have a lower impact on the environment due
to their integration in a circular process, ensuring the sustainability of the dyeing
process. Adopting these strategies could be reduced the use of the synthetic dyes
used in the textile finishing sector. The use of the pigments extracted from vegetable
waste brings a number of advantages (biodegradability, renewability, low
environmental influence), but some disadvantages should also be considered (high
production cost, a less variety of colours and shades and lower intensity compared to
the synthetic ones, possible difficulties of supplying and sustainability, or toxic
effects following the skin contact) (Vankar & Shukla 2019).
In our present study, cotton fabrics were dyed using vegetable pigments with and
without mordants. The treatment without mordants is an eco-friendly one, and it is
recommended even if the colour strength obtained is less intense.
We believe that these results are a good example of the application of a circular
economic model. As the food wastes are not always possible to be minimised, these
approaches should be considered for further advanced processes.


The dyeing treatments were made on 100% cotton woven fabric with the following
characteristics: width (150 ± 3 cm), weight (200 ± 10 g/m2), and warp of 100%
cotton yarn with Nm 25/2 and weft of 100% cotton yarn with Nm 25/1.
For the bioscouring, the pectinolytic product Beisol PRO, a mixture of pectinases
and Denimcol Wash RGN as surfactant supplied by CHT Bezema Company were
used.
The sodium hydroxide, sodium silicate, hydrogen peroxide, tannic acid, acetic acid,
Felosan RG-N, sodium citrate and the iron sulphate were purchased from Sigma-
Aldrich. All reagents used had purity between 97-99%.
The dyeing pigments were obtained from red cabbage outer leaves, red and yellow
onions peel, and red pepper spine with seeds.
Preliminary washing
The cotton samples were washed with hot water (100°C) in an AATCC standardized
Lander-Ömeter, model M228-AA from SDL Atlas Company-USA. Subsequent,
were dried, conditioned and weighing as specified by the international standards.
Bioscouring treatment
The bioscouring was made in the same AATCC standardized Lander-Ömeter, model
M228-AA with a commercial enzymatic product. The enzyme concentration was
2% (o.w.f-concentration over fibre), 2 g/L sodium citrate and 0.5% Denimcol Wash
RG-N. The reaction was developed at 55oC for 35 minutes in liquor to fabric ratio of
1:20. After applying the above treatment, the cotton samples were washed with hot
(70°C) and cold water and dried at room temperature.
Bleaching treatment
The bioscoured cotton samples were treated with an aqueous solution containing 3
mL/L hydrogen peroxide, 4.5 mL/L sodium silicate and 1 g/L sodium hydroxide.
The bleaching process was performed at a material to liquor ratio of 1:20 and
temperature of 95oC for 60 min with stirring in AATCC standardized Lander-
Ömeter. The bleached samples have been neutralized with a solution of 10% acetic
acid and washed several times with hot water then with cold water and finally dried
at ambient conditions.
Dyeing solution
To obtain the dyeing solutions red cabbage outer leaves, red and yellow onions peel
and red pepper purchased from a local store were used. The outer leaves of cabbage,
onions peel and spine with seeds of the red pepper were used. 40 gr. of each
vegetable material was mixed with 500 mL of distilled water and boiled for 1 hour.
The cooled extract was filtered and used for dyeing the cotton fabrics.
Mordanting
To form the reactive carboxylic and amino groups on the cotton samples surface, the
fabrics were treated with 3% tannic acid for 2 h followed by the treatment with 35
g/L iron sulphate. Both treatments were made in the Lander-Ömeter with constant
agitation at 80oC.

Dyeing treatment
The dyeing treatments were carried out on various pre-treated cotton samples with
and without mordanting. 1:20 material to dyeing solution ratio was used at a
temperature of 95°C for 60 min. After that, the dyeing bath temperature was reduced
to 70°C and the dyeing treatment was continued for 15 min. Dyed cotton samples
were washed at 80°C for 10 min with 1 g/L Felosan RG-N and then successively
rinsed with hot and cold water, squeezed and air dried (Chirila et al 2018).
Analysis of the material properties after preliminary treatments

After drying and conditioning of the bioscoured samples till constant weight, the
hydrophilicity and weight loss were determined. The weight loss was determined by
gravimetric method. The samples were dried at 105 °C in an oven from Caloris
Group, Romania till constant weight. The weight loss was calculated using the
following equation:
% weight loss = (W1-W2) x100/W1 (1)
where W1 and W2 are the weights of dried samples fabric before and after the
treatment.
The hydrophilicity of the bioscoured samples was determined according to
AATTCC Test Method 79-2007. Whiteness and yellowness index were determined
after the bleaching treatment of cotton material on a Datacolor 500
spectrophotometer. For an opaque view each sample was folded twice to give four
plies and the whiteness was measured four times at different points. The reflectance
(R %) at 420 nm was measured in comparison with a standard of barium sulphate
for absolute white. The Hunter Whiteness Index and DIN 6170 Yellowness Index
were calculated automatically by Datacolor Tools 2.0 software.
Colour measurements
Colour measurements were performed according to AATCC Evaluation Procedure
6-2008 by using Datacolor 500 spectrophotometer. The data obtained for colour
difference represent the average of three determinations made in different areas on
dyed samples. To evaluate the colour strength of dyed samples the K/S value was
calculated at dominant wavelength (420 nm) based on Kubelka-Munk theory:
K/S = (1−R)2/2R (2)
where K is the absorption coefficient, S is the scatter coefficient and R is the sample
reflectance value at the dominant wavelength.
Wastewater analysis after dyeing

The wastewater resulted after the dyeing treatments was collected and analysed with
a WTW multi-parameter inoLab Multi 740. pH, salinity, TDS (total dissolved
solids), conductivity and total dissolved oxygen were determined. For the
determination of the turbidity a HI 88713 HANNA Instruments Turbidimeter was
used.

In order to obtain efficient and uniform dyeing of the material, a good preparation is
required. The cotton fabric undergoes different chemical pre-treatments such as
scouring and bleaching to withdraw impurities which negatively influence the
subsequent technological operations and to improve fibre whiteness and dyes
affinity. Table 1 presents the characteristics of cotton fabric after bioscouring and
bleaching treatments.
Table 1. The parameters obtained for cotton fabric after bioscouring and bleaching
treatments
Weight loss Hydrophilicity Whiteness Yellowness
No.
[%] [s] index index
1 1.65 0.78 73.07 12.20
2 1.80 0.79 74.45 11.32
3 1.93 0.80 74.67 11.27
4 1.97 0.77 74.00 11.60
5 1.77 0.86 73.52 12.30
6 1.80 0.87 73.85 12.47
Row cotton
- >500 45.79 27.35
fabric
The weight loss values of bioscoured samples show the effectiveness of bioscouring
treatment by removing non-cellulosic attendants, which is also confirmed by the
values of hydrophilicity. For all treatments, the weight loss is in agreement with the
data from the literature which mention values below 5% for enzymatically
treatments (Bashar et al. 2015). Also a hydrophilicity lower than 1 second is
considered to be optimum.
A good whitening of the material was obtained after bleaching with hydrogen
peroxide (~75) compared to the raw cotton fabric (~46). The whiteness index was
increased with ~61% and the yellowness index was decreased with ~41%.
Evaluation of the chromatic parameters, using the spectrophotometric measurement

allowed establishing the colour intensity K/S and colour differences of naturally
dyed samples with pre-mordanting with those without mordanting. Colour
difference was determined considering as reference the bleached undyed cotton
fabric. The K/S values recorded at dominant wavelength (λdominant=574 nm) and total
colour difference DE between all dyed samples and the reference are shown in
figure 1.
To highlight the influence of pre-mordanting treatment on colour intensity, the

samples were analysed by comparing the K/S and total colour difference (DE)
values obtained for pre-mordanted samples and those obtained for un-mordanted
and dyed samples.

Figure 1. K/S and total colour differences (DE) between the naturally dyed and pre-
mordanted naturally dyed cotton samples
Note: R-reference; P-red pepper; C-red cabbage; O-onions peel; P-M-pre-mordanted red
pepper; C-M-pre-mordanted red cabbage; O-M-pre-mordanted onions peel
From the data presented in Figure1 it can be observed that the best results were
obtained for samples pre-mordanted and dyed, this is positively influencing the
adsorption capacity of the natural dye in the cotton fibres, leading to darker colours.
The behaviour is given by the specific chemical structure of the cotton, this being a
predominant cellulosic fibre it has low affinity to many of the natural dyes, so a
mordanting treatment being necessary. In the both cases, with mordanting and
without mordanting, more saturated colours were obtained for the samples dyed
with onions peel followed by samples dyed with red cabbage and red pepper.
For a better characterization of the proposed dyeing treatments, the evaluation of the
wastewater parameters was done. For comparison, all values used as a reference
represent the minimum admissible values reported in the literature in the case of
cotton dyeing wastewaters. pH, conductivity, total solids dissolved, salinity, total
dissolved oxygen and turbidity were analysed. Figure 2 and figure 3 present the
wastewater parameters resulted from all variants of natural dyeing treatments.
Conductivity and total solids dissolved are two complementary parameters used
frequently for wastewaters characterisation. From figure 2 it can be seen that in all
studied cases the values registered are 10 times lower compared with the results
obtained after the dying of the cotton with synthetic dyes. Mordant utilisation does
not have a significant influence on the two parameters. Another important parameter
of wastewater is the turbidity. This is given by the soluble coloured products,
organic and inorganic compounds in suspension. In the case of onion and cabbage
dyeing solution with mordants, this indicator has values 10 times higher compared
with the one reported in the literature for dyed cotton. In the case of the cotton dyed
with cabbage without any mordants in the bath, was registered the lowest turbidity
value, 15.5 NTU.
The pH values registered are in the acidic domain, around 3.4. Higher values can be
observed for the cases with cabbage and pepper cotton dyeing wastewater.

Figure 2. Waste water conductivity, Figure 3. Waste water pH, salinity and
total solids dissolved and turbidity for dissolved oxygen for all variants of
all variants of natural dyeings natural dyeings
Note: R-reference; P-red pepper; C-red cabbage; O-onions peel; P-M-pre-mordanted red
pepper; C-M-pre-mordanted red cabbage; O-M-pre-mordanted onions peel.
The salinity data recorded vary between 0.2 g/L (pepper) to 0.4 g/L (cabbage with
and without mordant and onion with mordant). The ions types which determine this
parameter could determine the appearance of different toxic phenomena on plants or
problems in water absorption if the wastewater is not well treated before reaching
the environment. In all of the discussed cases, the recorded values for the total
dissolved oxygen are higher (2.5-3 times) compared with the reference one. There
are almost the same values in all 6 cases presented (2.95-3.6 mg/L). Increase
quantity of dissolved oxygen inhibits the development of anaerobic microorganism,
but it is a growth factor for the aerobic one.
Conclusions
The obtained results revealed that the natural pigments obtained from vegetables
waste, in some cases, might be an alternative for synthetic dyestuffs for cotton
fabrics dyeing.
The preliminary treatments like bioscouring and bleaching have provided adequate
hydrophilicity and whiteness degree of the cotton fabric, leading to an even dyeing.
Pre-mordanting has positively influenced the adsorption capacity of natural dye in
cellulosic fibres and darker colours were obtained compared with the un-mordanted
samples. Good results for colour intensity were obtained for all pre-mordanted and
naturally dyed samples. A high increase of the colour strength was observed for
samples dyed with onions peel in both cases.
The wastewater resulted from all dyeing variants is less polluting compared to the
parameters of the wastewater reported for dyeing with synthetic dyes, but some
corrections are needed before disposal on water bodies or in the environment in
order to assure less pollution and an eco-friendly environment.

Acknowledgements
This work was funded by the Romanian Ministry of National Education-National Authority for
Scientific Research UEFISCDI, www.uefiscdi.ro. Award Number PN-III-P1-1.2-PCCDI-2017-
0569, Closing the bioeconomy value chains by manufacturing market demanded innovative
bioproducts-PROSPER.
References
Abdel-Halim, ES, Fahmy, HM & Fouda MMG 2008, 'Bioscouring of linen fabric in
comparison with conventional chemical treatment', Carbohydrate Polymers,
vol.74, pp.704-711.
Bashar, MM, Siddiquee, MdAB & Khan, MA 2015, 'Preparation of cotton knitted
fabric by gamma radiation: A new approach', Carbohydrate Polymers,
vol.120, pp.92-101.
Benli, H & Bahtiyari, MI 2015 'Combination of ozone and ultrasound in
pretreatment of cotton fabrics prior to natural dyeing', Journal of Cleaner
Production, vol.89, pp.116-124.
Chirila, L, Popescu, A, Cutrubinis, M, Stanculescu, I & Moise, VI 2018, 'The
influence of gamma irradiation on natural dyeing properties of cotton and flax
fabrics', Radiation Physics and Chemistry, vol.145, pp.97–103.
Gupta, N, Poddar, K, Sarkar, D, Kumari, N, Padhan, B & Sarkar, A 2019, 'Fruit
waste management by pigment production and utilization of residual as
bioadsorbent', Journal of Environmental Economics and Management,
vol.244, pp.138-143.
Nayak, A & Bhushan, B 2019, 'An overview of the recent trends on the waste
valorization techniques for food wastes', Journal of Environmental Economics
and Management, vol.233, pp.352-370.
Özlenen, Eİ & Yıldırım, L 2019, 3-Metal mordants and biomordants, Woodhead
Publishing, India, pp.57-82.
Pisitsak, P, Hutakamol, J, Thongcharoen, R, Phokaew, P, Kanjanawan, K &
Saksaeng, N 2016, 'Improving the dyeability of cotton with tannin-rich natural
dyethrough pretreatment with whey protein isolate', Industrial Crops and
Products, vol.79, pp.47-56
Sheikh, J & Bramhecha, I 2019, 6-Enzymes for green chemical processing of cotton,
Woodhead Publishing, India, pp.135-160.
Ticha, M B, Haddara, W, Meksia, N, Guesmi, A & Mhenni, M F 2016, 'Improving
dyeability of modified cotton fabrics by the natural aqueous extract from red
cabbage using ultrasonic energy', Carbohydrate Polymers, vol.154, pp.287-
295.
Vankar, PS 2017, Natural Dyes for Textiles. Sources, Chemistry and Applications,
Woodhead Publishing, India, pp.33-43.
Vankar, P & Shukla, PD 2019, New Trends in Natural Dyes for Textiles, Woodhead
Publishing, India, pp.159-282.

POLLUTION ASSESSMENT & MANAGEMENT SYSTEMS
Section Pollution Assessment & Management Systems 121

A FINITE ELEMENT METHOD FOR ENVIRONMENTAL AND

POLLUTANT TRANSPORT PREDICTION
Victorita Radulescu
University Politehnica of Bucharest, Splaiul Independentei nr. 313, Sector 6, Bucharest, Romania
e-mail: vradul4@gmail.com
Abstract
In the last decades, significant researches were dedicated to model the water-quality
trends, soil erosion and material losses, contaminant transport, and their ecological
impacts. The present paper investigates theoretically and presents a numerical model
with finite elements of the pollutant transport and diffusion in 2-D environmental
flow. It is a general model based on the physical groundwater flow equations
presented into a new approach, in quantity structure. The mathematical model is
based on mass conservation, including the main flow of the fluid and existing
pollutants. The fluid mass conservation includes the changes in the groundwater
volume flow in a selected time interval and the appeared modifications in the aquifer
characteristics due to the pollutant presence are used in the numerical model. Some
supplementary considerations concerning mathematical modeling are briefly
presented. This model can be used to simulate the groundwater behavior in different
situations, with a concentrated source of the pollutant, or with 2 sources of pollution.
In the present paper are simulated only the aquifers with mainly horizontal
groundwater flow and with a relatively known aquifer’s structure. The model is
tested for a landfill near the Dimbovita River, to predict the groundwater
contamination and the time variation of concentration. Finally, some conclusions
and references are presented.
Keywords: Environmental engineering, Mathematical model, Numerical modeling,

Quality of water, Water pollution
Introduction
The pollution of the aquifers, pollutants transport and dispersion due to improper
waste management or due to different accidents in mines has become an actual
problem for the Romanian authorities. The accelerated process of urbanization and
industrialization, improvement of the standard living conditions, population growth,
and fast economical development are sources of a large number of waste materials,
needed to be deposited (Kontos et al. 2005), (Rojanschi et al. 2002). Mines that have
not been rehabilitated for many years, the tanks of deposits, the sorting and washing
stations are another possible source of pollution; it should not forget the
environmental accident, five years ago, when they were discharged harmful
substances in river Crisul Repede. Nowadays, waste management strategies should
consider the public health and environmental protection. In Romania, generally, the

main waste deposits are near to river courses, for example, Olt, Crisul Repede,
Crisul Negru, Dambovita, Prahova, etc. In these conditions, if there are not
deposited properly, for deposits older than 12 years, they can pollute the
groundwater aquifers. In rainy years, as it is 2019, due to the water infiltration may
appear a rapid transport of pollutants in the aquifer, closely related to the type of
soil, (Romanian law 211 2011), (Normativul tehnic 150 2003).
At European Union level, the waste management is based on some key principles,
such as prevention of waste generation, recycling and reuse, improving and
monitoring of waste disposal methods. The final waste disposal in landfills must be
considered only after having applied preventive measures regarding waste
generation and recovered useful materials and energetic power. The studies on the
suitability of the waste landfill emplacement are particularly important, as they
provide landfill design and construction models considering environmental
protection. Various international specialized studies were conducted to identify
suitable areas for waste landfill location, several using GIS techniques. In Romania,
several studies on waste landfill sitting requirements were completed, but waste
management is still being inadequately implemented.
According to the latest Eurostat report, which includes data considering waste
management, 96% of the collected municipal waste in Romania is disposed of in
dumps and landfills, while only 4% is recycled. Romania is ranked among the last
places in the EU regarding municipal waste recycling. Therefore, the management
of the waste disposal must consider the restrictive environment variables, which can
be numerically modeled, and efficiently analyzed.

Once it has appeared pollutant in soil, due to its permeability and of water
infiltration, dispersion occurs. The phenomenon can be described as in Fig. 1-a, and
in Fig. 1-b the pollutant transport through soil porosity up to the aquifer (Kjeldsen et
al. 2002).
Figure 1. Pollutant transport
The field is considered an unsaturated porous medium. In these conditions, the mass
transfer equation in an elementary volume can be written:

  C x , y , z , t   
div x , y , z ,t D x , y , z , t  x , y , z ,t  grad  
   x , y , z ,t  

  
 div U x , y , z , t C x , y , z , t    x , y , z , t C x , y , z , t    b S    w x , y , z , t C 
t
 s b S   w x, y , z ,t    s (1)
Where: C(x,y,z,t) [kg/m3]- the volumetric concentration of pollutant, D(x,y,z,t)
[m2/s] – the dispersion coefficient of pollutant in the aquifer water, S- punctual
source of pollution, b(x,y,z,t) [kg/m3]-density of the mixed composition (soil and
water), U(x,y,z,t) [m/s] – the components of velocity,  - the soil humidity, w[s-1]-
the decreasing rate of pollutant’s concentration in the liquid phase of the porous soil,
and s [s-1]- the decreasing rate of pollutant’s concentration in the solid phase of the
porous soil [6]. After some calculations and noting:
  K  
  w  w b d ; 1   s  s b (2)
 
Where Kd is a coefficient depending on the pollutant type. Finally, equation (1)
became:
CR   div x , y , z ,t D x , y , z , t  x , y , z , t  grad C x , y , z , t   

   
t     x , y , z , t  

 
 divU x , y , z ,t Cx , y , z ,t   C   1 (3)
A practical solution to pollutant transport in an aquifer is a complex problem and
can be solved in two ways:
1. Density and viscosity of the mixture are considered constant in time and space.
The hydrodynamic equations are independent of the dispersion equation (3) because
density and viscosity do not depend on C. To be useful such modeling it must be
updated at a time step no more than two days, based on local measurements
(Schiopu, & Gavrilescu 2010). In this case, the pattern of dispersion is reduced at a
system of partial differential equations and the working steps will be the following:
- are solved the hydrodynamic equations, the Darcy equation, and the continuity
equation, taking into account the boundary conditions and initial conditions. It is
obtained the velocity distribution in space and time, for different time intervals
- the coefficients of the dispersion equation, are expressed depending on the velocity
at each time step
- the simplified equation of dispersion may be solved
There is obtained the distribution of concentration, space and time, for all time steps.
2. The general case, =(C), C. The velocity and the dispersion coefficients
depend on concentration. It can not be obtained simultaneously the solutions for all
equations. To solve the dispersion problem are considered the next steps:
a) Are made some simplifying assumptions:
- The distribution of concentration is known at time t; then corresponding and 
will be estimated
- It is assumed that for a time interval dt, small, the C, R, and h are constants
b) It is calculated the velocity distribution at time t + dt
c) It is estimated the concentration at time t + dt
d) All parameters are calculated for time t + dt.

With the forward-backward method, all necessary parameters will be determined,

assuming that the dispersion tensor must be decomposed in three directions x, y, z to
make the integration.
To solve the problem of the pollutant dispersion in a porous medium involves the
simultaneous integration of the equations describing the water flow into the soil
pores and the equation of pollutant dispersion. The coefficients of the dispersion are
linear functions, variables in time and space, depending on the flow regime. The
permeability coefficients are nonlinear functions depending on the soil
characteristics, and the density and the dynamic viscosity depend on the solution
concentration. It is considered the dispersion problem in the soil near a river, with
higher soil moisture.
The problem is solved in the next steps:
- Dispersion problem is solved as previously stated in paragraph two
- Are collected some samples of the soil for proper calibration of the model: the soil
permeability, flow discharge in the river, rainfall amount, type and concentration of
pollutant, etc.
- It is predicted the phenomenon.
Further will be analyzed a 2D-dispersion problem, near a river. The x, y directions
are considered perpendicular, then the dispersion equation may be written:
C  2C  2C  2C D D
 Dxx  2 D xy  D yy  vx  vy  C   Qi i (4)
t x 2
x 2
y 2 x y
Where:
v2 v 2y v2 v 2y
D xx  Dl x  DS ; D yy  DS x  Dl ;
2 2 2 2
vxv y
D xy  Dl  DS Dl (5)
2
After a few calculations, the equation (4) may be transformed and integrated for
solving the specific problem. A quantity of water may be directly added or removed
from the aquifer in top or bottom, due to the processes of infiltration, rainfall or
vertical leakage. The mathematical model assumes that the vertical water added in
the aquifer immediately turns and merges with the horizontal flow of the
groundwater (Oroian, & Odagiu 2012). The equation of mass conservation is:
h   h    h 
D         Q  Ql (6)
t x  x  y  y 
Where: h (x ,y, t) – the hydraulic head in the aquifer, - the transmissivity for a
confined aquifer, Q(x,y) - the strength of a source function, representing the fluid
volume per time, added per horizontal area of the aquifer, Q l(x,y) – the liquid
pollution leakage into the aquifer, equal with:
Ql  C h  hi   hi  h A 
k
(7)
l
Where hi-(x,y)–initial hydraulic head in the aquifer, hA(x,y)–hydraulic head after
pollutant admission, k(x,y) – hydraulic conductivity, l(x,y) – thickness layer.
N
hx , y ,t    H j t  j x , y  (8)
j 1
Where Hj-the hydraulic head in node j and j(x,y,t)- the node j characteristics, the
basic functions. In the Galerkin method, the residue is forced to be orthogonal to all
basic functions and thus, the average becomes zero over the entire mesh of finite
elements. This implies N orthogonally requirements in the interest area. Terms of
space derivative may be integrated:
 h   h  i h  i 
`   D  Q  Ql i x , y dxdy      dxdy 
A  t  A  x x y y 
 h h 
    cos x  cos y i x , y dx  0 (9)
B  x y 
Where cos(x), cos(y) are the cosine directions between the outward normal to the
output boundary B, A- input boundary area.
Integration of the two-dimensional dispersion equation is performed by alternating
directions. It is considered the punctual pollutant, from a source of known
concentration. Integrating equation (5) must be made imposing one unique solution
- initial conditions, input A boundary area C(x, y, t) = C i(x,y), t=0
- boundary conditions
- vertical input cross section, C(x=0, y, t) = C f(o,y,t)- known
- vertical output cross section, C(x=Lx,y,t) = C f(Lx,y,t)- known
- horizontal upper side aquifer, C(x,y=Ly/2,t) = Cf(x,Ly/2,t)- known
- horizontal bottom aquifer, C(x,y= - Ly/2,t) = Cf(x,-Ly/2,t)- known
The meshing system, at time t + dt/2
C t 1 i , j  1 p  s   C t 1 i , j  2 p  2  C t 1 i , j  1 p  s  
 C t i  1, j  c  q   C t i , j 2c  2  C t i  1, j c  q   dtS t 1 i , j  (10)
Where
Dl dt v dt Dtl dt v y dt
p ; s x ; c ; q (11)
2 2 dx 2 2dy
dx dy
And for time moment t + dt
C t 2 i  1, j c  q   C t 2 i , j  2c  2  C t 2 i  1, j  c  q  
 C t 1 i , j  1 p  s   C t 1 i , j 2 p  2  C 1t i , j  1 p  s   dtSt 2 i , j 
(12)

In Romania, there are currently 68 landfills that are not complying with the
European regulations concerning the ground storage, their sealing, places where
they have been allocated and finally the consequences on the environment. Of these
32 are in the vicinity of the rivers. There are also industrial basins of washing
associated with mines that have not been rehabilitated for more than 20 years. Five
years ago was recorded an ecological accident, when contaminated water has been
infiltrated into the ground, with major consequences on agricultural production.

In present paper is analyzed the variation in time and space of the pollutant
concentration derived from a landfill that continually infiltrates into an aquifer, for
long time-interval. The analyzed landfill is located near the river Dambovita, Fig. 2;
the market is the modeled area.
Figure 2. A landfill near Dambovita River
The sizes of the aquifer are Lx =200 m, Ly =1000 m, the flow rate in aquifer is 0.1
m/day, longitudinal dispersivity L= 2 m, and transverse T = 20m, concentration at
source C1=160 mg/l, flow velocities in aquifer vx=0,12 m/day, vy=0,038/day,
concentration at the initial moment C(x,y,0) = 0,00012 mg/l, at the domain frontiers
at initial moment CF(x,y,0) = 0, and the injection flow rate is 0.002 m/day.
In Fig. 3, Fig.4 are presented in detail only the areas where the infiltration occurs,
during the time. In Fig. 3 is shown the variation in concentration at the interval of
three months for the first year and in Fig. 4 the predicting model for ten years.
Curves represent equal concentration for different time intervals.
3 months 6 months 9 months
780
760
740
720
700
680
660
640
0 10 20
Figure 3. Dispersion of pollutant material for the first nine months
During the numerical modeling, it was observed that for t=1 day there are no
significant changes in the dispersion of the pollutant. The first significant results
were observed after 5-6 days. It has therefore selected a minimum gap of 7 days.
The numerical solution is stable and convergence. The change does not alter the
time step for the obtained solution and was chosen dx= 5 m and dy=20 m. In the
first year, the flow is more pronounced in the x-axis direction.

1000
900
800
700
600
500
400
300 Year 1 Year 2 Year 3
200 Year 4 Year 5 Year 6
100 Year 10
0
0 50 100 150 200
Figure 4. Dispersion of the pollutant material for ten years
Starting the second year of pollution due to the soil permeability the shape of the
pollutant area tends to increase its width and the shift direction through x direction
diminishes. From the third year, there are only predictive results. Starting the sixth
year, the pollutant reaches the watercourse. If it is extended the analysis to a larger
area, after about 30 years the problem becomes stationary. In Fig. 5-a is shown the
concentration variation in the direction of axis X for ten years, and Fig. 5-b has
compared the numerical results with experimental results for the first three years;
since the third year, there are only numerical results.
C(%) 100
100 C(%)
90
90 Year 1-theoretical
Year 1 Year 2 80 Year 1-experimental
80
Year 3 Year 4
Year 2-theoretical
70
70 Year 2-experimental
60 Year 3-theoretical
60
50 Year 3-experimental
50
40
40
30
30
20
20 x(m)
x(m) 10
10
0
0 0 20 40 60 80 100 120 140 160 180 200
0 20 40 60 80 100 120 140 160 180 200
Figure 5. Concentration variation in direction x
Step's change for the time, in a reasonable way, does not alter the curves allure. Any
modification for steps on x-direction does not influence on curves distribution. The
concentrations on the domain border, considered as the limit conditions does not
fundamentally alter over time.
Conclusions
Using the finite element method was determined the velocity distribution of the
pollutant transport and the variation of concentration on x-direction.

If there is horizontal bedrock in the domain's bottom, the streamlines will be

modified and will appear a different distribution of the concentration dispersion.
Utilization of the proposed model assumed some essential steps: determination of
the grid mesh for finite element method, estimation of the aquifer concentration and
its position, knowledge of the hydrologic regime, boundary conditions, etc.
They have traced the equal concentration curves for different intervals of time and
have been compared the numerical results with the experimental measurements.
After 20 years it is estimated that the pollutant front moves about 450 m. By
comparing the analytical and numerical results it was observed that for a distance
greater than 400 m from the source, the differences are negligible.
References
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and Technology, vol. 32, no. 4, pp. 297–336, doi:http://dx.doi.
org/10.1080/10643380290813462
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spatial multiple criteria analysis methodology’, Waste Management 25, pp.
818–832
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monitorizarea si inchiderea depozitelor de deseuri, 150/07/March/2003, [in
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ANALYSIS OF THE MIGRATION OF A POLLUTANT IN THE SOIL

STRUCTURE
Maria Popa, Loredana Irena Negoita

Petroleum – Gas University of Ploiesti, Bd. Bucuresti, no.39, postal code 100680, Ploiesti,
mariapopa2007@gmail.com, Romania
Abstract
This paper presents a study on the migration into a soil structure of a pollutant, a
liquid petroleum product. Accidental pollution with a liquid petroleum product can
also be considered to crack a transport pipeline. This leads to the displacement of the
pollutant in the soil structure, both horizontally and vertically. The study presents an
analysis of the migration velocity in the soil structure, with certain physical
properties, of both the soil and the pollutant petroleum product.
The penetration of petroleum products to a certain depth in soil is influenced by its
humidity, grain size and density, pollution intensity, viscosity and pollutant density.
It was possible to calculate for the first time at the experimental laboratory level the
depth of penetration of the pollutant.
Keywords: contaminated, diesel oil, pipeline, soil
Introduction
The soil pollution with oil products is one of the most obvious environmental
problems facing Romania in recent years, given the increasing and intensified use of
these substances to meet the energy needs. It can be noticed that both in Romania
and in the world every year there are reported a multitude of accidental or deliberate
spills of oil products on the soil or in waters, which cause economic, social and
environmental problems. Ensuring soil quality protection as a means of increasing
soil resources and protecting the environment, among other things, includes the use
of depollution processes and technologies to neutralize or block the flow of
pollutants and to ensure the desired efficiency and enforcement of the protection
legislation soil quality (Neag 1997).
This work is part of an extensive study that aims to highlight the influence of soil
and pollutant properties in case of accidental spillage.
The direction and speed of displacement of the pollutant depend mainly on its
viscosity and the permeability of the soil. The main force acting on the pollutant is
gravity. Therefore, if the soil is permeable, the pollutant infiltrates into the
predominant soil after a vertical component. There is also a lateral impregnation of
the pollutant, due to the dispersion, which is controlled by the soil porosity.
Advancing to the aquifer, the pollutant can be filtered by soil particles, can be
absorbed, volatilized, precipitated, biodegraded and to a lesser extent, hydrolyzed,
oxidized, reduced, or even stopped by an impermeable barrier (Popa & Negoita
2016a, Popa & Onutu 2016b, Popa et al 2017, Patrascu et al 2005).


At laboratory level, it was attempted to simulate the real accidental cracking
environment of a pipeline carrying a liquid petroleum product. How the pollutant
penetrates into the soil structure is responsible for the physical properties of the two
components: soil - pollutant.
The experimental assembly consisted of a transparent vessel in which a cracked pipe
was buried in a soil layer. By this it circulated controlled quantity of petroleum
product. Measurements have been made on the stains seen after the controlled
pollution.
The migration velocities of the pollutant in the soil structure could thus be set at
different measuring times.
As ascending and descending speeds are variable over time, the calculation was
incremented for each time interval between two consecutive measurements. The
values obtained are used for the calculation of average speeds in each time interval.
Experimental scheme is shown in fig. 1.
Figure 1. Experimental scheme
The geometric characteristics of the experimental glass box and the soil layer are
shown in Table 1.
Table 1. Geometrical characteristics of the experimental glass box

Materials Height, cm Width, cm Length, cm Volume, cm3
Box 13 22 32.5 9295
Soil 8.5 22 32,5 6078

In the experimental experimental glass box was initially discharged a volume of 20
cm3 of petroleum product and the stains observed on the front wall were measured.
When the dimensions of the stain remained constant, after 60 minutes, the volume of
20 cm3 was added. Table 2 shows the variation of the horizontal petroleum product
spot, the horizontal product stain variation is shown in fig. 2, while fig. 3 shows the
variation of the vertical stain.

Table 2. Horizontal petroleum product variation

Crack size, Volume of spilled oil product, Time, Width of stain petroleum
mm cm3 min product, cm
15 10
30 10,5
20
45 10,8
60 11
1,5
75 11,3
90 12,3
20+20
105 13,8
120 13,9
Figure 2. Variation of the width of the Figure 3. Variation of the height of the
stain in time stain in time
Table 3. Vertical petroleum product variation

Time, min 15 30 45 60 75 90 105 120
ha,
Petroleum 4 6 7 7 8 10 14 17
mm
Soil
product hd,
62 62 62 62 62 62 62 62
mm
Figure 4. Experimental installation after pollution

Fig. 4 presents petroleum product stain images visible in the experimental

installation at the end point of time, while the ascending velocity variation is shown
in fig. 5.
In order to express the speed of movement of the pollutant vertically in a soil, the
measured values for the Δha and Δhd heights of the formed pollutant fronts were
presented. They are presented in table 4.
The ascending – wa – and descending velocities – wd – are calculated according to
the heights of the upward motion liquid ha and descending hd at different time
points from the start of the experiment.
ha , mm/min (1)
wa 
m
hd , mm/min (2)

wd 
m
Table 4. Variation for Δha and Δhd
 f   i , min 15-
0
30-
15
45-
30
60-
45
75-
60
90-
75
105-
90
120-
105
   f   i ,min 15 15 15 15 15 15 15 15
 m , min 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5

Δha 4 2 1 0 1 2 4 3
Petroleum
product
Soil Δhd 62 0 0 0 0 0 0 0
Figure 5. The ascending velocity variation
To determine the maximum penetration depth (H) of the pollutant into the soil,
rigorous calculation methods were applied in the unsaturated zone (Neag 1997).
,m (3)
where, K- specific coefficient for pollutant, dimensionless, A-the infiltration surface,
m2, R-retention capacity, l/m3, k-correction coefficient, dimensionless, Vi - volume
of pollutant discharged, m3.

The results obtained are presented in the table 5. It is observed that for the
experimental installation studied the maximum penetration depth of the soil in the
soil, H, is 1.46 m.
Table 5. Dimensions calculated for penetration depth

Calculated sizes Symbol Value
Retention capacity, l/m3 R 5
Volume of pollutant discharged, m3 Vi 40∙10-6
Specific coefficient for pollutant K 400
The correction coefficient k 0,5
The infiltration surface, m2 A 95.91 ∙10-4
The maximum penetration depth, m H 1.46
Conclusions
The evolution of the pollutant in the soil is influenced by the soil and pollutant
properties. When polluting the soil with liquid petroleum products, the formed stain
develops both horizontally and vertically. The experiment initially polluted with a
volume of 20 cm3, and a decrease in ascending speed was observed over time, after
which, at a further 20 cm3 pollution, it increased to a maximum and then dropped
again. For this experiment it was possible to calculate the maximum penetration
depth of the pollutant in the unsaturated zone, 1.46 m.
References
Neag, G 1997, Depoluarea solurilor si apelor subterane, Editura Casa Cartii de
Stiinta, Cluj Napoca.
Patrascu, C, Brebeanu, G, Dobre, L & Popa, M 2015, Analiza relatiilor dintre viteza
de migrare a poluantilor petrolieri lichizi in sol, proprietatile solului si
compozitia poluantilor, Revista de Chimie, 56, nr.7, pp774-778
Popa, M & Negoita, L 2016a, Comparative studies on remediation techniques in
laboratory of soils contaminated with liquid petroleum products, , SIMI 2016,
International Symposium “The Environment and the Industry”,
https://doi.org/10.21698/simi.2016.0024 p.187-192.
Popa, M & Onutu, I 2016b, Studies on the Seed Germination after Thermal
Decontamination of Crude Oil Polluted Soils, Agriculture and Agricultural
Science Procedia, Available online at www.sciencedirect.com, 10/2016,
https://doi.org/10.1016/j.aaspro.2016.09.014 .
Popa, M, Negoita, L, Oprescu, E & Radulescu, S 2017, Laboratory studies on
accidental pollution and soil remediation techniques, SIMI 2017 International
Symposium “The Environment and the Industry”, DOI:
http://doi.org/10.21698/simi.2017.0006, p.49-55.

APPROACHES CONCERNING THE CONCEPTUAL MODEL FOR THE

ASSESSMENT OF THE NATURAL FUND VALUES OF THE SOIL AND
WATER IN NATURAL PROTECTED ZONES
Bogdan Stanescu, Adriana Cuciureanu, Georgiana Cernica, Gina Alina Catrina (Traistaru)
National Research and Development Institute for Industrial Ecology - ECOIND, 71-73 Drumul
Podu Dambovitei Street, 060652 Bucharest, district 6, evmt@incdecoind.ro, Romania
Abstract
This article provides a detailed analysis of the fundamental elements required prior
to conducting on-field research of an areas chosen as case studies for the assessment
of soil and water quality in the unpolluted zones. The ultimate goal of the research
to be carried out over the next two years is to obtain solid and reliable data on the
quality of the two environmental components in these areas. All the data obtained
will be integrated into a solid and georeference database, consisting of a sample
identification module (soil and water) and a module of a varied parameters that will
contain up to 42 parameters analyzed in the testing laboratories.
Finally, the article presents the conclusions regarding the transposition of the
proposed objectives into field and laboratory activities, graphical and descriptive
details integrated into a conceptual model, universally valid in order to evaluate
protected natural areas without direct anthropogenic impact. Particular importance
in assessing these areas is attributed to detailing aspects that can influence the
research results in major way. Issues related to the sampling and subsampling of soil
and water samples, their conservation and transport to the laboratory are considered
relevant and major. Geomorphological criteria of details, geographic and geological
information are considered important in assessing the areas chosen as case studies.
The five areas selected in the present study have been described and a number of
objectives and activities have been proposed for on-site research to be carried out in
the near future.
Keywords: assessment, conceptual model, heavy metals, on-site research, sampling
Introduction
The starting point can be constituted by the basic concepts of geochemistry. It is
considered an appropriate approach to initiation in geochemistry, the concept
described by Mason in 1958, according to the geochemical cycle of the Earth
(Figure 1). The geochemical cycle is presented as a sum of circulation patterns of
elements in nature at geological, pedological and ecological time scales. It is a
conceptual model with two parts, one geological one, and another related to
environment. The geological part (the major geological cycle) occurs in depth in the
internal structure of the earth. It begins when sedimentary rocks are accumulated in
deep and are transformed by processes of diagenesis, that is to say, they sum up the
physico-mechanical and chemical processes that affect postsedimentation to
metamorphism and metasomatism, and later transformed into metamorphic
consolidated rocks, respectively in crystalline rocks (Mason 1958).
The geochemical minor cycle, or the environmental part of the cycle, begins when
the formed rocks are exposed to external factors, such as the surface of the earth's
crust. This is where erosion and transport occur in different stages and ways and
ends with the formation and storage of sedimentary rocks that end the cycle and
continues from the point where it began.
Figure 1. Diagram of the geochemical cycle (Mason 1958)
A second geochemical conceptual model is that of the pedosphere described by

Mattson in 1938 (Figure 2). This concept is important because it introduces the idea
of the interaction of the four geospheres and the events occurring at landscape level
in geological and pedological time. Mattson mentions that when the four geospheres
interact at ground level, there is a fifth geosphere - the pedosphere. More
specifically, the nature of the pedosphere varies depending on the climate,
geological conditions and time, when the pedosphere is formed (Mattson 1938).

Figure 2. Diagram of the possible intractions between the Litosphere (L), the
Hydrosphere (H), the Atmosphere (A) and Biosphere (B). Whenthey interact they
form the Pedosphere (P). (modified after Mattson, 1938)
For each interaction of geospheres, the author has indicated a series of landscapes
that can be formed in the following:
LA - Barren desert where the dispersed system consist of mineral particles and air.
There is no water and life;
AB - Uppermost part of the soil consisting of plant cover;
HB - A pond with countless organisms;
LH - Waterlogged sand or clay under sterile conditions;
LAH - Extreme conditions in some saline soils;
LAB - Deposits of guano by migratory birds;
HAB - Organic soils and forest litter;
LHB - Waterlogged soils and lake bottoms.
More researchers consider that the chemical composition of the sediments depends
on the type of material deposited, the weathering processes and the diagenesis and
geochemistry of individual elements (Rollinson 1993), (Solecki & Chibowski 2000),
(Mahjoor et al. 2009).
There are many studies to be determined was to determine the geochemical
heterogeneity of the sediments in lakes situated within the protected areas to identify
reference sites for monitoring programme with the aim to detect changes in the
environment exposed to strong anthropopressure (Cieślewicz et al. 2018).
Returning to the current coordinates, leaving them the basic conceptual ones, there
was defined the "natural environment" by the specific Romanian legislation,
respectively the Emergency Ordinance no. 57 of 20 June 2007, regarding the regime
of natural protected areas, preservation of natural habitats, wild flora and fauna
respectively as the ensemble of natural, terrestrial and aquatic physico-geographic,
biological and biochemical structures and processes, having the quality of life
preserver.
It is important to mention that heavy metals are naturally occurring elements that are
found throughout the earth’s crust, most environmental contamination results from
anthropogenic activities (Dediu et al. 2016).
The research concerns that are presented in this article are focused on finding and
highlighting the background values of quality indicators for soil and water samples
in protected areas in Romania, where the anthropic influences, especially pollution
are minimum. In this regard, 5 areas as case studies were highlighted in Figure 3
along with a description of the activities proposed for 2019.
Figure 3. Diagram of activities and case studies chosen
Experimental part
The location of study areas on the maps are presented in Figure 4.
Activity planning targets wil be conducted in two main directions:
A. Field activities:
- dimensioning the number of samples to soil and water to be sampled;
- establishing of appropriate equipment for sampling;
- appropriate techniques sampling soil and water samples;
- obtaining relevant information and details (relief, geology, hydrographic network,
vegetation, climatic influences, manifestation of geomorphological phenomena etc)
B. Laboratory activities:
- establishing quality indicators that will be determined by analytical techniques;
- preparing the appropriate test method;
- adequate test equipments;
- ensuring an efficient project management with increased attention to the human
resources involved in meeting the deadlines for finalizing the research reports.
Figure 4. Maps to indicate zones for case studies
Figure 5 shows the activities to be carried out in 2019 and the quality indicators
chosen to be investigated in the selected areas (case studies).

A. Field activities On-site observations On-site establish

(on-site) environmental
sampling points
-Geomorphology;
-Lithology; For each zone (case
-Hydrographic studies):
network; -10 soil samples /
-Vegetation; 4 replicates…total
-Springs or wells; 40 samples;
-Photos; -10 water samples /
-Gps coordinates; 4 replicates…total
-Other relevant 40 samples.
observations
B. Laboratory Established Established

activities (off-site) environmental environmental
quality parameters quality parameters
for SOIL for WATER (surface
and underground
- pH waters)
-Dry matter; -pH
-Humus -Iron
-Kjeldahl Nitrogen -Aluminum
-Iron -Ammonium
-Arsenic -Nitrates
-Boron -Nitrites
-Barium -Boron
-Cadmium -Cadmium
-Cobalt -Chromium total
-Total Chromium -Copper
-Copper -Manganese
-Manganese -Mercury
-Molybdenum -Nickel
-Nickel -Selenium
-Lead -Antimony
-Selenium -Lead
-Antimony -Zinc
-Vanadium -Chlorides
-Zinc -COD / CCOMn
-Calcium
-Magnesium
-Sodium
Figure 5. Schematic presentations of activities and parameters for laboratory tests

The judicious preparation and planning of the activities in order to achieve the
proposed objectives is essential to ensure the success of a project, especially as the
activities will take place between August and December 2019.
For a better understanding of the proposed activities, the logical schemes of the
proposed laboratory activities for soil investigation (Figure 6) and water
investigation (Figure 7) were drawn up.

Figure 6. Schematic presentation of the soil samples laboratory tests
Figure 7. Schematic presentation of the water samples laboratory tests
The proposed activities will constitute an experimental field that will provide solid
analytical data that will be the main results obtained within the project. These data
will constitute a database which at this point is presented as a conceptual model (a
project) in Figure 8.

Figure 8. Schematic presentation of project of the database architecture
Conclusions
Planning of in-terrain (on-site activities) and in laboratory (off-site activities)
activities is essential in achieving major investigative objectives in extented areas
located at appreciable distances one from another. It is especially important that
activities carried out before those in-terrain to be solidly documented and clearly
understood to facilitate on-site research. Criteria for establishing sampling points on-
site are particularly important and should not be neglected. Any aspect of detail that
can be considered relevant must be recorded and notified. The experience and
expertise of the key project team is particularly important in such situations, because
any sample taken from the field must provide a representative of the chosen area, of
course, related to the research objectives.
The introduction of the replicated samples in the analysis is able to lead to statistical
interpretations and to a high degree of confidence in the results obtained.
The initiation of a solid database with geo-referenced is able to lead to objective
observations regarding the quality of environmental factions in protected areas,
respectively where the impact of anthropic activities is minimally invasive.
In the future, this database, as new and new information will be added, will be
useful for an in-depth understanding of the environmental aspects of pollution and
climate changes, the evolution of pollution over time, and the adaptability of
ecosystems to induced by climate changes.
References
*** Emergency Ordinance no. 57 of 20 June 2007, regarding the regime of natural
protected areas, preservation of natural habitats, wild flora and fauna,
published in: Official Monitor, no. 442 of 29 june 2007
Cieślewicz, J, Kobierski, M & Cichosz, M 2018, Geochemical assessment of lake
sediments in protected areas in Poland - a search for reference conditions,
Journal of Limnology, vol. 77 no. 1, pp. 35-45
Dediu V, Kim L, Cosma C & Guta D 2016, The determination of lead, chromium,
arsenic and selenium in sedimentsand soil samples by electrothermal atomic

absorption spectrometry using chemical modifiers, International Symposium –

SIMI 2016“The environment and industry”, Proceedings Book, pp. 416-421
Mason BH 1958, Principles of Geochemistry (second edition). John Wiley, New
York
Mattson S 1938, The constitution of the Pedosphere, Annals of the Agricultural
College of Sweden no. 5, pp. 261-76
Mahjoor AS, Karimi M & Rastegarlari A 2009, Mineralogical and geochemical
characteristics of clay deposits from South Abarkouh District of clay deposit
(Central Iran) and their applications. Journal of Applied. Science, no.9, pp.
601-614.
Rollinson, HR 1993, Using geochemical data: Evaluation, presentation,
interpretation, Longman, New York, pp. 352
Solecki, J & Chibowski S 2000, Examination of trace amounts of some heavy
metals in bottom sediments of selected lakes of south-eastern Poland, Polish
Journal of Environmental Studies, no.9, pp. 203-208.

ASSESSMENT OF THE AIR POLLUTION DUE TO COMBUSTION

PROCESSES OF DIFFERENT WASTES
Mihai Bratu1, Luoana Florentina Pascu1, Mihaela Petrescu1, Andrea Cozea1, Maria Pasca2
1
National Research and Development Institute for Industrial Ecology – ECOIND, 71-73
Drumul Podu Dambovitei Street, sector 6, zip 060652, Bucharest, Romania,
2
SC Oehler Mecanica SRL, str. Uzinei, nr. 1, Marsa-Avrig, jud. Sibiu
Abstract
The continuous increase of the volume of waste, in direct correlation with the
number of the population represents an important problem for the specialists
involved in waste management and the identification of the most efficient solutions
for their management in an environmentally friendly way with minimal impact on
the environment. A large-scale waste reduction solution is to incinerate them in
dedicated installations with strict control over air pollutant emissions from the
incineration process. The paper presents the results of the tests carried out in two
types of waste incinerators for the assessment of pollutant emissions in the air in
order to reduce them and to meet the requirements of the environmental regulations
in this field.
Keywords: combustion gases, combustion process, incinerator, pollutants, waste
Introduction
Among many environmental problems that threaten our planet, a major problem are,
without a doubt, wastes, as the result of multiple human activities. The wastes
represent an important issue due to both the continuous increase of the quantities
and their types (which, by degradation in the natural environment, can pose a danger
to the environment and the health of the population), as well as to the significant
quantities of raw materials, reusable materials and energy, which can be recovered
and introduced into the economic circuit (Bucur & Danet 2016; Danciulescu and all
2015; Danciulescu and all 2017). The most important waste disposal advantage is
incineration as a fast waste treatment method, which means that very large quantities
can be destroyed in a relatively short time. The amount of solids resulting from
combustion represents only 15-20% of the initial weight of the waste, leading to a
reduction in storage space (Bratu and all 2016; February 2018; Guta and all 2007;
Ramona and all 2007; September 2010; Serbanescu and all 2018). The
environmental effects of municipal waste incineration are mainly related to
emissions released into the atmosphere by incinerators ,losses of organic matter and
other biomass-containing materials. The overall environmental performance of
municipal waste incineration, including bio-waste, depends on a multitude of
factors, in particular fuel quality, plant energy efficiency and the replaced energy
source that can greatly influence air emissions. (Danciulescu and all 2017, Petrescu
and all 2017, January 2015). As a result of the incineration process of different types
of waste, a number of pollutants are evacuated to the environment.
The paper presents the results of the tests carried out in two types of waste
incinerators for the assessment of air pollutant emissions in order to reduce them and
to meet the requirements of the environmental regulations in this field; the tests were
carried out in an animal waste incinerator and a municipal waste incinerator. The
obtained values are compared to in force legislation, depending on the type of
incinerator and waste used in incineration (Bratu and all 2018, Directive 2008/98;
Law 211/2011; Petrescu and all 2017).
The tests that were the subject of this study were conducted between 2016-2018 and
assumed the measurement of the concentration of pollutants specific to air emissions
from waste incineration, combustion gases, powders, volatile organic compounds
(VOC) and dioxins and furans in May , September and December of each year. For
a series of pollutants measurements were made in 2019, too.
Waste incinerators
Technological waste incineration processes, indiferent of the type of waste used,
include: the combustion system, the heat recovery system, the treatment of waste
gases and the residues resulting from incineration (Fig. 1). The research in this paper
is carried out for two categories of incinerators: i) Municipal waste incinerators:
plastics material with traces of oils, paint, toothpaste with expired validity periods,
residues from different industries, sanitary materials, solid or liquid detergents,
chlorine, laundry conditioners , medical waste, and (ii) animal waste incinerators
(poultry or pig bodies)
Figure 1. Scheme of the technological process of waste incineration
Pollutants discharged into the atmosphere following the burning process from
incinerators are: combustion gases, dusts, volatile organic compounds (VOCs) and
dioxins and furans, compounds whose emission levels are set by law 278/2013
(Tabel 1). (Law 278/2013).

Table 1. Limit values in the law 278/2013

Pollutant Limit values Measure units
CO 100 mg/Nmc
NOx 200 mg/Nmc
SO2 50 mg/Nmc
powders 10 mg/Nmc
dioxins & furans 0.1 ng/Nmc
volatile organic
10 mgC/Nmc
compounds
To measure the concentration of pollutants emitted in the air, automatic methods

(CO, NOx, SO2, volatile organic compounds (VOC) were used, as well as manual
methods involving field sampling and laboratory analysis (dioxins and furans,
powders). In Fig. 2 shows a series of equipment used for the sampling /
measurement of airborne pollutants.
(a) (b)
(c) (d)
Figure 2. Equipment used for the emission / measurement of pollutants emitted in
the air: isokinetic particle sampler (a) burn gas analyzer (b) dioxin and furans
sampler (c) and automatic volatile organic compounds analyzer (d).
For the isokinetic powder extraction, the equipment shown in Figure 2a was used. In
order to obtain an isokinetic sampling, it is necessary to determine and introduce in
the isokinetic calculation some physical parameters: the dynamic pressure [mbar] of
the gaseous effluent at the point of measurement; gas temperature [K]; chemical
composition of gaseous effluent for gas density determination (kg/m³); gas humidity
[%]; atmospheric pressure [mbar]. Also, for the determination of the combustion gas
concentration was used the combustion gas analyzer shown in Figure 2b, and the
isokinetic sampling equipment provided with sampling pump and condenser was
used for the sampling of dioxins and furans - Figure 2c. Also, the dust particles and
gas aerosols are retained to determine the concentration of dioxins and furans on the
filter and XAD resin. The condenser allows condensation of the gaseous effluent
leaving the sampling probe so that the condensed fluid is analyzed analytically to
determine the concentration of dioxins and furans. To determine the concentration
of volatile organic compounds, the Thermo-FID analyzer presented in Figure 2d was
used. Sampling in this work is done according to the standards SR EN 15259:2009;
SR EN 13284-1:2008; SR ISO 10396:2008; SR EN 12619: 2013 (SR EN
15259:2009, SR EN 13284-1:2008; SR ISO 10396:2008; SR EN 12619: 2013)
Results and discussion

The values obtained for the pollutants studied in this paper are shown graphically in
the following figures.
i. Burn gases
(a) (b)
Figure 4.Variation on the concentration of CO, NOx, SO2 during 2016-2018; 4a.
animal waste incineration, 4b. municipal waste incineration
The limit values in the legislation for the studied pollutants are: CO-100mg/Nm3;
NOx-200 mg/Nm3; SO2-50mg/Nm3. Thus, concentrations higher than the limits for
CO for May 2016 and December 2018 for the animal waste incinerator are
observed. Also high NOx values were determined in May 2016 at the animal waste
incinerator.

ii. Total powders.
(a) (b)
Figure 5. The variation in the total powder concentration during the period 2016-
2018; 5a. animal waste incineration, 5b. municipal waste incineration
Total powder concentration values are calculated in mg/Nm3 with O2 reference of

11%. From the graphs shown in Figure 5a for the animal waste incinerator and
Figure 5b for the Municipal Waste Incinerator it is observed that values were shown
showing a higher concentration of total dusts emitted in the case of the animal waste
incinerator for September / 2016 and December / 2018. Exceedings of combustion
gases and dusts produced by the animal waste incinerator are caused by the fact that
the incinerator is old, without reduction systems for the pollutants discharged into
the environment, so the construction of high performance incinerators has been
imposed.
iii. Dioxins & Furans
(a) (b)
Figure 6. The variation in the dioxins & furans concentration during the period
2016-2018; 6a. animal waste incineration, 6b. municipal waste incineration
From the graphs shown in Figure 6 it is observed that for the animal waste
incinerator higher values were obtained for the concentration of dioxins and furans
compared to the concentrations obtained for the municipal waste incinerator. Higher
values were recorded in 2017, namely 0.033 ngTEQ / Nmc (TEQ-toxic equivalency
factor). The maximum limit value for this pollutant is 0.1 ngTEQ / Nmc.

iv. Volatile organic compounds
(a) (b)
Figure 7. The variation in volatile organic compounds concentration during the
period 2016-2018; 7a. animal waste incineration, 7b. municipal waste incineration
Volatile organic compounds determined over the period studied in this paper show
higher values at the animal waste incinerator for May 2017 and 2018 calculated with
measured oxygen and reference oxygen of 11%. Compared with the concentrations
of volatile organic compounds determined by another type of technological process
(Figure 8, according to Subsidiary contract No. 2142 / 12.02.2019), the
concentrations of volatile organic compounds are lower for incinerators than for
other types of technological processes.
Figure 8 Values of volatile organic compound concentration in technological

processes
However, given the limit value in the legislation (Law 278/2013) of 50 mgC / Nm3
and in this case the measured values are within limits.
Conclusions
The resulting values for pollutants discharged into the environment depend on both
the combustion conditions and the waste used for incineration. Thus, the values
exceeding the limits of the legislation for the pollutants studied in this paper are due
to incineration plants. So, municipal waste incinerators are reliable, efficient
installations, made up of complex equipment with filtering and cleaning systems
that are discharged into the environment. Incinerators for animal waste where the
pollutant determinations made in this paper have been made do not have gaseous
effluent filtration equipment. Therefore, it is recommended to modernize the
incineration / burning technology of animal waste so that the concentration values of
pollutants discharged into the environment fall within the limit values in the
legislation.
Acknowledgements
This work was realized with the support of Operational Program Competitiveness 2014-2020,
Contract no. 55/05.09.2016, Project ID P_40_300, SMIS 105581, Subsidiary Contract
2142/12.02.2019.
References
Danciulescu, V, Bucur, E, Bratu, M, Andrei, M, Petrescu, M, Diodiu, R, Tanase, G 2017,
'Emissions of greenhouse gases from the livestock sector', 20th International
Symposium “The Environment and the Industry”, Proceedings Book, National
Research and Development Institute for Industrial Ecology - ECOIND , Bucharest,
Proceedings Book, Bucharest, pp. 371-375.
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of sound waves by using panels made of composite materials', Roumanian
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***SR EN 15259:2008 – Air quality. Measurement of fixed source emissions.
Requirements relating to measurement sections and locations, as well as to the

objective, plan and measurement ratio
***SR EN 13284-1:2008 - Stationary source emissions - Determination of low range
mass concentration of dust - Part 1: Manual gravimetric method

***SR ISO 10396:2008 · Emissions from fixed sources. Sampling for automatic
determination of the gas concentrations emitted for fixed monitoring systems

***SR EN 12619: 2013 Stationary source emissions - Determination of the mass
concentration of total gaseous organic carbon - Continuous flame ionisation

detector method

BIOLOGICAL MONITORING USED IN ASSESSMENT OF THE AIR

POLLUTANTS
Andreea Cozea, Elena Bucur
National Research and Development Institute for Industrial Ecology ECOIND, 71-73
Drumul Podul Dambovitei Street, code 060652, Bucharest, Romania,
elena.bucur@incdecoind.ro
Abstract
Nowadays, the air pollution has become a major environmental problem due to rapid
increase of industrialization and anthropogenic activities which led to climate
change. Air pollution is considered as a harmful agent for human health. Different
classes of pollutants like gaseous (SOx, NOx) are continuously released in air and
perceived/recognized as pollutants. Among the biological models, plants could
indicate pollution load in a particular area via alterations in physiological parameters
so, there is a need for reliable and sustainable air pollution monitoring and control
methods.
Keywords: air quality, bioindicators, biomonitoring, climate change
Introduction
Air is the environmental factor that is the fastest medium that support the transport
of pollutants into the environment. Air pollution has many and significant adverse
effects on human health and it can cause damage on flora and fauna. For these
reasons, special attention is paid to the surveillance, maintenance and improvement
of air quality (Bakiyaraj & Ayyappan 2014, Bermadinger et al 1988).
Air quality is determined by emissions to air from stationary and mobile sources
(road traffic), as well as long-distance transport of air pollutants (Bucur et al 2018).
In Romania, the "air quality" field is regulated by the Air Quality Legislation with
the purpose of protecting together the human health and the environment, which are
inseparable entities and the existence of human’s activity is environmentally
dependent.
The regulating measures aimed at maintaining the quality of ambient air where it
meets the ambient air quality objectives established by this law and its improvement
in other cases (Kozlowski 1980, Neidoni et al 2018). Based on the development of
the industries, the adverse effects on the environment have also emerged (Ashmore
et al 1978).
The aim of this study was to identify and select certain species of plants for using
them in experimental biomonitoring studies. An experimental fumigation closed
system with controlled environmental characteristics and pollutant delivery was
used to study the effects of air pollution on plants species. The relative degrees of
plant injury as a response of plants to pollutants fumigation were assessed.


The European Standard, SR EN 16789 - Biomonitoring with superior plants was
used as a source of documentation. “Standardized exposure method for tobacco”.
with the extension of its applicability and for other species of the same family as the
Solanaceae (SR EN 16789: 2017; SR EN 14625: 2005; Tingey 1989).
The plant species and varieties used for the nitrogen dioxide test were as follows: P1
- Nicotiana rustica, P2 - Nicotiana tabacum, P4 - Petunia hibrida. Plants were
grown from seeds in a standard soil mix. After about four weeks, the seedlings were
transplanted into cylindrical vessels with a capacity of about 750 ml containing a
fresh soil mixture (Petrescu et al. 2017, Pakeman et al 2000). Three plants of each
variety were placed in the fumigation chamber for about 7 days until four-seven-leaf
stage (Cozea et al 2018). Only the healthy leaf plants were exposed to ozone in the
fumigation system in the enclosed room (Begu et al 2006). The fumigation method
in the closed room. In this study, the plant responses to fumigation of nitrogen
dioxide were evaluated according to the relative degree of injury of different
tobacco varieties (Partha 2014). To assess the susceptibility of three Solanaceae
family plants to nitrogen dioxide (NO2), two rounds of fumigation experiments were
performed for seven days each round. Plant pots were watered and covered with
plastic bags, before fumigation, the plants were watered to keep the stomata open.
The exposure period was 24h/day, 7 days along/exposure. These tobacco varieties
were exposed to a series of concentrations of nitrogen dioxide (0.1 ppm first round
and 0.2 ppm) in a one-pass growth chamber fumigation system for short periods of
time. The method used to fumigate plants in these experiments was actually a
naturally illuminated glass chamber. The fumigation chamber had a total size of 100
cm in length × 45 cm in height × 50 cm in width with a volume of 225 liters. The
sidewalls were built from glass sheets, except for a single top of Plexiglas, (Figure
1) where the air treatment plant was mounted.
As the air inside the glasshouses has not been recirculated synthetic nitrogen dioxide
portions has been added to maintain stable concentrations inside the glasshouses
during fumigation periods. Awareness of the susceptibility levels of these plant
varieties at the laboratory level is useful for the biological monitoring process of
nitrogen in field experiments.
For microscopy Tests, with the role of observing the necrotic plant tissue was used
Leica M205 FA stereomicroscope, one of the most advanced, multidimensional
stereo imaging system providing unsurpassed image resolution from panorama to
the finest microstructure. Zoom range of 7x - 160x, the Leica M205 FA, allows 3D
macro-to-micro viewing. Leica's Triple Beam technology for fluorescence
illumination enhances image contrast, details, and intensity.

Figure 1. The fumigation glasshouse

Biomonitoring is a new field of research for our country as well as the use of
sentinel species. The previous research activity in this study involved preliminary
stages before this work, regarding biomonitoring with sentinel plants, which had the
aim the identification of the species of plants with specific pollutants response,
selection of certain plant species and utilization of the species plants selected in field
experimental biomonitoring studies.
The research activities of the first stage were aimed to select specific species of
plants with a specific response for a series of chemical compounds by tests carried
out in test rooms with known pedo-atmospheric conditions, and in terms of
concentration the pollutants present in the air as well as the physical parameters
(temperature, humidity, lighting level, etc.).
P1-Nicotiana rustica was clearly the most sensitive at 0.1 ppm nitrogen dioxide
during the 1st exposure, followed by P2-Nicotiana tabacum (Figure 2) and P4-
Petunia hybrida compared to control plants. The scale bar on Leica
stereomicroscope represents for Figure a) 10 mm and for Figure b) 5 mm. These
plants showed necrosis and chlorosis on the leaves.
The polluting sensitivity of plants was different. Thus, the results of the experiments
varied according to the type of plant. After each fumigation round, visible injuries
were evaluated as the percentage of injured leaves, and these were determined by
visual estimates. The lesions / percentage of damage to plant leaves after two rounds
of exposure to Nicotiana rustica were about 74% of the final leaf area and about
30% of the area of Nicotiana tabacum leaves and about 23% injury to Petunia
hybrida. In parallel, the control was a set of plants that were similar in number and
size to the experimental set were kept under the same conditions but without
exposure to pollutants. No major noxious effects were observed when the plants
were exposed to concentrations of 0.1 ppm nitrogen dioxide compared to
concentrations of 0.2 ppm (Figure 3). Doses of 0.1 ppm did not cause visible leaf
damage in any tobacco varieties. Doses higher than 0.2 ppm caused visible damage

to the leaves characterized by necrosis and chlorosis and ultimately the irreparable
destruction of exposed plants.
Figure 2. Nicotiana tabacum - nitrogen dioxide fumigation effects (a, b)
The air temperature varied within the experiment rooms. The treatments were
applied at temperatures between 24°C and 35°C. Dose-response relationships were
characterized by estimating the relationship between the dose or exposure level and
the severity of exposure-induced effects (Figure 3).
Figure 3. Dose-Response Curve
For the carried out experiments, a correlation between the concentration and the
intensity of the pollutants was observed by analysing the response in the case of the
exposed plants, the cause-effect relationship. The two different concentrations
represented the minimum number to detect a pattern of response and the relationship
between the affected leaf area and the pollutant concentration suggests that the
injury threshold may be close to the exposure concentration of 0.2 ppm.
Causality was sustained by the presence of a pollutant (or other stressors)

immediately before or during observation of structural or functional dysfunctions of
the observed community or individuals (Mocuta 2017). Demonstration of noxious
effects of pollutants can only proceed using living organisms that either react
sensitively to specific pollutants/pollutant mixtures. Such bioindicators also
integrate the effects of all environmental factors including interactions with other
pollutants or climatic conditions (Velickovic & Perisic 2006). In this way risks from
complex pollutant mixtures and even chronic stress below pollutant thresholds can
be recorded.
Bioindicator plants like that used in that study have already been used for many
years in scientific studies to demonstrate pollutant effects. In some countries such as
Germany, Austria, the Netherlands and Italy, some methods have found their way
into the routine monitoring of industrial plants by private companies and
environmental authorities. At a Europe-wide level the use of bioindicator plants has
not been yet established (with a few notable exceptions) (EEA 2017a). One reason
for the lacking acceptance amongst decision makers in politics, public
administration and private enterprises is the insufficient standardization of the
procedures, a fact making it difficult to compare different results obtained from their
use (Gombert et al 2006).
The application and validation in the laboratory of the developed models / methods
took into account the research on laboratory testing of the method of biomonitoring
of air quality with plants. Biomonitoring is considered a valuable method for
assessing the level of pollutants for situations where monitoring of air pollution
through instruments in inaccessible locations is too expensive (Joshi et al. 2009).
The growth was not evaluated. We’re not included into count the lesions that were
not induced by nitrogen dioxide for this experiment or if the degree of injury that
occurs cannot be assessed as being characteristic of this pollutant (Lu et al. 2018).
This was very important because the relative sensitivity depends on the level of
exposure to the pollutant. A data study was carried out in order to achieve the
methodology for approaching the research on biomonitoring the air with sentinel
plants to contribute to a standardisation of method applied at a European level and
also to demonstrate the noxious effects of air pollutants on living beings in a clear
and sustainable manner (SR EN 16789: 2017). The future step is the exposition of
bioindicator plants cultivated under standardized conditions to ambient air on the
sites in order to assess and to demonstrate the effects of different air pollutants. The
tests were carried out in parallel with the selected species with a recognized
response, selected in the previous studies in the presence of ozone in the air, and
tests with the same plants on nitrogen dioxide (NO2). The scientific and technical
investigations were accompanied by the concept developed within the scope of the
study.
During the test period the selected plants were subjected to dioxide gas of two
different concentrations of 0.1 and 0.2 (ppm). Two rounds of fumigation were
performed. The closed-chamber method that was used for these experiments has
facilitated the classification of the susceptibilities of the test plants. Chlorosis,

necrosis and variable-point follicular burns, with punctual appearance, were

observed.
Variation of symptom expression among tobacco varieties was distinct. These plants
showed necrosis and chlorosis of the leaves Thus the wild type of tobacco P1-
Nicotiana rustica was clearly the most sensitive to nitrogen dioxide, followed by P2-
Nicotiana tabacum and P4-Petunia hybrida. The difference between plant species
and different sensitivity at the same pollutant concentration was attributed to the
following factor: different stomatal conductance. Although this indicates
detoxification, the decomposition products of nitrogen dioxide may affect the
photosynthesis of the plant by the phenomenon of chlorosis.
Advantages of Biomonitoring vs. Instrumental Monitoring:
-can provide indications of time variation, accumulation or effect of interaction of
certain abiotic factors, and the response of individual living organisms or
community organisms to environmental changes.
-the use of bioindicators to monitor populations and, implicitly through
extrapolation on ecosystems exposed to pollution phenomena and can provide
timely intervention to protect the integrity of the environment and indirectly the
health of the human population.
Conclusions
Performing tests plant's response to air pollution (the concentration of compounds in
the air) have been monitored changes in leaf integrity, growth rate and plant growth
in general, as well as tissue changes.
The biological response integrates the direct influence of the pollutant with the
individual responses of each individual species and each individual response, which
varies depending on the genotype structure and in close correlation with the other
environmental factors that acts on living organisms (temperature, luminous
intensity, humidity). Additional information on plant tissue that provided an analysis
on effects associated with the intensity of exposure and its action showed by visual
inspection the presence of necrosis at the stomata level in Test plants versus Control
plants.
In order to be used as bioindicators, the selected species exhibited a characteristic
reaction to the action of a certain pollutant, in this case nitrogen dioxide, which is
not involved with that produced by other stressors, as demonstrated by these tests
and the correlations made.
Effective action to reduce the impacts of air pollution requires a good understanding
of its causes, how pollutants are affecting humans, ecosystems, the climate, and
subsequently society and the economy. The real advantage of using biological
monitoring methods is that they integrate the influence of different factors (the most
important being the pollutants), and the answer is the result of their action and the
reaction of the living organism.
The research activity in this study involved the completion of some stages that will
form the basis of future studies on Biomonitoring with sentinel plants, a stage that

will continue to be studied and will offer a starting point of understanding for a
better biomonitoring.
Acknowledgements
This study was accomplishing through the “Nucleu” Research Project, developed with the
Ministry of Research and Innovation support, Agreement no. 20 N/2019, project no. PN – 19
04 02 02; the authors would like to thank all those who contributed to this study.
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COMPARATIVE TOXICITY EFFECTS OF CLEANING PRODUCTS ON

FISH, ALGAE AND CRUSTACEA
Stefania Gheorghe1, Irina Lucaciu1, Daniel Mitru1,2, Lucian Ionescu1, Mihai Nita-Lazar1
1
National Research and Development Institute for Industrial Ecology ECOIND Bucharest, 71-
73 Drumul Podul Dambovitei Street, 060652, Bucharest, Romania,
stefania.gheorghe@incdecoind.ro.
2
The Polytechnic University of Bucharest - Faculty of Chemistry Engineering
Abstract
The hygiene process imposes a high usage of household cleaning products and
personal care products, which after use reach the municipal and industrial
wastewater of the sewerage networks and finally the surface waters. Depending on
the physic, chemical and biological properties of the constituent substances, they
could manifest various harmful effects on the aquatic organisms such as mortality,
inhibition or stimulation of growth / development, and changes of the community
structure linked to particular ecosystems and water quality degradation.
The study objective was to highlighted the aquatic toxicity effects of some cleaning
products on freshwater fish, green microalgae and planktonic crustaceans in order to
correspond to EU ecolabel criteria. Three products based on anionic, non-ionic and
amphoteric surfactants were tested using OECD methodologies. The laboratory
experiments showed non-toxic acute effects on tested organisms. The acute toxicity
concentrations (EC50 / LC50) being more than 100 mg/l for each tested product.
Acording to international norms for toxicity clasification all the products were non
harmful for aquatic live.
Keywords: toxicity, aquatic, detergents
Introduction
The modern world standards generate a continuous market development of the
cleaning products, especially for the ecological products. Unfortunately, the
surfactants have polluted the fresh waters and affected aquatic organisms such as
zooplankton, phytoplankton and fish (Tomislav 2010). Non-harmless effects of the
products and their active substances on living organisms could be proved by
ecotoxicological studies (Gheorghe 2012). The criteria for cleaning product EU
ecolabel are set by Regulation (EC) No 66/2010 of the European Parliament. The
products must to meeting high environmental standards throughout their life-cycle:
from raw material extraction, to production, distribution and disposal. The norm
limits the presence in to the product composition of the substances with harmful
effects on aquatic environment, promote a high biodegradability and the small and
eco-friendly packages. In 2018, the statistics showed a gradually increase of the
number of EU Eco labelled products mainly indoor and outdoor paints and
varnishes, converted paper, tissue paper and hard surface cleaning products
(http://ec.europa.eu). The European Commission make available a User Manual for
Ecolabel of detergents and cleaning product that include all the criteria.

Toxicity to aquatic organisms is one of most important criteria for eco labelling and
is applied both for the ingredients and also for the final products. Their toxicity shall
not be classified as hazardous for the aquatic environment according to REACH
Regulation. This paper presents the toxicity responses of three freshwater species
(fish - Cyprinus carpio, microalgae – Pseudokirchneriella subcapitata and the
planktonic crustacean - Daphnia magna) under acute intoxication with commercial
cleaning products based on anionic, non-ionic and amphoteric surfactants.
Material and methods

Three commercial products based on anionic, non-ionic and amphoteric surfactants
have been tested. The composition and CAS number are presented in table 1.
Table 1 – Tested cleaning products (ingredients)

Product 1 – hard surface Product 2 – sanitary Product 3 – hand dish
cleaning product cleaning product cleaning product
(10% a.s.)
15-20% s.a
Alcohols, C12-C14, Alcohols, C12-C14, Alcohols, C12-C14,
ethoxylated, sulphate, sodium ethoxylated, sulphate, ethoxylated, sulphate,
salt (SLES) – anionic sodium salt (SLES) – sodium salt (SLES) –
CAS 68891-38-3 anionic anionic
CAS 68891-38-3 CAS 68891-38-3
Alkane C6-C8 (even Alkane C6-C8 (even Coco Fatty Acid
numbered), 1-sulphonic acid, numbered), 1-sulphonic Diethanolamide -
sodium salt) – anionic acid, sodium salt) – anionic amphoteric
CAS 5324-84-5 CAS 5324-84-5 CAS 8051-30-7
Alcooli, C8-18 etoxilați Alcooli, C8-18 etoxilați Cocoamidopropil betaina
propoxilati – non-ionic propoxilati - non ionic (CAPB) - amphoteric
CAS 69013-18-9 CAS 69013-18-9 CAS 61789-40-0
Other ingredients: Alcohol Citric Acid monohidrated; Potasium cocoate

izipropilic, 1-methoxy-2- Acid fosforic Glicerina
propanol
* a.s. – total active substance
The tested organisms belonged to three trophic levels: vertebrates (fish),

invertebrates (crustaceans as Daphnia) and plants (algae). Indigenous species were
used to evaluate the acute toxicity on aquatic ecosystem. The working methodology
respect the OECD principles concerning the use of vertebrate and is aligned to
Detergent Regulation no. 648/2004 and RECH Regulation and their amendments
(Gheorghe 2011). Using the step-down approach, the LC50 biotests with fish were
developed considering the EC50 values obtained for algae and crustacean.
At least five concentrations between 1 - 1000 mg product / l, were incubated, in

static conditions, up to 96h, in the presence of the testing biological models (table
2).

Table 2. Toxicity methods (Gheorghe 2012)

Type of Test period /
Species Test Endpoint effect
test incubation
OECD Static, Mortality, LC50
Cyprinus carpio 96h, 21-22oC
203 acute Clinical signs
OECD Static, Mortality /
Daphnia magna 24-48h, 20oC
202 acute immobilization LC50
Pseudokirchneriella OECD Static, Algal growth rate 72h,
subcapita 201 acute inhibition EC50 21-25oC
Daphnia magna test

The tested products revealed no toxicity on planktonic crustacean Daphnia magna.
After 48h of exposure the Product 1 based on anionic and non-ionic surfactants
don’t induced mortality effects for concentrations between 31.25 - 250 mg /l. The
Product 1 at 500 mg /l induced small toxic effects of around 5-10%.
Product 2 based on the same anionic and non-ionic surfactants (table 1) was non-
toxic in concentrations between 31.25 – 62.5 mg / l. At 125 mg/l about 5% mortality
was observed. In concentration more than 250 mg/l the effects increased to 45 -
100%. The toxicity differences could be influenced by the other chemical
ingredients such as citric acid or phosphoric acid.
Products 3 based on anionic and amphoteric surfactants revealed non toxicity of
crustacean. About 5% mortality effects at 60 mg product/l, 30% at 125 mg product/ l
and 70 – 95% at 250 and 500 mg product/ l were obtained.
Algae test
The two products (products 1 and 2) based on 10% active surfactants (anionic and
non-ionic) don’t induced toxic effects on algal growth, but they could enhance the
water eutrophication if their concentrations exceed the 500 mg / l and the water
temperature is growing more than 25 degrades. Product 1 at 62.5 – 1000 mg /l
showed a great algal growth about 90 - 95 % from the control (figure 1). Products 2,
similar with Product 1 showed the same increase of algal biomass at 62.5 – 125 mg /
l. In this case inhibitions about 40% for 500 mg/l and 70% for 1000 mg/l were
obtained. A decrease specific growth rate about 0.41 / day compared with the control
1.58 / day was observed (Figure 2).
Product 3 have demonstrated a different behaviour on algae growth. At small
concentrations about 1 - 10 mg / l the results were in the control limits. At 50 – 100
mg / l showed a small stimulation of algal growth (3-6%) fallowed by a significant
inhibition estimated at 65% (Figure 3).

Figure 1. Algal growth induced by Figure 2. Algal growth induced by

product 1 product 2
Figure 3. Algal growth induced by product 3
Fish test
All the products were tested in concentration of 100 – 1000 mg product/ l. The fish
tests showed that the cleaning products don’t induce any mortality effects even at
the highest concentrations (500 mg/ l or 1000 mg/l). A stress factor for the fish was
the foam occurred especially at the highest tested concentrations, especially in case
of Product 3 based on amphoteric surfactant. An increased frequency of opercula
ventilator movement was observed in all tested containers.
The foam intensity decreased to the end of test, this fact being correlated with the
surfactant presence.
The concentration of total active substances was instable during fish tests, decreased
more than 50% after 96h of exposure, due to a high volume of tested solutions, large
surface of test containers and tank aeration.
Overall, the total active substances used for crustacean and alga tests were reduced
less than 20% after 48h or 72h.
The order of toxicity level on tested aquatic organisms was: Product 3 > Product 2 >
Product 1. The laboratory experiments showed non-toxic acute effects on tested
organisms, the acute toxicity concentrations (EC50 / LC50) being >100 mg/l for
each tested product (table 3).

Table 3 Aquatic toxicity results

Daphnia magna Pseudokirchneriella Cyprinus carpio
Product subcapitata
EC50 /LC50
1 >1000 mg/l >1000 mg/l >1000 mg/l
2 382.55 596.53 >1000 mg/l
3 181.55 463.23 >1000 mg/l
Toxicity class Non-toxic Non toxic Non – toxic
Conclusion
Acording to Regulation (EC) no 1272/2008 on Classification, Labelling and
Packaging (CLP) of substances and mixtures based on the United Nations’ Globally
Harmonized System (GHS) of REACH 1907/2006 modification, non toxic
clasification was established for all tested cleaning products. The results showed that
the most sensitive was Daphnia magna and fish were the least senzitive (Lechuga
2016). Product 3 was more harmful comparing to Product 1 and 2 because of the
presence of amphoteric surfactant. These results have been confirmed through
previuos studies on cocamidopropil betaine (Gheorghe 2012).
Even if the commercial cleaning products can be classified as non-hazardous to the
aquatic environment, a differentiated sensibility was observed according to the type
of active substances or other ingoing ingredients or the solution acidification. Only
in case of algae, it could be observed some eutrophication effects. No other effects
were observed in case of recommended doses for use.
The tested products meet the EU Ecolabel criteria for the final products referring to
the harmful to the aquatic environment.
Acknowledgements:
This work was financially supported by NUCLEU Programme, contract 20N/2019, project no.
PN 19-04 02 01.
References
Gheorghe Ş., Lucaciu I., Grumaz R., 2011, Detergents legislative framework and
ecotoxicological testing methodology, Journal of Environmental Protection
and Ecology, book 3A, vol.12, 1525-1532, ISSN 1311-5065.
Gheorghe Ş., Lucaciu I., Grumaz R., Stoica C., 2012a, Acute toxicity assessment of
several cationic and amphoteric surfactants on aquatic organisms, Journal of
Environmental Protection and Ecology, nr vol.13, no.2, 541-553.
Lechuga M., Jurado E, Núñez-Olea J.,2016, Acute toxicity of anionic and non-ionic
surfactants to aquatic organisms, Ecotoxicol Environ Saf., 125:1-8.
OECD 201 – Freshwater alga and cyanobacteria, growth inhibition test - Metoda C-
03 publicata in Anexa C a Regulamentului CE 440/2008, cu completarile/
modificarile ulterioare din Regulamentul CE 761/2009;
OECD 202 – Daphnia sp. acute immobilization test – Metoda C.2, Anexa C la
Regulamentul CE 440 / 2008, cu completarile/ modificarile ulterioare din
Regulamentul CE 761/2009;
OECD 203 – Fish, acute toxicity test - Metoda C.1 – Anexa Partea C – Regulament
CE 440/2008 cu completarile/ modificarile ulterioare din Regulamentul CE
761/2009;
OECD series on testing and assessment nr. 23 – Guidance document on aquatic

toxicity testing of difficult substances and mixture, ENV/JM/MONO (2000)6;
Regulamentul (CE) nr. 1272/2008 al Parlamentului European si al Consiliului din 16
decembrie 2008 privind clasificarea, etichetarea și ambalarea substanțelor și a
amestecurilor (CLP);
Regulation (EC) no. 2004/648 of European Parliament and European Council,
Official Journal of European Union, L104/1, April 2004.
Tomislav Ivankovic and Jasna Hrenovic, 2010, Surfactants in the Environment, Arh.
Hig. Rada Toksicol: 61: 95-110.

CPM AND PERT TECHNIQUES FOR SMALL-SCALE R&D PROJECTS
Marius Simion, Gabriela Vasile, Cristina Dinu, Roxana Scutariu
National Research and Development Institute for Industrial Ecology-ECOIND, 71-73 Drumul
Podu Dambovitei, District 6, 060652, Bucharest, Romania, mariussic@outlook.com
Abstract
Contemporary Project Management has conceived tools based on mathematical
models for planning, scheduling and controlling the projects, the costs and
resources. Critical Path Method (CPM) and Program Evaluation and Review
Technique (PERT) are two network-based methods which were independently
developed to assist the project managers in order to schedule complex real-life
projects. A scheduling of a small-scale R&D project using these optimization time-
oriented methods was accomplished. In many models of project network some
activities are closely related to each other such as procurement activities of basic
resources and research activities. If this precedence relationship is on the critical
path, that means whitout no event slack or float time for activities, then some
procurements delay may cause lag in the project’s completion time. Thus a good
estimation for procurement and research activities duration is needed for a Just-in-
Time project.
Keywords: CPM, network scheduling, PERT, procurement, project management
Introduction
Planning is the most important stage of project management. In this phase are
established objectives of the project, well-defined tasks or activities, resources and
are estimated the costs and durations. Scheduling refers to the allocation of
resources in terms of space, time and effort. Techniques usually used for planning
and scheduling are network-based methods. The network diagram is a graphical
description of logical relationships among project activities. The project plan is a
graph where the sequence of activities is drawn as chains of nodes and arrows.
Many various of planning tools have been developed such as CPM, Metra Potential
Method, PERT, Precedence Diagram Method, Critical Chain Project Management
etc. In the following sections data processing have been performed by using CPM
and PERT. In the late 50s Walker from DuPont Company and Kelley of Remington
Rand established mathematical foundations of the Critical Path Method (Kelley &
Walker 1959). They solved the problem of cost optimisation by parametric linear
programming. It is a problem of optimum path in a graph to maximize a value. In
the same time, the USA Navy has succeeded to find new technique to carry out their
military projects. PERT was developed in order to support the U.S. Navy's Polaris
missile program (Malcolm et al. 1959). The network approach of the project
planning and controlling continues to be widely used today.

Methods of project planning

Project Schedule Management covers the processes required to manage the timely
completion of the project. According to PMBOK methodology the processes are:
Plan schedule management, Define activities, Sequence activities, Estimate activity
durations, Develop schedule and Control schedule (PMBOK® Guide 2017).
Critical Path Method (CPM)
Critical Path Method is a step-by-step schedule technique which estimates the
minimum project duration on the logical network paths. Mathematically speaking, a
form of the Ford-Fulkerson network flow algorithm is used to solve this scheduling
problem. The simplified Ford algorithm applied to directed acyclic graph with one
start and one finish node is an algorithm for the shortest-path problem. Three types
of information are needed to describe any project: activities, relationships and
durations (Hillier & Lieberman 2015). Activities of the project graph plan are
represented by arrows and events are depicted by nodes as seen in Figure 1. Events
mark out the logic between activities.
Figure 1. Typical project network diagram
CPM technique calculates the early start, early finish, late start, and late finish dates
for all activities by performing a forward and backward pass analysis through the
project network (Figure 2). The necessary elements for CPM time computation are
the sequence of activities, dependencies between them and estimated duration of
each activity.
Figure 2. Activity earliest and latest times
Work Breakdown Structure (WBS) could be used to build the activities found in the
project network (Larson & Gray 2017). A single-point estimating for activity
duration is accomplished. The project network with events and activities is designed.
There are two types of diagrams: Activity on Arrow (AoA) and Activity on Node
(AoN). The CPM analysis for an AoA network approach follows two steps:
Forward pass
The earliest event and activity times within the network are computed
EET (j) = max [(EET (i) + d (i,j)] (1)
EST (i,j) = EET (i) (2)
EFT (i,j) = EST (i,j) + d (i,j) (3)

Backward pass
The latest event and activity times in the network are calculated
LET (i) = min [LET (j) - d (i,j)] (4)
LFT (i,j) = LET (j) (5)
LST (i,j) = LFT (i,j) - d (i,j) (6)
where: EET is earliest event time, EST is earliest starting time, EFT is earliest
finishing time, LET is latest event time, LST is latest starting time, LFT is latest
finishing time, d is activity duration.
Total float of activity (i,j)
TF (i,j) = LFT (j) - EST (i) - d (i,j) (7)
Free float of activity (i,j)
FF (i,j) = EST (j) - EST (i) - d (i,j) (8)
The float time of activity is the maximum time interval that the activity can be
delayed without slowing the project completion. The path whose length is equal to
the minimum duration of the project is called critical path. Activity on the critical
path and any activity that does not have a float time is called critical activity.
Program Evaluation and Review Technique (PERT)

PERT is a technique appropriate for projects where the time needed to complete the
activities are not known well. PERT uses a probabilistic approach while CPM is a
deterministic model. In network activity, durations are defined by stochastic
variables. The distribution of activity durations follows a beta distribution with
parameters: min, max and mean value. PERT-beta distribution is defined by the
three point estimate illustrated in Figure 3 where:
to = optimistic time (under the most favorable conditions)
tm = most likely time (most probable length of time)
tp = pessimistic time (under the worst conditions)
The mean value or expected duration te of activity is
te = (to + 4tm + tp) / 6 (9)
the variance (square of the standard deviation ) is
V = (tp - to)2 / 36 (10)
The Beta distribution was chosen by original PERT team for a simple reason:
“...the analysis requires some model for the distribution of activity times, the
parameters of the distribution being the mode and the extremes. The distribution
that first comes to the author’s mind is the beta distribution” (Clark 1962).
Figure 3. Density function of the PERT-beta distribution

The PERT-beta distribution has been criticized by many researchers and many
distributions were suggested. The effect of different activity distributions on the
project duration, such as PERT-beta, triangular or uniform distribution does not
result in significant differences from a practical point of view (Hajdu & Bokor
2014). The three-point estimate is a better estimate compared to a single-point
estimate. In the PRINCE2 methodology approach, estimating techniques can be top-
down and bottom-up, comparative and parametric estimating, single-point or three-
point estimating or Delphi technique (PRINCE2® 2017).

Obviously, in R&D projects many experimental activities cannot begin without
necessary equipments, materials or some services. In the project network the
procurement activities P1, P2,..,Pi will precede most of the R&D activities as seen in
the diagram from Figure 4. They are closely related to each other.
Figure 4. Precedence relationship between two activity types P and A for an

ordinary one-chain project network
The research activities are provided by Work Packages (WP) from WBS or Product
Breakdown Structure (PBS). The network from Figure 5 representing research work
packages is condensed in a R&D subnetwork D noted WP (ij) but the precedence is
still preserved.
Figure 5. Research project activities WP (ij)
Numerical Case Study

We propose for study a typical small-scale R&D project with CPM and PERT
without considering resource constraints.
Data processing with CPM Method
The usual activities of a sample project with descriptions, durations and precedence
relationships are listed in the Table 1. The duration of activity is a single-point
estimation. The type of logical relationships is Finish-to-Start (FS) without lag.
Project Network Diagram of the project‘s schedule is shown in Figure 6. AoA
representation requires three fictitious activities called dummy activities of zero
duration for not distorting the project network logic.

Table 1. List of activities with precedence relationships for sample project #

Project Immediate Estimated duration
Activity description
activity predecessors (days)
A - 20 Theoretical part
B - 50 Various acquisitions
C - 30 Basic procurements
D A, C 30 Experimental part WP (ij)
E D 5 Completion of experiments
F D 20 Results dissemination
G D 10 Final report for project closure
The data are provided by forward and backward step calculus.
Figure 6. The AoA network diagram for sample project #
FORWARD PASS calculation

The computations of the earliest time of events and activities start from the first
node 1 and advance recursively to final node 7 by using formulas (1), (2) and (3).
The results can be seen in Table 2.
Table 2. Earliest Times of events and activities in Forward Pass

Earliest Time of Events Earliest Time of Activities
Activity finished
Event EET (j) Activity EST (i,j) EFT (i,j)
in node
1 - 0 A 0 20
2 A,C 30 B 0 50
3 C 30 C 0 30
4 D 60 D 30 60
5 F 80 E 60 65
6 G 70 F 60 80
7 B,E,F,G 80 G 60 70
BACKWARD PASS calculation

In Table 3 are determined latest times by starting at the end of network towards
beginning of the diagram with Eq. (4), (5) and (6).

Table 3. Latest Times of events and activities in Backward Pass

Latest Time of Events Latest Time of Activities
Event Activity started LET (i) Activity LFT (i,j) LST (i,j)
from node
7 - 80 A 30 10
6 - 80 B 80 30
5 - 80 C 30 0
4 E,F,G 60 D 60 30
3 D 30 E 80 75
2 D 30 F 80 60
1 A,B,C 0 G 80 70
The critical activities and float times are calculated in Table 4 by Eq. (7) and (8).
As seen in table 4 the critical events are: 1→3→2→4→5→7 and critical activities:
C, D, F and they define the Critical Path with a thick line in Figure 6. Total float
(TF) is the amount of time that an activity can be delayed without increasing the
project completion time. Free float (FF) gives the time that an activity can be
delayed without affecting any of the activity that follows.
Table 4. Critical activities and Float times

Activity Starting Time Finishing Time
Act. Arcs TF FF
duration EST LST EFT LFT
A (1,2) 20 0 10 20 30 10 10
B (1,7) 50 0 30 50 80 30 30
C (1,3) 30 0 0 30 30 0 0
D (2,4) 30 30 30 60 60 0 0
E (4,7) 5 60 75 65 80 15 15
F (4,5) 20 60 60 80 80 0 0
G (4,6) 10 60 70 70 80 10 10
The calculated project duration is 80 days and the total floats are: 10 days for
activity A, 30 for B, 15 for E and 10 for G. Generally speaking, the float indicates
how much allowance each the activity has. The project was also scheduled in MS
Project as seen in the Gantt chart (Figure 7).
Figure 7. Tracking Gantt in MS Project software
Naturally, two milestones were proposed one before starting of experimental

activities D  WP (ij) (after basic procurements are finished) and second after
research completion (for results evaluation) associated with events 2 and 4.
Data processing by PERT method

In Table 5 are determined the mean time (expected) and variance with Eq. (9) and
(10). Results revealed after computations that the Critical Path is C→D→F.
Table 5. PERT computations of Mean Value and Variance

Optimistic Most likely Pessimistic Mean Variance
Activity Predecessors
time (to) time (tm) time (tp) Time (te) (V=2)
A - 15 20 30 20.83 6.25
B - 35 45 50 44.17 6.25
C - 20 30 40 30.00 11.11
D A, C 20 25 35 25.83 6.25
E D 3 6 10 6.17 1.36
F D 15 20 25 20.00 2.78
G D 5 8 12 8.17 1.36
The project expected duration tn = 75.83 days is equal with sum of the expected te
along critical path. Sum of the variance along the critical path is 20.14. The
probability factor:
Z = (Ts - tn) /  (11)
If the scheduled time Ts = 80 days, then normal distribution function finds a

probability of 82.34 corresponding to Z = 0.9285 with Eq. (11). Hence there is 82.34
% probability of the project completion in 80 days. According to Central Limit
Theorem even if the duration of each activity follows a β-distribution, the total
duration of the project is a random variable with normal distribution.
Public Procurement Procedures

If the project is subject to public procurement legislation then the durations of
project procurement activities have to be sized with the timescales of procurement
procedures. For short-time R&D projects the procurements must be treated carefully
if they are under this legislation. Public procurement in the European Union (EU) is
regulated by a set of Directives such as Directive 2014/24/EU. The award of public
contracts has to comply with principles of non-discrimination, mutual recognition,
proportionality and transparency. The Public Procurement System has simplified
procedures. Even so, for public contracts above a certain value the appeal
procedures may extend procurement duration (Georgieva 2017). The review
procedures and remedies under Directive 2014/23/EU could lead to the automatic
suspension of a procurement procedure.
Modern intelligent systems in Project Management

Artificial Intelligence (AI). The environment dynamics have a great impact on
projects constraints increasing their complexity becoming similar to Complex
Adaptive Systems which are nonlinear dynamical systems. The project could be
scheduled in Time-Constrained approach (Bodea et al. 2010) by using multi-agent
methods as Swarm Intelligence Algorithms such as Genetic Algorithm or Ant
Colony Optimization.
Artificial Neural Network (ANN). Artificial neural networks are complementary
technologies as data mining tool used for pattern recognition, time series analysis,
prediction and clustering. The input variables may come from an enterprise’s
internal database such as ERP system (Relich & Muszynski 2014).
Fuzzy project management. Fuzzy logic is used to improve the classic CPM/PERT
planning, with considering fuzzy activity durations and resources (Lootsma 1989).
through different heuristic and metaheuristic algorithms.
Conclusions
The result of this research is scheduling of a typical small-scale project without
constraints by implementation of PERT/CPM techniques. The Critical Path and
critical activities were defined. The calculation refers to project duration and the
total and free floats of each activity of the project.
For small-scale R&D projects, some activities are closely related to each other such
as procurement activities of basic resources and research activities. This sequence of
activities could be on the critical path. This fact highlights that any procurement
delay may cause a lag not only in the following R&D activiy but also in the
completion date of the project.
If the contract above a certain value is subject to public procurement legislation,
then this situation increases uncertainty in the process of estimation of the project
activitiy duration. The Public Procurement System, regulated by a set of Directives,
has few procedures that are not contested. The means of appeal, challenge and
complaint, could extend the procurement durations or even suspend the contract and
stop the project until proper settlement. Thus a good estimate for procurement and
research activities duration is sometimes difficult for a Just-in-Time project.
Someone may think that flair and intuition are enough to plan and control smaller
projects, but common things like estimation of project duration and activities floats
or allocation of resources and leveling can not be easily achieved without project
management scheduling techniques.
References
A guide to the project management body of knowledge (PMBOK® Guide) 2017, 6th
ed., Newtown Square, Pa.: Project Management Institute, Inc.
Bodea, CN, Badea, IR & Purnus, A 2010, ‘Complex project scheduling using multi-
agent methods: A case study for research projects’, Management and
Marketing, vol. 3, pp. 21-40.
Clark, CE 1962, ‘The PERT model for the distribution of an activity time’,
Operations Research, vol. 10, pp. 405-406.
Georgieva, I, Using Transparency Against Corruption in Public Procurement: A
Comparative Analysis of the Transparency Rules and their Failure to Combat
Corruption, 1st ed., Springer, Cham 2017.
Hajdu, M, & Bokor, O 2014, ‘The effects of different activity distributions on
project duration in PERT networks’, Procedia - Social and Behavioral
Sciences, vol. 119, pp. 766-775.
Hillier, FS & Lieberman, GJ 2015, Introduction to Operations Research, Mcgraw-
Hill Education, 10th ed., New York.
Kelley, Jr JE & Walker, MR 1959, ‘Critical-path planning and scheduling’
Proceedings of the Eastern Joint Computer Conference, Boston, pp. 160-173.

Larson, EW & Gray, CF 2017, Project management: The managerial process, 7th
ed., Mcgraw-Hill Education, New York.
Lootsma, FA 1989, ‘Stochastic and fuzzy PERT’, European Journal of Operational
Malcolm, DG, Roseboom, JH, Clark, CE & Fazar, W 1959, ‘Application of a
technique of research and development program evaluation’, Operations
Managing Successful Projects with PRINCE2 2017, Axelos, TSO, London.
Relich, M & Muszynski, W 2014, ‘The use of intelligent systems for planning and
scheduling of product development projects’, Procedia Computer Science,
vol. 35, pp. 1586-1595.

ECOLOGICAL ASPECTS OF AGROECOSYSTEMS OF SOYBEAN IN THE

CONDITIONS OF THE SOUTH-EAST OF KAZAKHSTAN AT CLIMATE
CHANGE
Naziya Suleimenova1, Margarita Filipova2, Elnara Kuandykova1, Gulnar Orynbasarova1,

Kuanish Zholamanov1, Kenzhe Erzhanova1
1
Department of Ecology, Kazakh National Agrarian University, Almaty, Kazakhstan,
kzh06@mail.ru
2
Department of ecology and environmental protection, University of Rousse, Rousse, Bulgaria
Abstract
In this article results of studying of an environmental problem as pollution of the
soil at use of mineral fertilizers are proved against the background of traditional
technologies of cultivation of soy. A comparative assessment of efficiency of
resource-saving technology with the studied norms of mineral fertilizers in
optimization of an ecological situation of an agroecosystem is given. At traditional
technology it is revealed that use of the increased norms of N60P180K90 causes
increase in level of impurity of the soil heavy metals and decrease in efficiency of
the cultivated culture of soy. The value of resource-saving technology in rational use
of bioenergy potential of an agroecosystem is revealed and elements of intensive
technology with lower norms of mineral fertilizers for increase in efficiency of an
agroecosystem of soy are chosen. It is proved that mineral fertilizers are one of the
main factors of stabilization of an ecological condition of the soil, providing
increase in efficiency of soy at resource-saving technology of cultivation in the
conditions of irrigation of the southeast of Kazakhstan. Application evidence-based
resource-saving receptions with elements ecologically safe intensive allows to
support technologies rather quickly stability of an agroecosystem.
Keywords: Agroecosystem, environmental problems, soybean, fertilizers,

technology
Introduction
At the present stage aggravation of an ecological situation in Kazakhstan, as well as
around the world is considerably connected with the impact of activity of agrarian
production on the environment, with rendering the greatest impact on resources of
the biosphere (Odum 1986, Shilov 2000). In essence, agrarian production is an
ensuring food security of the country using, natural resources of the environment of
an agroecosystem. In increase in efficiency of cultures, the applied traditional
technologies cause significant resource-technological changes. Results which
decrease in fertility of the soil, the maintenance of a humus, destruction of
agrophysical indicators and deterioration in the nutritious mode of the soil are. The
last years of the XX century agrarian production was focused on use of the intensive
technology of cultivation of crops providing application of high doses of mineral
fertilizers and chemical means. Here the duality of processes at use of intensive
technology of cultivation of crops was brightly shown. As it besides preservation,
increase in fertility and optimization of the nutritious mode of the soil and growth of
productivity of cultures, carries negative load of the environment. The soil cover
more is exposed to pollution, degradation and destruction (Milashchenko 2000) as
all proceeding processes are connected with transformation, accumulation and
migration of substances in soils. The great concern is caused now by pollution of the
soil and products the toxicant who are contained in the applied fertilizers. First of
all, it is radionuclides, fluorine and TM which are natural impurity of agricultural
ores. The quantity them depends on initial raw materials and technology of its
processing. As on set, and concentration of TM impurity phosphoric fertilizers are
the most essential. The composition of domestic phosphates raw materials,
especially local fields, is extremely insufficiently studied on contents in them toxic
impurity (Postnikov et al 1994). The efficiency of use of fertilizers depends not only
on physiological features of plants, norm and a combination of fertilizers, but also
on change of the soil environment as biogenous system, on the nature of the
processes proceeding in the soil (Zhuchenko 2005). The soil is the ecological
communication center of the biosphere in which interaction of live and lifeless
matter most intensively proceeds. In this regard as especially important question
ecological purity of the soil environment at chemicalization farming as on it
processes of a metabolism between a lithosphere, the hydrosphere, the atmosphere
and organisms living on it become isolated can act (Vrazhnova & Kushnirenko
2003). At ecological assessment of consequences of application of agro methods of
technology it is necessary to consider the change of soils connected with the arriving
toxicant and their transformations. It leads to decline in quality of products, increase
in contents in it residual amounts of mineral fertilizers. At the same time, violations
of an ecological situation of an agroecosystem bring to the economic losses
connected with smaller efficiency of an arable land and smaller efficiency of the
made investments of technology. That is there are such alternative expenses as
additional costs of preservation and restoration of fertility of soils. Despite violation
of ecology-economic balance in an agroecosystem, universal application of means
of chemicalixation without ecological factors in the conditions of agriculture of
Almaty region is observed. Such situation causes special alarm for deterioration in
an ecological situation which makes negative impact on agriculture not only at the
moment, but also on prospect. In this regard, studying of an environmental problem
of an agroecosystem of soy in concrete soil climatic conditions climate change
southeast Kazakhstan has practical value and is very relevant.
In this work results of studying of an environmental problem as pollution of the soil
at use of mineral fertilizers are proved against the background of traditional
technologies of cultivation of soy. A comparative assessment of efficiency of
resource-saving technology with the studied norms of mineral fertilizers in
optimization of an ecological situation of an agroecosystem is given.


In this regard, environmental problems of agroecosystems of soy in the conditions of
the southeast of Kazakhstan are studied by classic methods as observation and an
experiment. Experimental researches were conducted in the territory of the
educational-experimental station (EES) of the Kazakh national agricultural
university of Agrouniversity which is located in a northwest part of Almaty region.
Environmental problems use of mineral fertilizers against the background of
traditional and resource-saving technology of cultivation of soy in 2012-2018 were
studied. Objects of a research are unique leguminous culture - soybean (a grade
Eureka), it is short - a rotational fruitshifts crop rotation. Control in experiences was
served by traditional technology of cultivation of soy according to the
recommendations of the System of farming of Almaty region (2005). Field
experiments and pilot studies are conducted by the standard classic methods:
experiment and observation. All methodical requirements imposed to a technique of
laying of field experiments are sustained and were carried out according to B.A.
(Dospekhov 1985) and according to Methodical Recommendations, 2004 (Boyko &
Karyagina 2004) by JSC Vita. Biometric and phenological observations were made
according to the recommendation of Institute of field husbandry and vegetable
growing, and the Method of STATE crops of cultivation of grain, leguminous and
oil-bearing crops. The received experimental materials are processed by a statistical
method. For determination of content of heavy metals in the soil the atomic and
absorbing Shimadzu AA7000 spectrophotometer, with lamps with the hollow
cathode, made of the elements Cr, Zn, Cu, Pb, Cd was used. For preparation of
samples for a research used the RD 52.18.286-91 method.

In the conditions of ours researches cultivation of valuable leguminous and at the
same time oil-bearing crop was carried out on intensive traditional technology, with
application of the raised dose of N60P180K90 of mineral fertilizers. This dose of
mineral N60P180K90 fertilizers it is recommended to one of the large
agroenterprises - JSC Vita of Kazakhstan which is in the territory of the southeast
and which is engaged in cultivation of soy and is brought by scattering before
hulling of an eddish at the rate of 330 kg/hectare. Soy is characterized by
consumption of a large number of mineral elements, uneven on phases of
development. Creating big vegetative weight and forming seeds with the high
content of fat and protein (Zubkov 2004), soy needs intensive mineral food.
According to researchers, 8-10 kg of nitrogen, 2.0-3.5 kg of phosphorus and 3-4 kg
of potassium are spent for formation of 1 c of grain of soy on average (Gamzikov
2007). Considering the above, for justification of environmental problems
application of the overestimated doses of mineral fertilizers at traditional technology
of cultivation of soy we carried out the comparative assessment by two options of a
dose of mineral fertilizers. Therefore, at traditional technology of cultivation of soy
the comparative assessment of prolonged use of the raised doses of mineral
fertilizers is carried out and the nutritious mode of the soil is defined. Development

of resource-saving ecologically safe technologies of cultivation of soy is reached by

means of technology with the minimum processing of the soil and with application
of optimum doses mineral fertilizer. For identification and the level of pollution of
the soil heavy metals at use of mineral fertilizers (Ilyin 2004, Chernykh, et al 2003)
were carried out against the background of traditional and resource-saving
technologies of cultivation of soy. At traditional technology are established that at
prolonged use of high doses of mineral N60P180K90 fertilizers the amount of heavy
metals in a root habitable layer of earth significantly increases. By results definition
the content of the heavy metals (HM) in 0-20 cm a layer of earth was various by the
studied options. Against the background of traditional technology of cultivation of
soy, without introduction of mineral fertilizers the soil is characterized by the low
maintenance practically of all types of heavy metals. Especially low contents noted
cadmium - 0.35 mg\kg and copper - 0.41 mg \kg that respectively on 57 and 7 times
it is lower than the maximum allowable concentration level. Content of the defined
following heavy metals as Cr, Pb, Zn in the meadow-chestnut soil does not exceed
their maximum allowable concentration.
It is established that at prolonged use of the raised doses (N60P180K90) of mineral
fertilizers the amount of heavy metals in a root habitable layer of earth significantly
increases. At introduction of mineral fertilizers in N60P180K90 dose the amount of
the arrived cadmium to the soil increases from 0.35 mg \kg to 8.6 mg/kg, - is lame -
from 0.61 to 5.29 mg/kg, - lead from 0.57 to 4.83 mg/kg, - zinc from 1.13 to 10.9
mg/kg and - copper from 0.41 to 3.2 mg/kg. Content of the listed heavy metals
(HM) in an arable layer of earth after application of the overestimated doses of
mineral fertilizers sharply increases several times (Table 1).
Table 1. Pollution of the soil heavy metals at use of mineral fertilizers depending on
technology of cultivation of soybean (mg/kg)
1 background - Traditional 2 background - Resource-saving Threshold
Heavy technology technology limit value,
metals mg/kg
mg/kg Without N60Р180К90 Р60К30 N30Р60К30
fertilizers
Cr 0.61±0.018 0.57±0.017 0.74±0.025 0.81±0.017 6.0
Pb 0.57±0.017 4.83±0.13 1.29±0.04 1.61±0.04 6.0
Zn 1.13±0.053 1.29±0.04 1.38±0.03 2.54±0.05 23.0
Cu 0.41±0.012 3.2±0.064 0.69±0.01 0.72±0.02 3.0
Cd 0.35±0.01 8.6±0.24 1.28±0.03 1.82±0.05 20.0
Content of the listed heavy metals (HM) in an arable layer of earth after application
of the overestimated doses of mineral fertilizers sharply increases several times. In
Cr given a case the contents and Cd Pb – by 8 times, Zn – the 10th time increased by
24 times. It should be noted that the content of these heavy metals (HM) does not
exceed value of threshold limit value yet (maximum allowable concentration,
mg/kg). But, create big risk to pollution of the soil heavy metals as chrome, Cr
keeping of whom in three years increased from 0.61 mg/kg to 5.29 mg/kg and lead,

Pb keeping of whom also increased from 0.57 to 4.83 mg/kg and is in limits of
maximum allowable concentration and create the risking range pollution of the soil.
Pollution of the soil at traditional technology is revealed application of the
overestimated doses (N60 P180K90) of mineral fertilizers under soy crops by
copper (Cu) which content raises by eight times, from 0.41 to 3.2 mg/kg of the soil
that above a threshold of admissible concentration which maximum allowable
concentration is only 3.0 mg/kg of the soil. On the level of impurity of the soil
copper belongs to highly dangerous classes that proves on a high environmental
problem of application of high doses of mineral fertilizers traditional technologies of
cultivation of soy. In the solution of this environmental problem of an
agroecosystem influence of a dose and a combination of types (P60K30 and
N30P60K30) of mineral fertilizers at the resource-saving technology of cultivation
of soy developed by us are studied. At resource-saving technology results of
application of P60K30 of fertilizers and a full range of types of mineral fertilizers -
N30P60K30 show that the greatest number of Zn and Cd is noted on these options.
Comparative largest content of Zn = 1.38-2.54 mg/kg it is revealed in options of use
of mineral fertilizers according to P60K30 and N30P60K30. Their value is much
lower than the maximum allowable concentration level (i.e. in 9.7 and 6.5 times).
The maintenance of Cd higher and makes 1.28 and 1.82 mg/kg, they also, are lower
in 15.7 maximum allowable concentrations and 10.9 times. It should be noted that
contents in the soil of a mobile form of heavy metals is dynamic in time and does
not cause danger of pollution of the soil of TM. Thus, at resource-saving technology
ecological conditions of the soil for cultivation of soy are optimized, the content of
heavy metals is much lower than maximum allowable concentration, for Sg 8.1-7.4
times, Pb by 4.6-3.7 times, Zn by 16.7-9.0 times, Cu in 4.3-4.2 and Cd by 15.6-10.9
times. The received results show that the resource-saving technology at introduction
of mineral fertilizers in a dose of P60K30 and N30P60K30 provides ecologically
safe environment for soy cultivation. Therefore, there is a full justification to
consider that it by scientifically based doses of mineral fertilizers at cultivation of
soy is P60K30 and N30P60K30 which do not accumulate heavy metals in an arable
layer of earth, with the subsequent improvement of the nutritious mode of the soil
(Suleymenova et al 2014) and increase in efficiency of culture. The comparative
assessment of traditional and resource-saving technologies for justification of the
nutritious mode and increase in efficiency of soy is carried out. It is revealed that at
traditional technology of cultivation of soy during the critical period of development
- soy branching security of crops with mobile forms of nutrients low, (Suleymenova
& Razmanova 2012) and at introduction of the raised dose of fertilizers their
contents increase only to the average level (Fig. 1).

Figure 1. Dynamics of mobile forms of soil nutrients depending on the technology

of cultivation of soybean
At resource-saving technology there is an optimum nutritious mode of the soil.

Application of fertilizers in a dose of P60K30 and N30P60K30 the maintenance of
mobile forms of nitrate nitrogen increases up to 25.6 mg/kg with fluctuation on the
horizons from 22.9 mg/kg to 28.3 mg/kg on the soil horizons. At introduction of
P60K30 mobile forms of phosphorus are made by 21.2 mg/kg with fluctuation from
17.7 mg/kg and 24.8 mg/kg on the soil horizons that for 13.3% and 39.4%
respectively it is more, than in control option at traditional technology of cultivation
of soy. Improves ensuring need of soy for nitrogen, especially during the critical
period of development when there is a progressive growth of green vegetative
material of a plant and has significant effect on productivity of soy (Table 2).
Table 2. Productivity of soy depending on introduction of mineral fertilizers,

c/hectare (An average for years of researches)
Technology of Use of fertilizers Productivity, Increase in
cultivation c/hectare
c/hectare %
Traditional Without fertilizers 19.3±0.61 St -
N60Р180К90 24.8±0.67 5.5 28.5
Mini-Till, Without fertilizers 21.9±0.72 2.6 13.0
Plainly carved
Р60К30 26.5±0.64 7.2 37.3
Resource-saving
processing of the
soil on depth the N30Р60К30 27.8±0.77 8.5 44.0
12-14th cm
Mini-Till,
Plainly carved Without fertilizers 21.5±0.68 2.2 11.4
processing of the Р60К30 26.3±0.73 6.0 31.1
soil on depth the
16-18th cm N30Р60К30 26.4±0.71 7.1 36.7

The productivity of soy at traditional technology without fertilizers is only

19.3±0.61 c/hectare. Introduction of the recommended overestimated dose of
mineral fertilizers at traditional technology – N60P180 K90 productivity of soy
increases up to 24.8±0.67 c/hectare. Full application of fertilizers in a dose of 330
kg/hectare at traditional technology promoted receiving an additional harvest within
5.5 c/hectare. It should be noted that soy well reacts to introduction of phosphoric
fertilizers, especially against the background of the low content of mobile
phosphorus in the soil as under our conditions researches. When studying influence
of resource-saving technology with introduction of phosphoric fertilizers is revealed
that the productivity of soy increases up to 31.1% - 39.4%. Therefore, on this option
and at joint introduction of phosphorus-potassium fertilizer the productivity of soy
increases up to 26.9±0.64 c/hectare. Full application of fertilizers (N30Р60К30) at
the studied resource-saving technology promoted additional increase where the
increase of a harvest makes 7.1 c/hectare. Comparative assessment of
responsiveness of soy on the level of mineral food showed that soy distinctly reacts
to changes of the nutritious mode of the soil. And in the conditions of our researches
soy positively reacts to introduction of phosphorus-potassium fertilizers, at increase
in its productivity on 7.6 c/hectare. And so, mineral fertilizers are one of the main
factors of stabilization of an ecological condition of an agroecosystem, providing
increase in efficiency of plants of soy at resource-saving technology of cultivation in
the conditions of the southeast of Kazakhstan.
Conclusions
Aggravation at the present stage of an ecological situation in Kazakhstan, as well as
around the world is considerably connected with the impact of agricultural activity
on the environment. The changes of an ecosystem resulting from anthropogenic
influence formed a basis of studying of ecological aspects of an agroecosystem of
valuable leguminous and at the same time oil-bearing crop, soy and development of
receptions resource-saving to technology. The current state use of mineral fertilizers
is studied and environmental problems of an agroecosystem at traditional
technology of cultivation of soy are proved. Are revealed degree of impurity of the
soil by heavy metals and ecotoxicological aspects use of mineral fertilizers. As a
result of studying of an environmental problem of agroecosystems of soy in the
conditions of the southeast of Kazakhstan it is revealed that against the background
of traditional technologies of cultivation of soy, applied (recommended to
production) norms of fertilizers (N60Р180К90) cause increase in level of impurity
of the soil heavy metals. It is established that at prolonged use of high doses of
mineral fertilizers the amount of heavy metals in a roothabitable layer of earth
significantly increases. At introduction in N60Р180К90 dose the amount of the
arrived cadmium to the soil increases from 0.35 mg \kg to 8.6 mg/kg, - is lame -
from 0.61 to 5.29 mg/kg, - lead from 0.57 to 4.83 mg/kg, - zinc from 1.13 to 10.9
mg/kg and - copper from 0.41 to 3.2 mg/kg. Content of the listed heavy metals
(HM) in an arable layer of earth after application of the overestimated doses of
mineral fertilizers sharply increases several times, Cr and Cd increased by 24 times,

Pb – by 8 times, Zn – the 10th time. Significant pollution of the soil is revealed by

copper (Cu) which content from 0.41 to 3.2 mg/kg of the soil increase that above a
threshold of an allowable limit and on the level of impurity of the soil belongs to
highly dangerous classes. In the conditions of ours researches very technological
culture, soy is characterized by consumption of a large number of mineral elements,
uneven on phases of development.Creating big vegetative weight and forming seeds
with the high content of fat and protein, soy needs intensive mineral food. At
resource-saving technology ecological conditions of cultivation of soy are
optimized, the content of heavy metals is much lower than maximum allowable
concentration, for Sg 8.1-7.4 times, Pb by 4.6-3.7 times, Zn by 16.7-9.0 times, Cu in
4.3-4.2 and Cd by 15.6-10.9 times. Introduction of mineral fertilizers in a dose of
Р60К30 and N30Р60К30 provides ecologically safe environment and it is necessary
to consider them scientifically based doses for soy cultivation which do not
accumulate heavy metals in an arable layer of earth, with the subsequent
improvement of the nutritious mode of the soil and increase in efficiency of
culture.Improves ensuring requirement of soy to the nutritious mode, especially
during the critical period of development when there is a progressive growth of
green vegetative material of a plant and has significant effect on productivity of soy,
in the conditions of our researches soy positively reacts to introduction of
phosphorus-potassium fertilizers, at increase in its productivity on 7.6 c/hectare.
Thus, mineral fertilizers are one of the main factors of stabilization of an ecological
condition of an agroecosystem, providing increase in efficiency of plants of soy at
resource-saving technology of cultivation in the conditions of the southeast of
Kazakhstan.
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EVALUATION OF ASH RELATED PROBLEMS DURING SEWAGE

SLUDGE COMBUSTION
Agnes Serbanescu1, Mona Barbu1, Ionut Cristea1, Gina Catrina1, Georgiana Cernica1, Mihai
Stefanescu1, Ioana Bercu2
1
National Research and Development Institute for Industrial Ecology - ECOIND, 71-73
Drumul Podu Dambovitei Street, 060652, Bucharest, District 6,
agnes.serbanescu@incdecoind.ro, Romania
2
S.C. Kema Tronic SRL, 16 Minerilor Street, Baia Mare, kematronic@yahoo.com, Romania
Abstract
A good function of waste-to-energy installation requires knowledge of the
combustion characteristics of the fuel and fusion characteristics of the ash produced
in the combustion process. Sewage sludge could be considered as renewable fuel
due the high quantity of organics of sufficiently high calorific value. The
combustion of sewage sludge can cause operating problems due to high ash content
containing mineral compounds.
This paper presents the oxide composition of three kinds of sewage sludge ashes and
the influence on the slagging and fouling process in combustion. For comparation,
two coal samples were selected, a low and a high rank coal. The mineral matter were
investigated by the X-ray fluorescence analytical technique using the Rigaku CG X-
ray Spectrofluorimeter. The evaluation of slagging and fouling process was
performed on the basis of some indices: the basic oxides, the base-to-acid ratio, the
slagging index and the fouling index.
The conclusion based on experimental studies is that depending on mineral content
the sewage sludge ash can cause high to moderate slagging and fouling hazard.
Keywords: ash, fouling, sewage sludge, slagging index
Introduction
The use of sewage sludge as a source of renewable energy is an option, both in the
EU and in the Romanian sludge management strategy (PNGD 2017). In dehydrated
form sewage sludge could be considered as renewable fuel due to its calorific value
(Serbanescu et al 2017). The combustion of sewage sludge is becoming more
attractive, due to the destroying of hazardous constituents and considerable volume
reduction. Thermal processes involve removing the organic part of the sludge,
leaving only the ash component for final disposal.
Sewage sludge can be directly incinerated in different types of incinerators or co-
incinerated with other fuels. Compared to other solid fuels, such as coal, the sewage
sludge has a greater ash content, between 20-50% wt % on dry basis, which involves
ash handling systems and flue gas cleaning systems.
The complex characterization of sewage sludge plays an important role both in the
design and exploitation of combustion installations. For the good function of the
sewage sludge combustion or incineration installations is important to know the
energy and fusion characteristics of the ashes. Sewage sludge combustion can lead
to exploitation problems, by slag formation in the combustion chamber and
refractory material, producing heat transfer efficiency decreasing, boiler flow rate
decreasing refractory material degradation and deposits formation on pipes.
A scheme of the ash formation and transformation mechanism in the combustion
processes is shown in fig. 1 (Yanqing Niu et al 2016).
Similar to pulverized coal combustion during the combustion of sludge particles and
the formation of char particles, volatile organometallic compounds are first released
followed by devolatilization; then, partial alkali and alkali-earth elements (e.g. K,
Na, and Ca) and volatile trace elements (e.g., Hg, As and Se) diffused out of the
char. As the gas temperature decreases, the volatile components nucleate and
condense to form submicron sized particle. Also, some volatile material condenses
on residual fly ash (Yanqing Niu et al 2016). Important issues related to ash in the
combustion processes are the slagging (ash fusion) and the agglomerations.
Figure 1. Scheme of the ash formation and transformation mechanism in the

combustion processes (Yanqing Niu et al 2016)
During the combustion, there are a number of physical changes of the ashes in the
furnace. As the temperature rises, the ash particles soften until they are completely
fused. Fuels with low fusion temperatures of ash, lead to increase the slag formation
risk on grates. The fusion temperature varies depending on several factors, most
important of which is the nature of the waste fuel used.
The major ash formers elements (Al, Ca, Fe, Mg, P, K, Si, Na, and Ti) are
responsible for the ash fusion, the deposits formation and corrosion processes. In
addition, volatile elements, such as Na and K, are the main components of aerosols,
in the form of solid particles, dispersed in the gases removed from the combustion.
Volatile minor elements (As, Cd, Hg, Pb, Zn) play a major role in gas emissions
(Kim et al 2017).
The article presents the influence of ash oxide composition for three sewage sludge
samples and two coal samples on slagging and fouling tendency in combustion
processes.


The experimental study was carried out on three dehydrated sewage sludge samples
from different wastewater treatment plants. Samples were noted: NA, NB, NF. For
comparison, 2 samples of coal were selected, a high rank coal (pit coal-H) and a low
rank coal (lignite-L).
For characterization, the 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. The higher
calorific value was determined by calorimetric method (ASRO 2009) using PARR
6200 calorimetric bomb. The elemental analysis, carbon, nitogen and hydrogen
content was determined by a chromatographic method using the Thermo Scientific
FlashEA 1112 Elemental Analyser (ASRO 2011). The sulphur content was
determined spectrophotometric (ASRO 2017).
The sewage and coal samples ash composition was determined by the X-ray
fluorescence technical analysis according to method (ASRO 2007) using the Rigaku
CG X-ray fluorescence spectrometer. For the sewage sludge samples, the oxide
composition was determined from the ash obtained at three temperatures: 550 0C,
8150C and 9150C.

The technical and elemental characteristics of the studied coal and sludge samples
are presented in table 1. The three sludge samples had a lower calorific value
between 2108 kcal/kg and 2677 kcal / kg at dry bases (8.8-11.2MJ/kg at dry bases)
and a high ash content higher than 47% at dry bases, which indicates that
combustion can be used for energy recovering.
Table 1. Main physical-chemical characteristics of analysed samples

Ultimate analysis (wt.% d.b.) HHV LHV
Ash
Sample C H N S (kcal/kg d.b.) (kcal/kg d.b.)
(wt.% d.b.)
H 7.36 75.37 3.83 2.53 0.80 7296 7108
L 32.01 41.79 3.04 1.10 2.58 3907 3758
NA 54.12 23.54 2.85 3.28 1.13 2248 2108
NB 56.33 23.58 2.77 3.36 1.08 2393 2257
NF 47.35 27.62 3.31 4.76 0.77 2840 2677
d.b.-dry basis; HHV-high heating value; LHV-low heating value
The ash composition expressed as oxides for the studied coal and sewage sludge
samples are presented in table 2.
The main components of the studied ashes are SiO2, CaO, Al2O3, Fe2O3, P2O5. The
oxide composition of the studied samples are relatively different. The NA sample
had a lower content of acid oxides (SiO2, Al2O3) than the NB and NF samples but a
CaO content much higher than the NB and NF samples. The results for the oxide
composition are not different for the three temperatures used for calcination.

Table 2. Ash composition expressed as oxides, wt. %

Sample/
SiO2 CaO Al2O3 Fe2O3 P2O5 MgO Na2O K2O TiO2 MnO SO3
oxides
H 47.59 4.80 24.75 9.53 0.71 1.62 2.65 1.52 1.23 0.09 4.35
L 40.97 9.70 22.69 7.31 0.17 1.86 3.10 1.38 0.87 0.06 10.79
NA1 27.77 30.76 9.14 8.46 5.68 2.20 4.67 1.39 0.69 0.11 7.62
NA2 30.22 30.29 9.99 8.31 5.91 2.46 3.77 1.53 0.72 0.11 5.14
NA3 28.50 31.33 9.52 8.56 5.94 2.35 3.92 1.29 0.72 0.11 6.28
NB1 50.06 7.46 12.83 9.49 3.62 2.13 2.67 1.81 0.70 0.26 4.88
NB2 50.15 8.23 13.71 10.33 4.34 2.15 2.20 2.07 0.83 0.29 4.33
NB3 51.12 8.49 13.08 10.58 3.96 2.11 1.66 2.06 0.83 0.29 2.36
NF1 43.33 13.87 10.55 4.95 10.2 4.43 3.34 2.27 0.81 0.19 4.65
NF2 44.06 13.98 10.71 5.04 10.39 4.65 3.00 2.32 0.83 0.19 3.47
NF3 46.28 14.38 10.57 5.21 9.70 4.56 2.62 2.43 0.83 0.20 1.85
There are four characteristic temperatures for the ash flow: the shrinking
temperature (ST), the deformation temperature (DT), the hemisphere temperature
(HT) and the flow temperature (FT).
For the ash behaviour estimation in combustion processes some slagging
and fouling indices are used (Pronobis 2005). This index was established based on
the effects of the temperature on the ash. The following indices have been used:
- Basic oxides: (Rb = Fe2O3 + CaO + MgO + Na2O + K2O + P2O5), which
lower the melting temperature. The minimum ash softening temperature occurs by
Rb = 35-55%;
- Acid oxide: (Ra = SiO2 + Al2O3 + TiO2), which increase the melting
temperature;
-The base-to-acid ratio (Rb/a(+P) = (Fe2O3 + CaO + MgO + Na2O + K2O +
P2O5)/ (SiO2 + Al2O3 + TiO2). For Rb/a <0,15 both hemisphere temperature (HT) and
the flow temperature (FT) exceed 16000C. The smaller the Rb/a, the higher the HT
and the FT, the slagging tendency decrease. For Rb/a ~ 0.75, HT and FT are below
12000C, resulting in a very high slagging tendency.
-The slagging (Babcock) index: RS = (B/A) * Sd, Sd represents the sulphur
content in dry sample. For RS < 0,6 the slagging tendency is small; RS = 0,6 – 2,0
the slagging tendency is medium; For RS = 2,0 – 2,6 the slagging tendency is high;
RS > 2,6 the slagging tendency is extremely high.
- The fouling index Fu = RS * (Na2O + K2O) / Sd = (B/A) *(Na2O + K2O). For
Fu ≤ 0.6 the fouling tendency is low; 0.6 < Fu ≤ 40 the fouling tendency is high; Fu >
40 the fouling tendency is extremely high, there are a tendency for sintering of
deposits.
For the calculation of the slagging and fouling indices during the combustion
process, the oxide composition of the ash was normalized to 100% for a base
without SO3.
The indices for slagging and fouling tendency calculated for the analysed samples
are presented in table 4. In fig. 2 and 3 are presented the variation of basic and acidic
oxides.

Table 4. Indices for slagging and fouling tendency evaluation

Sample/Indices RA RB RB/A RS Fu
H 73.57 20.12 0.27 0.22 1.14
L 64.53 23.35 0.36 0.62 1.62
NA1 37.60 47.48 1.26 1.43 7.65
NA2 40.93 46.36 1.13 1.28 6.00
NA3 38.74 47.45 1.22 1.38 6.38
NB1 63.59 23.56 0.37 0.40 1.66
NB2 64.69 24.98 0.39 0.42 1.65
NB3 65.03 24.90 0.38 0.41 1.42
NF1 54.69 28.86 0.53 0.41 2.96
NF2 55.60 28.99 0.52 0.40 2.77
NF3 57.68 29.20 0.51 0.39 2.56
Figure 2. The content of basic oxides in the analysed ash samples
The pit coal sample (H) has the lowest content of basic oxides, and the highest
content of acid oxides. The basic oxides for the lignite sample (L) is comparable to
that of the NB sludge sample. The basic oxides for NA is between 35 and 55%,
which places it in the area with the minimum softening temperature for the ash. The
NB and NF sludge samples, as well as the coal samples, are located outside for this
area of risk.
The base-to-acid ratio (Rb/a) for the analysed samples is presented in fig. 4.
The hemisphere temperature (HT) and the flow temperature (FT) both for coal and
NB and NF sludge samples are below 16000 C. For the NA sludge sample, base-to-
acid ratio exceeds the limit of 0.75, resulting in a very high slagging tendency.
The slagging (Babcock) index RS for the analysed samples is presented in fig. 5.
Analysing the tendency of slagging according to this index, only NA sludge sample
shows a medium slagging tendency.

Figure 3. The content of acidic oxides in the analysed ash samples
Figure 4. The base-to-acid ratio (Rb/a) for the analysed ash samples
Figure 5. The slagging (Babcock) index (RS) for the analysed ash samples
The fouling index Fu for the analysed samples is presented in fig. no. 6. The fouling
index Fu is based on the base-to-acid ratio (Rb/a), but also considering the sum of Na
and K oxides. Alkali metals are known to form eutectic in combination with SiO2.
Consequently, as the values of the Fu index are higher, the tendency of the deposits
formation is higher.
Figure 6. Fouling index (Fu) for analysed ashes
For a value of Fu ≤ 0.6, the deposits tendency of ash is low, for 0.6 <Fu ≤ 40 the
deposits tendency of ash is high, and for Fu > 40 the tendency of agglomeration
(sintering) of deposits is high. All the studied ashes present a high tendency of
deposits formation (0.6 <Fu≤40).
Analysing the slagging and fouling indices for the analysed sludge and coal samples,
the high rank coal sample (H) presents the lowest slagging and fouling tendency,
followed by the sludge sample (NB), due to the high acidic oxide (SiO2, Al2O3)
content of the ash 73,57% and 64,53%. The low rank coal sample (L) and the sludge
sample (NF) present a medium slagging tendency. The sludge sample (NA), due to
the basic oxide content of the ash (~47%), presents a high slagging tendency.
Conclusions
The paper presents an analysis of slagging and fouling tendency in combustion
process for three sewage sludge and two coal samples, using some indices (basic
oxides, acid oxides, base-to-acid oxides, slagging and fouling indices)
The full characterisation of the sludge samples, including the ash composition and
ash slagging and fouling tendency, has an important role in the design and
exploatation of combustion installations, where sewage sludge is used for
incineration or co-incineration.
Acknowledgements
This work was realised with the support of Operational Programme Competitiveness 2014-
2020, Contract no. 55/05.09.2016, Project ID P_40_300, SMIS 105581, Subsidiary Contact no.
6538/27.04.2018.
References
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ASRO 2017, SR EN 14582:2017, Characterization of waste–Halogen and sulphur
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of elemental composition by X-ray fluorescence
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2017, 'Experimental models of characterization and analysis of industrial
waste', 20th International Symposium the Environment and The Industry, SIMI
2017, Bucharest, pp. 142-150.
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no. 11 bis from 5 th January, 2018.
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boilerfurnace slagging by means of fusibility correlations', Biomass and
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combustion: Alkali-induced slagging silicate melt-induced slagging (ash
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61.

IMPACT OF TERRESTRIAL AND MARINE POLLUTION ON THE

BLACK SEA QUALITY OF WATER
Victorita Radulescu
University Politehnica of Bucharest, Splaiul Independentei 313, Sector 6, Bucharest, Romania,

e-mail: vradul4@gmail.com
Abstract
Black Sea represents a direct link between the European Union, EU candidate
countries and some Asian countries such as Russia, Georgia, etc. During the last
decades, the Black Sea has been confronted with unexpected environmental
problems. In the south part of the Romanian seashore has appeared erosion, in the
North-East part of the Black Sea appeared a massive algae development, followed
by modification of the maritime biological balance. In parallel, the maritime water
parameters have been changed, partly due to the water discharged from the main
rivers as Danube, Dnieper, Dniester, partly from the amount of freshwater from deep
currents new appeared in the last decades, and partly due to the impact of the
pollutant sources. Firstly, are mentioned some data, based on the local
measurements and registered data, which underlines the actual situation, referring at
the existing sources of pollution, the hydrocarbons and ions concentration, etc. with
immediate consequences on the local equilibrium of the marine bio-system. The
registered Turkish accidents with spilled oil briefly mentioned, were followed in a
short term by a process of nitrification, with many consequences. Next are presented
the appeared modifications, registered in the Black Sea fauna, some endangered
species, correlated with the simultaneous apparition of some invasive species.
Finally, some conclusions and references are presented.
Keywords: Biodiversity, Environmental factors, Environmental monitoring Marine

pollution, Sea measurements.
Introduction
The Black Sea is a zone of particular interest for the European Union because
represents the eastern border, a connection between the EU and Asian countries. The
Black Sea also has strategic importance in energetic infrastructure, being a zone
which confronts with political conflicts (peninsula Crimea), permanent discussion
referring to the marine traffic, fishing quotas, etc. Anyway, members or non-
members of UE, each country which is bordering the Black Sea should maintain the
regional ecologic equilibrium, and respect the treaties of excellent proximity and the
regulatory environment rules (Protocol on Protection of the Marine Environment of
the Black Sea from Land-Based Sources and Activities 2009), (Strategic Action
Plan for the Environmental Protection and Rehabilitation of the Black Sea 2009).
In the last decades, in the Black Sea environment, marine biology and the water
characteristics have recorded some changes, affecting the entire ecosystem. The
south part of the Romanian Black Sea shore has confronted with massive erosion,
with several cliffs collapsed, sometimes more than 4-5 m. The main cause was
considered the registration of many small earthquakes near the border with Bulgaria,
for Romania the zone between resorts Venus and Vama Veche. In time, a Bulgarian
team registered the apparition of a freshwater current, with a significant flow rate.
Moreover, new environmental and social problems appeared mainly due to
mismanagement of the main rivers flowing in the Black Sea, Danube, Dnieper,
Dniester, etc. with significant input of wastewater, solid waste from the industrial
activities, and contaminated water due to improper utilization of fertilizers on
agricultural lands. This year, confronted with many floods, has transported
supplementary solid waste. The chemical fertilizers often used in Danube meadow
are another responsible factor in marine water contamination, but the leading causes
remain the existent shipyards and the industrial activities. Any changes in the
ecological balance affect the standard of living in this zone. The beaches width has
decreased in Eforie, Mangalia, 2 Mai, and Vama Veche, reducing significantly the
number of tourists, which have turned to outbound tourism.
The Black Sea has specific characteristics because over 90% of its deep-water is
anoxic. In natural conditions, without any perturbations, the interaction between the
water-rich in oxygen from the surface and the anoxic deep one is minimal. With
specific measurements was observed that the Black Sea has a layering structure,
with significant consequences on the biologic diversity. The newly registered
current in deep water interferes between these layers, with impact on the
ecosystems. The Black Sea is almost a close body of water, with the fauna diversity
approximately three times smaller, compared with that one from the Mediterranean
Sea.
Starting 1997 there were registered three accidents in Turkish shipyards and their
vicinity, with oil spills. One of them due to the massive oil spilled in the Black Sea
water has been followed by some chemical and biological modifications, especially
massive felt on the seaside from Ukraine and Georgia. In 2005 and 2007 the
Romanian shore was also affected. In Mamaia, Mangalia, and near the Bulgarian
border, for more than three weeks in full season during the summer holidays,
massive quantities of dead fish and jellyfish have appeared on the sea surface,
followed by a vast amount of destroyed marine vegetation.
In the local analysis of the Romanian Black Sea coastal water should be considered
both the source of pollution from waste-waters discharged by sewage pipes from
municipal and industrial treatment plants but also the coastal water nearby the
discharges from the agricultural lands. There are four domestic waste-water
treatment plants, Constanta North, Constanta South, Eforie South, and Mangalia, a
petrochemical industrial waste-water treatment plant in Petromidia, and a shipyard
in Mangalia. All these factors have major influences in the marine environment and
local ecologic balance.
Experimental Materials
The Black Sea represents a region of particular interest because it is rather sensitive
to climate and anthropogenic influences. It is considered a deep sea, as the
maximum depth is about 2200 m. The Black Sea receives drainage from almost one-
third of the continental free water flow of Europe, being meanwhile an isolated sea.
It is the reason why it is regarded as a vulnerable water basin, being permanently
monitored, Fig. 1-a; green–marine currents, blue-temperature, red-water parameters,

cyan-biologic registration. The purple line represents the territorial waters. Since
2002 a total of 37 boats have been deployed in the Black Sea, with 11 permanently
active with cycles of 5 days for monitoring and marked depths, between 200-1000
m. Most ships alternate the average depth with maximal profiling depths between
700 and 1500 m. Fig. 1-b presents the routes of the ships for two months.
Figure 1. a- Monitored points on 20 March 2019, b-Routes for March-April 2019

Internationally, a report created jointly by the countries bordering the Black Sea has
highlighted the main factors for water pollution, Table 1.
Table 1. Types and pollutant sources in the Black Sea

Sources of pollution
Types of pollution
1 2 3 4 5
Contamination with chemicals:
• nutrients and organic matter + + + + +
• oil and petroleum products + + + + +
• persistent organic pollutants + + + + +
• trace elements + + + + +
Radioactive contamination + +
Marine litter (solid waste) pollution + + + ? +
Biological pollution:
• microbial/faecal contamination + + + +
• introduction of exotic species +
1 – Industrial liquid wastes and insufficiently treated or untreated sewage from
coastal cities and settlements;
2 – Inputs from the agriculture, industry, mining, and municipal sewage from the
whole Black Sea drainage area;

3 – Inputs from the agriculture, animal husbandry and non-managed tourism mainly
through the run-off from land (coastal pluvial effluents and ground waters);
4 – Inputs from various sources of air pollution (smokes, fumes, dust, and exhaust
gases) no matter where in the world;

5 – Dumping of the solid waste, and dredged matter; discharge of untreated sewage
and ballast waters; oil spills; lost fishing nets; introduction of alien marine
organisms owing to the bio-fuel.
To establish the influence of the waste-water discharges by the municipal sewage
stations in Romania, have been analyzed the chemical and bacteriological pollutants,
identified in samples from the waste-water, collected inside the sewage treatment
plants, before being discharged into the sea. There were compared with the values
obtained in seawater samples as to be determined the level of pollutants within the
footprint of the profile weirs at 0 m, 5 m, and 20 m. In 2017 the collected samples
from the municipal wastewater treatment plants, after the refurbishments carried out
during 2007-2010, showed levels of total hydrocarbons within the range of 82-503
g/l, values accepted by The Commission on the Protection of the Black Sea
Against Pollution. The only amount that has exceeded the permitted limit was
registered in the station Petromidia, Table 2, where CN-Constanta North, CS-
Constanta South, ES- Eforie South, M-Mangalia, P-Petromidia
Table 2. Average values of the hydrocarbons concentration

CN CS ES M P
Waste water 82 88 503 280 1840
Sea 0 m 145,4 154,7 180,6 810 884
Sea 5 m 122 195,6 150,3 640 819
Sea 20 m 101,8 118 120,2 224 740
The spatial distribution of the hydrocarbons pollutant confirms the petroleum

dispersion on the east direction, along the discharge channel in the marine
environment. At level 20 m, the load of the total hydrocarbons determined in
seawater decreased at four stations in the direction of the waste-water treatment
plants. There were analyzed the concentration levels of heavy metals Cu, Cd, Pb;
there are within the accepted range 9.45-32.06 g/l for Cu, 8.05-14.9 g/l for Cd,
and 0.91-9.54 g/l for Pb, Table 3.
Table 3. Average values of metals concentration

Wastewater Seawater 0 m Seawater 5 m Seawater 20 m
CN Cu 11,3 14,4 11,3 10,1
Cd 14,8 7,8 6,3 5,9
Pb 2,33 2,1 1,7 1,6
CS Cu 9,5 19,7 11,4 8,2
Cd 8,4 6,4 5,3 2,14
Pb 1,1 6,8 5,32 4,84
ES Cu 34,9 12,8 7,84 6,8
Cd 16,6 14,1 8,6 5,4
Pb 9,14 5,73 4,82 3,7
M Cu 19,4 16,7 12,3 11,2
Cd 9,23 7,4 5,4 2,8
Pb 3,47 12,5 10,8 8,3
P Cu 32,3 38,4 27,3 23,1
Cd 14,8 12,8 12,7 13,9
Pb 4,83 5,1 5,3 5,6
If there are compared the measured values for heavy metals, with those recorded in
2000-2005 the values constantly have decreased until 2007. After the accidents
registered in 2005, 2007, and 2009 in Ukraine and Turkey, the concentrations
increased again (Final ¨Diagnostic Report¨ to guide improvements in the Black Sea
environment 2010), (Zaitsev 2006). In the mentioned period in Romania was tested
the concentration of the poly-aromatic hydrocarbon. Of the five poly-aromatic
compounds investigated from samples of the wastewater treatment plants have been
identified three compounds in Petromidia, Eforie Sud, and Mangalia, and two
compounds in Constanta South and Constanta North, Table 4.
Table 4. Content of poly-aromatic hydrocarbons

Poly-aromatic CN CS ES M P
Naphthalene 0 0 69,3 74,8 493
Acenaphthene 0 0 5,4 2,43 0,688
Fluorine 0 0 2,1 2,4 0,378
Acenaphthylene 0,29 0,32 0 0 0
Benzopyrene 0,31 0,28 0 0 0
The highest concentration of poly-aromatic hydrocarbons was recorded at 5 m

depth, of 124,3 ng/l, which is 5 times higher than at 20 m. In three points of
measurements near Constanta North, Constanta South, and Mangalia, from the
southern part of the Romanian seaside where there are more farmlands have been
investigated eight types of pesticides organic-chlorides, Table 5.
Table 5. Average HCB and Lindan

CN CS M
HCB Lindan HCB Lindan HCB Lindan
2000 430 47,9 68,5 1042,4 118,4 86,7
2001 520 85,2 112,7 894,7 143,7 132
2002 617 221,7 314,7 1247 212,2 473,6
….. ….. ….. ….. ….. ….. …..
2017 780 714,5 714,5 1770 690,6 706,4
The highest level of pesticides is recorded at the level 20 m in seawater, with an

average of 473,8 ng/l, value about 32% greater than the value recorded near the
seashore. The superior load of the organic chlorine pollutants recorded in deep
seawater is the result of cumulative effects between the concentration of the
pollutants of fluvial origin, domestic urban, but also produced by the marine
currents, that bring polluted water mainly from the southern. The pollution with
pesticide was made due to the fungicides HCB and lindan in high concentrations in
water, offshore, between 270 ng/l and 1774 ng/l, exceeding about of nine times the
maximum allowed value by the European normative of 200 ng/l. From the recorded
data could be observed that three monitored wastewater treatment plants, Constanta
South, Eforie South, and Mangalia contain large amounts of feces, with maximum
values of 1.7 x 107 germs/100 ml for the indicators total coliforms CT, and CF fecal
coliforms, and 2.105 for SF- fecal streptococci. The highest level was found in the
Eforie South station. The realized measurements prove that the southern coastal
waters are insufficiently treated, downloading in the marine environment large
amounts of germs, including pathogens.

The oil spills by accidents or by common industrial activities have produced the
main disturbances in the last decades, followed by chemical and biological
modifications, with effects in the nitrification process. The maximum values
recorded for the nitrates were reached in 1997 and 2009. The values for the
Romanian marine waters involved in the eutrophication process was determined

based on the measurements recorded at station Constanta and showed a monthly
average of N = 372 mg/l. In the south part of the Romanian seashore it has increased
dramatically, N = 3024 mg/l, (Boltachev & Karpova 2006), (Dobrovolov et al.
2003). In Fig. 2-a, the affected areas by eutrophication are illustrated. As it may be
observed the Romanian shore is affected, mainly due to Ukrainian pollution. As a
consequence of the supplementary freshwater amount, the water salinity from the
Black Sea was changed, Fig. 2-b, followed by modification of the temperature, and
biologic structure.
Figure 2. Affected area: a- by eutrophication, b- salinity modification
Special marine conditions characterize the areas where the hypoxia and the anoxia
were registered: vertical gradients of density in 6 conventional units, salinity
variation of 6%/m, and temperature variations of 15o C, with an important role in the
eutrophication process. However, in the spring of 2016, water was over-saturated
with the oxygen of 170%, and the pH level on the surface has reached 9.25,
(O'Higgins et al. 2014). In these conditions, in the bottom layer, the pH of water has
decreased to 7.8. As a consequence, a destructive process has appeared: the constant
speed of the organic matter oxidation exceeds by 3-5 times and the BOD-
Biochemical Oxygen Demand value reaches 2-4 mg/l. All these modifications
recorded in the water's composition, causes a removal of the fish from the shore,
causing it to stay only in deep water, a decrease of fish quantity, and an increase of
the amount and sizes of the jellyfish. In 2016 for the Romanian sea-fishing was
recorded one of the smallest quantity from the last 30 years.
The Black Sea is now confronted nowadays with some invasive species. As
eutrophication's consequence has evolved the saprophytic bacterial plankton,
suddenly increasing, mainly the cocci and bacilli. This is a consequence of high
levels of organic matter dissolved particles, being an additional source for nutrition
for the saprophytic microorganisms. The populations of bacteria, especially the
pathogenic organisms, have reacted at changes appeared in marine conditions,
increasing the organic matter in the water volume and bottom sediments. The most
advantaged species in these eutrophic conditions are the plankton of small sizes,
such as Euglenoids, Coccolithophores, and Dinoflagellates. The phytoplankton
species composition is represented by 148 species and subspecies. The unfavorable
conditions, such as intense solar radiation recorded in the last years have provoked
also massive development of algae.
Intensive algae development has induced a sharp decline of the dissolved oxygen
and has increased the bio-sedimentation of the decaying plants. The light penetration
and transparency of the marine waters have decreased. Consequently, an important
modification of the zooplankton communities was determined by massive increasing
of species as Cassiopea Andromeda and Cotylorza tuberculate, the largest ones in
the Black Sea, but also Aurelia aurita and Rizzhosstoma Pulmo. These four species
have large dimensions, are poisonous, and newly developed in the Black Sea, Fig. 3.
Figure 3. Invasive poisonous species of jellyfish
In the Black Sea, there are about 200 fish species, more than 500 mollusks and many
macrophytes water plants, as the green, red, blue, and brown algae. Among the
recorded fish species, economic value is represented by about two dozens of species
representing 98% of the catches from the last two decades. Between them, must be
mentioned the Pontic shad, gray mullets, and sturgeons. In the last years, the number
of Pontic shad permanently decreases. But the main threat for all species remains the
over-fishing. By exclusive international agreements, this aspect may be solved. The
problem remains with critically endangered species, Fig. 4 due to:
- Eutrophication: as the angel shark, starry sturgeon, and beluga
- Salinity modifications: as the sea horse, thorn-back ray, crabs
- Oil pollution, the European eel, and smooth hammerhead.
By making a comparison, the situation of shad's stock is better than the sturgeon,
due to the natural abilities of shad to more rapid recovery. As an example of over-
fishing: it is recommended the sturgeon capture of 10 trawlers/year; in 2017 were
registered 15 trawlers and in 2016, 18 trawlers. It can be seen that only in recent
years has been fished almost two times more than the recommended amount of
sturgeon; but the problem is repeated with mackerel, turbot, etc.
Figure 4. Endangered species a- beluga, b- sea horse, c-angel shark

Unfortunately, in the Black Sea region, there is not a regional fisheries management
organization. Each riparian country promotes its regulatory framework in fisheries,
even for the migratory species. The EU Scientific, Technical, and Economic
Committee for Fishery try to solve the problem by creating international projects
and committees with sub-commission of the stock's assessment for species like
sprat, turbot, anchovy, whiting, mackerel and shark from the Black Sea.
Conclusions
The Black Sea represents a transit route (more than 50000 ships, including 10000 oil
tankers) for the oil and gas exports, which means that there are risks associated with
these activities, such as oil spills and accidental pollution. Signed in 2015, the BS-
SAP an updated Strategic Action Plan for rehabilitation and protection of the Black
Sea represents a new step in the ecologic rehabilitation, by solving any trans-
boundary environmental problems. It contains realistic objectives, including legal
and institutional reforms, suggestions for necessary investments in solving the

ecological issues, as diminishing the insufficient treated waters and pollution from
priority sources, eutrophication, surveillance of traces for metals and radio-nuclides,
to avoid the chemical pollution. Several projects developed by international teams
have restored partially some environmental aspects. Introducing in 2018 the Beroye
ovata, which is feeding with Mnemiopsis leidyi (invasive species), has been
observed a decrease of the algae number and biomass. The problem of the
venomous jellyfish is remaining; they become more significant in number and
dimensions. The increase of fodder zooplankton is followed by an increase in the
stocks of small pelagic fish, but national efforts and international cooperation in the
framework of the MSFD brought the first signs of recovery of the Black Sea
ecosystem.
References
Boltachev, A & Karpova EP 2006, ‘Findings of New and Rare Fish Species in the
Coastal Zone of Crimea’, Journal of Ichthyology, vol.49, no. 4, pp. 277-291
Dobrovolov, I, Ivanova, P & Apostolu, A. 2003, ‘Systematic of the Atherinidae
species in the Black Sea and Mediterranean basins based on biochemical-
genetic data’, Sixth International Conference on the Mediterranean Coastal
Environment, MEDCOAST 03, Ravenna, Italy, pp. 721-728
Final ¨Diagnostic Report¨ to guide improvements in the Black Sea environment,
August 2010, from http://www.blacksea-commission.org/_publ-BSDiagnostic
Report 2010 .asp [20 March 2019]
O'Higgins, T, Farmer, A, Daskalov, G, Knudsen, S & Mee, L 2014 'Achieving
good environmental status in the Black Sea: scale mismatches in
environmental management’, Research, part of a Special Feature on Systems
Science for Managing Europe’s Seas, http://dx.doi.org/10.5751/ES-06707-
190354
Protocol on Protection of the Marine Environment of the Black Sea from Land-
Based Sources and Activities 2009, from http://www.blacksea-commission.
org/od_LBSA Protocol.asp [12 March 2019]
Strategic Action Plan for the Environmental Protection and Rehabilitation of the
Black Sea, 2009 Adopted in Sofia, Bulgaria, from http://www.blacksea -
commission.org/_bssap2009.asp [16 March 2019]
Zaitsev, YP 2006, ‘Introduction on the Black Sea Ecology’, Even, Odesa, pp. 86-98

INFLUENCE OF THE pH INDICATOR ON DISSOLVED ORGANIC

CARBON FOR DETERMINATION THE HAZARDOUSNESS OF
INDUSTRIAL WASTE
Georgiana Cernica1, Georgeta Madalina Arama1, Adriana Cuciureanu1, Gina Catrina

(Traistaru)1, Diana Stroia2
1
National Research and Development Institute for Industrial Ecology ECOIND Bucharest, 71–
73 Drumul Podu Dambovitei Street, 060652, Bucharest, evmt@incdecoind.ro, Romania
2
SC SETCAR SA, 6 Gradinii Publice Street, 810022, Braila, Romania
Abstract
The paper presents the influence of pH on the dissolved organic carbon in industrial
waste samples as a decision indicator in determining the hazardousness of the waste
at storage according to the environmental legislation. Waste storage is a common
method of management and is realizing according to GO 95/2005, which requires
limit concentrations of the indicators analyzed according to each type of deposit
(inert, non-hazardous, and hazardous). For the analysis of the dissolved organic
carbon, 6 samples of waste from different sectors of activity were subjected to the
leaching test and the eluate was analyzed on a multi N/C 3100 equipment at both the
pH of the waste, itself and between 7.5 and 8 pH units. From the results obtained it
is found that the modification of the pH leads to significant variations in the
concentration of the dissolved organic carbon, variations which can provide
essential information for the subsequent management of the waste.
Keywords: dissolved organic carbon, hazardous, industrial waste, inert, non-

hazardous
Introduction
Waste management has become a priority in the 21st century because of the increase
in global population, high food consumption and industrialization. Until 2100, waste
generation is expected to triple globally (Minelgaitė & Liobikienė 2019). The largest
chemical industries such as refineries, pharmaceuticals, automobiles and textiles use
water, solvents and polymers to reach hazardous waste. They can generate a large
amount of hazardous organic waste with a high moisture fraction, that is, a low ratio
between free and bound water (Worrall et al. 2019). Because of the large amounts of
waste generated, it is becoming increasingly difficult to place new storage facilities.
That is why an important issue is to develop new strategies for reducing the volume
of waste (Li et al. 2018). Also, waste management is considered an activity of public
interest carried out in accordance with the provisions of this law and the regulations
adopted under this law. According to GO 95/2005, it helps those who own or
manage the waste. A characterization is made to determine the hazardous / non-
hazardous nature and to include them on the waste list, to observe transport forms
and also to determine the type of deposit in which a waste can be accepted (Kim et
al. 2018).

To be accurate and conclusive results, there must be a sampling process and all the
preliminary operations of the real waste analysis (packaging, storage, preservation,
transport, pretreatment, etc.) (Arama et al 2015). To be included on the list for a
particular storage class, a waste is subject to testing, consisting of a general
characterization performed with standardized methods of analysis for the
determination of physical-chemical composition and for testing of leachate behavior
and / or variation in characteristics in the short and long term. The indicators to be
tested and the maximum admissible limits are set for each type of deposit. GO
95/2005 specifies the categories of solid, granular waste, chemical characteristics for
admission to storage and methods of testing these specific properties. The main test
is the leachability analysis, which simulates in the laboratory the washing of stored
material by natural precipitation. The liquid resulted from washing is called
“Leachate”. The test is complex by the various conditions in which it is performed
and the way the results are calculated. According to GO 95, if the waste exceeds
minimum value for DOC at its own pH, it can alternatively be tested at L/S=10 l/kg
and at pH between 7.5 and 8.0 pH units (GO 95/2005).
The paper presents the influence of pH on dissolved organic carbon in industrial
waste samples for determination the hazardousness of the waste at storage according
to the GO 95/2005.

To achieve the main objective, 5 types of samples from different fields of activity
from industrial waste were selected and listed below (Figure 1):
D1 - sludge from the sewage treatment plant - textile industry;
D2 - sludge resulted from industrial wastewater treatment plant;
D3 - sludge resulted from car wash;
D4 - sludge resulted from urban wastewater treatment;
D5 - waste from the ash hearth from the incineration plant;
D6 - waste from filter ash from the incineration plant.
Figure 1. Study types of waste

For analysis of dissolved organic carbon, a Multi N/C 3100 analyzer was used. This
is a compact and very efficient device for determining the total carbon content
and/or the total nitrogen content of aqueous samples. Decomposition takes place in
the multi N/C 3100 by thermocatalytic high temperature oxidation in the presence of
special catalysts. This enables quantitative decomposition even for stable, complex
carbon and nitrogen compounds. The modular versatility of the multi N/C 3100
(Figure 2) permits individual adaptation. Analytically, dissolved organic carbon
(DOC) is characterized as organic molecules capable of passing through a 0.45μm
filter (Regan et al 2017).
Figure 2. Analyzer with sample dispenser
For DOC analysis the samples most of the time need filtration. The most commonly
often used filter is 0.45 µm, but sometimes when the sample is too dense, the filter
pump can be used. If small amounts of water are being filtered (30 or 40 mL), more
practical is to use syringe filters. Most important is that the filters do not release any
DOC during filtration.
pH Correction
For pH correction, 40 mL of each sample was introduced in a vial and corrected
with a HCl 0.1 N or NaOH 0.1 N solution and bring between 7.5 – 8 pH units (Table
1).
Table 1. pH correction, pH units
Samples Initial - pH Final – pH
D1 4.1 8.0
D2 6.1 7.5
D3 6.6 7.5
D4 8.7 7.5
D5 9.1 7.7
D6 9.6 7.6

Preparation of waste samples

The preparation of the waste samples for the readability of the dissolved organic
carbon was carried out in several steps according to the scheme in Figure 3.
Figure 3. Sample preparation scheme

In Table 2 are presented the results obtained for all types of waste samples analysed.
Table 2. Results
pH – initial DOC – initial pH – final DOC – final
Samples (pH units) (mg/kg s.u.) (pH units) (mg/kg s.u.)
D1 4.1 634 8.0 401
D2 6.1 980 7.5 787
D3 6.6 869 7.5 692
D4 8.7 938 7.5 785
D5 9.1 878 7.7 996
D6 9.6 543 7.6 611
From the results obtained it is found that the DOC shows different concentrations by
pH variation, even if this variation is not significant. Thus, pH correction in the
basic range (9.1 - 9.6 pH units) leads to an increase in DOC concentration. The pH
correction between 4.1 – 8.7 pH units range decrease the DOC concentration (Figure
4 and Figure 5). These variations depend on how organic matter is bound in each
type of waste.

Figure 4. Experimental results of pH
Figure 5. Experimental results of DOC
Through the GO 95/2005, the maximum admissible values for leachate-specific

indicators are established, based on which the class of landfill (inert, non-hazardous,
hazardous) in which the analyzed waste can be accepted as well as the limit values
for certain waste indicators used as additional criteria for establishing the deposit
class.
The evaluation of leachate quality resulting from leaching tests is done by
comparing the values of the quality indicators determined for leachate with the limit
values stipulated in the GO 95/2005.
In Table 3, the maximum admissible limits for the leachate-specific indicators (for
L/S of 10: 1 between the levigator and the sample weight) are presented in order to
accept a waste in one of the mentioned storage classes, according to the GO
95/2005, as well as the values of the indicators determined for leaching
corresponding to the analyzed waste.

Table 3. Results for the DOC indicator analysis reported to GO 95/2005

The maximum permissible value
Determined
(mg/kg s.u)
Samples UM Values - DOC
L/S =10 l/kg
Initial Final inert non-hazardous hazardous
D1 mg/kg s.u 634 401 500 800 1000
D2 mg/kg s.u 980 787 500 800 1000
D3 mg/kg s.u 869 692 500 800 1000
D4 mg/kg s.u 938 785 500 800 1000
D5 mg/kg s.u 878 996 500 800 1000
D6 mg/kg s.u 543 611 500 800 1000
The leachate quality analysis, resulting from the leaching test, at the L/S ratio of 10
l/kg, and the comparison of the values of the quality indicators determined with the
values stipulated in the GO 95/2005, highlighted the following:
Before correction (initial values):
The values of the samples: D1, D6 are within the appropriate limit values required
for acceptance of the waste at storage on non-hazardous waste landfills.
The values of the samples: D2, D3, D4, D5 are within the appropriate limit values
required for acceptance of the waste at storage on hazardous waste landfills.
After correction (final values):
The value of the sample: D1 is within the appropriate limit values required for
acceptance of the waste at storage on inert waste landfills.
The values of the samples: D2, D3, D4, D6 are within the appropriate limit values
required for acceptance of the waste at storage on non-hazardous waste landfills.
The value of the sample: D5 is the within the appropriate limit values required for
acceptance of the waste at storage on hazardous waste landfills.
Conclusions
The influence of pH depends of type of waste and also to be more neutral. A value
appropriate of 7.5 pH units is more stable than a higher one. The industrial waste
depends on what they are made. For final values of DOC, the conclusions are next:
D1 could be storage on inert waste landfills, D2, D3, D4 and D6 could be storage on
non-hazardous waste landfills and D5 could be storage on hazardous waste landfills.
Acknowledgements
no. 4384/20.03.2019.
References
Arama, MG, Pascu, LF & Guta, D 2015, 'Decision model based on analytical
hierarchy process for managing the environmental risks within the
environmental management systems', International Symposium “The
Environment and The Industry”, Bucharest, pp. 118-123.
GO 95/2005, Government Order no. 95 establishing acceptance criteria and
preliminary procedures for the acceptance of waste storage and the national

list of waste accepted in each class of landfill, Romanian Official Monitor no.
194 from 8th March, 2005.
Li, W, Zengyi, M, Huang, Q & Jiang, X 2018, "Distribution and leaching
characteristics of heavy metals in a hazardous waste incinerator", Fuel, vol.
233, pp. 427-789.
Kim, L, Muresan A, Cuciureanu, A, Guta, D, Arama, M, Cristea, NI & Dediu, V
2017, "Experimental models of characterization and analysis of industrial
waste", International Symposium “The Environment and The Industry”,
Kim, L, Arama, MG, Cuciureanu, A & Guta, D 2018, “Handling specific issues of
waste hazardousness evaluation according to waste type”, Environmental
Engineering and Management Journal, vol. 17, pp. 2945-2956.
Minelgaitė, A & Liobikienė, G 2019 "Waste problem in European Union and its
influence on waste management behaviours", Science of the Total
Environment, vol 667, pp. 86-93.
Regan, S, Hynds, P & Flynn, R 2017, "An overview of dissolved organic carbon in
groundwater and implications for drinking water safety", Hydrogeology
Journal, vol. 25, pp. 952-967.
Worrall, F, Howden, N, Burt, T & Bartlett, R 2018, "Declines in the dissolved
organic carbon (DOC) concentration and flux from the UK", Journal of
Hidrology, vol. 556, pp. 775-789.

METHODOLOGY FOR QUICKLY DETERMINING

THE QUALITY OF PELLETS
Georgi Komitov1, Violeta Rasheva2, Ivan Binev3
1
Department of Agricultural Mechanization, Agricultural University Plovdiv, 4000 Plovdiv, 12
Mendeleev blvd., gkomitov@abv.bg, Bulgaria
2
Department of Industrial Thermal Engineering, University of Food Technologies, 4000
Plovdiv, 26 Maritza blvd., v_rasheva@abv.bg, Bulgaria
3
Department of Energetics, Trakia University St. Zagora, Faculty of Technics and Technology,
8600 Jambol, 38 Graf Ignatiev Str., ivan.binev@trakia-uni.bg, Bulgaria
Abstract
A methodology for quickly and easy determination the quality of pellets offered on
the market is developed on the basis of "theory of graphs". The pellet quality
assessment is performed in two ways - by direct control (non-destructive
measurements) and by combustion. The following pellets parameters are determined
at the direct control stage: friability, homogeneity, presence of dark stains and
moisture content. The experimental measurement of following parameters of the
combustion process is carried out at the stage of pellet burning assessment under
real conditions: temperature in the combustion chamber, time for complete
combustion of the pellets and the amount of ash after pellets combustion. The
calorific value of the tested pellets is determined on the basis of the experimentally
obtained parameters of the combustion process. The the obtained parameters values
are statistically processed according to the described in the paper equations at the
next stage. Then the results for the investigated pellet parameters are compared with
the normative values. The proposed methodology could be calibrated by
experimental determining the calorific value of investigated pellets by a calorimeter.
Practical application of this methodology is that by not so complicated
measurements and calculations the required amount of pellets for heating a building
with a certain energy consumption for heating season could be determined.
Keywords: biomass, green energy, energy efficiency, pellet quality
Introduction
Global energy policy aims at limiting climate change, energy security and
competitiveness. In accordance with (Treaty on the Functioning of the EU 2012),
promoting renewable forms of energy is one of the goals of the Union energy policy.
The increased use of energy from renewable sources represents an important part of
the package of measures needed to reduce greenhouse gas emissions and comply
with the Union's commitment under the 2015 Paris Agreement on Climate Change
and with the Union 2030 energy and climate framework, including the Union's
binding target to cut emissions by at least 40 % below 1990 levels by 2030. The
increased use of energy from renewable sources also has a fundamental role in

promoting the security of energy supply, sustainable energy at affordable prices,

technological development and innovation (Directive (EU) 2018/2001).
Energy consumption for heating and domestic hot water accounts more than 70% of
the total energy consumption of the household, so the type of energy source and the
efficiency of energy conversion systems are of exceptional importance. The final
energy consumption for space heating in Bulgaria is as follows: wood and coal -
52.6%, electricity - 38.5%, natural gas - 2.4% and natural gas for district heating -
6.5% (Guidance for Household Energy Auditors 2015). The use of renewable
energy sources is negligible, but more and more people living at houses choose
pellets as heating fuel for their homes.
In domestic heating with non-efficient stoves and solid fuel boilers and the use of
coal containing ash and sulfur and wet wood, pollutants such as sulfur dioxide,
nitrogen dioxide, carbon monoxide and fine particulate matter are the main problem
in cities (Angelov at al 2018, Valtchev 2012). Analyses indicate that this type of
heating causes at least 85% of fine particulate emissions, so measures to improve air
quality are mostly targeted in this area (Guidance for Household Energy Auditors
2015).
Nearly 11 % of the EU’s population cannot adequately heat their homes at an
affordable cost (https://ec.europa.eu/energy/en/news/energy-poverty-may-affectnearly-
11-eu-population). The situation is estimated to affect more than 50 million
households in the European Union. The scale of the problem is due to rising energy
prices, low household incomes, a lack of access to finance, and inefficient buildings
and appliances (Good Practice in Energy Efficiency 2018). Energy poverty is
particularly prevalent in Central, Eastern and Southern Europe, with more than 30%
of households in South-Eastern European countries experiencing energy poverty
(EU Fuel Poverty Network 2015).
Energy poor people could replace solid fuels (wood and coal) with pellets to heat
their homes. The production of pellets from solid biomass is a technology which
transforms biomass to an energy carrier efficiently. Biomass is milled, dried and
densified under high temperature and pressure. The result is a homogeneous solid
fuel with a much higher energy density. State-of-the art technology of pellet
production can achieve overall conversion losses both for drying, milling and
densification that are lower than 10 %. Excess heat from the production is recycled
and used for drying the row material for new pellets (Renewable energy in Europe
2010).
Pellets are as convenient to use as fossil fuels. Due to their high energy content and
the convenient delivery and storage feature, pellets are an ideal fuel for replacing
also heating oil or gas. They are a key technology for increasing biomass use in
Europe and thus replacing fossil fuel, natural gas or electricity in the heating sector.
Pellets meet the need for high-calorific fuel and are also environmentally friendly.
When burning pellets, less carbon dioxide is released than if the wood from which
they are produced is left to rot (Renewable energy in Europe 2010).
Heating with pellets has advantages compared to heating with solid fuels. The solid
fuel (coal and wood) requires more storage space. Pellets are more calorific than
solid fuels. Their calorific value is 4.8 kWh/kg pellets. When burning pellets, less
carbon dioxide is released. Pellets have one more advantage - this fuel pollutes
much less. When burning, they release much less soot and ash (Renewable energy in
Europe 2010).
Pellets are successfully used for heat production and are especially suitable in small
scale heating systems (stoves and boilers) due to their automatic heating process,
easy storage, relatively low cost and a very low amount of ash and other emissions
released. The advantages of biofuels over traditional fuels are expressed in greater
energy security, reducing harmful effects on the environment, financial savings and
socio-economic aspects related to rural development (http://ener-supply.eu 2012).
Pellets have a cylindrical shape with a diameter of 6 mm and a length of up to 30
mm. The efficiency of combustion systems using pellets as fuel ranges from 85% to
95%. For comparison, the efficiency of combustion systems using wood as fuel is
about 79%. The ash content of the pellets is very low, at most 1.5%, as they burn
almost completely. Coniferous pellets are more preferred because they have a higher
heat output, and the ash content after burning is less. Most pellet burning equipment
are designed to work with pellets from both types of wood. Practice shows that the
efficiency of combustion systems depends more on the quality of the pellets and less
on the type of wood from which they are produced.
In this respect, the purpose of this paper is to develop a methodology for quickly and
easily determine the quality of the pellets offered on the market.

The methodology is based on the "theory of graphs" as the interconnections between
the different elements of the methodology are shown in fig. 1.
The first element of this methodology is the ‘aim of experiments’ (AE). At this
stage, the purpose of the developed methodology is clearly stated, namely that it is
easy and precise determine the quality of the pellets.
The second element of this methodology is the ‘introduction‘ (I). Due to the wide
variety of pellets available on the market, it is necessary to formulate several
indicators and to monitor their quality. Not always the quality of the pellets stated on
the package corresponds to the real quality. As a result, burned biomass releases
more harmful substances and ash content, resulting in increased consumption and
clogging of the outlet system. Frequent stops for prevention and cleaning of the
heating system are necessary. On the other hand it is reasonable to buy biomass in
the form of pellets before the start of the heating season. The price of pellets
increases significantly during the heating season due to their increased demand. So,
the current methodology is designed to avoid buying such unsuitable biomass
(pellets).
The next element in this methodology is the correct formulation of the ‘tasks to be
performed‘ (PT). In the present case, the pellet quality assessment is to be carried
out in two ways - by direct measurement (non-destructive control) and by
combustion.
In the stage ‘direct control ‘ (DC) a package of 15 kg of pellets is to be evaluated for
external signs. These indicators illustrate the state of the pellet, its density and
possibilities for cumbastion as well as the presence of impurities. The external
characteristics that can be used to assess the quality of the pellets are:

Figure 1. Multigraph of the interrelations between the main elements of the

methodology: AE – purpose of study; I - introduction; PT – performed tasks; DC –
direct control; EC – experimental control; F - friability; OK – optical control; H -
humidity; E – energy; T - temperature; BT – burning time; A - ash; AR – analysis
of results; PA - practical application
The first tested external characteristic is ‘friability‘(F). By indirect measurement of

this feature, it is possible to judge the presence of bark and impurities in the pellets,
which will worsen the combustion process and reduce the calorific value of the
pellets. Pellets are loaded into the sieve with a hole diameter of 4 mm. This
diameter is selected so that the destroyed pellets can be separated and whole pellets
with a minimum diameter of 6 mm will remain on the sieve. The pellets should be
well shaken so the dust and small fractions will be separated beneath the grate. The
dust content means a lower pellet density. The bulk density of the pellets must be
650 kg/m3 (https://peleti.xyz/). The dust and broken pellets are weighed with a scale
mark “Еlicom” model “EVL+PK-T”. It has a measuring range of 0-3 kg and
accuracy 0.1 g. The percentage of friability is determined by equation (1):
MD
F= , kg (1)
MP
where M D is the mass of dust and broken pellets in kg and M P – the total mass of
the pellets in the package in kg. Typically, the pellet packages have a mass of 15 kg.
The sieved pellets are then placed in a specially sized container with internal
dimensions 100х100х100 mm. For sealing the pellets are pressed against the
container with the pressure up to 30 N. They are weighed on scales ”EVL+PK-T”
and their bulk density is determined by equation 2:
mVC = mS  mt , kg (2)
where mS is the total mass of the pellets with the container in kg and mt is the mass
of the container in kg.
The value obtained is compared with the reference value (ISO 17225-2:2014,
https://peleti.xyz/).
- The second tested external parameter is ‘optical control‘ (OK). Already sieved
pellets are subjected to optical control to check their homogeneity and the presence
of dark stains. The presence of dark stains in this subjective method implies non-
homogeneity of the pellet composition and the presence of bark and impurities to
reduce their calorific value. After sieving 100 pellets are counted from the pile of
pellets. The diameter of the pellet and its length are measured by a caliper with a
range of 0-150 mm and an accuracy of 0.05 mm. A statistical survey of dimensional
scattering is carried out. It is judged For the uniformity of the pellets by the
scattering of a given mean value of the dimensions.
- The last external parameter tested by direct measurement is ‘moisture content‘ (H)
of the pellets. Pellets should have a moisture content of 10-12% according to (ISO
17225-2:2014, https://peleti.xyz/). The moisture content is measured directly using a
moisture meter of company "Merlin", model "HM8-WS-25" with a range of 4-99%
operating at pellet density up to 670 kg/m3.
The second stage is ‘experimental control‘ (EC) aims to determine the quality of
pellets under real combustion conditions. The methodhodology for determining the
energy of the pellets is indirect. It uses for this purpose a specially designed mobile
combustion chamber. The mobile camera resembles a real combustion chamber in a
pellet boiler but is smaller in size. The chamber is thermal-insulated with 10 cm
thick rock wool to reduce the heat loss between the walls and the surrounding air.
The amount of 0.05 kg of pellets are placed in the bed of the mobile combustion
chamber. A precise amount of air is fed through the ventilation system of the
chamber via a pressure blower so that the pellets can burn completely at a certain
speed. The excess air ratio of 1.4-1.6 according to (Yossifov 2005). An electric
heater mounted after the pressure blower is used to heat the air supplied to the
chamber to a temperature of 90 °C. Ignition is switched off after the appearance of
visible fire. The presence of a flame is counted from a photo detector, and its
indication is used to initiate the data collection from input-output card of company
"National Instruments", model "USB 6001". This usually occurs after 1-3 minutes.
The CO content of the flue gases is monitored over a period of 30 s during the
combustion process. The CO content must correspond to the reference value
established by the legal regulations (ISO 17225-2:2014). A suitable gauge for
measuring the CO content is portable gas analyzer of the company "Testo", Model
"T 310" (https://www.testo.com/en/).
The first controlled parameter in the pellet burning process is the ‘temperature‘ (T)
that is reached in the combustion chamber. Temperature measurement is done
directly with a thermocouple mounted to the bottom of the bed in the combustion
chamber. A suitable thermocouple is "TSNA-1J.T4.1" type J with a range of 0-800 °
C. The signal is logged directly from the input-output controller. The thermocouple
information is recorded in every 30 seconds. Thus the energy generateted from the
pellets can be analyzed.
The second controlled parameter is the ‘burning time‘ (BT) for the complete burning
of 0.05 kg of pellets. The time is recorded from the initial ignition of the pellets to
their extinction. This is a complete cycle of burning and the burning rate of the
pellets is determined against it. The burning rate of the pellets is determined by the
equation 3:
mp
VB = , kg/s (3)
BT
where m p is the mass of the pellets to be burned in kg;
The last controlled parameter is the ‘ash‘ content of the pellets (A). The amount of
ash is determined after the pellets in the bed of the mobile combustion chamber are
completely burnt. The solids remaining in the bed of the combustion chamber are
collected and weighed on the "EVL + PK-T" scale. The ash content is determined by
the equation (4):
M
PP = P .100 , % (4)
ms
where M P is the mass of ash remaining after burning the pellets in kg.
After the ash collection it is possible to determine the percentage of solid waste in
the ash. The solid waste after weighing the ash is removed and weighed again on the
"EVL + PK-T" scale. The percentage of solid waste is determined by equation (5):
H
HP = .100 , % (5)
MP
where H is the mass of the solid waste in kg.
An option for determining the pellet energy potential is direct determination by a
calorimeter, for example a calorimeter "KL 11 Mikado". This measurement will be
calibrating to the proposed methodology in this paper. A temperature of 17-20 0C is
set in the calorimeter casing. Two kg of distilled water with a temperature lower by
1 degree than that established in the housing of the calorimeter is placed in a
calorimeter vessel. The inside walls of the calorimetric bomb are washed with 10 ml
of distilled water for dissolving the nitrogen and sulfur oxides. A 100 mm helical
semiconductor and 1 g ground pellets (with an accuracy of 0.0001 g) are measured.
The ground pellets are pressed around the semiconductor. The resulting block is
placed in the calorimeter and the two ends of the semiconductor engage the
electrodes of the ignition system. The container closes tightly and oxygen is
delivered through the valve to 30 MPa. The so prepared system is placed in the
calorimeter and the automatic mode is started. The cycle time is between 10 and 30
minutes and is controlled by a microprocessor. After completion of the experiment,
the calorific value of pellets is read directly from the display in Joules. The container
is removed from the vessel, then opened, and unburned residues of helical wire are
removed. Their mass is subtracted from the initial mass of the helical wire. The
resulting value is the mass of burnt helical wire. This mass is multiplied by 6688 J/g
(calorific value of the heel) and the resulting value is subtracted from the calorific
value found by the pellet’s sample (Todorov et all 2010).
The next stage of the methodology is the data processing and analysis of the results
(AR). At this stage, a pellet quality analysis is carried out according to the
applicable regulations (ISO 17225-2:2014, Yossifov 2005, https://peleti.xyz/). The
energy potential of the pellets is determined based on the carried out experiments.
The final stage of the methodology is its practical application (PA). At this stage,
with non-complex calculations, it is possible to determine the amount of pellets
needed to heat a building with a known energy consumption.


A methodology for quickly and easy determination the quality of pellets offered on
the market is developed on the basis of "theory of graphs". The practical application
of this methodology is that by not so complicated measurements and calculations the
required amount of pellets for heating a building with certain energy consumption
for heating season could be determined. The methodology will raise consumer
awareness about the benefits of using pellets to heat their homes, assist them in their
choice of pellets and will lead to a possible reduction of harmful gases emited into
the environment.
Conclusions
A methodology for quickly and easy determination of pellet quality has been
developed. The methodology enables an effective determination of the energy
potential of the investigated pellets.
The methodology can accurately determine the amount of pellets required for the
heating of a building with a known energy consumption.
References
Angelov, B Kunev, D & Тоtev, T 2018, ‘Contamination of the environment with
mercury in the burning of Bulgarian lignite’, Energy Forum, IHS Varna, pp.
10 – 18.
BDS EN ISO 17225-2 Solid biofuels - Fuel specifications and classes - Part 2:
Graded wood pellets, 2014, (ISO 17225-2:2014)
Directive (EU) 2018/2001 of the European Parliament and of the Council of 11
December 2018 on the promotion of the use of energy from renewable
sources, 2018, Official Journal of the European Union.
EU Fuel Poverty Network, Households unable to afford to keep their home
adequately warm. European Commission 2015, Available at:
http://fuelpoverty.eu/wpcontent/uploads/2011/12/eu-fp-map-final-v2.jpg
[05.06.2019].
Good Practice in Energy Efficiency. Guide on for Central and South Eastern
Europe, European Union, 2018, Doi 10.2826/605264, Available at:
http://s3platform.jrc.ec.europa.eu/documents/20182/238542/Guide+on+good+
practice+in+energy+efficiency+for+Central+and+South+Eastern+Europe/3f8a
1d96-e259-4ab7-8da0-723e389f4abf, [05.06.2019].
Guidance for Household Energy Auditors, 2015, (in Bulgarian), Available at:
http://reach-energy.eu/ wordpress/wp-content/uploads/2015/01/D3.4-EAP.pdf,
[05.06.2019]
Markets, Trends and Technologies. European Renewable Energy Council (EREC),
2010, Renewable energy in Europe., second edition, Earth scan, London,
Washington, DC
Todorov, N et al, 2010, Practicum for animal feeding, East - West Publishing
House, Sofia, pp.158-159 (in Bulgarian)
Treaty on the Functioning of the European Union, 2012, Official Journal of the
European Union, Available at: https://eur-lex.europa.eu/legal-
content/EN/TXT/PDF/?uri=CELEX:12012E/TXT&from=EN, []05.06.2019].

Valtchev, G 2012, Combustion equipment and technology, 2nd Edition, Academic

Publishing House of UFT, Plovdiv. (in Bulgarian)
Yossifov, N 2005, Briquettes and pellets from plant biomass. Sofia, (in Bulgarian)
https://ec.europa.eu/energy/en/news/energy-poverty-may-affectnearly-11-eu-
population
https://peleti.xyz/, [05.06.2019].
https://www.testo.com/en/, [05.06.2019].
http://ener-supply.eu/downloads/ENER_handbook_en.pdf Handbook on Renewable
Energy Sources, [05.06.2019].

METHODS OF THE END-USE OF END-OF-LIFE TIRES
Nevena Ivanova, Margarita Filipova, Ivanka Zheleva
Ruse University, 7017 8 Studentska, Ruse, nsivanova@uni-ruse.bg, mfilipova@uni-ruse.bg,

izheleva@uni-ruse.bg, Bulgaria
Abstract
The main objective of the study, presented in the article, is to review the possible
methods of final recovery of End-of-Life Tires (EOLT). Applied methods of the
end-use of EOLT used in Republic of Bulgaria and in some other countries in the
European Union are presented and commented in the paper. Also the end-use of
EOLT waste criteria is discussed. The possibilities for post-recovery including
recycling of the waste generated by the tire recovery process have been explored.
The application of the identified methods in Republic of Bulgaria and other
European Union Member States have been analyzed and assessed.
Keywords: end of waste, recovery process, recycling, tyre
Introduction
End-of-life tires are a source of serious environmental pollution. In recent years they
have become a major problem for many developed countries. EOLT are not subject
to natural decomposition, are flammable and pose a serious environmental risk.
Therefore, landfills for the storage of such tires are considered as posing a danger to
public health.
To date, over 10 billion spent tires have accumulated around the world. Add to them
annually 13 to 14 million tons of new tires.
Tires can be recycled at 100%. Crushing of the tires is one of the most attractive
methods of their processing, as it allows the maximum physical preservation of the
physical properties of the rubber in the resulting final product from the processing.
They consist predominantly of rubber, soot, metal and textile.
In accordance with the (UN Basel Convention 1998) used tires are not dangerous
and harmful when processed, transported and stored properly.
There is no special EOLT Directive at this stage.

The necessary information for the analysis is providing through:
- using available public information from the official website of the
European Environment Agency (EEA);
- using publicly available information from the official website of the
Bulgarian Environmental Executive Agency;
- using publicly available information from the official website of the
Bulgarian Ministry of Environment and Waters;
- Statistics information for the methods for the sound treatment of waste
generated as a result of the recovery processing of EOLT;

- Examination of the end-of-waste standards in Bulgaria concerning rubber

piecies obtained from old tires in shredder plants and a study on the
availability of accredited laboratories within the European Union under
this standard;
- A study on applied end-of-waste standards in other European countries,
including guides with "end of waste" criteria.

Methods for EOLT recovering
The methods for the EOLT treatment are described and summarized in the Revised
technical guidelines for the environmental sound management of used and waste
pneumatic tires (UNEP / CHW.10 / 6 / Add.1 / Rev.1). The data are summarized in
Figure 1.
Figure 1. Methods for EOLT recovery
Application of EOLT waste treatment methods across the EU

According to the data from the ETRMA - European Tire & Rubber Manufacturers
Association 2016, 40 000 tones old tires are being generated and collected in
Bulgaria in 2016. Of this, only 2000 tones are reclaimed, 2000 tones used as fuel to
produce heat, and 27 000 tones are recycled. 9000 tones are directed to the landfill
for disposal, which is a significant amount.

Unlike in Bulgaria, in England for example, the amount of generated and collected
EOLT is 536 000 tones in 2016, with a significant amount of them being
regenerated. There, 29 000 tones were used in civil-engineering and only 2.43% of
the total amount of tires is targeted at landfills.
Figure 2. Methods for EOLT treatment used in England (UK), Italy (I), Poland (PL)
and Bulgaria (BG) in 2016 (Used Tyres/ELT Management in Europe 2016)
From the survey we can conclude that in Bulgaria, the recycling methods are
67.50% and the reuse and energy recovery represents each only 5% for the year
under review.
Methods for EOLT treatment in Bulgaria

To identify the methods used for EOLT treatment in Bulgaria, an extensive study
was carried out in the (National Information System for Waste NISW), maintained
by the Executive Environment Agency (EEA) at the Ministry of Environment and
Waters (MEW). According to the Public Register of persons holding documents for
waste activities at NISW there are a significant number of legal entities holding
permit documents for waste treatment under the code 16 01 03 (EOLT) (Regulation
№2 on the classification of waste 2014). The permitted activities for EOLT waste
are presented in Figure 3.

Figure 3. Number of authorized persons for EOLT treatment in Bulgaria

We study recycling activities, which are 67.50% of all activities carried out on
EOLT treatment in 2016.
These activities include activity R05 representing the recycling / recovery of other
inorganic materials and activity R04 - Recycling / recovery of metals and metal
compounds (Waste Management Law). In Bulgaria there are only 3 legal entities
that carry out these activities.
However, in the used statistics of the ETRMA – (European Tire & Rubber
Manufacturers Association 2016), tire recycling activities include R12
(pretreatment, including shredded tires) and tire pyrolysis is included in activity R1
(Waste Management Law). Taking into account the specific definitions of the
statistical data used, we should include in the investigated recycling activities
another 87 legal entities, which are authorized on the territory of Bulgaria for these
activities.
In conclusion, we can summarize that, in the context of the observed statistics for
Bulgaria, a significant percentage of recycling of tires is achieved.
Waste arising from recycling operations with shredder plants. Problems.

In this part of the study we will look at the waste generated from the added recycling
activities in the context of ETRMA data exported in 2016 (Used Tyres/ELT
Management in Europe 2016), namely R12 / R05 (Waste Management Law),
representing the tire shim to rubber granulate (rubber chips).
A flowchart of the process (An application for a waste permit for a company
„Pyrolysis“ OOD) in a shredder installation is presented in Figure 4.
From the block diagram presented below (see Figure 4), it could be seen that as a
result of the operation of the shredder, two primary wastes are formed - waste of
mechanical treatment with code 19 12 04 and metal waste with code 19 12 02
(Regulation №2 on the classification of waste 2014). The metal recycling sector is
well developed in Bulgaria. This means that for the metal waste from the plant the
possibility of end of the waste is ensured, mainly through metal recovery processes
(activity R4 Waste Management Law) in existing foundries.
Figure 4. Block scheme diagram of the process (An application for a waste permit
for a company „Pyrolysis“ OOD) in a shredder installation
Certification of the produced rubber chips from the shredder under the conditions of
a waste permit issued by the competent environmental authority requires that the
material obtained from the installation to be tested according to the standard
CEN/TS14243:2010 Materials from end of life tyre. Specification of the categories
on the basis of their size(s) and impurities and methods for determining the size(s)
and impurities. This standard is in force in the European Union.
For product certification purposes, letters have been sent to certification bodies in
the member states of the European Union on the availability of accredited
laboratories for the purpose of assigning the test and certifying the compliance of the
product. The responses received so far are from the Bulgarian Accreditation
Agency; Ente Italiano di Accreditamento; Swedish is the national accreditation body
for Sweden; Deutsche Akkreditierungsstelle GmbH; Czech Accreditation Institute;
Instituto Português de Acreditação, I.P.; Swiss Accreditation Service; The Latvian
National Accreditation Bureau and the United Kingdom Accreditation Service.
All accredited certification bodies inform us that there is no accredited laboratory on
the standard CEN / TS 14243: 2010 in their countries.
Under these conditions, the block diagram of the shredding process, represented in
Figure 4, changes significantly, as the "rubber chips compliant with CEN / TS
14243: 2010" has to be removed. Thus the produced product - a rubber chips -
according to the legislation in force in Bulgaria is obligatorily classified as waste.
The activity carried out by the shredder without the CEN/TS14243:2010 certificate
is no longer R05- final recycling, but is the interim R12 (Waste Management Law)
preparation operation. As a result, only waste is generated as a result of this activity,
which, under national law, should be passed on to persons holding permits for waste
operations.
In order to study the presence of persons to whom the waste was legally delivered
with code 19 12 04 (Regulation №2 on the classification of waste 2014) - primary
grinders and chips from the plant, the Public Register of the persons holding
documents for carrying out waste activities to NISW was again used (National
Information System for Waste). The results of the study are presented in Figure 5. A

considerable number of registered companies carry out storage and pre-treatment

activities of non-interest, as they do not include final recycling.
The surveyed waste for which the study was conducted includes plastic waste and
rubber waste generated as a result of waste treatment activities.
Figure 5. Number of persons authorized to handle waste with code 19 12 04

(Regulation №2 on the classification of waste 2014) on the territory of Bulgaria
In Figure 5 activity R1 (Waste Management Law) is present, as it is allowed for

plastic waste generated by waste treatment activities. This activity according to the
MEW guidelines is not applicable to the rubber chips from shredder installations
and is therefore excluded from the study.
There are 123 legal entities in Bulgaria operating R03 (Waste Management Law)
activity with the waste. Surveys on the subject matter of these companies show that
they do not work with rubber pulp / chips, but with plastic granulates. We have
already commented activity R05 (Waste Management Law) above.
As a result of the present study, a significant problem was found to complete the
waste recycling process generated by the recycling of EOLT. The problem stems
from the strict legal provisions on the territory of Bulgaria and the lack of developed
criteria for the end of waste from shredder installations.
End-of-waste criteria applied in United Kingdom

The leading country in the statistics concerned is England. For this reason, the study
is aimed at end-of-waste criteria in the territory of that country. End-of-waste
criteria for EOLT have been developed and published at England national level
(Tyre-derived rubber materials).
This Guide details the applicable standards for the use of tire waste streams in the
civil engineering sector - Appendix C: Engineering standards to which this Quality
Protocol applies. Guidelines to which guidance is directed are applicable across the

EU, and our study shows many laboratories that are accredited to conduct tests on
them.
Conclusions
The lack of developed end-of-waste criteria in the various recovery processes of
EOLT in Bulgaria creates problems with the subsequent recycling of the waste
streams generated by these processes.
No accredited laboratories for rubber chips testing are available in the EU as
applicable in Bulgaria standard CEN/TS14243:2010.
The material obtained from the shredder installations due to strict regulation is
classified as waste, which makes it difficult to use it for the production of industrial
and consumer products.
The lack of end-of-waste criteria for the use of tires in civil engineering on the
territory of Bulgaria leads to zero results in the field.
References
Basel Convention on the control of transboundary. Movements of hazardous wastes
and their disposal, 1998, www.basel.int
Revised technical guidelines for the environmentally sound management of used
and waste pneumatic tyres, UNEP/CHW.10/6/Add.1/Rev.1, available from:
https://www.moew. government.bg/wp-
content/uploads/file/Waste/Nasoki_rakovodstva/TG_waste_ tyres.pdf
Used Tyres/ELT Management in Europe - Volumes Situation 2016, available from:
http://www.etrma.org/uploads/Modules/Documentsmanager/20180502---2016-
elt-data_for-press-release.pdf
National Information System for Waste, available from:
http://nwms.government.bg/wms/
Regulation №2 on the classification of waste from 23.07.2014, available from:
https://www.moew.government.bg/static/media/ups/tiny/filebase/Waste/Legisla
tion/Naredbi/waste/Naredba_No2_2014_za_klasifikacia_na_otpadacite.pdf
Waste Management Law, Annex 1, 2, available from:
https://www.moew.government.bg/static/media/ups/tiny/filebase/Waste/Legisla
tion/Zakoni/ZUO.pdf
An application for a waste permit for a company „Pyrolysis“ OOD
Tyre-derived rubber materials, End of waste criteria for the production and use of
tyre-derived rubber materials, available from: https://www.gov.uk

OPTIMIZING CHARACTERISTICS IN MINERAL INSULATING OIL

USED IN HIGH POWER TRANSFORMERS
Irina Alina Chera Anghel, Loredana Popescu
INCD-ICEMNERG Bucharest, irina.alina.chera@gmail.com, Romania
Abstract
The most commonly used insulating liquid in transformers is mineral oil. Special
synthetic applications such as silicone, ester, perchloroethene, etc. are used today in
special applications, with different characteristics, very low or nonexistent toxicity
to mineral oils used in transformers.
On the other hand, they have a much better biodegradability than mineral oils in
both aerobic and anaerobic conditions. But they cannot directly replace the mineral
oil in operation or in repaired units.
They have dielectric properties and good heat transfer but have limited their use to
special transformers due to the relatively high cost and availability.
Keywords: biodegradability, characteristics, mineral oil, liquid ester,

investigations
Introduction
The purpose of this paper is to compare the results of the mineral oil, liquid ester
investigations and, for this, the characteristics of the mixed insulating liquids with
those of pure insulation liquids under extreme aging conditions.
Mixtures are a combination of mineral oil and a specific amount of a liquid ester that
has similar electrical properties and presents a lower risk of pollution but with high
hygroscopicity. The water saturation limit is more than 40 times higher than that of
mineral oils.
Pure liquids have also been investigated to provide basic data for comparison. In
addition to pure mineral oil and liquid ester, short- and long-term behaviours of
insulating fluids were determined.
Generally, if the transformer is routinely operating at very low temperatures, the
application of mineral and ester blends offers increased insulation reliability.
Furthermore, adding the ester to mineral oil helps to reduce the gas trend under
stress (Beyer et al. 1986).
Experimental
The mineral oil and an amount of ester liquid were poured into a vessel and mixed
slowly with the aid of a stirrer. To assess the degree of miscibility, the dissipation
factor and the relative permeability were determined for three types of mixtures.
The results presented in Figure1 demonstrate that there is no significant difference,
regardless of the amount of added ester. To see the temperature effect on the liquid
mix, they were heated to 90°C and after a few days, no visible separation was found.
We can say that the two liquids are miscible with up to 50% of the ester liquid.

Figure 1.The relative permittivity and dissipation factor of three mixtures
When preparing the insulating liquids for a transformer, it must be kept in mind that
gases can be found dissolved in the insulating oil. The electrical resistance of an
insulating liquid is reduced by the presence of dissolved or dispersed gases, which
are the main degradation products of low energy discharges that may occur in oil-
filled transformers.
Dissolved gases such as hydrogen, oxygen, methane, carbon dioxide, etc. are present
in crude oils as residues due to improper handling prior to use or manufacturing
process. Hydrogen has low solubility in transformation oils so that gas bubbles can
easily form.
Bubbles can intensify the partial discharge activity and/or trigger the breakdown in
the affected regions.
Before it is inserted into a transformer, it is advisable to dry and filter the insulating
fluids (Borsi 1991). For this experiment, the liquid samples were dried and degassed
using two-step drying (Borsi 1991). The mixture obtained has a percentage of less
than 0.5% gas and very low water content.
Dielectric characteristics of mixed liquids

The dissipation factor (tan δ) and relative permittivity (εr) are important dielectric
properties of insulating oil.
Determination of relative permittivity of mixed liquids

A previously proposed concept by Aguet et al it is assumed (Aguet & Ianoz 1987): a
liquid mixture can be considered as two different dielectric layers where indices 1
and 2 are the mineral oil and ester, the thickness d1 and d 2 of each depends on the
percentage of each liquid. Relative Permittivity (εr) Figure 2 varies with temperature
for samples of crude mineral oils, aged and uncoated liquid mixtures.

Figure 2. Values of the relative permittivity of mineral oil and mixed liquids
The (εr) values at each temperature are the average of the results for all the water
content. The following conclusions can be drawn:
increasing the proportion of the liquid ester in a liquid mineral / liquid ester mixture.
This can be seen in Table 1.
Table 1. Values of the Relative Permittivity (εr) and Dissipation Factor (tan δ) for
Various Mixtures of Mineral Oil and Ester Liquid.
Ester liquid
amount (%) 0 10 20 50 100
εr 2.1±0.1 2.274±0.1 2.354±0.1 2.63±0.1 3.2±0.1
tan δ (10-4) 5.4±4.5 12.2±10.7 19.6±17.3 42.2±40.7 103.2±93.5
There is a correlation between experimental and theoretical results for all liquid
mixtures studied.
With a relatively high value (εr> 2.6), the 50% ester liquid mixture could improve
the electrical resistance of liquid / solid composite insulation when used in
transformers, and these are similar to silicone fluids (Borsi 1991).
Values εr were higher for mixed elderly samples of and sometimes lower than non-
target specimens, but the variation was less than 5% of the absolute value Figure 2.
The mixture of fluids is only slightly influenced by the aging process.
The dissipation factor (tan δ)

The temperature dependence of the dissipation factor of the aged and new aged
mineral and aged liquid samples is shown in Figure 3a, where in the tan δ values are
the average for all water content at a certain temperature.

Figure 3a. Values of the dissipation factor of mineral oil and mineral oil/ester liquid
mixtures.
For all oils and oil mixtures, the higher the temperature, the mixtures of mineral oil
and liquid ester do not behave differently (Borsi 1991).
However, the values for all mixtures for unmasked and elderly specimens are within
the 0.005 required by the IEC and VDE (IEC 60296) for the new oil.
The presence of water in mixtures has only a slight influence on their dielectric
behavior due to the saturation limit, which is higher than that of mineral oils.
From Figure 3b it can be seen that the higher the ratio of the ester liquid to the aging
rate.
Figure 3b. Aging effect on the dissipation factor tan of the mineral oil and the
mineral oil mixed with different amounts of ester liquid
The higher the amount of liquid mixed with mineral oil, the more it will have a
beneficial effect on the aging of the insulating oil. The air that normally enters the
transformer passes through a dehydrated apparatus filled with silica gel.
A malfunction of this appliance may cause the insulating fluid to come in contact
with atmospheric humidity. It is necessary to monitor the moisture absorption of
mixed insulating liquids under such conditions. Thus, the dry samples of each
insulating liquid were exposed to the same atmospheric conditions in which the
water content was well controlled.
Figure 4 shows the variation in moisture absorption of pure and mixed liquids.
Figure 4. Variation of relative moisture absorption of different insulating liquids

versus time.
Viscosity
The viscosity of an insulating liquid is important for the process of dissipation and
impregnation of heat.
When the viscosity decreases with temperature, the viscosity of the ester fluid at the
working temperature is relatively close to that of the mineral oil. Generally, the
viscosity of a mixture increases with increasing molecular size and molecular weight
of the constituent compounds (Rouse 1998). The viscosity of the mineral oil is very
low compared to that of the liquid ester. By mixing the two liquids, an increase in
viscosity due to the proportion of ester fluid is observed. Figure 5 shows the
viscosity of the mixtures as well as pure liquids at different temperatures.
Figure 5. Cinematic viscosity of liquid mixtures versus the ester proportion.
Dissolved Gas Analysis (DGA)

The behavior of gas insulating liquids in thermal insulation stress during operation is
usually accompanied by gas generation, which can cause DP. The gas can either be
dissolved in liquid or bubble. Dissolved gases are detected by Dissolved Gas
Analysis (DGA) methods (Dumke 1998). Gas bubbles, which are generally caused
by large defects in a short time or small defects after a long time in which the gas
saturates the liquid, find their way to the Buchholz relay (Borsi 2000).
At temperatures between 250 and 300°C, the first gas bubbles in mineral oil
appeared, while the temperature of the ester liquid was 350 to 400°C. The higher the
gas content, the greater the risk of failure in the insulating liquid. By adding the
esteric liquid to the mineral oil it was found that the gas tendency was reduced to the
local thermal stresses.

Their determinations were made at different temperatures of 25, 60 and 90°C and at
different water contents.
Relative Permissibility (εr) increases in proportion to the amount of liquid ester
added in a liquid mineral/liquid ester mixture. The (εr) values for mixed age samples
were sometimes higher and sometimes lower than the target specimens, but the
variation was less than 5% of the absolute value. Mixed samples are only slightly
influenced by aging.
The higher the ester ratio, the higher the dissipation factor (tan δ). The tangent of the
mixtures with the 50% ester is about twice as high as the mineral oil; however, the
values for all mixtures for unmasked and elderly specimens are within the 0.005
range required by the IEC for new oils.
The presence of water in mixtures has only a slight influence on the dielectric
characteristics, the saturation limit being greater. A large amount of liquid ester
mixed with mineral oil appears to have a beneficial effect on the aging of the
mineral oil mixture.
The damping of mixed liquid absorption relative to relative humidity is less than that
of mineral oil. The mixture of 10% of the liquid ester has the same characteristics as
mineral oil, while 20% and 50% mixture has the characteristics of pure mineral oil
or ester oil. It is important to monitor the absorption of mixed moisture in the
insulating liquid under such conditions.
To do this, the samples of the dried samples of each insulating liquid were exposed
to the same atmospheric conditions in which the water content was well controlled.
High viscosity values, such as those of ester fluids, have the advantage of rapidly
achieving the expected service temperature compared to mineral oils during the cold
start of the transformer. If the viscosity decreases with temperature, the viscosity of
the ester fluid at the working temperature is relatively close to that of the mineral
oil.
The first large bubbles of gas occurred at a temperature of 250 to 300°C for the
mineral oil, while for the liquid ester a temperature of 350 to 400°C was required.
Conclusions
The electrical and physical characteristics of the mixed liquids investigated are not
inferior to those of typical transformation oils, especially for mixtures with an ester
content of less than 20%.
50% of the ester mixture liquid density and kinematic viscosity of the obtained
values of the standards proposed limit.
In conclusion, thermal insulation and insulation properties are very low, which
makes a much better choice of the insulating fluid mix compared to mineral oil.
Acknowledgments
Thanks to all of ICEMENERG Bucharest researchers and collaborators.

References
Aguet, M & Ianoz, M 1987, Haute tension,”Traité d’électricité,d’électronique et
d’électrotechnique, Dunod.
Beyer, M, Boeck, W, Möller, K & Zaengel, W 1986, Hochspannungstechnik
Theoretische und praktische Grundlagen, Springer-Verlag.
Borsi, H 1991, 'Dielectric behavior of silicone and ester fluids for use in distribution
transformers', IEEE Electrical Insulation Magazine, vol. 26, no. 4, pp. 755-
762.
Borsi, H 2000, 'Gassing behaviour of different insulating liquids for transformers',
Electra, no. 188, pp. 21-41.
Dumke, K 1998, Untersuchungen an einer Esterterflüssigkeit als Isolierstofffür
Transformatoren, PhD. thesis, University of Hanover, Germany.
IEC 60296 or DIN 57370, 'Specifications for new insulating oils for transformers
and switchgear' (similar to VDE 0370 part 1 and 2).
Rouse, TO 1998, 'Mineral oil in transformers', IEEE Electrical Insulation Magazine,
vol. 14, no. 3, pp. 6-16.

SOLUTIONS FOR OBTAINING HIGH QUALITY VITICULTURAL

PRODUCTIONS IN THE CONTEXT OF CLIMATE CHANGE
Diana Elena Vizitiu1, Lucian Dinca2, Viorica Enache3, Alina Donici3, Ana-Maria Radomir1
1
National Research and Development Institute for Biotechnology in Horticulture Stefanesti
Arges, Stefanesti City, Bucharest – 37 Pitesti Road, Arges, 117715, vizitiud@yahoo.com,
Romania
2
Marin Dracea National Institute for Forestry Research and Development, 128 Eroilor
Blv.,Voluntari, Ilfov, 13 Closca Street, Brasov 500035, dinka.lucian@gmail.com, Romania
3
Research and Development Station for Vine and Winemaking Bujoru, 65 G-ral E. Grigorescu
Street, Tg. Bujor, Galati, 805200, donicialina79@gmail.com, Romania
Abstract
Climatic conditions from areas where vine is cultivated or intended to be cultivated
are essential and important to be acknowledged especially in the context of climatic
changes that have taken place during the last 50 years. In this regard, prevention
solutions are recommended to be implemented as well as solutions that decrease the
damages caused by climatic changes or other stress factors. Among these solutions
we mention the reorientation of vine areas, planting shelter-belts in areas and
regions exposed to high intensity winds, reconsidering the structure of viticultural
varieties or selecting the cultivated vine varieties.
Keywords: drought, forest shelter-belts, genotype, grapevine, temperature
Introduction
In present times, the impact of climatic changes is felt in viticulture and is predicted
to amplify in the future (Dinca et al 2018a, Vizitiu et al 2018, Dinca et al 2018b).
According to the latest IPCC estimates, the climate will warm up this century, while
precipitations will change so that winters will become more humid and summers
drier.
Identifying viticultural biosystems and establishing the exact ecologic relationships
between grapevine species and the environment is important for scientifically
organizing quality viticultural productions as well as for selecting the biotypes with
the maximum favourability for a long-lasting and qualitative viticulture.
Experimental
In order to obtain qualitative and quantitative grape harvests, solutions for
preventing and reducing damages caused by climatic changes and other stress
factors are mandatory. Taking this into consideration, the present study highlights
the actions that can reduce the harmful effect of climatic factors, namely:
 Reorienting the zoning of grapevine culture areas in order to favour eco-climatic
resources;
 Planting shelter-belts in regions exposed to high intensity winds;
 Reconsidering the structure of viticultural varieties in average and tolerant areas,
in order to introduce genotype plantations with increased resistance to frost;
 Selecting cultivated grapevine genotypes by correlating local environmental

conditions with their degree of resistance to the limiting vegetation conditions
(drought, water stress).
Climatic changes are determined both by internal factors (changes that appear inside
the climatic system or are caused by 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).

Choosing the viticulture culture areal
Based on the favourability of eco-climatic resources, the edible grape-wine varieties
from our country can be divided in: very favourable, favourable, of average
favourability and tolerant. However, due to climatic changes from the last 50 years,
a superior quality production can be obtained by knowing very well the climatic
conditions from the areal in which the grape-wine is or will be cultivated.
Our country is characterised by regional eco-climates generated mainly by the
presence of the Carpathians, Apuseni Mountains, Danube or the Black Sea. These
regional ecosystems overlap with the historical geographic regions of our country
(Maramures and Crisana, Transylvania, Moldavia, Muntenia and Oltenia, Dobrogea,
Banat) where regions favourable for the cultivation of grapevines are delimited
(Tardea & Dejeu 1995).
Choosing and differentiating the favourability of viticultural areas and species
requires the understanding of main eco-climatic characteristics. Knowing the value
of climatic indexes helps in zoning species.
The evaluation of favourability climatic levels for delimiting wine cultivating areas
is mandatory. The climatic characterisation of a biotope uses climatic indexes for
light, temperature and humidity. Amongst the eco-climatic factors, insolation and
temperature, as light and heat sources, play an essential role (Dumitriu 2008).
The sum of potential and real insolation hours (sun radiance), as well as the
insolation coefficient are used in viticulture in order to appreciate the favourability
of light. The centres with over 1300 hours up to 1450-1500 hours of real insolation
are appropriate for white wines, aromatic ones with an accentuated combustion of
the acids, sparkling wine or distilled from wine. The centres with over 1500 hours of
real insolation are recommended for red wines and aromatic ones with a slow acid
combustion. If the number exceeds 1600 hours, the areas are used for edible grapes.
However, it is important to acknowledge that temperature and not light determines
this distribution of favourability, as light regularly exceeds the necessary minimum.
Generally speaking, the field distribution model for global radiation values suggests
their diminishing, from South-East towards North-West, a fact that is connected
with the Romanian atmospheric circulation particularities. As such, the North-West
and central part of Romania are under the influence of Atlantic circulation that
brings more humid and relatively opaque air masses.

The presence of high relief stages causes through altitude effect substantial changes
in the atmosphere’s optical characteristics as well as an altitude variety of global
radiation fluxes.
Unlike lower regions (of approximately 500 m), where most measurement points are
situated, the values of the global solar radiation fluxes at altitudes present a series of
particularities, both as values as well as annual day variation (Sandu et al 2008).
Planting forest shelter-belts
Law number 289/2002 regarding forest shelter-belts was changed through Law
number 21/2017 that was adopted on 26 March 2017. According to this law, “forest
shelter-belts for agricultural fields are created in areas frequently affected by
drought, blizzards, floods and landslides”.
Planting forest shelter-belts is a measure for fighting against drought and
desertification and is considered to be a viable and economic alternative for
irrigation systems that are more expensive.
The positive influence of forest shelter-belts is well-known, especially for growing
and bearing grapevines. For example, the plants from the west shelter-belts (that
protects plants from Oltenia’s sands against dry winds from the West) have
produced approximately 100% more grapes than the ones situated on the east side
(Dejeu 2010).
The main advantages and benefits of forest shelter-belts are: protecting
viticultural fields, roads and human shelters against wind and snow; diminishing and
controlling wind erosion; the uniform distribution of snow on the fields; increasing
soil humidity at the beginning of the viticultural season; diminishing and even
stopping the deflation on sands and light soils; decreasing frost depth and duration
as well as evapotranspiration; improving growth and development microclimatic
conditions for viticultural cultures up to a distance of 30 times over the shelter-belt’s
height in the covered part and of 4-6 times in the exposed part; reducing wind speed
with 30-60 % in the covered part and with 10-20 % in the exposed one; reducing the
variation of air temperature cu 1-4°C in the culture’s area and with 1-2°C for the
annual temperature; increasing humidity and the air’s ionization degree at the soil’s
level; increasing fertility and preserving soils from protected areas; decreasing the
level of toxic atmospheric gases, stocking 40 t/ha/year of carbon dioxide in the
biomass and producing 30 t/ha/year in the oxygen; limiting the number of rodents by
creating habitats for predatory birds.
The main works that can be executed for creating foster shelter-belts are:
- Preparing the soil by autumn tillage and on strips of maximum 80 cm length at a
depth of 30-40 cm; the distance between strips is determined based on the plantation
composition and scheme that will be used;
- Rod marking, will be done in straight and parallel rows in order to mechanize
maintenance works;
- Plantation, mandatory with watering the seedling roots in order to avoid their
drying and for eliminating air voids;
- Fighting against weeds and ensuring periodic watering. Weeds will be
removed manually (with a hoe) in the first years and then mechanized. Both works

are executed from the moment the shelter-belts are created up to the moment in
which it develops by itself and it doesn’t require any kind of maintenance;
- Soil aeration from near the seedlings will be done with the vertical wheels of
maintenance equipment, together with weed extraction.
The specialty literature mentions a number of criteria for classifying forest shelter-
belts. As such, they can be classified based on their creation purpose, density,
stand’s structure or the nature of its species, to mention just a few. Based on the
purpose with which they were created (Popov et al 2017, Kachova & Dinca 2015)
shelter-belts can be for: protecting fields; protecting viticultural cultures against
harmful agents and for improving climatic conditions; antierosion; protecting soils
under erosion phenomenon; protecting communication and transportation means;
protecting banks and shores against currents, floods and ice; protecting buildings
from near viticultural farms.
Based on their density, shelter-belts can be grouped in:
 Compact or impenetrable shelter-belts: the wind does not go through them,
creating an absolute calm area in the back;
 Semi penetrable shelter-belts: the wind can go through them, diminishing its
strength and being recommended for field protection purposes;
 Penetrable shelter-belts: the wind easily goes through them, especially under the
tree crown level.
Based on the stand’s structure, shelter-belts can be: pure (when they are formed
of only one species) and mixture (when they are formed of more tree and shrub
species).
Based on the nature of the species from their composition, shelter-belts can be:
forest (when only tree species or fruit shrubs are used) or forest-horticultural or
mixed (when the main species are forest ones, but are accompanied by ornamental
species or fruit trees etc.).
Based on the location, field shelter-belts can be: main, situated perpendicularly on
the direction of the main wind; secondary, situated perpendicularly on the direction
of main shelter-belts that complete this way the network of shelter-belts from a
certain perimeter.
The species that are recommended for plating as forest shelter-belts are
(Constandache et al 2016, Silvestru-Grigore et al 2018): resinous (Pinus nigra) and
broad-leaved (Fraxinus excelsior, Ulmus sp., Quercus robur, Robinia pseudoacacia,
Gleditsia triachantos, Sophora japonica, Fraxinus ornus, Acer platanoides, Syringa
vulgaris, Crataegus monogyna, Rosa canina).
Choosing genotypes
The production of grapes can be reduced due to climatic factors such as: low
temperatures, drought, hydric stress or hailstone. As a consequence, it is very
important to choose the genotypes when viticultural plantations are created. The
grape-wine’s resistance to frost is different based on the species, wood maturity
degree, respite stage, or the frost installation manner (slow or abrupt).
When viticultural plantations are created, it is recommended to select the varieties
based on the temperatures recorded in each area. As such, frost-resistant species
can be selected such as: Rkastiteli, Riesling de Rhin, Burgund mare, Pinot noir,
Pinot gris, Cabernet Sauvignon, Feteasca neagra Feteasca regala, Arcadia,

Codreanca, Niagara (-24….-22°C), average-resistant ones: Feteasca alba, Creata
de Banat, Grasa de Cotnari, Furmint, Riesling italian, Traminer roz, Aligoté,
Oporto, Merlot, Muscat Ottonel, Moldova, Doina, Muscat Chihlimbariu, Coarna
neagra, Chasselas (-22°…..-20°C); as well as relatively resistant species (-20°…-
18°C) such as: Sauvignon, Chardonnay, Perla de Csaba.
The following species are not recommended to be planted in viticultural regions
characterized by a climate with hard winters: Cardinal, Regina viilor, Muscat
alb (resists at temperatures between -7°…. -18°). In addition, regardless of the area
in which they are planted, they must be cultivated in a protected or semi-protected
system.
A major danger for the culture of grapevine is represented by rime and spring or
autumn frosts. Specialty studies have proved that grapevine species with late buds
are especially red wine varieties and are recommended to be planted in regions
vulnerable to these meteorological phenomenon (Merlot, Cabernet sauvignon,
Burgund mare). However, white wine species (Galbena de Odobesti) as well as
edible grapes (Bicane, Victoria) can also be planted.
In order to fight against rimes and late spring frosts, a series of measures can
be applied in order to prevent their damages such as: planting genotypes that are
resistant to frost in areas known for the frequency of this phenomenon; realizing
cutting works during autumn in order to delay budbreaking; irrigating plants before
winter bud inflation, in order to lower soil temperature and delay root activity and
bud opening; choosing vigorous species that have late budbreaking; selecting
species with late maturation of shoots and berries; applying amendments and
phosphorus and potassium fertilizers for consolidating the resistance towards low
temperatures; orienting the vineyards towards the South, East or West exposition;
avoiding the mobilisation of soil until the frost has passed in the viticultural
plantations situated at the slope’s basis, in basins; leading grapevines on stems to a
height of 0,8-1,2 m in regard to the soil surface; draining cold air masses (shelter-
belts, live fences); creating protection screens that block caloric rays at the plant’s
level.
As in other areas with temperate climate, Romania also has periods with excessive
weather or extremely hot summers when average daily temperatures exceed with
5°C the multiannual average or when maximum temperatures reach 35°C.
Heath waves can increase the air and soil humidity deficits, leading to the apparition
of hydric stress.
In comparison with other plants, Vitis species manifests a higher tolerance and
resistance to drought due to its strong radicular system through which it explores a
large volume of soil in searching water and food sources.
In the bleeding phenophases, the sprouts and buds growing, during blooming and
the growth of grapes, an average temperature of 25-30°C is necessary. For the
grape’s maturity, the temperature increases to 28-30°C, while for the leaves falling it
should be of 20°-25°C. Dumitriu I.C., 2008, considers that the growth of sprouts is
strong at temperatures of 28°C, while this process is slowed down at 4°C.

According to the specialty literature, some positive temperatures are unfavourable

for grape-wines as follows: temperatures lower than 10°-12°C are unfavourable for
the growth of sprouts; temperatures lower than 14°C are unfavourable for the
blooming period; temperatures lower than 20°C affect the grapes’ growth
phenophase; temperatures lower than 12°C are unfavourable for the sprout’s
maturity and for leaves falling.
The highest deficit of water from the soil appears on slope fields, on thin, skeletal
soils, even in areas with precipitations of over 300 mm in the vegetation period.
However, their distribution is very irregular during long drought periods.
If water retention is weak, the risk for the apparition of severe hydric stress is high,
leading to the loss of the plant. If the soil drainage is weak, a water excess occurs in
the grapevines radicular area. As such, the risk of pathogen agents attacks on roots
and the consumption of nutritive elements from the soil increases. Water excess
leads to the cooling of the soil, a fact that can have negative effects on the
production. Hydric stress leads to the decrease of sprout growing, stops the growth
of grapes and favours at the same time the accumulation of phenolic substances,
aromatic substances and tannin in the grapes. Hydric stress can have negative effect
both on the plant, as well as on the wine. In order to conserve internal water, the
plant tries to limit the loss through transpiration. The stomata from the leaves
inferior part are closing in order to reduce the quantity of evaporated water. At the
same time, the absorption of carbon dioxide from the atmosphere is also reduced. If
the stress continues, the entire photosynthesis process is blocked.
The grapevine resistance to drought is influenced by a multitude of factors: species,
used parent stock, leading form, plantation age, stump virility, eye charge kept at
cutting, development depth of the radicular system and many others (Dejeu 2010).
Grapevine has a relatively high resistance towards drought. However, it is not
sufficiently investigated. The species that support high temperatures and the lack of
humidity are considered as resistant to drought, offering a satisfactory harvest both
quantitatively as well as qualitatively.
It is recommended to select the most tolerant and resistant genotypes of
grapevines in regard with drought such as: resistant species (varieties for wine:
Alphonse Lavalleé, Chardonnay, Pinot gris, Traminer roz, Creata de Banat,
Mustoasa de Maderat, Rosioara, Pinoit noir, Cabernet Sauvignon); averagely
resistant species (table grapes varieties: Regina viilor, Chasselas doré, Muscat de
Hamburg, Muscat d' Adda, Italia; varieties for wine: Feteasca regala, Feteasca
alba, Sauvignon); species that are not recommended for areas characterised by
precipitation deficits and that are frequently affected by drought (table grapes
varieties: Perla de Csaba, Cardinal; varieties for wine: Muscat Ottonel, Italian
Riesling, Grasa de Cotnari, Galbena de Odobesti, Tamaioasa romaneasca, Merlot,
Cadarca Afuz Ali.)
According to (Fregoni 2005) the parents stock resistance to drought can be divided
in three categories: high resistance (140 Ruggeri, 1103 Paulsen, 779 Paulsen, 110
R, 44-53 M, 17-37, 775 Paulsen, 1447 Paulsen); good or average resistance (41B,
333 E.M., 99 R, 31 R, 1045 P, 216-3, 16-16, Rupestris du Lot, 420 A); low

resistance (K 5 BB, 161-49, SO4-4, 101-14, Riparia, 34 E.M., 1202 C); very low
resistance (3309, 3306, Schwarzmann).
The negative effects and risks associated with hailstone are conditioned by more
factors, with the majority of damages registered in the full vegetal cycle; when it is
accompanied by strong winds; when the greloans diameter exceeds 10 mm; when
the phenomenon exceeds 15 minutes; when the phenomenon appears after long
pluviometric deficit periods, a fact that favours the erosion of dry soils, especially if
the field is situated on a slope.
In Romania, vulnerable territories towards hailstone ca have a high vulnerability in
the Central-South part of our country – Romanian Plain, Getic Plateau, Getic
Subcarpahtinas and Curvature Subcarpathians. They are characterised by the
interference of East and West circulations and by a strong development of
convective clouds. Low vulnerabilities can be found in areas with continental
influences from the East and South-East part of the country (Moldavia Plain,
Dobrogea Platea), areas with Pontic influences (seashore, Danube Delta), areas with
oceanic influences from the North-West part (Somes Plain, Casurilor Plain) as well
as in regions affected by foehn processes such as Turda-Alba Mia corridor.
Methods for fighting against hailstone: installing anti-hailstone cannons; using
anti-hailstone meshes.
Solutions for preventing the effects of drought and hydric stress in viticultural
plantations:
 Installing an irrigation system, adapted to the cultivated surface, conditioned by
the existence nearby of a lake or river with permanent water. The existence at the
depth of 5-10 mm of a permanent layer of phreatic water is mandatory and must be
able to be brought at the surface through a well or pumping station;
 Tests regarding soil properties as well as the soil’s capacity for retaining water
and the depth at which roots can grow;
 Monitoring all aspects before applying irrigations, during and after administering
water norms as well as choosing the moment for applying and verifying the water
circuit by measuring the performance and uniformity;
 Using more monitoring mechanisms for planning irrigation. The most used ones
include measuring soil humidity, observing the plant’s state and testing drainage
tubes after irrigation in order to apply the necessary changes for the next watering;
 Establishing a control program for irrigations. Current technologies have the
option of automatically scheduling this based on sample soil analysis;
 Applying fertigation, an economic method that requires special construction but
that allows for a fertilisation with smaller quantities of chemical fertilizers during
the vegetation period;
 Applying subterranean irrigations – the most favourable irrigation method as it
administers water, air and mineral substances. However, it might involve large
financial investments;
 Applying partial root irrigations by locating watering water along row axes while
maintaining a non-irrigating side and concentrating water on the other side, a
technology known as “Partial Root Drying-PRD”. The two sides of the row (humid
and dry) alternate periodically. As a consequence, a part of the roots situated in the
dry soil function on sensors for the synthesis of abscisic acid. This is translocated
towards the aerial part, a fact that leads to the partial and controlled closing of the
stomata without affecting the photosynthesis process and reducing transpiration. As
such, by implementing this technique, the usage of irrigation water is optimized.
 Mulching the soil in order to protect it against climatic excesses as it fights
against drought by conserving soil humidity, it detains intense evaporation and it
reduced excessive humidity, blocking surface hydric erosion. Furthermore, it
favours the air-hydric regime in a positive way and it evens the organic-mineral
balance;
 Soil grassing in viticultural plantations as an alternative ecological and economic
method for preserving soil water as it: diminishes the speed of surface water
drainage; subdues the evaporation of soil water; the water infiltrates faster due to
macro-pores; increases the degree and capacity for stocking humidity in the soil;
determines the increase of hydric stability for the soil’s structural aggregates;
favourably influences the balance of the soil’s thermic regime; imprints an optimum
internal soil drainage; intercepts precipitation water, reducing soil erosion;
 On fields ready for irrigation, the rows of plants are oriented so that an irrigation
with minimum energetic and economic efforts is possible.
Conclusions
Our country has areas with cultivated grapevine varieties that can be divided into
very favourable, favourable, medium and tolerant.
Forest shelter-belts offer different advantages and benefits such as: protecting
vineyards; diminishing and controlling wind erosion; uniformly spreading snow on
lands, increasing soil moisture at the beginning of the viticultural season;
diminishing and stopping the deflation on sands and light soils; decreasing the depth
and period of frost, as well as the evapotranspiration; improving the microclimatic
conditions of vineyards growth and development.
Damages caused to viticultural plantations by climatic factors such as low
temperatures, drought, hydric stress or hailstone can be reduced and even stopped in
some cases if certain measures are applied. Among them, we mention the correct
choosing of genotypes when creating plantations, using monitoring mechanisms and
planning irrigations, mulching and grassing.
Acknowledgements
This paper was supported through the project 6 PCCDI” Increasing the institutional
bioeconomic research capacity for innovative exploitation of local plant resources to obtain
horticultural products with high added value”. This project is funded by the Executive Unit for
Financing Higher Education, Research, Development and Innovation (UEFISCDI).
References
Constandache, C, Peticila, A, Dinca, L &Vasile, D 2016, ‘The usage of Sea
Buckthorn (Hippophae rhamnoides L.) for improving Romania's degraded
lands’, AgroLife Scientific Journal, vol. 5, no. 2, pp. 50-58.
Dejeu, L 2010, Viticultura Editura CERES, pp. 479.
Dinca, L, Vizitiu, DE, Donici, A, Popa, L& Murariu, G 2018a: ‘The health dynamic
of forest and vinicultural ecosystems from Romania during the last two decades
in the context of current climatic changes’, International Scientific Conference
on Earth and Geosciences-Vienna Green Scientific Sessions, vol.18, no. 1.5,

pp. 789- 796.
Dinca, L, Buciumeanu, EC, Vizitiu, DE, Enache, V & Cociorva, D 2018b: ‘Main
regulations and standards concerning the protection of forests and vinicultural
plantations from Romania, with a special focus on improving the effects caused
by climatic changes’, International Scientific Conference on Earth and
Geosciences-Vienna Green Scientific Sessions, vol.18, no. 1.5, pp. 719-726.
Dumitriu, IC 2008, Viticultura, Ed. Ceres, Bucuresti, pp. 440.
Fregoni, M 2005, Viticoltura di Qualità, Phytoline, 2005, pp. 819.
Kachova, V & Dinca, L 2015, ‘Establishment of agroforestry systems along river
basins-functions and features’, Revista de Silvicultura si Cinegetica, vol. 20,
no.36, pp. 64-68.
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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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Romaniei, Editura Academiei Romane, Bucharest pp. 365.
Silvestru-Grigore, CV, Dinulica, F, Sparchez, G, Halalisan, AF, Dinca, L, Enescu, R
& 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.
Tardea, C & Dejeu, L 1995, Viticultura, Editura Didactica si Pedagogica, pp. 509.
Vizitiu, DE, Dinca, L, Enache, V, Donici, A, Popa, L, Cociorva, D & Murariu, G
2018, ‘Identifying and describing the main climatic and stress factors that are
affecting forest and vinicultural ecosystems’, International Symposium “The
Environment and The Industry”, SIMI 2018, Proceedings Book, pp. 232-241.

STRUCTURAL MODEL OF FOREST ECOSYSTEM SERVICES’

PAYMENT FOR WATER QUALITY IMPROVEMENT
Mariyana Lybenova1, Alexandre Chikalanov2, Yulian Petkov2

1
Department of Ecology and Environment Protection, Faculty of Biology, St. Kl. Ohridski,
University of Sofia, 8 Dragan Tzankov Blvd., 1164 Sofia, ryana_l@mail.yahoo.com, Bulgaria
2
Department of Computer Science, Faculty of Information Sciences, University for Library
Studies and Information Technologies, 119 Tzarigradsko shosse Blvd., 1784 Sofia, Bulgaria
Abstract
The publication deals with the development of a structural model of payment
schemes for ecosystem services (PES) oriented to usage of forests for water, soil and
microclimate quality improvement. Proposed structural model is built on the Meta
analyses base of more than 50 PES schemes worldwide. The proposed structural
model has three top down levels – groups of categories, categories and attributes.
There are seven groups of categories, 17 categories and more than 120 attributes.
The structured information about studied PES schemes is stored in a warehouse
managed by unique web platform created by the authors. An important part
presented study is the developed generic use case of PES schemes with definition of
seven participated actors.
Keywords: PES scheme, structural model, forest, water quality, web platform
Introduction
Payments for ecosystem services or PES programs are defined as formal or informal
contracts where landowners receive remuneration for managing their land and
offering one or more ecosystem services and which include actual payments
between at least one willing buyer and one willing seller (Mercer et al. 2011).
Three basic types of PES are known in the past practice. The first type is
government-funded schemes. In them, the buyer (e.g. the European Commission, a
particular government or local authority) is a third party (often a hierarchy) acting
on behalf of service users. Funding under these schemes is to compensate service
providers by allocating revenue derived from targeted tax revenue or from the
general budget (Porras et al. 2012). The second type of PES is the schemes funded
by private users. In these schemes, buyers are end-users of the services. These
schemes can be considered as "private transactions" and reflect genuine customer
demand for services. The third type of PES is schemes funded by utilities. The
purpose of the funding is to compensate suppliers by allocating revenues from user
charges or tariffs, from a public service or a regulated private service. For example,
charges for the use of downstream water facilities, installations and facilities for
land use activities that affect the function of the catchment area. Such schemes may
also include large irrigation or hydropower areas.
According to Smith et al. 2013, PES schemes can be developed on a number of
spatial scales - international, national, catchment level, local and neighboring levels.
According to Muradian et al. 2010, the green economy includes three schematic
components. The first concerns the importance of economic stimulus. This idea
refers to the relative weight of the economic stimulus and can bring about social,
moral or other non-economic incentives. The second component is the directness of
the transfer related to the degree of interaction between end buyers and sellers
(Tacconi 2012). The most direct payments will be made between one buyer and one
seller without intermediaries. According to Fripp 2014, there are a number of
options for PES, how it should be formulated and the most appropriate means for its
funding. In any case, robust scientific data is needed to build appropriate PES. PES
payments can only be made if the value of the service is recognized by the buyer
and the seller and the appropriate transaction infrastructure (market) exists.

The presented study is based on a meta-analysis of more than 50 PES schemes for
water, microclimate and soil quality improvement. The schemes studied cover
much of the world and they are from Europe, Asia, Africa, North and Southern
America. Table 1 provides a sample list of countries as well as data source used in
conducted analysis.
Table 1. Excerpt from listed countries of analyzed PES schemes
Country Source of information
Austria https://www.wien.gv.at/english/environment/protection/eco/
Bolivia http://www.watershedmarkets.org/casestudies/Bolivia_ICO.html
Brazil http://www.watershedmarkets.org/casestudies/Brazil_CPCJ_E.html
Bulgaria http://www.wwf.bg/what_we_do/policy_and_green_economy/natur
e_protection_and_sustainable_rural_development/bulgarka/drinkin
g_water_conservation/
China http://www.watershedmarkets.org/casestudies/China_SLCP_eng.ht
ml
Colombia http://www.watershedmarkets.org/casestudies/Colombia_Campoale
gre_E.html
Germany http://www.urbem.net/WP2/WP2_case_studies.pdf
Uganda http://www.watershedmarkets.org/casestudies/Uganda_beer_for_w
etlands.html
United The Water Industry Commission for Scotland
Kingdom
United States http://www.methowsalmon.org/
In order to store the structural description of investigated PES schemes, the authors
created a Web platform for PES schemes warehouse. In paper, the developed
structured model will be illustrated by means of that platform.

As noted in introduction, the definitions of the main PES schemes types depend on
the stakeholders and their relationships. Therefore, before going to the description of
proposed structural model, we will define base actors of PES scheme and their
relationships.
Buyer actors are focused on prospects looking to solve a problem or meet an

objective that ES help them to achieve. Buyers encompass all of the different roles
or stakeholders involved in the purchase decision and are usually represented by
decision maker. The buyers pay for chosen ES.
User actors solve their initial problem by choosing ES. This means that their context
must build from this new status quo to what’s next. The objective for user actors is
to create higher loyalty and retention, as well as increase account value through
renewals, cross and up sell.
Beneficiaries are actors, who derive advantage from ES, for improving their
activities or other non-material needs as better environment, health etc.
Payer are actors that fund ES due to work done or goods received. Usually, payers
are not the end user or beneficiary of ES.
Volunteer actors refers to activities performed willingly and without pay to provide
ES for others outside the volunteers’ household or family.
Intermediary actors act as a link between ES interested parties in order to try and
bring about an agreement. Intermediaries can buy ES from one or more suppliers
and sell it to interested buyers.
Benefit from
Beneficiary
Cooperate
Volunteer
Implement ES
Perform Use
User
Purchase
Get the payment Pay for ES

Provider
Execute
Buyer
Execute
Perform Mediation
Payer
Intermediary
Figure 1. Generic use case of PES scheme
Provider actors are vendor that provides ES solutions and/or services to end users,
buyers, and beneficiaries in exchange of payment. This broad term incorporates all
ES businesses that provide products and solutions through services that are on-
demand, pay per use or a hybrid delivery model.
The potential benefits and participants in PES schemes according to Bulgarian
legislation are presented on Fig. 2.
The developed structural model of PES schemes is focused mainly on usage of
forests for environment improvement mainly water quality, agro ecological
conditions betterment and local climate mitigation. In the created model a PES
scheme is considered as structure composed by groups of categories (classes) named
General, Geography, Governance and financial, Environmental, Indicators, Benefits
and Other information (Fig. 2).
Each group contains one or more categories or classes. In turn, each category
contains one or more attributes. The group General consists of following categories
– Respondent information, Scheme general information and Implemented categories
of ecosystem services; Geography – Scheme scale and location and Population area
of the scheme; Environmental – Ecosystem, Water uses and issues, Wetland

characteristics; Forest ecosystem characteristics and Water body characteristics;
Governance and financial – Scheme governance, Scheme timeline and Scheme
implementation costs; Indicators – Water quality indicators, Microclimate
indicators, Soil indicators; Benefits – Benefits; Other information – Availability of
further data.
The most complex groups of categories are Environmental, Governance and
financial, and Indicators, which are the corollary of the model (Fig. 3).
In the developed platform, PES scheme structure is presented as a web form and the
composing categories as tabs (Fig. 4).
Figure 2. High level of PES Figure 3. Structure of Environmental, Governance,

and scheme structure and financial information. Indicators.
The description of a particular PES scheme is materialized (or instantiated) by

setting of specific values for the attributes. In this case, we say that there is an
instance of the PES scheme. One instance consists of instances of composing
categories. The instances of categories, in turn are represented by values of their
attributes. Each category may have either only one or multiple instances. A with
multiple instances is illustrated on Fig. 5.
The categories having more than one instance will be identified to be of a vector
type. The one-instance categories we denoted as of a scalar type. The categories of a
vector type are – Water quality indicators, Microclimate indicators, Soil indicators
and Benefits. The remaining categories are of a scalar type.
The attributes of categories may be text fields, text areas, selectable from a list of
alternatives, dates, and images. They also may be of a scalar or vector type. On Fig.
6, the attribute named Forest area is a scalar and Tree species is a vector. Only the
selectable, date and image types may be either a scalar or vectors.
Figure 4. Structure of PES scheme implemented as a web form

Figure 5. Multi-instance category
Below we will describe categories with their attributes consolidated by the groups to
which they belong.
General. Respondent information contains contact information and country names
and the attributes, such as Name of respondent, Contact person, Address of contact
person – text fields of scalar type, and Country - selectable of vector type. The
reason the attribute Country is a vector is that a PES scheme can be implemented in
more than one country.
Scheme general information sets out a general description of the PES scheme. The
attribute Scheme scale is a text and a scalar one. The attributes Scheme geographical
location NUTS - broad region, Scheme geographical location NUTS - region and
Scheme geographical location NUTS – district are of vector type. The rationale
behind this approach is that a scheme may cover more than one NUTS unit. The
category Implemented categories of ecosystem services contains descriptions of
ecosystem categories relevant to described PES scheme. The attributes containing
these descriptions are scalar text areas – Regulating, Provisioning, Socio-cultural
and Supporting. The last attribute is image of vector type and may contain one or
more images illustrated the descriptions in the other four attributes.
Geography. Population area of the scheme has following attributes: Number of
beneficiaries (if relevant and available), Area of case study (if relevant and
available), Local communities, Area of afforestation created by the case study,
Households, Firms, Farmers, Area of existing forest participating in the case study,
which are scalar.
Population area of the scheme is composed of: Number of beneficiaries (if relevant
and available), Area of case study (if relevant and available), Local communities,
Area of afforestation created by the case study, Households, Firms, Farmers, Area of
existing forest participating in the case study. All of them are test fields and scalar.
Environmental. Ecosystem, water uses and issues All attributes belonging to that
category are selectable of vector type namely - Type of ecosystem targeted by the
case study, Use of water targeted by the case study, Water issues targeted by the
case study: quality, Water issues targeted by the case study: other, Management
measures rewarded by the case study, General water benefits generated by the case
study, Specific water benefits generated by the case study. Wetland characteristics
contains two selectable vector indicators – Wetland type and Wetland subtype. The
both attributes are vectors, because a scheme may contain different wetlands types
and subtypes. Forest ecosystem characteristics has scalar and vector attributes. The
attributes Forest canopy and Forest origin are of type selectable scalars. The
attributes Forest area, Forest location and Forest age are scalar text fields. The
attributes Tree species and Forest type are selectable and of a vector type, because a
forest can consist of more than one tree species and can combine more than one type
of forest. Water body indicators encompasses following attributes: Type of water
body, Waterbody quality, Lake basin surface, Water body surface, Flow rate of
water body and River basin surface - text field and scalar values.
Figure 6. Vector and scalar attributes
Governance and financial. Scheme governance is mainly focused on actors of PES

scheme - Providers of services, Users, Buyers, Payers, Intermediaries, and
Volunteers, which are vector attributes. Two additional attributes - Case study
description and Degree of scheme voluntariness are text area and scalar. Scheme
timeline is relative simple one having three text fields of scalar attributes - Case
study establishment year, Case study duration (time horizon) and Case study status.
Scheme implementation costs consists of four pairs of attributes. Each pair of
attributes consists of one vector-type attribute that contains a detailed description of
a specific cost group and scalar attribute that is equal to the sum of the costs
incurred in that group. The cost groups are Transaction starting, Implementation,
Opportunity, and Recurring transaction costs.
Indicators. Water quality indicators is a complex category. It contains four groups of
indicators – Physical, Chemical, Biochemical and Biological indicators together
with their x-ant, x-target and x-post values. The meaning of their x-ant, x-target and
x-post values is as follows - x-ant attribute is value of measured pollutant before
applying the PES scheme; x-target is the target value to be reached, when the
scheme will be implemented and x-post - the achieved measured value of that
pollutant at the end of PES scheme implementation. Each indicator is a generic for
the specific pollutant. Because of the wide variety of pollutants pertaining to a
particular indicator, a PES scheme may target several specific pollutants of one
indicator. For example, organic pollutant can be of different types. In order to list all
pollutants treated by a PES scheme, it is necessary to create more than one of these
categories. That is why the category is of a vector type. The vector components are
set up by creating the new pages. Each page records the specific indicators and their
respective values. Microclimatic indicators have four attributes - Microclimatic
indicator and the respective x-ant, x-post and x-target values. Since any number of
microclimatic indicators is possible, this category should of a vector type. Each
component of the vector consists of the specific microclimatic indicator and its x-
ant, x-post and target values. Soil indicators are of selectable type together with their
x-ant, x-post and x-target values. Since the category is of a vector type, any number
of soil indicators can be added along with their x-ant, x-post and x-target values.
Benefits. The reason that Benefits are of a vector type is the same as for Soil
indicators. In such a way, we may add arbitrary number of benefits. Each Name of
benefit attribute is packaged together with its x-ant, x-post and x-target value.
Other information. Availability of further data is a map dataset - the attributes
contain answers of following questions: Are the economic data related to the case
study implementation available?; Are the monitoring data for the case study
available?; Is the information on the monetary amount of payments available?; Are
the maps or GIS data for the case study available?; Are the cost-effectiveness
estimates for the case study available?; Do you think this is an interesting case for
further investigation and why? The questions are considered as keys to answers
related to specific PES scheme described.
Conclusions
The proposed structural model is a first attempt to create detailed structural model of
PES schemes related to the use of forests to improve the quality of water,
microclimate and soil. It is more oriented toward forest ecosystem services and their
application to improve the quality of surface water. The developed platform is
unique application dealing with PES schemes information. It is an open warehouse
for gathering and browsing PES schemes information. The future development of
PES reviewing platform will be in the directions of improving and facilitating the
reporting tool. Additionally, the authors consider computation effectiveness and cost
effectiveness of reviewed schemes. Another foreseen direction is adding Big data
and Decision making support. The platform allows rapid analysis and evaluation, as
well as team work online, which will significantly speed up the process of creating
new PES schemes. The proposed platform can be the useful tool for ecosystem
services payment and sustainable development of regions. It is free of use and can
be found on http://dev.elliot.virtech-bg.com/review.
Acknowledgements
The research has been carried out in relation to COST Action Payments for Ecosystem Services
(Forests for Water), 2016-2020 and project DCOST 1/30/20.12.2017 "Development of a
scheme for assessment of forest ecosystem services, efficiency of their provision through the
creation of poles for the purpose of purification and protection of waters and other natural
components in the regions" funded by the Research Fund, Bulgaria
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assessing the feasibility of PES projects' Bogor, Indonesia: CIFOR.
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Ecosystem Services in the United States', Forest Trends and USDA Forest
Service, Washington, DC, p. 56
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and practice: An alternative conceptual framework for understanding
payments for environmental services', Ecological Economics. Special
Section - Payments for Environmental Services.
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Conference on “Resource Economics, Biodiversity Conservation and
Development”, 18 -20 September, 2012, Kings College, Cambridge.
Available from: http://www.bioecon-
network.org/pages/14th_2012/Porras.pdf
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Eves, C & White, C 2013, Payments for Ecosystem Services: A Best Practice
Guide, London: Defra.
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Economics, vol.73, pp. 29–36, doi: 10.1016/j.ecolecon.2011.09.028.

STUDY OF THE POSSIBLITIES TO REUSE CONSTRUCTION AND

DEMOLITION WASTE
Denitsa Hvarchilkova, Margarita Filipova, Ivanka Zheleva
Ruse University, 7017, 8 Studentska Str., Ruse, Bulgaria

dhvarchilkova@uni-ruse.bg , mfilipova@uni-ruse.bg, izheleva@uni-ruse.bg
Abstract
For environment protection in the European Union (EU) it is very important the
construction waste to be recycled and reused. The potential for the construction
waste recycling and reuse is high, as their components have high cost. There is an
opportunity for re-use of such materials in road construction, for drainage systems,
for outdoor sports grounds and other construction sites.
In 2012 a regulation on the management of construction waste and on the use of
recycled building materials was adopted in Bulgaria, aiming to introduce a new
model for the management of construction waste. This would guarantee: creation of
favorable legislative and economic conditions for implementation of technologies
ensuring the achievement of recycling and recovery targets but which are also
financially viable in line with the country's incomes; identifying the persons
responsible for covering the costs of building waste management and achieving the
recycling and recovery targets; creating conditions for the production and marketing
of materials from recycling of construction waste at a price that is competitive with
the same new raw materials used in construction.
The main effect expected from this normative document is to contribute to
Bulgaria's development towards European trends, environmental protection through
an integrated framework for the management of construction and demolition waste
that will reduce the harmful impacts on it caused by construction waste, improving
the efficiency of resource use, increasing the responsibilities of pollutants and
stimulating investment in waste management.
Keywords: construction waste, recovery process, recycling, re-using
Introduction
Construction waste is generated by activities such as construction and/or complete
or partial demolition of buildings and urban infrastructure as well as road planning
and maintenance. Within the EU, different definitions apply to this group of waste,
making it difficult to carry out comparative analyzes between countries. In some
countries even ground leveling materials are classified as construction waste.
The construction industry is a major source of pollution, accounting for about 40%
of total pollution as a result of the industrial activity. From construction activities
the main contamination is for air, water, soil and noise pollution. All construction
sites generate high levels of dust and harmful emissions in the air - usually from
concrete, cement, silica. Materials used in construction, such as paints, solvents,
toxic chemicals, can cause contamination in water and soil.

There is a possibility to recycle many elements of construction waste (Construction

and demolition waste production in the EU 2019; Waste treatment 2014;
Kourmpanis et al. 2008).

Construction waste (CW) consists of unwanted material produced directly or
incidentally by the construction or industries. This includes building materials such
as insulation, nails, electrical wiring, shingle, and roofing as well as waste
originating from site preparation such as dredging materials, tree stumps, and
rubble. It is necessary to remove hazardous components of construction waste such
as asbestos, tar, radioactive components, polychlorinated biphenyls, lead, electrical
elements containing mercury, insulating materials containing dangerous substances,
etc. This is related to the protection of the environment, for reasons of safety and
health protection of workers and residents in the vicinity of the site.
In addition, removing hazardous waste is important in order not to pollute recyclable
materials.
The biggest part of the building waste consist of bricks, concrete and wood
damaged or unused for various reasons during construction. Observational research
has shown that CW can be as high as 10 to 15% of the all materials that are used to
the building construction. This is much higher percentage than the 2.5-5% usually
assumed by quantity surveyors and the construction industry. Since considerable
variability exists between construction sites, there are meny opportunities for
reducing this waste.
Construction and demolition waste (C&DW) is one of the heaviest and bulkiest
wastes which are generated in the European Union. They include many materials
such as concrete, bricks, gypsum, wood, glass, metals, plastics, solvents, asbestos
and excavated earth. Many of these components can be recycled. To date, about
54% of construction waste is recycled in the Republic of Bulgaria, but the national
targets imposed by the Waste Framework Directive require 70% of CW to be
materially utilized by 2020, and for some species, such as metals, the share also
reaches 90%. Each construction of a building over 700 m2 must have a construction
waste management plan (CWMP) developed. For Bulgaria this is obliged according
to Ordinance on the management of construction waste and for the reusing of
recycled building materials (Ordinance No. 2/2014), which entered into force at the
beginning of December 2018.
C&D Waste generation by economic activities and households for EU member
states (Waste treatment 2014) could be seen on Table 1.
The current position of EU on C&DW classification according to (Symonds Group
Ltd 46967 Final Report 1999) the report of the C&DW Priority Waste Streams
Project recommended (in its recommendation number 2) is that:
“Member States should be encouraged to adopt the following classifications (taken
from the European Waste Catalogue) as the framework within which future
construction and demolition waste management planning will be undertaken, and
waste arising data collected and reported:
 concrete, bricks, tiles, ceramics, and gypsum-based materials (EWC code 17
01 00);
 wood (EWC code 17 02 01);
 glass (EWC code 17 02 02);
 plastic (EWC code 17 02 03);

 asphalt, tar and tarred products (EWC code 17 03 00);
 metals (including their alloys) (EWC code 17 04 00);
 soil and dredged spoil (EWC code 17 05 00);
 insulation materials (EWC code 17 06 00);
 mixed construction and demolition waste (EWC code 17 07 00).
There are some specific matters worthy of note (Symonds Group Ltd 46967 Final
Report 1999):
 in Germany and the Netherlands, for instance, a pile of concrete waste with
comparatively small proportions of brick and gypsum mixed in with it would
be recorded under 17 01 00;
 in the UK, by contrast, the same material would probably be recorded as 17 07
00.
Hazardous components of construction and demolition wastes should also be
identified.”
Different types of construction and demolition waste are subject to specific

recycling and recovery methods. Methods for recycling and subsequent recovery of
construction waste vary according to the type of waste.
For the most part of C&DW (about 80% by mass), they are inorganic and non-toxic
and subject to re-use or recycling. The degree of recyclability of the construction
waste depends on several factors - the share of the different types of waste, the
degree of pre-treatment (sorting), the pollutant with harmful or hazardous
substances, which depends on the processes of waste generation. Building design
and practice also have an impact. Waste related to the renovation and rehabilitation
of buildings has a less favorable profile, as they are most often mixed, generated
over an extended period, in relatively small quantities and by different owners,
posing challenges for their recycling (Zaharieva 2015).
The most common construction waste is concrete and reinforced concrete. The main
generator of such waste is the reconstruction and demolition of old buildings.
Concrete waste contains rock and cement (aggregate) materials and, in recycling,
including crushing and crushing, reinforcement separation, screening and
purification, new crushed stone fractions are produced. These recycled fractions can
be used as embankment or aggregate materials for concrete and asphalt. Another
problem that does not stimulate recycling activities and the production of quality
recycled products is the practical ban (for concrete with compressive strength above
C16 / 20) according to the Bulgarian state standard (BSS) EN 206 to use recycled
aggregates to produce concrete. There is no reason to do so, especially since BSS
EN 206 itself allows up to 50% substitution of natural crushed stone or gravel with
recycled concrete with a compressive strength even above C 30/37.

Table 1. C&D Waste generation by economic activities and households (Waste

treatment 2014)
Building ceramics is another material that can be used extensively after recycling.
For example, for fillers and drainage works, for pavements, for park lanes and
others. It is possible to recycle the ceramic products in the form of recycled
aggregates to produce lightweight concrete. In terms of bricks, which are the most
used ceramic products in the construction, due to the high mechanical strength of
ceramics and its durability, the bricks are fit for new masonry. The possibilities for
re-use of building ceramics largely depend on the recycling process, the demolition
methods of old buildings and the construction site technology, which aim to separate
the ready-to-use ceramic construction waste.
There is a clear relationship (Symonds Group Ltd 46967 Final Report 1999)
between the possible destinations to which C&DW may be sent and the final fate of
the waste materials concerned. It is possible to define a range of possible
destinations/uses to which they may go once they have been collected on-site. These
include one or more of the following:
Re-use options
 re-use on-site for the original intended purpose;
 re-use off-site for the original intended purpose;
Recycling options
 on-site processing to recover high value saleable materials;
 off-site processing to recover high value saleable materials;
 recycling on-site for a low-value purpose (including non-essential land
raising);
 recycling off-site for a low-value purpose (including non-essential land
raising);
Incineration options
 off-site incineration with energy recovery;
 off-site incineration without energy recovery;
Landfilling options
 off-site landfilling of segregated waste materials;
 off-site landfilling of unsegregated waste.
Average rate of recycling of C&DW for some EU countries for 2011 could be seen
at Table 2.
Table 2. Average rate of recycling of C&DW for some EU countries (Calvo et al.
2014)

On the territory of the regional waste disposal landfill in Rousse, experiments were
carried out to determine the optimum particle size that can be used for the
surrounding embankments and for temporary roads. In Table 3 the recycled
quantities of CW for the last 5 years are presented.
Table 3. CW Recycled quantities for the last 5 years for Ruse, Bulgaria
Year CW quantity recycled,
tonnes
2018 36,46
2017 150
2016 3770
2015 5019
2014 6788
The main machines are related to the processing of the main volume and recyclable
building material - crushing and screening installation.
The Ruse landfill has 2 machines - the crusher RM 80 (fig.1) and the R105 Screeper
(fig.2). The crusher is an Austrian production, made in 2012 and purchased by the
landfill in 2014. Its performance is up to 160 t / h, and the particle size is up to 70
mm. The scraper was purchased in 2015. Thanks to this equipment, 3 types of
fractions can be obtained: - Up to 31 mm - ash + finger; used to deploy the landfill;
- 40 to 70 mm (0.63 mm) - for backfill; - Over 70 mm - for grinding.

At the landfill, materials are broken down with the following codes in accordance to
Ordinance 3 Classification of construction waste: ORDINANCE № 3 OF 1 APRIL
2004 FOR CLASSIFICATION OF WASTE replaced by ORDINANCE No 2 of
23.07.2014 on the classification of waste, issued by the Bulgarian Minister of
Environment and Water and the Minister of Health, published on 08.08.2014:
17 01 01 concrete; 17 01 07 mixtures of concrete, bricks, tiles, tiles, faience and
ceramics, other than those mentioned in 17 01 06; 17 04 05 iron and steel; 17 05 06
excavated earth masses other than those mentioned in 17 05 05 (Ordinance No.
2/2014).
Figure 1. Crusher RM 80 (VIP Logistic ltd)
Figure 2. R105 Screener (VIP Logistic ltd)
A major problem in Bulgaria is the lack of washing facilities. They are needed
because there is a lot of dust in the crushing of the concrete and the building
materials experts need to tell where they can be used.
Construction waste recycling facilities are not yet in place. The lack of sufficient
installations also leads to a lack of competition between them, they are produced
only in the form of recycled products, and there is a real risk that recycled products
do not have the necessary construction and technical properties.

Almost there are no companies registered for recycling glass from construction sites,
but only from packaging for which there is a market. The same applies to wood.
The issue of dangerous CW is not entirely solved. The lack of a uniform sampling
methodology, adapted to the specifics of CW.
At present, no sustainable solution has been found for the separation and treatment
of a number of hazardous substances contained in construction waste.
There is also no single national platform on the amount of construction waste
generated by branch organizations.
All this indicates that future coordination between CW-generating companies,
control and management bodies must be carried out in order to achieve the recycling
goals of the CW.
Acknowledgements
This paper contains results of the work on project No 2019 – AIF – 03, financed by Scientific
Research Fund of Ruse University, Bulgaria.
References
Calvo, N, Varela-Candamio, L & Novo-Corti, I 2014, ‘A Dynamic Model for
Construction and Demolition (C&D) Waste Management in Spain: Driving
Policies Based on Economic Incentives and Tax Penalties’, Sustainability, vol.
6, pp. 416-435
Construction and demolition waste production in the EU 2019. Available from:
https://www.tnnltd.uk/construction-and-demolition-waste-production-in-the-
eu/
Kourmpanis, B, Papadopoulos, A, Moustakas, K, Stylianou, M, Haralambous, KJ &
Loizidou, M 2008, ‘Preliminary study for the management of construction and
demolition waste’, Waste Management & Research, vol.26, no.3, pp.267–75
Ordinance No. 2 of 23.07.2014 on the classification of waste (Bulgaria), available
from:
https://www.moew.government.bg/static/media/ups/tiny/filebase/Waste/Legisl
ation/Naredbi/waste/Naredba_No2_2014_za_klasifikacia_na_otpadacite.pdf
Symonds Group Ltd 46967 Final Report February 1999 12 , available from:
http://ec.europa.eu/environment/waste/studies/cdw/cdw_chapter1-6.pdf
VIP Logistic ltd. Available from: https://viplogistic.bg/product/rubble-master-rm-
80/
Waste treatment, 2014 YB17, available from: https://ec.europa.eu/eurostat/statistics-
explained/
Zaharieva R 2015, Principal problems in applying the national legislation on
construction waste management (in Bulgarien). Available from:
http://stroitelstvoimoti.com

THE INFLUENCE OF EMISSION SOURCES ON PARTICULATE

Valeriu Danciulescu1, Luoana Florentina Pascu1, Mihaela Petrescu1, Andreea Cozea1, Raluca
Diodiu1, Gheorghita Tanase1, Maria Pasca2
1
National Research and Development Institute for Industrial Ecology – ECOIND, 71-73
Drumul Podu Dambovitei Street, sector 6, zip 060652, Bucharest, Romania,
2
SC Oehler Mecanica SRL, str. Uzinei, nr. 1, Marsa-Avrig, jud. Sibiu
Abstract
Particulates generated by anthropogenic activities are found in the ambient air in
varying amounts, in a wide range of sizes and in a wide variety of chemical
composition. The concentration of particulates at one site, as well as their
composition, are influenced by their origin and dispersion factors. By chemical and
dimensional analysis of particulates in an area, we can draw preliminary conclusions
about the origin and level of pollution in that area.
This paper presents the results obtained by concomitant monitoring of particulates
emissions and the concentration of particulate matter in ambient air in the adjacent
area of an industrial plant.
The result of the measurements obtained and their correlation with the specific
conditions during the monitoring period lead us to the conclusion that the
concentration of particulate matter at the emission sources directly influences the
concentrations of particulate matter in the neighbouring area.
Keywords: air, concentrations, emissions, particles, pollution
Introduction
Air pollution with particulate matter from anthropogenic sources worries both the
scientists, the authorities, and the regular people. A permanent concern for the
reduction of particulate pollution is also provided by industrial units that in order to
meet the requirements for emissions and ambient air imposed by the authorities
apply the best manufacturing technologies (Danciulescu et al 2018) along with the
techniques for reducing particulate emissions (Bucur & Danet 2016, Danciulescu et
al 2015, Danciulescu et al 2017).
In urban areas, particulates come mainly from industrial emissions, transport, energy
industry, natural sources, and gas-particle conversion processes, generally having
higher mass concentrations than in rural areas; the particulates usually contain also
significant quantities of specific pollutants such as heavy metals or organic
compounds (Bucur et al 2018, Bratu et al 2016, Bratu et al 2018).
Immissions of particulate matter at one point represent a sum of the pollution in an
area, under the influence of dispersion factors. They directly influence the
concentration of particulates at a measuring point.
By measuring concentrations of particulates at emission sources and particulate
concentrations in the ambient air in areas adjacent to emission sources, we examine
concentration correlations taking into account dispersion factors such as the

direction and speed of the wind, temperature, pressure, etc.

Measurements of particulates at emission sources were performed with isokinetic
samplers for particulates, Paul Gothe, according to SR EN 13284-1:2018. The
particulate matter suspended in ambient air was monitored according to STAS
10813:76. At the emission sources, a series of physical parameters were monitored
with the TESTO 350 analyzer: the dynamic pressure [mbar] of the gaseous effluent
from the measuring point; gas temperature [K]; chemical composition of gaseous
effluent for density determination (kg/m³); gas humidity [%]; atmospheric pressure
[mbar].
Figure 1 shows the equipment that was used to measure the emission of particulates.
Figure 1. The equipment used for sampling/measurement of particulate matter

emissions: isokinetic sampler for particulates (a), and analyzer of combustion gases
(b).
The results of the measurements have been input into a dispersion program, and the
highest concentration points have been obtained on the isoconcentration curves,
located at various distances around the emission sources. At these points we placed
particulate samplers Tecora in order to perform sampling of particulate matter from
the ambient air. The values for particulate matter in the ambient air have been
compared with the values obtained from the dispersion program.
To estimate the concentrations of particulates at emission sources we used the
inverse dispersion method, starting from the values of particulate concentrations
obtained by direct measurements in the ambient air.

The research that was the subject of this study was carried out in a June 2019
campaign that involved the measurement of the concentrations of particulates
generated by a car subassemblies manufacturer, the particulate matter pollution
being specific to this manufacturing unit.
As part of the measurement operations, the levels of particulate matter emissions
and the concentrations of particulates in the ambient air have been determined by
direct measurements. The results obtained from measurements have been compared

with the results obtained by mathematically modelling the dispersion of the

particulate matter emissions.
Table 1 shows the results of the measurements: the particulate matter concentrations
from six emission sources that were monitored, S1-S6, and the corresponding mass
flows of the emission sources.
Table 1. The particulates concentration in the emissions from static sources.

Source Measurement value Mass
Pollutant Unit flow
Det.1 Det.2 Average
(g/h)
S1 particulates mg/Nmc 14.80 15.74 15.27 416
These results have been input into the dispersion program together with the weather
parameters recorded at the time of the measurements and we obtained the
isoconcentration curves for particulates in the area adjacent to the emission sources
(Figure 3). Figure 2 shows the wind directions.
Figure 2. Wind directions Figure 3. Isoconcentration curves for

particulate matter
From the isoconcentration curve, one observes a movement of the pollution peak
(area) in the direction of the wind. Consequently, there are higher concentrations of
particulates at a point in the wind direction, compared with the pollutant
concentration at another point at the same distance but not located in the wind
direction.
Based on the results of the dispersion, 8 monitoring points were set up linearly in the
direction of the wind in the West direction. The 8 points were located at 100 m
intervals in the west direction from 100 to 900 meters away.
In these points, we performed three series of measurements of the concentrations of
particulates in suspension in the ambient air under similar weather conditions, with
the emission sources in operation and stopped, to investigate the influence of

emissions on the pollution level in the area.
The variation of particulates concentration in the ambient air at the 8 monitored
points is shown in Figure 4 with the emission sources stopped and in Figure 5 with
the emission sources in operation.
Figure 4. The variation of the Figure 5. The variation of the

concentration of particulates with the concentration of particulates with the
emission sources switched off. emission sources switched on.
The influence of emissions from emission sources on the pollution level of the
ambient air in the vicinity and the direct correlation with the distance from the
emission sources can easily be noticed; thus, the influence of the emission sources in
point 8 is practically irrelevant.
The data series containing the results of monitoring the concentration of suspended
particulate matter in the 8 points were used to verify a method for assessing the level
of particulate emissions from static sources by inverse dispersion. The method can
be useful for situations where, for various reasons, direct measurements can not be
performed. The AermodView dispersion program was used for modeling. Figure 6
shows comparatively the results of the inverse modeling with the results of the direct
measurements obtained in two different days (a and b).
(a) (b)
Figure 6. The results of measurements and estimates of particulates emissions in
two situations (a and b)
By comparing the results obtained by the inverse dispersion and the measured
concentrations in the direct monitoring, we can constantly observe higher values by
up to 30% than in the direct measurements due, we believe, to the influence of other
sources of dust pollution of the ambient air (traffic, re-suspension, etc.).
However, the method can be used, taking into account the value of the identified
deviation that falls within the domain of uncertainty specific to mathematical
modeling estimates.
Conclusions
The result of the measurements carried out, correlated with the specific conditions
during the monitoring period, and leads us to the conclusion that the level of
concentrations of particulates emitted from static sources directly influences the
concentrations of suspended particulate matter in the adjacent area. The main factors
of influence are the distance from the sources, and the weather parameters, first of
all, the speed and direction of the wind.
Also, the method of estimating the level of particulates emission from static sources
by inverse modeling has led to values within the error margin characteristic of
mathematical modeling methods and can be used in situations that do not permit
direct measurements. The method can be applied in other locations or for other
pollutants using input data and weather parameters specific to the studied area.
Acknowledgements
no. 2142/12.02.2019.
References
Danciulescu, V, Cozea, A, Petrescu, M, Diodiu, R, Tanase, Gh & Vasile, A 2018,
New approches regarding bat conclusion implementation', 21th International
Research and Development Institute for Industrial Ecology - ECOIND,
Bucharest, Proceedings Book, Bucharest, pp. 250-257.
Bratu, M, Pascu, L F, Cristea N I & Nicolescu I 2018, 'Microstructural and chemical
characterization of some wastes for phonoabsorbant materials obtaining', 21th
International Symposium “The Environment and the Industry”, Proceedings
Book, National Research and Development Institute for Industrial Ecology -
ECOIND , Bucharest, Proceedings Book, Bucharest, pp. 400-408.
Bucur, E. & A. Danet, 2016, 'Particulate matter and polycyclic aromatic
hydrocarbon air pollution in areas of Bucharest with heavy road traffic',
Chemistry Journal, vol. 67, no 4, pp. 621-625.
Bucur, E, Vasile, A, Pascu, L F, Lehr C B & Vasile, G 2018, 'Environmental Impact
Assessment Regarding Indoor Air Quality Using Statistical Methods'
Chemistry Journal, vol. 69, no 11, pp. 3225-3228.
Danciulescu, V, Bucur, E, Pascu, L F, Vasile, A & Bratu, M 2015, 'Correlations
between noise level and pollutants concentration in order to assess the level of
air pollution induced by heavy traffic', Journal Of Environmental Protection
And Ecology, Vol. 16, No. 3, pp. 815-823.

Danciulescu, V, Vasile, A, Pascu, L F, Stanescu, B & Nicolescu, I 2017, 'The

evaluation of the levels of greenhouse gases due to activities carried out on a
livestock farm', Chemistry Journal, vol. 68, no. 8, pp 1700-1703.
Bratu, M, Ovidiu, D, Ovidiu, V, Ioan R & Pascu, L F 2016, 'Research on
attenuation of sound waves by using panels made of composite materials',
Roumanian Journal of Materials, vol. 46, no.1, pp. 121-126.
SR EN 13284-1:2008 - Stationary source emissions - Determination of low range
mass concentration of dust - Part 1: Manual gravimetric method.

THE ORIGIN OF AMMONIUM IN CARBONATED MINERAL WATERS

AND ITS UNDERGROUND TRANSPORT TO ONE PRODUCTION WELL
IN MIDDLE CIUC DEPRESSION FROM EASTERN CARPATHIANS
Olariu Andra1, Palcu Marin 2, 3

1
Geo – Line Ltd, olariu.andra@yahoo.com
2
Geo Aqua Consult Ltd, marin.palcu@geoaqua.ro
3
Romanian Association of Hydrogeologists
Abstract
In many cases in Romania, the mineral waters (in the Neogene Volcanic area of the
Eastern Carpathians), especially the carbonate waters, have ammonium in
concentration over 0.5 mg/l. The main issue regarding the presence of ammonium is
identifying if the concentration is due to the anthropogenic pollution or it is of
endogenic origin.
The geological, hydrogeological and hydrochemical data analysis resulted in a
conceptual model of the aquifer’s spatial position, groundwater movement and
mineralization, and ammonium occurrence. The geological and tectonic aspects,
aquifer’s recharging, groundwater flow direction, absence of surface pollution
sources and correlation of hydrochemical data, all indicate the underground origin of
ammonium. The aquifer is generated in pliocene - quaternary granular deposits. In
the basement of these granular deposits, in the fracture areas, the groundwater is
mixed with carbon dioxide and ammonium emissions, produced in the volcanic
chambers. The surface data correlation and the hydrochemical data analysis resulted
in the confirmation of the deep ammonium origin.
After groundwater flow modeling and ammonium transport simulation, the
ammonium plume size and preferential transport directions have been finally
elucidated.
Keywords: ammonium origin, ammonium plume, groundwater flow, mass

transportation modeling, mineral waters
Introduction
In a great part of cases, in Romania, the mineral carbonated waters have ammonium
concentrations of over 0.5 mg/l. The presence of ammonium is accepted over this
limit only in case of endogenic origin of this cation. The goal of this study is to
demonstrate the ammonium origin, the geological and hydrogeological conditions of
mineral water occurrence and to identify the underground ammonium migration.
The study takes into consideration the spatial extension of the aquifer’s structure, the
genesis of carbonated water resources, the groundwater flow, both in uninfluenced
mode and under the conditions of a production well with a flow rate of 10 l/s, as
well as the identification of the ammonium origin and the main access routes of this
cation through the porous medium.


General presentation
The study area is located in Romania, in the intramountain depressions of Eastern
Carpathians, in Harghita County, north of Miercurea Ciuc city, area known as the
Middle Ciuc Depression. The zone presents itself as a submerged area due to the
deep tectonic fractures. In the western part are present the volcanic mountains of
Northern Harghita Chain, to the north and the south the tectonic uplift from
Sandominic, respectively Jigodin, and in the eastern part are the mountain chains of
Hasmas and Ciuc (Figure 1).
In the Middle Ciuc Depression, the basin area consists of sedimentary pliocene -
quaternary deposits. The deposits cover the older fractured formations, their
thickness varying between a few meters and 250 - 400 m. In these deposits are
generated groundwater resources. Near the tectonic fractured areas, due to the
mixture of the water stored in the granular rocks and the carbon dioxide
manifestations coming from the depth, carbonated mineral water resources are
occurring. In some of the cases, the presence of the ammonium cation with a
concentration comprised between 0.9 and 3.5 mg/l were determined.
Taking into consideration that the limit for ammonium in mineral waters is 0.5 mg /
l, unless ammonium has an endogenous origin, the study aims to elucidate the origin
of the ammonium and the propagation of this cation in the groundwater in Ciceu
area, where a well with a depth of 150 m was drilled for mineral water exploitation.
Fig. 1 Topographic map of the study area

The achievement of these objectives involves the construction of a conceptual model

concerning the ammonium occurrence, the groundwater flow, the dominant
groundwater chemical facies, the analysis of the presence of ammonium and finally
modelling of the groundwater flow and the transport of the ammonium through the
porous medium.
The conceptual model

The aquifers exposed to modelling are complex systems with a high variability of
their characteristic parameters. By conceptualisation or by construction of the
conceptual model (Dassargues 1995), can be found the fundamental assumptions
that support the modelling. The fundamental assumptions may include aspects
relating to the aquifer’s geometry, litho - stratigraphic characteristics, homogeneity,
anisotropy, recharge and discharge of the aquifer’s formations, groundwater flow
regime, boundary geometry, chemical compounds involved in transfer and the
transfer mechanisms within porous media, the presence or absence of the pollution
sources and their temporal and spatial distribution, the chemical processes inside the
aquifers, etc. The geometry of the aquifer is dependent on the geology of the region.
The Middle Ciuc basin area is a sedimentary type, having pliocene – quaternary
sands and gravels, in alternance with impermeable clay deposits and coal beds. In
the western and northern part, the sedimentary basin limit (Radulescu 1964, Ionescu
et al. 1985, Seghedi et al 1995, Szakács & Seghedi 1995, László 1999) is
represented by volcanic rocks (volcanogenic – sedimentary formations and andesitic
rocks). In the north - eastern part, the crystalline formations outcrop. On the eastern
boundary of the pliocene-quaternary basin there are (Bancila 1941, 1958, Pricajan &
Bandrabur, 1955 Patrulius et al 1962, Murgeanu et al 1963, Mutihac & Ionesi 1974,
Mutihac & Mutihac 2010) mostly cretaceous formations, such as sandstones,
marlstones and calcareous marls and to a lesser extent Jurassic and Triassic deposits,
represented by manly limestones, sandstone marls and respectively white
limestones.
In the south – eastern and southern boundary of the sedimentary basin, andesitic
rocks are present.
The sedimentary basin of Middle Ciuc was formed (Airinei et al. 1965) on a lowered
area, along the tectonic fractures that have a north north west - south-south-east
direction (figure 2). As a result of the geological and hydrogeological boreholes
researches, the geometry of the pliocene - quaternary deposits, which fill the basinal
area, as well as the information regarding the groundwater flow, were obtained. In
an overview, the morphology of the sedimentation basin (figure 3) is also found in
the spatial form of the deep aquifer’s formation. Consequently, with the boundaries
of the sedimentation basin, the aquifer formations are in vicinity to the ground level
with low thicknesses (3-10 m), while in the axial areas of the basin they can reach
60 - 80 m thickness, being found at depths between 70 and 230 m. In the marginal
areas of the basin, deep aquifer deposits are located under the porous quaternary
deposits, either of the main river terraces or of the dejection fans, forming with them
unitary hydraulic structures.

The lithology of the main aquifer consists of pliocene - quaternary rocks, like fine to
coarse gravels, interbedded with sands, ranging from fine to medium sands and only
rarely coarse sands. Both the lower and the upper aquifer base are bordered by
impermeable or partially permeable clays. According to the lithological distribution
of the permeable rocks, it is observed that the aquifer’s structure presents an
advanced degree of inhomogeneity and anisotropy. In a global appreciation, it can
be concluded that the main aquifer from the Middle Ciuc Depression extends in
surface and depth in concordance with the pliocene - quaternary sedimentation
basin. The stream network is subordinated to Olt River and the drainage basin area,
the surface waters being completely discharged into this river. The course of Olt is
Figure 2. Geological map of Middle Ciuc Basin
oriented approximately north – south, with an average slope of 2.5 0/00. At the exit
point from the Middle Ciuc basin, the river Olt has a multiannual average flow rate
less than 5 m3 / s, and in Sancraieni, with the probability of 80%, the daily flow rate
is of 0.55 m3 / s. In the western, eastern and north eastern part of the main
hydrogeological structure, the surface waters subordinated to Olt River have a direct
connection with the deep aquifer through the porous quaternary deposits in which
the phreatic aquifer is generated. In these areas, the aquifer’s structure is recharged
both from surface waters and from atmospheric precipitations at levels ranging from
710 to 720 m on the western side, 730 to 780 m on the north east and 725 to 820 m
on the eastern boundary.

Figure 3. Hydrogeological cross sections
The atmospheric precipitation has values up to 1200 mm in the high

geomorphological zones, while in the depression area it drops to 520 - 540 mm. If
the recharge of the main aquifer is produced from surface waters and atmospheric
precipitation infiltration, in some areas, the discharge of the groundwater is diffused
into the stream network subordinated to Olt River and, in others cases, the discharge
is carried out through the springs.
Taking into account the known data from the axial area of the aquifer’s structure,
based on the field observations of the deep wells and the vicinity of the natural
boundaries, from the domestic wells, as well as from the observations made on the
rivers, a potentiometric map has been edited. On the basis of this cartographic
material, the groundwater flow conditions were underlined, without the influence of
drainage. In consequence, in the eastern part of the main aquifer, the groundwater
flow is produced from the east north east at the elevation of 820 m to the elevation
of 680 m in the west south western part. In the western part, the direction of
groundwater flow is from the west, at the maximum elevation of 725 m to the east to
the elevation of 680 m, while in the vicinity of the Olt River the groundwater flow is
convergent with the river from the elevation of 680 – 685 m in the northern part, to
the elevations of 660 – 665 m in the southern part. If in the marginal areas the
hydraulic gradients have high values (0.09), they are decreasing substantially to
0.009 – 0.004 in the convergence area of the groundwater flow. The hydrodynamic
spectrum of the groundwater flow depends not only on the echipotentials
configuration, but also on the hydraulic properties of the aquifer’s environment.

Therefore, after the hydrodynamic tests were carried out on the well FH Ciceu, the
transmissivity with a value of 11 m2 / day, the hydraulic conductivity of 0.5 m/day
and the storage coefficient, specific to a confined aquifer, of 0.0005 were calculated.
(figure 4)
Due to the fact that the basement of the Middle Ciceu sedimentary basin is strongly
fractured, on the deep faults zones the circulation of the carbon dioxide (CO2) and
other volatiles occur. Within the deep aquifer structure, near these tectonic
accidents, the mixture of groundwater from the granular rocks and the carbon
dioxide coming from the depth is achieved. The result of this process is the
carbonated water with a greater or lower carbon dioxide concentration, which is
depending on the distance to the tectonic accident.
Figure 4. Hydraulic parameters calculation using

Papadoupulos – Cooper method
In groundwater, the carbon dioxide presence accelerates the mineral disintegration

processes, resulting in soluble chemical compounds such as carbonates, hydrogen
carbonates, calcium sulphates, sodium, magnesium, potassium, alkaline silicates,
chlorides and other salts. The dissolution rate depends on the mineral type, solution
pH, temperature and on the presence of some reaction accelerators. In addition to the
chemical elements specific to shallow aquifers such as hydrogen carbonates, there
are also chemical species that originate in the deep groundwater and that are
mobilized by the carbon dioxide circulation. Among these, species of chlorides,
boron and even ammonium ions can be found predominantly in areas with volcanic
or post volcanic manifestations.

Analysis of the mineral water

samples indicate that the
hydrochemical facies of groundwater
corresponds to the predominantly
hydrogen carbonated type with a
massive presence of calcium,
followed by sodium and magnesium
cations and only to a much lesser
extent of potassium. In the case of
anions, the hydrogen carbonates are
present in the greatest
concentrations. The sulphates and
chlorides are in a much lower
proportion, but in approximately
similar concentrations (figure 5). The
hydrochemical facies of the
groundwater is in line with the
ability of the main minerals to be
dissolved. Thus, in the underground
aqueous solution, the dissolution of
the main minerals is done by the
solubilisation of dolomite (CaMg
(CO3)2), anhydrite (CaSO4), halite
(NaCl) and in low proportions
sylvine (KCl).
The deep aquifer structure is well
protected at the upper base by
impermeable clay deposits. They
provide good protection against
infiltrated surface water. As a result,
nitrogen compounds such as nitrates
(Bellia et al. 2015) and nitrites are
found in very low concentrations
(<0.5 – 2.3 mg/l and respectively
0.01 – 0.04 ml/l), indicating a very
low pollution risk. However, in the
Siculeni - Ciceu area, the analysis of
water samples revealed
concentrations of ammonium
ranging between 0.9 to 3.5 mg / l.
Figure 5. Piper, Schoeller and
hydrochemical facies diagrams of The ammonium origin
carbonated mineral waters The analysis of the ammonium
origin in groundwater is a complex
process (Scheiber et al. 2016),
involving chemical and
hydrogeochemical knowledge, uncovering the possible pollution sources,
understanding the structural and hydrogeological factors related to the groundwater
flow, contouring the recharge areas, risk area assessment, etc. In the aqueous
environment, ammonia (NH3), compared with ammonium (NH4+), has high toxicity
(Bucur 1999). In natural waters, for a pH between 5.7 and 8.3, the ionic form of
ammonium is found. For a pH of 9.3 in the aqueous solution, the NH 3 form is found,
(Varduca 1997, Bucur 1999) in a percentage of 50%, and when the pH falls below 8,
the amount of ammonia drops to 4.5%. The nitrogen compounds in the form of the
nitrates, nitrites and ammonium appear in the aqueous medium as a result of the
decomposition (Böhlke 2002, Caschetto 2014, Caschetto & Winner 2017) and
mineralization of the protein substances, that penetrate water either in the form of
waste water, industrial ones such as waters from the coke plants, benzene, water
from slaughter houses, used water from dairy or fertilizer factories, livestock farms,
distribution of the chemical fertilizer, etc. Separately from the decomposition of
proteinaceous products, ammonia or ammonium may also have mineral origin or
from the decomposition of vegetal matter. The mineral origin occurs by the action of
denitrifying bacteria in the ferruginous waters. Under such conditions (Varduca
1997), the presence of ammonium is not noxious, as in the case of the
decomposition of the vegetal matter.
A special case of the presence of ammonium and ammonia in the earth's crust is
represented by the volcanic manifestations. Like the hydrogen, the nitrogen is a
characteristic component of the volcanic manifestations. At contact with water,
nitrogen is released in the ammonium form. For the fixation of 73 g / cm2 of fossil
nitrogen, oxygen in quantity of 125 g / cm2 was released, which represents more
than half of the oxygen from the atmosphere. (Hutchinson 1944 quoted by Rankama
and Sahama 1970). These areas contain ammonium salts, such as ammonium
chloride (NH4Cl), boron nitride (BN) that can easily break down in the presence of
aqueous solutions. In most of the volcanic areas, ammonium salts can occur upon
contact with the boiling water vapours under the action (Berbeyer 1947 Rankama
and Sahama 1970) of the ferromagnetic minerals from the volcanic lava.
The nitrogen compounds can also be found (Lingle 2013, Lingle et al. 2017) in the
earth's crust in sedimentary deposits. These are the "caliche" formations, being
associated with chlorides, sulfates, borates, perchlorates and iodates. The "caliche"
formations environment has (Rankama and Sahama, 1970) the highest redox
potential known on Earth. The nitrocalite (KNO3) and nitronatrite (NaNO3) are the
most abundant nitrates in the” caliche” formation, but the nitrogenous salts are in a
low proportion in relation to the saliferous and gypsiferous levels from this
geological formation. In Ciceu - Siculeni area, in order to reveal the origin of the
ammonium from the mineral waters, in the period of 2018 and 2019, field works
were carried out. They aimed to identify the potential sources that can produce
ammonium pollution from the ground, as well as water sampling from the shallow
aquifer that could have been polluted from the ground. For the mineral water
samples collected from the deep aquifer, the laboratory analysis indicate that
ammonium concentrations vary between 0.87 and 1.023 mg / l (FH Ciceu well),
1.03 mg / l for F 513 Racu well and 3.38 mg / l for FH Siculeni well.

In the domestic wells from Ciceu and Barzava, which investigate the shallow
aquifer, the ammonium ion has concentrations up to 0.047 mg / l. The analysis of
the water collected from Olt River indicates an ammonium concentration of 0.119
mg / l. The nutrient analysis of the carbonated mineral water does not indicate
significant concentrations (figure 6). Thus, the results of the chemical analysis of
groundwater samples from the well FH Ciceu, indicate that the nitrites have
concentrations between 0.014 and 0.072 mg / l, while the nitrates have
concentrations ranging from 0.05 to 2.33 mg / l. Taking into consideration that in the
Ciceu - Siculeni area the deep aquifer is naturally protected from the shallow aquifer
by a 15 - 20 m thick impermeable rock deposit, the results of the ammonium and
nutrients chemical analysis, as well as the fact that in the Ciceu - Siculeni area there
Figure 6. NH4+, nitrates and nitrites time variation
are no industrial or agricultural units that generate organic nitrogen compounds, the
origin of ammonium as the degradation of the organic matter of protein type from
ground is excluded.
In the geological context of the Middle Ciuc Depression, the region is located in the
area of the neogene volcanism. While the volcanoes are no longer active, post
volcanic events are extremely common, especially in the crustal fracture areas,
generating CO2 gases, but also other gases such as ammonium. Taking into account
the chemical facies of the mineral water and considering that the wells from Siculeni
and Ciceu are near a deep fault, in the direction of Racu - Miercurea Ciuc, the origin
of ammonium ion is found in the depths of the magmatic chamber. On these tectonic
accidents, the carbon dioxide and aqueous solutions circulation can mobilize
ammonium from its salts.
Considering the geological and the hydrogeological factors, the possibilities of

groundwater contamination from the surface, accentuating the risk areas, the
chemical analysis and taking into account the parageneses and the association of
chemical species, etc., it can be concluded, that the ammonium cation occurrence in
the mineral waters from Ciceu – Siculeni area is endogenous.
Numerical model
For the simulation of groundwater flow and ammonium transport in porous medium,
the numerical model with finite differences (Bear 1972 and 1979, Cretu 1980,
McDonald and Harbaugh 1988 - i.e. MODFLOW) was applied. In case of the steady
groundwater flow, the finite differences method (FDM) consists in the numerical
solving of the explicitly written hydraulic diffusivity equation (McDonald and
Harbaugh, 1988) in the form:
  h    y    h  (1)
 K H  K H  
 K H W  0 
x  x  y  y  z  z 
xx yy zz
of finite dimensional approximation V of the space (Albu & Enachescu 1985,
Albu et al 1989) V  C2 ( CT )  C0 ( CT ) , using the next notations K xx , K yy ,

K zz the hydraulic conductivity [m/day] in the direction x, y and z, h the
hydraulic head [m], H aquifer thickness [m] and W is the leakage flow rate
[m3/day].
Figure 7. Potentiometric map in initial conditions
The numerical solving of the hydraulic diffusivity equation according to the finite
difference scheme implies the partition of the aquifer into representative sub-
domains, within which the satisfactory solution for the imposed boundary conditions
are found. Thus, the main aquifer was meshed into a network of 70 lines in the x
axis direction and 70 columns in the - axis direction, resulting in a number of 4900

elemental cells with a dimension of every cell of 153.8 m on the x - axis and of
181.8 m along the y - axis.
The parabolic equations associated with the groundwater flow give the possibility to
find an infinity of solutions. The solution corresponding the studied case is that
which verifies the boundary conditions corresponding to a particular process. In
numerical modelling, the main conditions on the boundaries can be (Dassargues
1993) the imposed constant head (Dirichlet type), the imposed groundwater flow
rate (Neumann type) and the flow rates conditions dependent by the potential
(mixed type). In the steady state groundwater bidimensional flow, the constant head
has the expression h  h x , y  . The imposed constant heads were chosen at the
contact between the aquifer and the river, lake or precipitation, equipotential lines
parallel to the boundary (Gheorghita 1966, Albu and Enachescu 1985), and outcrops
of permeable deposits. In the modelling process, the constant heads conditions were
imposed on the eastern, southern, western and northern aquifer limits as constant
time (figure 8), varying between 730 and 820 m on the eastern limit, 665 - 685 m on
the southern border, 705 - 725 m
on the western part and 685 - 760
m on the northern boundary.
In the case of non-zero flow, on the
boundary S with the surface
element ds , for the
bidimensional space and in the
conditions of the steady states, the
required flow condition
(Dassargues 1993) is:
h
 k r ds  q(x , y ) .
s
(2)
In the modelling process, Neumann

type boundary conditions (fig 8)
were imposed in the area of
carbonate mineral water extraction
through the well FH Ciceu with the
flow rate of 1.5 l / s. (129.6
m3/day).
In the steady state conditions of
Figure 8. Dirichlet and Neumann boundary
groundwater flow, the calibration
conditions of the flow model consists in
solving the mixed problem in the
initial stage, without water
recharge or extraction, requiring only constant heads conditions. By adjusting the
values of the hydraulic conductivities (figure 9) and of the storage coefficient, taking
into account the hydrodynamic testing of FH Ciceu well, the piezometric heads were
calculated, so that between the measured and the calculated values is not a
difference greater than 10%.

The transporting equation of the chemical solutions through porous media (Bear and
Verruijt, 1987, Fetter 1993) is resembling the groundwater flow equation. Thus, the
transport of the miscible chemical species through the porous media represents the
coupling of groundwater flow and the transport equations. For the aquifers where
the concentrations C [mg/l] in a chemical species changes over time, applying
Fick's second law, one equation can be written in one direction:
C  2C
  Dd 2 (3)
t x
in which  C represents the variation in concentration over time, and Dd is the
t
molecular diffusion. In the saturated porous media, excepting the concentration
changing by molecular diffusion, the dissolved chemical species are transported in
the direction of the groundwater flow. This process is called transport by advection,
in concordance to the equation:
C
 v gradC
t
(4)
where v [m / day]
represents the
groundwater flow
velocity tensor. The
variations of the
velocities along to
the stream lines
cause the dilution of
the chemical species
concentrations. The
transport variation
by advection is
achieved by
mechanical
dispersion of
Figure 9. Hydraulic conductivity distribution after longitudinal
model calibration DL   L v i  Dd
and transversal
[m2/day] type.

Figure 10. Groundwater flow simulation during

abstraction of 1.5 l / s from the well FH Ciceu
The mechanical dispersions represent a linear combination of the flow velocities

vi and molecular diffusion Dd by the means of the proportionality
coefficients  L and T , representing longitudinal and respectively transversal
mechanical dispersivities. In the bidimensional space, using the mass conservation
law, in an elemental volume, the variation of the massic fluxes occurs in accordance
to the coupled equation,
C    C    C    
   Dx   Dy   v x C    v y C  (5)
t   x   x   y   y    x y 
which represents the transport equation of the chemical species through the saturated
porous media, with the notations C the concentration in a soluble chemical species,
Dx , Dy and v x , v y the mechanical dispersions, respectively the groundwater
flow velocities in the direction x and y .
For the numerical solving of the equation (5), it is necessary to impose both the
boundaries conditions and the adjustment of the mechanical dispersivities. In the
case of the ammonium migration, the boundary conditions consisted in imposing
ammonium constant concentrations in a point manner, along a crustal fracture. The
concentrations imposed were considered constant over the time, with higher values
than the analysed samples of carbonated water from the wells. In this regard, the
imposed concentrations (figure 11) have values between 3 and 7.5 mg / l.

Figure 11. Concentration Figure 12. Dispersity distribution

boundary conditions after model calibration
The calibration process of the ammonium transport through the saturated porous
medium implies knowledge (Wang et al. 2013) of the mechanical processes
associated with groundwater flow, coupled with those of molecular diffusion and the
hydrodynamic dispersion, accompanied by chemical reactions and the retardation
processes. For the simplification, and considering the absence of information
concerning the parameters of some chemical reactions inside the aquifers system
and data of the retardation processes, only the mechanical dispersivities fields
(figure 12) were taken into consideration. These dispersivities have a variation of 5,
10 and 20 m. In relation to the period of physical – chemical processes related to the
ammonium presence in groundwater, the monitoring time in the well FH Ciceu is
very short. Thus, the calibration process, was realized so that the calculated values
are as close as possible to the measured ones (figure 13).

Figure 13. Concentrations calibration in the well FH Ciceu

Results referring to the conceptual model
The present study calls attention to more new information. These relate to the
geology, hydrogeology and hydrochemistry of the area, with special regarding to the
ammonium origin and the transport of this cation through the saturated porous
media. The conceptual model construction has brought to light new information
referring to the spatial configuration of the deep aquifer in which are stored the
carbonated mineral waters, the generating mode of these groundwater’s type (figure
5), their chemical facies, as well as the relation between the deep aquifer, the
shallow aquifer and the surface waters. In the presented context, the extents of the
deep aquifer were defined, it’s recharging areas, the groundwater flow and the
discharge conditions (figures 2, 7, 14), as well as the aquifer’s main hydraulic
parameters. Considering the hydrochemical facies of the underground water (figure
5), the aqueous solution is setting up on the basis of the dissolution of the dolomite
(CaMg (CO3) 2), anhydrite (CaSO4), halite (NaCl) and silvine (KCl).
Considerations concerning ammonium origin

Between 2018–2019, field investigations and laboratory analysis show that
ammonium cations in the domestic wells have concentrations less than 0.047 mg / l
for shallow aquifers and less than 0.119 for the surface waters. These results,
correlated with field observations, which indicate the absence of economic activities
with ammonia production in the area, exclude the origin from the surface of the
ammonium cation. Moreover, the concentrations between 0.87 and 3.38 mg / l of
ammonium are found only in the carbonated groundwater from the deep aquifer.
This cation has concentrations of 0.87 - 1.023 mg / l in the groundwater from FH
Ciceu well, 1.03 mg / l in F 513 Racu well and 3.38 mg / l in FH Siculeni well. In
the case of FH Ciceu well, following the correlation of the ammonium and nutrients
concentrations, it results that this cation has deep origin.
Results of the groundwater flow and ammonium transport modeling

In the case of the deep aquifer, after the calibration of the model, were simulated
both the groundwater flow processes (figure 7) and the transport of ammonium
through the saturated porous medium (figures 10, 13, 14), in the conditions of
extracting a 1.5 l / s (129.6 m3 / day) flow rate from the well FH Ciceu. The
simulations objective, were to elucidate the groundwater flow process, by
confirming the recharge and discharges areas, by configurating the piezometric
groundwater surface, in the conditions of a pumping well, observing the produced
drawdowns, the direction of groundwater stream lines, hydraulic gradients,
distribution of the aquifer hydraulic properties, and the position and the magnitude
of groundwater flow velocities.
The coupling of the groundwater flow and ammonium transport was materialized
(figure 14) in finding the possible area of ammonium impregnation, originated in the
depth, by elucidating the calibration conditions and the underground transport
mechanism and, in time observing the evolution of the ammonium plumes. Also, the
result of the simulation (figure 14) accentuated the evolution in time of the
ammonium plumes, depending on the hydrodynamic spectrum modification due to
pumping the FH Ciceu well.
(a) (b) (c)
Figure 14. The simulation of ammonium transport after 1000 (a); 7500 (b);10000 days (c)
Discussion referring to the conceptual model

The conceptual model has taken into account the entire data concerning the
geomorphology, climatology, hydrology, geology, hydrogeology, using data from
the drilling works, water wells, domestic wells, direct field observations, laboratory
analysis, etc. Even if the base of the conceptual model is consisting in a great
number of data, for the current stage, due to objective limitations, the conceptual
model has been transposed only in bidimensional format. In the future, by
developing other new complex researches, the current image of the conceptual
model can be substantially improved.
Ammonium origin
Concerning the ammonium origin, it can be concluded that it originates from the
depth, being transported together with the carbon dioxide on the deep tectonic
fractures due to the postvolcanic manifestations. The base of these considerations
consist in the ammonium absence in the shallow aquifer, in a good natural
protection of the deep aquifer regarding groundwater contamination from the
surface, as well as the setting of the studied area being in a postvolcanic
manifestations zones. As limits of the hypothesis regarding the ammonium origin,
can be considered both the high precision to identify the crustal fractures,
representing the gases circulation ways towards the granular aquifers, as well as the
ammonium concentration direct data in the crustal faults zones.
Groundwater flow and ammonium transport modeling
The groundwater flow simulation in the deep aquifer has shown (figure 14) that the
recharge areas are located to the eastern, northeastern, northern and to the western
boundaries, at elevations between 820 m in the north - east and 685 m to the north.
The groundwater flow is produced from the east north east to west south west on the
aquifer eastern part and from the west to the east in the western part. In the western
central area of the aquifer’s structure, the groundwater flow is radially converging
and the flow has the direction from the north to the south, along the Olt river
floodplain. The hydraulic gradients reach their maximum value of 0.09 in the
marginal areas of the aquifer’s structure, having low values of 0.0004-0.0009 in the
Olt floodplain. According to the permeable lithology variation and to the flow
conditions, the hydraulic conductivity varies from 0.1 to 11 m / day, in conformity
with an inhomogenous and anisotropic aquifer. The pumping of the well FH Ciceu
at a flow rate of 1.5 l / s (129.6 m3/day), induces the modification of the
hydrodynamic spectrum (figure 10), having 26 - 30 m drawdowns. This process
changes not only the piezometric contour layout, but also the direction of the
groundwater stream lines, increasing both the hydraulic gradients and the flow
velocities. Overall, the groudwater flow velocities vary from 0.1 to 0.2 m / day and
1.5 to 2.9 m / d, in the direction of the southern boundary of the main aquifer.
In the vicinity of the crustal faults, by imposing the ammonium concentrations of 3
to 7.5 mg / l (figure 11), as a result of the transport process simulation, after 10 000
days, the ammonium cation can reach the concentration of 2.4 mg / l in FH Ciceu
well. On the surface, the dissolved ammonium plume is expanded from 7.8 x 105 m2
in the initial stage to 3.9 x 106 m2, after 10 000 days. Largely, the ammonium
impregnation area of carbonated groundwater extends southwards, in the direction
of the groundwater flow. The axis of the impregnation plume increases from 790 m
at 1 000 days (figure 14 a) to 2100 m, after 7 500 days (figure 14 b), and according
to the 10 000 days’ simulation time (figure 14 c) this axis will increase to 3000 m.
On the lateral, the ammonium plume axis increases with much lower values than in
the direction of the groundwater flow.
Conclusions
In the Middle Ciuc Depression, the study performed to define the ammonium origin
and its migration through the saturated porous media, in the basin area, has a
contribution to the improvement of the spatial image of the aquifer structures. This
study calls attention for the first time, to the main aquifer heterogeneity and
anisotropy, to the groundwater storage and flow conditions, to the genesis of
carbonate waters, and to the ammonium cation origin. In the basin area, in case of
the deep aquifer, the groundwater flow is influenced not only by the recharge
elevations, but also by the aquifer hydraulic properties variation. The groundwater
flow is produced from the marginal areas, being dominantly drained in the area of
the Olt river floodplain.
In the sedimentary basin, being located in a post volcanic manifestations area, the
ammonium cation has its origin in the magmatic chamber. It runs from the depths to
the aquifer generated in the pliocene - quaternary rocks on a crustal faults system. At
the present stage, using the existing data, it is difficult to specify with accuracy both
the spatial position of the tectonic fractures, and the ammonium concentration in the
close proximity of the fault areas. The transport modelling of this chemical species
indicates the ammonium plume impregnation areas and their evolution over time.
This process is dominantly influenced by the advective factors and less than the
convective components. In relation with the revealed information, as a knowledge
developing process, the presented model can be improved by answering many
unexplained questions.
Acknowledgements
The present study was elaborated at the request of the authorities (National Agency of Mineral
Resources) regarding the origin of ammonium in carbonate mineral waters. The geological
company Geo - Line Ltd provided geological and hydrogeological data, field observations on
the occurrence of groundwater and sampling water samples for analysis. The cartographic
material developed by the Geological Institute of Romania was the basis for the construction of
the conceptual model of the aquifer’s structures.
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TOXIC EFFECTS OF NON-ACUTE LEAD EXPOSURE ON ANIMAL

MODEL
Gheorghita Isvoranu1, Daniela Ionela Popescu1, Elena Codrici1, Simona Mihai1, Ana-Maria
Enciu1, Gina Manda1, Marco Peretto2, Cristiana Tanase1,3
1”
Victor Babes” National Institute of Pathology, 99-101 Spl. Independentei Blvd., 050096,
Bucharest, gina_isvoranu@yahoo.com, Romania
2
Rafifarm SRL, Zaharia Stancu Street, 147135, Draganesti Vlasca,
business.development@rafifarm.ro, Romania
3
Titu Maiorescu University, Cajal Institute, 22 Dâmbovnicului Street, 040441, Bucharest,
cristianatp@yahoo.com, Romania
Abstract
Lead, a high-risk environmental pollutant and extensively used by industry, is one of
the most widely outspread toxic metal today. Lead toxicity is a public health
problem both for the children and for the adults. Lead does not have any useful
functions in the body, instead it produces only harmful effects once it gets into the
body. In this study, we investigated the toxicity of lead in an animal model of non-
acute exposure. Experimental groups received treatment of aqueous solution lead
acetate at different doses and time of administration. Toxic effects of lead were
investigated on haematological and behaviour of treated rats. We noticed the
disturbances of both haematological parameters and behaviour. Our results indicated
that non-acute exposure to lead induced toxic effects in the blood, and central
nervous system of adult Wistar rats.
Keywords: non-acute lead toxicity, haematology, anxiety, rat
Introduction
For centuries, lead (Pb) toxicity has been one of the most significant causes of
toxicant-induced neurologic morbidity related to irreversible damage of various
tissues. Lead poisoning has been reported in almost every country, generally in
industrial areas with storage battery manufacturing and ore mining, and it is more
common in developing countries. The Institute for Health Metrics and Evaluation
estimated that 540 000 deaths in 2016 result from lead poisoning, the highest burden
was in low- and middle-income countries (WHO 2018). In Romania, lead poisoning
represents 14.37% of the total occupational diseases registered in the last 10 years,
representing therefore a major health concern (Stoia et al 2009).
Lead, a heavy metal with not apparently biological function, is widespread and non-
biodegradable pollutant of great concern to human health (Andjelkovic et al 2019,
Meghea et al 2009). While acute lead poisoning related to occupational exposure is
quite uncommon, chronic lead toxicity is still a major problem. It is still present in
many commercial products, and the two main routes of lead exposure are ingestion
and inhalation. Lead poisoning can affect many organs and tissues, being associated
with a number of morphological, biochemical, hematological, physiological, and
behavioral changes (Sun et al 2017). The critical target for lead intoxication is the
hematopoietic system, but lead toxicity is linked to toxic effects on the nervous
system also (Abadin et al 2007, Flora et al 2012). On the central nervous system, the
lead exposure is associated with several neurobehavioral and psychological
alterations.
In this study, we investigated the toxicity of alone in an animal model of non-acute
exposure. The effects of the exposure to lead were investigated on hematological
parameters and the consequences of its toxicity on rat behaviour.

Animals. Male adult Wistar rats from Animal Husbandry of “Victor Babes”
National Institute of Pathology (Bucharest, Romania). The experiment was
performed on male rats weighing approximately 320-350 g. The animals were
maintained in optimal conditions: temperature 22±2˚C, humidity 55±10%, artificial
ventilation, lighting 12/12, light/dark cycle. Rats received standard chow and
drinking water ad libitum. All animals were kept under a rigorous cleaning and
hygiene program and were monitored daily. The experiments were done in
accordance with recognized principles of Laboratory Animal Care in the framework
of EU Directive 2010/63/EU for animal experiments. The study was approved by
the Ethics Committee from “Victor Babes” National Institute of Pathology and by
the National Sanitary Veterinary and Food Safety Authority through project
authorization, no. 449/02.04.2019 (Bucharest, Romania).
Study design. Healthy male rats were divided into five groups of 6 animals each,
one control group and four experimental groups. Intoxication of experimental
animals was done with lead acetate (Chemical Company, Iasi, Romania) dissolved
in distilled water, and the treatment of all animals was performed by an oral gavage
(150 μL per animal), as follows: group control, treated with water only; group
intoxicated 400mg/kg body weight/day for 4 weeks (Pb400); group intoxicated
200mg/kg body weight/day for 4 weeks (Pb200); group intoxicated 100mg/kg body
weight/day for 4 weeks (Pb100); group intoxicated 200mg/kg body weight/day for 6
weeks (Pb200*). Animals were sacrificed by cervical dislocation at the end of the
experiment.
Haematology analysis. For the haematological tests blood was collected by retro-
orbital puncture, and was immediately analysed for assessing the complete count of
white blood cell (WBC), lymphocytes (LY), neutrophils (NE), monocytes (MO), red
blood cell (RBC), haemoglobin (HGB), haematocrit (HCT), mean corpuscular
volume (MCV), mean corpuscular haemoglobin (MCH), mean corpuscular
haemoglobin concentration (MCHC), and platelets (PLT), using the fully automated
Hemavet 950 analyser (Drew Scientific, Miami Lakes, USA).
Behaviour test. The light/dark box test was assessed using a device divided into a
light chamber connected by a door to a dark chamber. Animals were placed initially
in the bright chamber, and their behaviour was recorded for 20 minutes. Before each
animal test the box was cleaned with 5% ethanol.
Statistical analysis. Data was analysed using Microsoft Excel. Results are presented
as mean ± standard deviation (SD) (n=6). For statistical analysis, the Student's t-test
(two-tailed, assuming equal variance) was used for statistical evaluation of the
differences between the experimental groups. P-value <0.05 was considered to
indicate a statistically significant difference.


Toxic effects of lead were investigated on haematological parameters, and behaviour
of treated Wistar rats.
Higher doses of lead in 4 weeks treated animals produced a decrease in the WBC
number compared to the control group and to a lower dose. The change in absolute
lymphocyte and neutrophil count had a similar trend. Animals from the group lead-
poisoning for 6 weeks, presented statistically increased absolute counts of WBC
(p<7.82E-05), NE (p<0.0035) and LY (p<4.25E-05) in comparison with controls
(Fig. 1). Monocytes count was not affected by the treatment (data not shown).
Figure 1. Effect of lead on WBC, NE, LY counts in rats after non-acute exposure.
Lead administration for 4 weeks did not affect the levels of red blood cells, but lead
treatment for 6 weeks led to a significant statistical increase in RBC count
(p<1.121E-05) (Fig. 2).
Figure 2. Effect of lead on RBC count in rats after non-acute exposure.
Regarding hemoglobin and hematocrit, the animals treated 4 weeks with lead have
presented proximate values to controls (Figure 3). Instead, in group lead-poisoning
for 6 weeks, there was a statistically significant increase in the number of hematocrit
(p<1.11E-05).
Figure 3. Effect of lead on HGB concentration and HCT percentage in rats after
non-acute exposure.
The most pronounced effects were observed on MCV, MCH, and MCHC.
Significant changes in MCH were noticed in both 4 weeks Pb-treated groups (Pb400
group where p<0.0259; Pb100 group where p<0.0178) when compared to the
controls. Pb100 group present also a significant decrease of MCH (p<0.0152). The 6
weeks’ treatment affects all three parameters, MCV (p<0.0116), MCH (p<2.3E-08),
and MCHC (p<4.74E-07) (Fig. 4).
Figure 4. Effect of lead on MCV, MCH, and MCHC in rats after non-acute
exposure.
In all experimental groups, regardless of the dose or time of administration, we

noticed an increase in platelets count in contrast to control, statistically significant
for Pb400 group (p<0.0020), Pb100 group (p<0.0105), and Pb200* group
(p<0.0004) (Figure 5).

Figure 5. Effect of lead on PLT count in rats after non-acute exposure.
Lead toxic effects on haematological parameters seem to be leukopenia lead

treatment, and leukocytosis for 6 weeks’ treatment. All experimental groups present
thrombocytosis.
The light/dark box test showed that the total time spent in the dark chamber in
controls is around 81% during a time period of 20 minutes, while the animals treated
with lead spent around 61-65% (Figure 6).
Figure 6. Behavioural response in the light/dark box indicated by the % of total time
spent by each group of animals in the dark chamber.
Exposure to lead causes disturbances in behaviour both in humans and animals.

These behavioural disturbances have been associated with alteration of the activity
of monoaminergic neurotransmitters in the central nervous system, lead intoxication
causing an increase in anxious behaviour. The light/dark box test evaluates the
axiogenic effects caused by the exposure to lead (Sansar et al. 2012). The time spent
by the animal in each room provides a measure of anxious or fear-induced inhibition
of normal exploration activity.
Assessment of animal behaviour using the light/dark box test suggests that lead
exposure may possibly induce the increasing of anxiety.

Conclusions
Our results showed that non-acute exposure to lead could induce toxic effects in the
blood, and central nervous system of adult Wistar rats, a longer exposure has
affected more haematological parameters. Future studies of our group will be
focused on other parameters and mechanisms implicated in lead toxicity in order to
develop more mechanism-specific drugs that address pathological processes and
molecular targets of lead intoxication.
Acknowledgements
Funded by Ministry of Research and Innovation in Romania, under Program 1 – The
Improvement of the National System of Research and Development, Subprogram 1.2 –
Institutional Excellence – Projects of Excellence Funding in RDI, Contract No.
7PFE/16.10.2018 and grant COP A 1.2.3, ID: P_40_197/2016.
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room/fact-sheets/detail/lead-poisoning-and-health

VERIFYING COMPLIANCE OF A METALLIC SURFACE TREATMENT

COMPANY WITH BAT REQUIREMENTS, TO MINIMIZE EMISSIONS OF
POLLUTANTS IN WATER
Marius Kovacs, Angelica-Nicoleta Calamar, Lorand Toth, Sorin Simion, Alexandru Simion
National Institute for Research and Development in Mine Safety and Protection to Explosion –
INSEMEX Petrosani, 32-34 G-ral Vasile Milea Street, Post code 332047, Petrosani, Hunedoara
County, Romania
Abstract
The main activity of the studied company is treatment and coating of metals
(galvanizing plating), trapping and treatment of waste water. Galvanizing consists in
creating a superficial diffusion layer of iron alloy.
BATs (Best Available Techniques) do not necessarily mean the most advanced
technique available, but the best technique from an economic point of view for a
particular installation.
Results of the research relate to compliance of the industrial water treatment plant to
BAT best available techniques, in order to minimize pollutants discharged into the
sewerage network. Furthermore, the current paper identifies possible dysfunctional
problems of the galvanizing plant and of the sewage treatment plant and makes
suggestions of remedies for possible technical and organizational problems.
Keywords: BAT, metallic, pollution, surfaces, water
Introduction
The analysed company is founded in 2003, specialized in the application of liquid
paint on different aluminium, polyamide, ABS, polypropylene supports. The
company has galvanizing, and also aluminium chrome plating and anodizing
systems, painting systems and two water treatment plants.
The unit under analysis is located in the S-E part of Deva industrial area, about 500
m from European road 79 (Figure 1).
Lately, the company has grown, now also comprising a galvanizing hall. The
decision to place a galvanizing line along with the sewage treatment plant was taken
to diversify and broaden the range of surface treatments that the company offers
against a background of rise of such surface treatments for the automotive industry.
The company's buildings are as follows: The administrative building; Galvanizing
Hall; The Chroming Hall; Warehouse.
In the last period of time, the company has developed a treatment plant for the
galvanizing line, which processes and treats the wastewater discharged from the
processing line.
The galvanizing line is provided with a polyethylene cuvette treatment plant and a
glass fibber decanter which takes up the flushing water from the line.
It should be noted that all of the station's vats have retention basins. The operation of
the wastewater treatment plant is automatically controlled and any deviation from
normal operating parameters is announced optically and audibly, immediately
leading to the automatic stopping of the wash water on the galvanizing line and,
implicitly, on the line signalling. If the failure probes are not remedied, it is
recommended to stop the chrome line. The access to the station control is made from
the control panel, protected by a password to avoid any change of parameters made
by someone other than the responsible person. Physical and chemical parameters of
water are measured in real time, displayed and recorded.
Station operating principle: The wastewater treatment plant takes gravitationally the
flushing water from the line and the mixing (gravitational and pumping) of the
wastewater. The pickup storage takes place in storage tanks and the contents are
dosed for pneumatic pump treatment.
Purified water is discharged into the sewerage network of Deva Town through a
venture device that allows flow measurement and sampling for analysis.
Figure 1. Overview of the company, Deva
Figure 1. Location of the analysed company
Description of the galvanizing plant

Galvanizing of metal parts is a galvanizing operation, representing the
electrochemical deposition of Zn2+ ions from the solution in the electrolysis bath on
the surface of metal parts. This operation takes place in the line’s active cuvettes, the
rest of the vats being reserved for the rinses and operations that take place before
and after galvanization. The technological process used by the company under
analysis is one of the newest galvanizing methods. (Ord 818/2003 completed by Ord
1158/2005)
Galvanizing a metallic part has mainly three important steps:
1. Preparing the part’s surface before galvanization - stage consisting of
(chemical or electrolytic) degreasing the parts (with nitric acid 0.3 %), removal of
metal oxide layer (pickling with 15-17% hydrochloric acid solution) naturally
formed on the surface of raw parts and activation of the surfaces by immersion in a
diluted acid solution;
2. Actual zinc coating of raw parts by galvanization - the process takes
place in the acidic zinc-coating or alkaline-zinc coating tanks (active tanks). Each
active tank has 4 working positions allowing for zinc coating of 4 pieces at the same
time; (SC EVALUARE IMPACT SRL, M 2016)
3. Protecting and / or decorating the surface of the parts after galvanizing,
with decorative and protective purposes against further corrosion, achieved by:
• yellow or blue deco passivation, performed only after acidic
galvanisation after a pre-activation of the surface in 0.3% nitric acid solution or in
10% hydrochloric acid solution.
• black passivation (alkaline galvanizing only) – optionally followed by
varnishing for additional protection; between stages and operations, intermediate
rinses and compressed air blowing are performed for partial drying. The final drying
of the parts is carried out in the oven until all humidity is removed.
Operation of the galvanizing line is programmable, the part’s supports are
transported by 3 robots, the personnel being involved only in loading / unloading of
the part’s supports. In addition to automatic operation, robots can also be handled
manually. The operation is based on cycles having a predetermined time (variable
depending on selected range and computer adjustable), the parts generally spending
an entire number of operating cycles in a particular cuvette. A running cycle lasts
about 5 minutes and the total time that a piece spends on the galvanizing line is
about 100 minutes.
The purification station for water resulting from technological processes of the
galvanizing line is placed in the S-part of the galvanizing hall.
The treated water is discharged into the sewerage network of Deva City through a
Venturi device that allows flow measurement and allows for sampling for analysis while
regarding the GD 188/2002 with subsequent modifications, maximum admissible values.
The current paper describes the current situation of the site and highlights the
pollutants and level of pollution as a result of the company's activity.
Methods of complying with BAT requirements and how to apply them to the
galvanizing plant
In addition to national and international law, companies must verify compliance
with European BATs in the field of each company. Thus, the company under review
should consider whether it complies with requirements of the Best Reference
Document on Best Available Techniques for the Surface Treatment of Metals and
Plastics 2006.
New open units must be designed to operate at levels similar to or superior to
techniques in the reference documents. This depends on technical and economic
capacity of each unit.
Although the documents do not establish a set of framework solutions, it
nevertheless provides information on overall orientation of Member States as
regards the levels to be achieved in the field of emissions and consumption of raw
materials.
The purpose of these documents is also that best practice is regarded as a starting
point for determining the current performance of existing installations or laying
down requirements for new installations.
Recycling and recovery of wastewater, either during the process or when treating
wastewater represents a BAT recommendation for Surface Treatment of Metals and
Plastics 2006, to facilitate the recovery and reuse of substances, which is achieved at

the analysed company by industrial water treatment plants. (Wieszczycka K et all

2018)
BAT recommends the implementation of environmental management system and
related procedures. In this respect, there are procedures for systematically reviewing,
based on advances in the field, the raw materials used and suggestions of some more
appropriate material, having a lower impact on the environment. The company has
integrated the ISO 14001/2015 Environmental Management System.
According to BAT, the plant's facilities are continuously monitored on energy
consumption, water consumption and raw material consumption, which allows for
internal comparisons of monitored parameter values and for finding niches to reduce
consumption. The data is recorded and analysed periodically by the technical service
belonging to the analysed company.
According to BREF, generating free cyanide gas is avoided by separate storing of
acids and cyanides.
There are hoods for aerosol suction at basic degreasing baths, acid pickling,
activation, galvanizing plating.
Regarding compliance with BAT recommendations on efficient energy use, the
Romanian company achieves the following:
- periodic metering of energy (monthly and annual);
- optimization of energy consumption, use of closed water circulation
systems and verification of insulation status in pipelines and buildings;
- automation of technological processes;
- minimizing energy consumption of any type, maintaining and using the
best available techniques for energy efficiency.
BATs associated with emission values are projected for samples of daily mixes. The
emission levels associated with BAT are:
Spills in the public sewerage (PRC) or surface water

Parameter (AS) (mg/L)
Cr (VI) 0.1- 0.2
Cr total 0.1 – 2.0
Ni 0.2 – 2.0
Fe
F
Phosphate as P
COD
HC total
VOX
The company monitors effluents from the treatment plants and the results are
compared with values set by GD 188/2002 (with subsequent modifications), namely:
Total Cr – 1.5 mg/L; Cr VI - 0.2 mg/L; Ni - 1.0 mg/L; Cu - 0.2 mg/L; Zn - 1.0 mg/L.

Due to the fact that the analysed industrial platform is located on the Mures River
Valley, 1 km away from it, in a flat area without obvious dishevelment, it is very
unlikely that the studied site will affect the quality of Mures River. The only
evacuated technological waters are discharged into the city's sewerage network.
According to table 1, analysis results of waste water from the galvanizing line’s
treatment plant are presented and compared with the admissible limit value set by
Government Decision no. 188/2002 which includes NTPA-002/2002 normative
regarding the conditions for evacuation of waste water in city sewerage networks.
Table 1. Analysis of discharged water from the galvanizing line’s treatment plant
No. Analysed indicators Measure Concentration Analysis method /
unit values reference document
1. pH upH 6.4(23.5°C) SR ISO 10523/2012 PSL3 0510
2. Suspension matter mg/L <5.0 SR EN 872/2005
PSL3 05-13
3. Chemical oxygen mg/L 20.74 SR ISO 15705/2002
consumption (COD) PSL3 01-04
4. Biochemical oxygen mg/L 6.8 SR EN 1899-1/2003/
consumption (BOD5) PSL3 01-02
5. Nitrites (NO3-) mg/L 22.44 SR ISO 7890-3 / 2000
PSL 3 02-03
6. Phosphates ( PO43-) mg/L 2.013 SR EN ISO 6878 / 2005
PSL 3 02-04
7. Fluorides mg/L <0.02 SR ISO 10359-1 /2001
(electrochemical) PSL 3 03-14
8. Chlorides (CI ) mg/L 69.28 SR ISO 9297/2001 PSL3 05-02
9. Sulphates ( SO42-) mg/L 451.23 SUA Turbidimetric method
4500/1995
2+
10. Copper (Cu ) mg/L 0.11 STAS 7795-80;
SR ISO 8288:2001
11. Zinc (Zn2)2 mg/L 0.27 STAS 8314-87;
SR ISO 8288:2001
Analysis of water in the treatment plant (Table 1) indicate some comments.

For pH, the value obtained is 6.4 upH, 0.1 upH lower than the limit value (6.5 ÷ 8.5
upH), indicating that the water discharged into the sewage is slightly acidic.
Suspended matter has values below allowed limits, of less than 5.0 mg/L, indicating that
the treatment plant performs an efficient filtration of suspended matter.
Concentrations of oxidizable substances expressed as COD and BOD are well below
allowed limits, indicating that there are few organic substances that decompose oxygen in
the discharged water.
Concentrations of nitrates, phosphates, fluorides and chlorides are not standardized by
GD no 188/2002 (with subsequent modifications), but the values are not problematical.
The concentrations of sulphates are below maximum allowed limits, at about 75%.
Metal concentrations (Cu and Zn) are below the legal limits (maximum admissible limit
for Cu = 0.2 mg/L and for Zn = 1.0 mg/L)
In conclusion, water discharged from the galvanizing line’s treatment plant corresponds
qualitatively, regarding the load with analysed indicators, resulting that pollution by these
substances is insignificant.
The company under consideration falls under GD 188/2002 with subsequent
modifications, on wastewater drainage conditions in the city sewerage networks, but also
has to implement requirements of BATs.
The following shows the company’s manner of complying with BAT requirements
regarding waste water discharged into the sewerage network.

According to the Best Reference Document on Best Available Techniques for Surface
Treatment of Metals and Plastics 2006, the Environmental Management System is very
important, namely the environmental impact of the operation and eventual final
shutdown of the installation - the development and use of cleaner technologies when it is
feasible to regularly apply the sector-specific benchmarking system, including energy
efficiency and energy saving, water efficiency and saving, raw material consumption and
the choice of input materials, air emissions, water discharges and waste generation.
According to the Best Reference Document on Best Available Techniques for
Surface Treatment of Metals and Plastics 2006, the Environmental Management System
is very important, namely the environmental impact of the operation and possible final
shutdown of the installation - development and use of cleaner technologies when it is
feasible, to regularly apply the sector-specific benchmarking system, including energy
efficiency and energy saving, water efficiency and saving, raw material consumption and
the choice of input materials, air emissions, water discharges and waste generation.
It is also recommended to minimize the energy used to heat treatment solutions,
optimize air intake and space heating. This is achieved by the studied company.
According to BAT recommendations, the selection of raw materials should observe:
- the use of quality chemicals (high purity);
- maintaining a detailed inventory of materials used on site;
- systematic replacement of raw materials and use of new, appropriate one
having a low-impact on the environment.
The analysed company maintains a detailed inventory of materials used and the
manner they are used in technological processes.
According to (BAT - Surface Treatment of Metals and Plastics 2006), the amount of
water in the processes should be minimized by:
- monitoring all water and material consumption points within an installation,
- regular recording of consumption and control activity information;
- water recovery from rinsing solutions.
In table no. 2 is shows the most important BAT requirements and compliance type of the
unit.
Table 2. BAT requirements and company action

Characteristic requirement of BAT Answer
Confirm that a detailed inventory of raw YES company makes an inventory of raw
materials used on site is maintained? materials used on site
The monitoring of the environmental factors
Compliance with environmental
that are made on site is compared with the
protection legislation
provisions of the legislation in force
The plant within the company is
permanently monitored on energy
BAT is the continuous optimization consumption, water consumption and raw
of input consumption (raw materials material consumption, which makes it
and utilities) relative to the reference possible to compare the internal
values comparison of monitored parameter values
and to find consumption reduction niches.
Data is recorded by the technical service

Avoid contamination of soils and The galvanizing line has a retention tank to
waters by leakage or leakage of avoid infiltration into the ground in case of
chemicals accidental leakage
Avoiding or preventing the corrosion
The solution tank are made of corrosion-
of storage containers, pipework,
resistant material and periodically checked
delivery systems and control systems
for possible cracks or corrosion
by chemicals or corrosive fumes.
Reducing water consumption by
Within the Firm is implemented permanent
monitoring all water and material
monitoring of water consumption, for
consumption points within an
comparative analyses and for the
installation, regularly registering
environmental gestation system, and in the
consumption and control information.
technological process is used the
The information is used to perform
technological rinse by cascading rinse
comparative analyses and the
technique
environmental management system
Avoiding the need for rinsing
between activities by using
compatible chemicals (e.g., using the The system is fully automated, and there is
same acid pickling or activate the no need for rinsing between activities
surface prior to treating the acid
based coating).
The current company performs regular monitoring of water consumption and

performs periodic checking of pipelines and buildings insulation status.
In the technological process, the analysed company does not achieve water recovery
from rinsing solutions, and its use for other purposes (e.g., washing the yard). This
will be implemented in the near future.
Also, according to BAT requirements, the company aims to extend the service life
of solutions by keeping them within acceptable limits, by periodically filtering the
solution. (Figoli 2017).
Conclusions
The paper describes the current situation and highlights water pollutants and the level of
contamination as a result of the activity of the studied company, identifying the
possibility of producing a major impact on the environment during operation of the
galvanizing plant and if remediation works are needed. Reviews of previous and current
data of the land and of activities carried out on the site, in order to present the manner of
complying with requirements of prevention and mitigation of pollution according to
national legislation, as well as the alignment to the best available techniques BAT, were
mustered.
They were done measurements of water quality indicators discharged from the galvanizing
line’s treatment plant have been performed, showing that the discharged water frames
within GD 188/2002 with subsequent modifications (NTPA-002/2002 normative), thus
pollution by these substances is insignificant.
In addition to complying to national law, the company must also comply with requirements
of BATs. According to the 2006 Best Available Techniques for the Surface Treatment of
Metals and Plastics, the process water must be recycled and recovered, which is performed
at the analysed company by the industrial wastewater treatment plants.
According to BAT, the plant's facilities are continuously monitored on energy

consumption, water consumption and raw material consumption, which allows for
internal comparisons of monitored parameter values and for finding niches to reduce
consumption. Data is recorded and analysed periodically by the technical service
belonging to the analysed company.
A non-compliance with BAT requirements was that the company under review did
not achieve water recovery from rinsing solutions, and use for other purposes (e.g.,
washing the inner yard). This will be implemented in the near future.
This paper serves the competent environmental authority to identify data on the actual status
of the site and is a benchmark against the previous situation. Also, this paper will enable the
business owner to establish necessary steps to comply with the best available techniques in
the field. Consequently, the measures to be applied are general, regarding good
management, aiming at the supervision and maintenance of controlled levels of water
quality.
References
Figoli, A & Criscuoli A 2017 ‘Sustainable Membrane Technology for Water and
Wastewater Treatment’, Springer, Institute on membrane Technology
National Research Council of Italy, pp.7
Order 818/2003 completed by Ord.1158/2005 - for the approval of the Integrated
Environmental Authorization Procedure issued by the Ministry of
Agriculture, Forests, Water and the Environment, pp.3-5
SC EVALUARE IMPACT SRL 2016, Report to the Environmental Impact
Assessment Study generated by the project: ‘‘Installation of galvanizing
plating line and wastewater treatment plant in existing building’’, pp. 180-
186
The European IPPC Bureau M 2006 ‘Best Reference Document on Best Available
Techniques for the Surface Treatment of Metals and Plastics’, pp.100-205
Wieszczycka, K, Tylkowski, B & Staszak, K, ‘Metals in waters’ 2018, pp.143

WASTE MANAGEMENT SYSTEM IN ROMANIA – STATUS AND

DEVELOPMENT FOR BIOECONOMY
Steliana Rodino1, Marian Butu2*, Raluca Ion1
1
Bucharest University of Economic Studies, Piata Romana, nr 1, Bucharest, Romania,
steliana.rodino@yahoo.com
2
National Institute of Research and Development for Biological Sciences, Spl. Independentei,
nr 296, Bucharest, Romaina, *marian_butu@yahoo.com
Abstract
The waste management strategies released and applied in EU countries endeavor to
achieve the improvement of natural resources use and efficiency towards reducing
the air, water and soil pollution due to improper waste disposal or treatment.
This paper is a blueprint on waste generation and waste management Policies, Laws
and strategies existing in Romania compared to EU countries. According to
Directive 2008/98/EC Waste, is defined as “any substance or object which the
holder discards or intends or is required to discard”. One of the main principles of
waste management strategies is to be able to process the waste generated towards
reaching as up as possible the Waste Management Hierarchy.
From the circular economy concept point of view, the incorrect treatment of waste is
representing an important loss of resources, both in raw materials and energy and
therefore recycling and reuse should reach a superior level every year.
Keywords: bioeconomy,circular economy, Romania, waste management
Introduction
The general options for waste management and the re-circulation of solid waste and
waste streams is a challenging issue, due to the ambitious targets for increasing
recycling of waste.
Sustainable waste management systems in the context of resources efficiency is a
key subject included in a broader topic of sustainable consumption and production
in Europe. This topic is one of the 10 priorities highlighted in the Sustainable
Development Indicators (SDI), of great concert for the economic and social
development in European Union (Gavrilescu & Teodosiu 2016).
In this context, the EU Member States are obliged to ensure, by 2020, the recycling
of at least 50% of the municipal waste and 70% of the waste from construction.
(Parliament and European Council, 2008). The strategy was recently revised setting
even more ambitious targets, namely: 55 % to be achieved by 2025, 60 % by 2030
and 65 % by 2035.
The European Union waste management approach is based on the principles of
prevention, recycling and re-use, as well as the improvement of methods and
technologies for final disposal and monitoring.

In the same time, the worldwide rate of waste generation is increasing fast and based
on current prognosis it seems to be un-manageable to locate proper landfill sites
(Singh et al 2017).
According to Directive 2008/98/EC Waste, is defined as “any substance or object
which the holder discards or intends or is required to discard”. The waste
management strategies released and applied in EU countries endeavor to achieve the
improvement of natural resources use and efficiency towards reducing the air, water
and soil pollution due to improper waste disposal or treatment.
From the circular economy concept point of view, the incorrect treatment of waste is
representing an important loss of resources (Filho et al 2016), both in raw materials
and energy and therefore recycling and reuse should reach a superior level every
year.
For example, waste electrical and electronic equipment (WEEE) presents the most
rapidly increasing waste stream, with an annual growth rate of 4%). The estimated
amount for 2017 was about 72 million metric tons in the year 2017 (Balde et al
2015, Patahak et al 2017). Unfortunately, as the technology advancement did not
provide some practical solutions yet, the WEEE growth was not succeeded by the
same trend in their collection, recycling (Patahak et al 2017), or recovery of valuable
materials (Butu et al 2017).

The paper uses the bibliographical method to present an overview of waste
management policies in Romania compared to other EU states. Official statistical
data were withdrawn from Eurostat and Waste atlas.

European Legislative framework
Waste management strategies and the proposed targets to be achieved are set at the
EU level, comprising minimum set of requirements by categories of waste. The
priorities envisaged by the EU waste management legislative framework include the
disposal of waste, the energy recovery, recycling, reuse, and waste prevention
(Stoeva & Alriksson 2017).
The most relevant pieces of the EU legislative framework on waste include the
following:
 Directive 2008/98/EC on waste (Waste Framework Directive)
 Regulation (EC) No 1013/2006 of the European Parliament and of the
Council of 14 June 2006 on shipments of waste.
 Council Directive 1999/31/EC of 26 April 1999 on the landfill of
waste.
 Directive 2000/76/EC of the European Parliament and of the Council
of 4 December 2000 on the incineration of waste

Figure 1. The waste hierarchy as stated by Directive 2008/98/EC on waste
Other directives regarding waste management, by waste category are as follows:

Sewage sludge
Council Directive 86/278/EEC of 12 June 1986 on the protection of the
environment, and in particular of the soil, when sewage sludge is used in agriculture
End of life vehicles
Directive 2000/53/EC of the European Parliament and of the Council of 18
September 2000 on end-of life vehicles
Packaging and Packaging waste
European Parliament and Council Directive 94/62/EC of 20 December 1994 on
packaging and packaging waste
Waste electrical and electronic equipment
Directive 2012/19/UE of the European Parliament and of the Council on waste
electrical and electronic equipment (WEEE)
Batteries and accumulators and waste batteries and accumulators
Directive 2006/66/EC of the European Parliament and of the Council of 6
September 2006 on batteries and accumulators and waste batteries and accumulators
and repealing Directive 91/157/EEC.
Following the adoption of the circular economy action plan in 2015 and the creation
of a stakeholder platform in 2017, in 2017, the European Parliament adopted its
position on the review of the four key waste directives with more ambitious targets
and provisions compared to the Commission's proposals issued in 2016.
Therefore, in January 2018 was adopted a new package of measures, including
several connected initiatives, such as:
 the strategy on plastics,
 model to address the interactions and linkages between chemicals
legislation, products and waste,
 the updated report on critical raw materials,
 the framework for monitoring progress towards bioeconomy EIR
Romanian Legislative framework

The EU Directive on waste management was transposed in Romanian Legislation
by Law 211 from November 2011 regarding waste regime, with subsequent
amendments. The superior authorithy in charge is Ministry of Environment.
The National Environmental Protection Agency (Agentia Nationala pentru Protectia
Mediului - ANPM) is the central public administration specialized institution with
competence in the implementation of environmental protection policies and
legislation. It is responsible with data gathering and reporting to Ministry of
Environment and European Agencies for Environmental protection.
The National Environmental Guard (Garda Nationala de Mediu - GNM) controls
activities with an impact on the environment, and applies sanctions for
contravention provided by environmental legislation.
National Plan for waste management (Planul național de gestionare a deșeurilor –
pngd), was released in 2018, and aproved by government decision
942/20.12.2017. PNGD includes also the National Plan for Prevention of waste.
Other regulatation on waste management, transposing the EU Directives are
Transport and storage of waste
Decision 788/2007 regarding meadures for application of European Parliamnet
regulation and of European Council no 1013/2006 regarding shipment of waste with
corresponding additions and modifications.
Decision 1061/2008 regarding shipment of hazardous and non-hazardous waste on
Romanian teritory.
Landfill waste
Decision 349/2005 regarding landfill waste ensure that European requirements on
landfill waste, in terms of building operation, monitoring, closure and post-closing
follow-up of new deposits, as well as those existing (Brasoveanu 2012).
Decision 210/2007 was released for amending and supplementing certain acts
transposing the acquis communautaire in the field of environmental protection, as
amended and supplemented
Incineration of waste
Law 278/2013 regarding industrial emmisions with subsequent amendments,
includes the guidelines previously set by Decision 128/ 2002 regarding incineraion
of waste.
Sewage sludge
Order 344/708 from 2004 for the approval of technical norms regarding
environmental protection with a special highlight on soils when sewage sludge is
used in agriculture
Order 27/2007 was released for amending and supplementing certain acts
transposing the acquis communautaire in the field of environmental protection, as
amended and supplemented
End of life vehicles
Law no. 212/2015 on the management of new vehicles and end-of-life vehicles sets
out measures to prevent the generation of waste from end-of-life vehicles, re-use,

recycling and other forms of recovery of end-of-life vehicles and their components
to reduce waste disposal as well as environmental improvement of the activity of
economic operators involved in the life cycle of vehicles, in particular of economic
operators directly involved in the treatment of end-of-life vehicles.
Packaging and Packaging waste
Law 249/2015 regarding the management for packaging and Packaging waste,
repealed the Decision 621/ 2005 that initially transposed the EU directive packaging
and Packaging waste. This law regulates the management of packaging and
packaging waste in order to prevent or reduce the environmental impact. It lays
down measures aimed, as a matter of priority, on the prevention of the production of
packaging waste and, as additional fundamental principles, the re-use of packaging,
recycling and other forms of recovery of packaging waste and, consequently, the
reduction of the final disposal of such wastes.
Waste electrical and electronic equipment
Emergency Ordinanc. 5/2015 regarding WEEE (in romanian deșeurile de
echipamente electrice și electronice - DEEE)
This Emergency Ordinance sets out measures to protect the environment and public
health by preventing or reducing the negative effects of generating and managing
waste electrical and electronic equipment, referred to as WEEE (DEEE), by
reducing the overall impacts of resource use and improving the efficiency of the use
of these resources,
Batteries and accumulators and waste batteries and accumulators
Decision 1132/2008 aims to establish the requirements for the placing on the market
of batteries and accumulators and specific rules on the collection, treatment,
recycling and disposal of waste batteries and accumulators to complement
harmonized national legislation on waste and to promote a high level of collection
and recycling of waste batteries and accumulators and regulating the ban on the
placing on the market of batteries and accumulators containing dangerous
substances.
This Decision seeks to improve the environmental performance of batteries and
accumulators and the activities of all economic operators involved in the life cycle
of batteries and accumulators, namely manufacturers, distributors and end-users, and
in particular operators directly involved in the treatment operations and waste
recycling of batteries and accumulators.
Wastes from extractive industries
Decision 856/2008 establishes the legal framework for guidelines, measures and
procedures and to prevent or reduce, as far as possible, any adverse effects on the
environment, in particular water, air, soil, fauna, flora and landscapes, as well as any
health hazards to the population , resulting from waste management in the extractive
industries.
Waste generation and recycling in Romania vs European Countries

Annually, in the EU countries, is produced an average of aproximately 480 kg of
waste per capita. More detailed, according to official data, the amount of municipal

waste generated in EU countries, in 2017, ranges between 250kg per capita up to

almost 800 kg per capita.
The EU Member State with a collection rate of 100 % of waste is Germany,
although it has a large rate of production of waste, 50.5 million tonnes per year and
almost 620 kg per capita. However, Germany also has the second highest recycling
rate of 47%.
Romania produces 5.8 million tonnes of waste per year, averaging 272 kilograms
per year per capita and with a collection rate of only 82.3% (Figure 2).
Figure 2. Muncipal waste generation in EU countries vs average EU 28

*Eurostat data
In Romania is recyled only around 3% of generated waste, while Slovenia is the EU

Member State with the highest recycling rate of 55%, plus a 100% collection rate
(Figure 3). However, Slovenia produces aproximately 853.000 tonnes of waste per
year, with almost 470 kg per capita which is almost equal to european average of
487 kg per capita.
Therefore, there are member States who manage to achieve high recycling rates
while there are other countries that apply landfill processes, and Romania is one of
them.

Figure 3. Waste recycling rate in Europe
The environmental stress calculated for eastern European countries is presented in

figure 4. This indicator shows the concentration of Municipal solid waste (MSW) by
including the country's land area.
Figure 4. Waste environmnetal stress in Eastern European Countries

*data source http://www.atlas.d-waste.com/
Conclusions
The proper waste management and its transformation into a resource in Romania is
fully supported by the implementation of EU legislation this area. However, the
circular economy is still weakly developed in Romania. First of all, it is necessary to

increase awareness on selective collecting of waste, and to reach the targets of

regulatory framework in force.
Acknowledgements
This work was supported by a grant of the Ministry of Research and Innovation through
Program 1 - Development of the National R&D System, Subprogram 1.2 - Institutional
Performance - Projects for Excellence Financing in RDI, Contract no. 22PFE/2018 and
program NUCLEU 25N-19270104/2019.
References
Balde, CP, Wang F, Kuehr, R & Huisman J 2015, The global e-waste monitor–2014.
Bonn, Germany: United Nations University, IAS – SCYCLE; 2015
Brasoveanu, F 2012, 'Legal status of waste', Proceedings of 7th edition of the
International Conference European Integration - Realities and Perspectives,
pp. 332-336.
Butu, A, Rodino, S., Fidler, G & Butu, M 2018, 'Resources management and eco-
efficiency - Critical metals, an example', SGEM 2018 Conference
Proceedings, vol. 18, no. 42, pp. 167 – 173.
Filho, W L, Brandli, L, Moora, H, Kruopienė, J & Stenmarck, Å 2016,
'Benchmarking approaches and methods in the field of urban waste
management', Journal of Cleaner Production, vol 112, no. 5, pp. 4377-4386.
Gavrilescu, DC & Teodosiu, C 2016, 'An assessment of the Romanian solid waste
management system based on sustainable development indicators', Sustainable
Production and Consumption, DOI: 10.1016/j.spc.2016.07.004.
Pathak, P, Srivastava, R & Ojasvi, R 2017, 'Assessment of legislation and practices
for the sustainable management of waste electrical and electronic equipment in
India', Renewable and Sustainable Energy Reviews, vol. 78, pp. 220-232.
Singh, S, Ramakrishna, S & Gupta, M K 2017, 'Towards zero waste manufacturing:
A multidisciplinary review', Journal of Cleaner Production, vol. 168, pp.
1230–1243.
Stoeva, K & Alriksson, S, 2017, 'Influence of recycling programmes on waste
separation behavior', Waste Management, vol. 68, pp. 732–741.
*Directive 2008/98/EC
*http://www.atlas.d-waste.com
*https://eur-lex.europa.eu/

POLLUTION CONTROL AND MONITORING
Section Pollution Control and Monitoring 301

NEW TOOLS FOR ASSESSMENT OF WASTEWATER QUALITY. CASE

STUDY, ONE RURAL REGION FROM ROMANIA
Florinela Pirvu1,2, Liliana Cruceru1, Marcela Niculescu1, Jana Petre1, Vasile-Ion Iancu1, Luoana
Florentina Pascu1, Toma Galaon1
1
Podu Dambovitei Street, Sector 6, code 060652, Bucharest, florinela_pirvu@yahoo.com,
Romania
2
University Politehnica of Bucharest, 313 Splaiul Independentei Street, sector 6, code 060042
Bucharest, Romania
Abstract
Global population growth is associated with an increase in the amount of water used.
A consequence of this increase is the high amount of wastewater volume resulted,
which can affect ecosystems balance. For this reason, the authorities are forced to
account and improve wastewater treatment processes to minimize environmental
impact. The physical-chemical properties of the effluent are unique and depend on
the origin of the leakage, the sewer system infrastructure, the level of development
of the area, the climatic conditions, and hence the wastewater stream has a unique
composition of organic and inorganic loads.
For a quick and easy understanding of wastewater quality, two types of water quality
indices were developed. This study presents the results of a complex analytical
investigation of effluents discharged from six rural WWTP’s situated in southern
part of Romania compared with a simplified interpretation of wastewater quality by
using a pollution index (PI) and a wastewater quality index (WWQI). Data recorded
with a monthly frequency between 2013 and 2017 were used. Regarding the WWQI
values calculated in this study, all wastewater analysed from the six WWTP’s, fit to
the ‘Marginal’ Designation.
Keywords: pollution index, water quality index, wastewater
Introduction
The discharge of effluents resulting from wastewater treatment plants (WWTP) into
surface waters became a cause of concern at national level (Pirvu et al. 2018). The
main reason is that most part of surface waters are used as raw water for drinking
purposes (Stoica et al. 2016, Paun et al. 2016, Paun et al. 2017). For this reason,
effluent quality assessment is required.
Measuring physical-chemical and biological parameters and comparing results with
the limit values indicated in lows and regulations is a general approach to water
quality assessment (Sapkal & Valunjkar 2013). This approach is time-consuming
due to the assessment of the large number of measured indicators (Dede et al. 2017)
and requires knowledge in environmental pollution control for understanding the
significance of the results.
An easy and more simplified method that can be used to estimate water quality is
represented by water quality indices. Practically, water quality indices are tools to

estimate water quality by reducing the great number of parameters into a single
expression (Wisam et al 2018, Bharti & Katyal 2011) using an unitless number
(Paun, 2016). Using simple terms (e.g., Excellent, Good, Fair, Marginal, Poor) water
quality can be reported to management and to the public, in a consistent manner.The
main applications of such indices include evaluation of drinking water, surface water
and groundwater quality (Canadian environmental sustainability indicators, 2007).
Concerning effluent quality assessment few quality indices have been developed
because, for such types of indices, multiple parameters that affect wastewater quality
are basically required (Raut et al. 2017).
Two main types of water quality indices were used also for identification of
wastewater quality. First one, refers to a pollution index whose reference value is 1
(Akpoveta et al. 2011, Winifred & Ifedayo 2014) and the second one is a water
quality index (WQI) which is expressed as a numeric value ranging from 0 (Poor)
and 100 (Excellent) (CCME 2001, CCME 2005).
This study presents the results of a complex analytical investigation of effluents
discharged from some rural WWTP’s situated in southern part of Romania
compared with a simplified interpretation of wastewater quality by using a pollution
index and a wastewater quality index (WWQI).
Experimental Part
The effluents investigated in this study were collected from six wastewater treatment
plants (S1÷S6) situated in rural area from south part of Romania, with a monthly
frequency, between 2013 and 2017.
A complex analytical investigation was performed using different analytical
techniques like: molecular absorption spectrometry, atomic absorption spectrometry,
volumetric, gravimetric and electrochemical methods. From 23 parameters which
were initially investigated, according to NTPA 001 Norm, only 8 were selected for
estimation of effluents quality: pH, Suspended solids (SS), Total dissolved solids
(TDS), Chemical Oxygen Demand (COD), Bio-chemical Oxygen Demand (BOD5),
Ammonia (NH4+), Total oil and grace (TOG), Anionic surfactants (AS).
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.
Samples were collected in polythene or in glass bottles and preserved by acidulation
at pH <2 or by keeping them at 40C, in the dark, function of the type of indicators.
Two types of quality indices were used in the investigations:

Pollution Index
Pollution index (Pi) is expressed as a function of the concentration of individual
parameters against the baseline standard.
Pollution index (Pi) = Concentration/Standard
It provides information on the relative pollution of individual samples. The critical
value is 1.0, values greater than 1.0 indicate a significant degree of pollution, while
values less than 1.0 are not polluting (Winifred & Ifedayo 2014).
Wastewater Quality Index
The Canadian Water Quality Index (CCMEWQI) provides a comprehensive method
of calculating quality indices that has become an important tool for authorities to
assess the degree of wastewater pollution. The WWQI measures the scope,
frequency and amplitude of water quality and then combines the three measures into
a score. The higher the score, the better the water quality is.
The mathematical expression for the Canadian Council Index (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,
Amplitude (F3) = individual value for each test of the determined quality indicators,
the values of which exceed the maximum allowed by the legislation. (CCME 2001,
CCME 2005). 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)
Index
Designation Description
Value
All measurements are within objectives virtually all of
Excellent 95-100
the time
Good 80-94 Conditions rarely depart from natural or desirable levels
Conditions sometimes depart from natural or desirable
Fair 65-79
levels
Marginal 45-64 Conditions often depart from natural or desirable levels
Conditions usually depart from natural or desirable
Poor 0-44
level

An analytical investigation of physical-chemical parameters from effluents
discharged by wastewater treatment plants was performed. A number of 360
samples were collected over a 5-year period, starting from 2013. Initially 23
parameters were investigated from each sample, but only 8 of them, presenting an
evident impact on pollution, were selected in the study.
On the basis of annual average values, the descriptive statistics were evaluated as
mean, minimum, maximum and standard deviation (Table3).

Table 3. Basic statistics of physical - chemical variables for the wastewater

treatment plants effluents (during 2013–2017)
Parameters
Basic
WWTP COD BOD
statistics pH SS TDS NH4+ TOG AS
mg mg
mg/L mg/L mg/L mg/L mg/L mg/L
O2/L O2/L
Min 6.5 14.0 . 38.4 2.8 0.4 <20 0.1
Max 8.0 219.0 789.0 806.4 315.5 115.7 28.6 5.0
S1 Median 7.4 54.0 435.5 112.8 41.5 24.6 <20 0.7
SD 0.2 24.8 58.2 86.0 32.5 11.0 <20 0.6
Average 7.4 65.1 419.8 152.6 52.6 35.1 <20 0.9
Min 6.5 20.0 138.0 38.4 4.9 0.22 <20 0.1
Max 7.9 197.0 962.0 1036.8 377.7 106.8 25.2 5.4
S2 Median 7.4 54.0 104.8 105.6 36.7 23.8 <20 0.5
SD 0.1 19.3 59.2 130.2 48.3 13.5 <20 0.7
Average 7.4 61.5 410.8 171.2 37.5 34.7 <20 0.9
Min 6.1 24.0 246.0 38.4 1.8 0.1 <20 0.1
Max 8.1 159.0 717.0 230.0 52.5 45.0 25.6 1.8
S3 Median 7.4 48.0 415.0 84.0 22.6 8.7 <20 0.5
SD 0.2 11.9 38.1 26.7 3.7 3.8 <20 0.2
Average 7.4 51.1 399.1 76.8 21.7 13.3 <20 0.5
Min 6.8 18.1 190.0 38.4 2.0 0.1 <20 0.1
Max 7.9 144.0 664.0 259.2 91.6 58.81 25.2 2.5
S4 Median 7.5 38.0 307.5 168.0 34.3 19.7 <20 0.5
SD 0.1 12.6 32.0 29.9 6.0 4.3 <20 0.3
Average 7.4 44.1 323.5 152.5 35.4 21.0 <20 0.6
Min 6.5 12.0 327.0 6.7 2.4 0.02 <20 0.1
Max 38.0 88.0 1379.0 503.0 147.1 75.6 22.4 4.4
S5 Median 7.6 40.0 561.0 52.8 14.9 7.4 <20 0.4
SD 0.1 6.1 112.0 76.0 15.7 11.1 <20 0.6
Average 7.6 40.8 588.3 83.8 20 16.9 <20 0.5
Min 6.8 8.0 223.0 30 1.9 0.1 <20 0.1
Max 8.3 88.0 987 393.6 147.1 88.1 <20 1.6
S6 Median 7.6 36.0 394.5 69.6 11.0 7.1 <20 0.4
SD 0.1 6.5 82.4 64.0 15.9 10.6 <20 0.2
Average 7.6 38.2 468.6 76.0 17.0 16.4 <20 0.5
Where: S1, S2, S3, S4, S5, S6 are wastewater treatment plants
The analytical results were compared with the maximum addmisible values imposed
by NTPA-001 Quality Norm (Table 2).
Table 2. Maximum admissible values (MAV) according to NTPA-001 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
NH4+ mg/L 2(3)
TOG mg/L 20
AS mg/L 0.5
The Influence of pH. The pH value of the water has an important effect on the body,
health and diseases that can occur, because the human body consists of 50-60%
water. The fluids in our body must be in the pH range of 7-7.2. If the pH is less than
5.3, vitamin or mineral uptake is not possible. When the body pH drops below 6.4,
digestion does not take place properly. An acidic pH in the 1-4 range can cause
emotional stress, toxic overload or any process that disposed cells oxygen and other
nutrients. If the pH is greater than 11, it causes eyes irritation. (Santosh et al. 2008)
The results obtained for the pH are compared to the limits imposed by NTPA 001.
For S1 wastewater treatment plant the minimum pH value is 6.5 and the maximum
value is 8.0 with an average of 7.4 and an SD of 0.2, during 5 years of analytical
investigation. At the S2, S3 and S4 wastewater treatment plants, an average pH of
7.4 was recorded, while for the S5 and S6 stations the pH values ranged between 6.5
and 8.3.
The Influence of Suspended Solids (SS). Organic and inorganic solids suspended in
the wastewater are usually measured by filtration and normally are removed during
the treatment process. In the case of solid suspensions, the average concentration for
the six wastewater treatment plants are: S1 = 65.1 mg/ L ± 24.8 (SD); S2 = 61.5
mg/L ± 19.3 (SD); S3 = 51.1 mg/L ± 11.9 (SD); S4 = 44.1 mg/L ± 12.6 (SD); S5 =
40.8mg/L ± 6.1(SD); S6 = 38.2 mg /L± 6.5(SD).
The influence of Dissolved Solids (TDS). Total dissolved solids or filterable residue
include salts and organic residues. Wastewater treatment plants S1 and S2 have the
same TDS minimum value of 138 mg/L. A maximum of TDS values is observed in
S5 wastewater treatment plant, 1379 mg/L. This can be correlated with an increase
contribution of TDS by upstream discharges.
The Influence of Chemical Oxygen Demand (COD). Natural waters contain
dissolved oxygen concentrations depending on altitude, salinity and water
temperature. COD is the factor that determines whether chemical changes are
brought by aerobic or anaerobic organisms. Thus, the measurement of COD is vital
for maintaining aerobic treatment processes for domestic and industrial wastewater
treatment (Santosh et al. 2008).
The values recorded in this study are between 138 mg O2/L and 1379 mg O2/L for
stations S1, respectively S5. The maximum of this recorded indicator exceeds 11
times the maximum admissible value of NTPA 001.
The Influence of Bio-Chemical Oxygen Demand (BOD). Biochemical oxygen
demand (BOD) determines the oxygen concentration needed to stabilize domestic
and industrial waste. The maximum values obtained for the BOD for the 6
wastewater treatment plants are as follows: S3 with the lowest value of 52.5
mgO2/L, followed by S4 with a maximum concentration of 91.6 mg O 2/L, the
stations S5 and S6 have the same value of the maximum concentration of 147.1
mgO2/L, the station S1 with a maximum concentration of 315.5 mg O2/L and the
highest value was recorded for station S6, 377.7 mg O2/L, which exceeds 15 times
the maximum admissible limit of NTPA 001.
The Influence of Ammonia (NH4+). In the wastewater treatment plants, the nitrogen
compound is found mainly as ammonium and comes from two sources: the influent
and the anaerobic digestion fluid returned from the treatment used in the treatment
plants (Yiwen et al. 2019).
In this case the highest ammonia concentration values were recorded in this order:
115.7 mg/l (S1) > 106.8 mg/L (S2) > 88.1 mg/L (S6) > 75.6 mg/L (S5) 58.8 mg/l
(S4) > 45.0 mg/L (S3). It can be noticed that in case of S1 station the ammonium
concentration exceeds 57 times the maximum admissible limit of NTPA 001.
This general approach for assessment of wastewater quality proved to be time-
consuming due to the assessment of the large number of measured indicators and the
correlation with the limits imposed by the environmental legislation. The conclusion
of this evaluation is clear for specialists in environmental pollution control but less
understandable for population that cannot interpret the significance of the results.
In this study two simplified methods to estimate wastewater quality, based on water
quality indices, were tested. The pollution index (PI) and the wastewater quality
index (WWQI) were calculated using the same results obtained from the analytical
investigation performed during 5 years in some rural wastewater treatment plants
from south part of Romania. The Pollution index (PI) for the 8 tested parameters is
presented in Figures 1÷6. Parameters having PI values greater than 1 indicate a
significant degree of pollution.
Figure 1. Pollution Index - Figure 2. Pollution Index – Figure 3. Pollution Index

Suspended Solids Chemical Oxigen Demand –Bio-Chemical Oxigen
Demand
Figure 4. Pollution Index Figure 5. Pollution Index - Figure 6. Pollution Index

–Ammonia Total Oil and Grace –Anionic Surfactants
The highest values of the pollution index (PI) were obtained in the order:
NH4+ > COD > SS> BOD5> TOG > AS
The quality of effluents from six wastewater treatment plants in a rural area in
southern Romania was also assessed using the wastewater quality index (WWQI)
The index values and the designation for each sampling point are presented in Table
3.

Table 3. Values of water quality sub-index and index calculated for each sampling
point
Sampling point F1 F2 nse F3 Index Value Designation
S1 75.00 44.80 2.284 9.49 49.26 Marginal
S2 75.00 43.09 7.460 9.77 49.74 Marginal
S3 75.00 28.13 0.651 8.59 53.48 Marginal
S4 75.00 35.00 1.344 9.22 51.91 Marginal
S5 75.00 19.23 0.861 8.88 55.00 Marginal
S6 62.50 17.82 0.779 8.78 62.11 Marginal
The calculated index for all effluents corresponds to the marginal designation, which
means that the values of the 8 determined parameters often exceed the limits
imposed by NTPA 001 Norm.
The results offered by the water quality indices are well corelated with that one
offered by the classical investigation of the pollution level of water effluents. The
advantage of using quality indices in wastewater characterisation consists in the
simplified mode of reporting the results to management and to the public.
Conclusions
The level of parameter concentrations from six wastewater treatment plants from a
rural area in southern Romania were assessed. For this, a classical approach based
on analytical investigation and comparison of the results with limits imposed by
legislation and a modern one, based on water quality indices estimation, were used.
The both approaches indicated an increased level of NH4+, COD, SS, BOD
especially in effluents tested from S1 and S2 treatment plants. For all effluents, the
calculated index corresponds to the marginal designation, which means that the
values of the determined parameters often exceed the limits imposed by NTPA 001
Norm. The wastewater quality indices assessment provides us with information on
effluent treatment efficiency, effluent quality and rapid assessment if it is
appropriate for the final destination.
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Environment International, vol. 123 pp. 10-19.

PCB CONGENERS OCCURRENCE IN SEWAGE SLUDGE FROM

MUNICIPAL WASTEWATER TREATMENT PLANTS IN ROMANIA
Alina Tatarus, Diana Puiu, Roxana Scutariu, Marius Simion, Marcela Antoaneta Niculescu,
Toma Galaon
Podul Dambovitei Street, code 060652, Bucharest, alina.tatarus@yahoo.com, Romania
Abstract
Sewage sludges originating from waste water treatment plants (WWTP) act as a sink
for various contaminants including polychlorinated biphenyls (PCBs). The fate of
organochlorine compounds in sewage sludge is shaped by their physical-chemical
properties and by environmental conditions. The high persistence of
polychlorobiphenyls (PCBs) in sewage sludge is given by an extremely reduced
degradation rate which varies from months to years (the half-life of PCB 28 is 10.9
years, and PCB 52, 11.2 years). Due to their increased hydrophobicity, these
carcinogenic compounds can be easily uptake by plants and transferred to the food
chain. The present study investigated the occurrence of these seven PCB congeners
in sewage sludge sampled from municipal waste water treatment plants from
different geographical areas in Romania for a two-year period (2018 and 2019). For
the analyzed PCB congeners a database was created concerning their occurrence
levels in sewage sludge from these WWTPs. A total number of 62 sewage sludge
samples were collected from different WWTPs between 2018-2019 and analyzed for
PCB congener content using a validated GC-ECD method according to SR EN
16167/2013. In all the samples that were analyzed in this study the sum of PCB
congeners was situated below the maximum allowable concentration (MAC = 0.8
mg/kg d.w.) stated by the Order 708/2004.
Keywords: PCB congeners, municipal waste water treatment plants, sewage

sludge, Romania
Introduction
Sewage sludge constitutes a threat to the environment due to its utilization in
agriculture. As opposed to its useful fertilizing properties, the hydrophobic character
of sewage sludge allows adsorption of various pollutants, mainly heavy metals,
pathogens and harmful organic compounds (Oleszczuk 2007), which are associated
with a potential danger to the environment. The content of PCB congeners in sewage
sludge is closely related to the presence of polychlorinated biphenyls in wastewater
and it depends on the wastewater type and the share of industrial wastewater and
rainwater. The source of PCBs in sewage is mostly liquid waste, e.g., transformer
oils or dielectric fluids and run-off from urban catchments, which contain organic
substances originating from combustion processes. Due to poor water solubility of
PCB, these compounds are prone to adsorption on solid phases like sewage sludge
(Gong et al 1998). One of the criteria for assessing the PCB sorption properties is

the hydrophobicity coefficient (log Pow), the more chlorine atoms are in the biphenyl
molecule, the greater the log Pow value. The concentration of PCB in sewage sludge
can vary over a wide range from trace values up to 10 mg kg−1 dry weight (d.w.).
The first reports on the occurrence of PCB in sewage sludge came from the United
Kingdom in 1942. Investigation on these micropollutants was carried out before it
was stated that PCB are compounds noxious to the environment (Wild et al 1990).
Since then a lot of data on PCB content in sewage sludge was collected, mainly in
Spain (Aparicio et al 2009, Eljarrat et al 2003), Germany (Umlauf et al 2011),
Greece (Katsoyiannis & Samara 2011, Mantis et al 2005), Italy (Lazzari et al 2000),
Great Britain (Stevens et al 2001), United States (Harrison et al 2006), Australia
(Clarke et al 2008) and Poland (Sułkowski & Rosińska 1999). During the sludge
stabilization a reduction in organic matter and pathogen organism amount is
obtained, and their hydration increases. Biochemical stabilization, aerobic or
anaerobic type, is the most frequently used processes. It has been shown that during
these processes changes in PCB content in sludge occur, which result from their
transformations and lead to reduction in PCB toxicity (Patureau & Trably 2006).
Some PCBs called dioxin-like congeners are carcinogenic to humans, while others
induce neurotoxicity and are endocrine disruptors, and their production is banned
(Borja et al. 2005). Despite this, PCB congeners are still identified in environment as
secondary products resulted from waste incineration or from industry. The organic
contaminants are being removed from soils by physical-chemical technologies or by
bioremediation processes which can follow 3 routes: by transferring in other
environment compartment (through volatilization, water run-off or by up taking into
the plants through the roots), by abiotic degradation processes like oxidation,
dehalogenation, dehydrogenation, or by biotic degradation. The hydrophobic nature
of PCBs immobilizes the compounds on the soil surface, but organic acids and
plant-derived sugars act as a surfactant, which favours the uptake of PCBs into plant
tissue or their biodegradation (James et al 2008, Puiu et al 2018). The presence of
pesticides in water sources, soil and sewage sludge is becoming a preoccupation in
drinking water production, waste water treatment, and water reuse applications due
to potential adverse health effects associated with these compounds (Scutariu et al
2018). The application of sewage sludge as a fertilizer for agricultural site can cause
health risks by infesting the soil and groundwater with PCBs, heavy metals,
pathogens and viruses. These issues have generated a special interest in another
elimination alternative, one of which is the combustion of sewage sludge
(Serbanescu et al 2018). The present study aims to assess the occurrence and spatial
distribution of PCBs in sewage sludge from municipal waste water treatment plants
from various locations in Romania. The data on concentration of PCBs in WWTP
sewage sludge will be used to show the geographical and temporal distribution of
these pollutants in Romania.
Experimental part
Equipments
All analyses were carried out using an Agilent 7890A gas chromatograph with an
electron capture detector (GC-ECD). SSL inlet was kept at 280°C and was used in
Pulsed-split mode with a split ratio of 5:1. 1 µL of final extract sample was injected
onto a fused-silica capillary column, HP-5MS (60 m, 0.25 mm I.D., 0.25 µm f.d.),
coated with 5% phenyl and 95% dimethylsiloxane at a 1.2 mL/min flow-rate (He
6.0). The oven temperature program started from 50°C (held 1 min), increased with
20 °C/min rate to 180°C (held 0.5 min), then increased with 10°C/min to 240°C
(held for 4 min), then step-up to 300°C by ramp of 14 °C/min and held 9.5 min. The
analytes were monitored by maintaining the ECD detector at 350°C.
Sample preparation
During a two-year period, a number of 30 sewage sludge samples (2018), and
respectively 32 sewage sludge samples (2019) were collected from different waste
water treatment plants (WWTP) located in Romania. All the samples were analyzed
to quantify PCB congeners, namely PCB 28, 52, 101, 118, 138, 153 and 180 using
the standardized method described in SR EN 16167/2013.
One of the least found PCB congener (PCB 209) was used as internal standard in the
analysis of PCB congeners. The samples were extracted with hexane and acetone;
the extracts were dried with anhydrous sodium sulfate. Due to the complex matrix of
sewage sludge (numerous interferent hydro and liposoluble chemical compounds),
sample clean-up was compulsory. This was achieved by passing 10 mL of sample
extract through a purification column (alumina, 3 g). The purification through
alumina gave best results, higher recoveries and less interference resulted from the
complex organic compound sewage sludge matrix.

The objective of the present study was to establish the contamination degree with
PCB congeners of municipal WWTP sewage sludge from different locations in
Romania. In order to accomplish this 30 sewage sludge samples have been analyzed
in 2018 and 32 sludge samples in 2019. The investigated municipal waste water
treatment plants were from the following cities: Petrobrazi, Satu Mare, Carei,
Tulcea, Campulung Muscel, Bucuresti, Vaslui, Botosani, Sf. Gheorghe, Tg.
Secuiesc, Calafat, Filiasi, Facai, Carei, Petrosani, Bacau and Arad.
In all the analyzed samples, during 2018 and 2019, the sum of PCB congeners was
situated below the maximum allowable concentration (MAC = 0.8 mg/kg d.w.)
stated by the Order 708/2004. Despite this, in 2018, some PCB congeners from
sewage sludge from waste water treatment plants were above the limit of
quantitation (LOQ <0.01 mg/kg d.w.): Petrobrazi-Prahova (PCB 52, 138, 180), Satu
Mare (PCB 52, 153), Trusesti-Botosani (PCB 53) and Bucuresti (PCB 153, 180,
138), (Figures 2a, 2b, 2c, 2d). In 2019, values higher than the LOQ (< 0.01 mg/kg
d.w.) were recorded for the waste water treatment plants in: Tg. Secuiesc-Covasna
(PCB 153), Sf. Gheorghe-Covasna (PCB 180), Bolintin Vale-Arad (PCB 153, 118),
Arad (PCB 118, 153, 138, 180), Pecica-Arad (PCB 118, 153, 180), Lipova-Arad
(PCB 118, 138, 180), Ineu-Arad (PCB 153) and Bacau areas (PCB 28, 52, 153,
101), (Figures 3a, 3b, 3c, 3d). Results obtained from the monitoring study are
presented in the following tables and figures.

Figure 1. Representative chromatogram of a 10 µg/L PCB congeners standard

mixture (PCB 28, 52, 101, 118, 138, 153 and 180).
Table 1. The sum PCB congeners levels in sewage sludge from municipal WWTPs
from different locations in Romania in 2018
LOCATION WWTP PETROBRAZI, PRAHOVA
SAMPLE CODE PH1 PH2 PH3 PH4 PH5
SUM OF PCBs
0.100 <0.01 <0.01 <0.01 0.039
(mg/kg d.w.)
LOCATION WWTP VASLUI
SAMPLE CODE VS1 VS2 VS3 VS4 VS5
SUM OF PCBs
<0.01 <0.01 <0.01 <0.01 <0.01
(mg/kg d.w.)
LOCATION WWTP BOTOSANI
SAMPLE CODE BT1 BT2 BT3 BT4 BT5
SUM OF PCBs
<0.01 <0.01 <0.01 <0.01 <0.01
(mg/kg d.w.)
LOCATION WWTP CRAIOVA WWTP TULCEA
SAMPLE CODE CR1 CR2 CR3 TL TL
SUM OF PCBs
<0.01 <0.01 <0.01 <0.01 <0.01
(mg/kg d.w.)
LOCATION WWTP SATU MARE WWTP SF GHEORGHE
SAMPLE CODE SM SM SG1 SG1
SUM OF PCBs
0.012 0.016 <0.01 <0.01
(mg/kg d.w.)
WWTP
LOCATION WWTP BUCHAREST WWTP CAREI
CONSTANTA
SAMPLE CODE B1 B2 C1 CO
SUM OF PCBs
0.041 0.022 <0.01 <0.01
(mg/kg d.w.)
WWTP CAMPULUNG WWTP DANUTONI,
LOCATION
MUSCEL HUNEDOARA
SAMPLE CODE CM D1
SUM OF PCBs
<0.01 <0.01
(mg/kg d.w.)

Table 2. The sum of PCB congeners levels in sewage sludge from municipal
WWTPs from different locations in Romania in 2019
LOCATION WWTP BACAU
SAMPLE
BC1 BC2 BC3 BC4 BC5 BC6 BC7
CODE
SUM OF PCBs
<0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01
(mg/kg d.w.)
SAMPLE
CODE
SUM OF PCBs
<0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01
(mg/kg d.w.)
SAMPLE
CODE
SUM OF PCBs
0.052 <0.01 <0.01 <0.01 <0.01 <0.01 0.021
(mg/kg d.w.)
WW WWT
WWTP WWTP P P
LOCATION WWTP ARAD
INEU DEZNA PECI LIPO
CA VA
SAMPLE
A1 A2 I D P L
CODE
SUM OF PCBs 0.054
0.104 0.014 0.015 <0.01 0.055
(mg/kg d.w.)
WWT
WWTP
P WWTP WWTP
LOCATION SANT
PANC BOLINTIN VALE COVASNA
ANA
OTA
SAMPLE
S PA BVA TS SG
CODE
SUM OF PCBs 0.060
<0.01 <0.01 0.094 <0.01
(mg/kg d.w.)
2a 2b
2c 2d
Figure 2. The graphics of the variation during 2018 monitoring study of PCB
congeners: PCB 153 (a), PCB 180 (b), PCB 52 (c), and PCB 138 (d), concentrations
which are higher than the LOQ method 0.01 mg/kg d.w.
3a 3b
3c 3d
Figure 3. The graphics of the variation during 2018 monitoring study of PCB
congeners: PCB 153 (a), PCB 180 (b), PCB 118 (c), PCB 28, PCB 52, PCB 101 and
PCB 138 (d), concentrations which are higher than the LOQ method 0.01 mg/kg
d.w.
From the available data, PCB 153 was remarked to be the most abundant in
contaminated sewage sludge samples (64% in 2019 and 53% in 2018), followed by
PCB 118 (45% in 2019), PCB 180 (45% in 2019 an 43% in 2018), PCB 52 (29% in
2018), while the lower chlorinated PCBs as PCB 138 (18% in 2019 and 29% in
2018), PCB 28 and PCB 101 were detected in lower amounts (9% in 2019).
Conclusions
PCBs are a category of highly toxic compounds affecting both human and animal
organisms. These pollutants can easily bio accumulate and enter the food chain, due
to their persistence in various terrestrial and aquatic ecosystems (soil, water) and due
to increased hydrophobicity.
The present study aims to assess the occurrence and spatial distribution of PCBs in
sewage sludge from several locations in Romania. In all the samples that were
analyzed in this study the sum of PCB congeners was situated below the maximum
allowable concentration (MAC = 0.8 mg/kg d.w.) stated by the Order 708/2004.
Following the monitoring of sewage sludge from municipal WWTP from different
geographical regions in Romania several conclusions can be emphasized.
Although there were no exceedances of the PCB MAC value (0.8 mg/kg) in any of
the monitored WWTPs, there were several locations for which PCB congeners were
detected in amounts higher than method LOQ (0.01 mg/kg d.w.). The highest values
of PCB congeners sum were observed for Petrobrazi (0.100 mg/kg d.w.) and Arad
(0.104 mg/kg d.w.) waste water treatment plants. From all available data obtained
during the monitoring interval (2018-2019), the PCB 153 congener was remarked to
be the most abundant in sewage sludge samples, followed by PCB 118 and PCB
180, while the lower chlorinated PCBs (PCB 28, PCB 52 and PCB 101) were
detected in smaller amounts. In 2019, PCB 153 was present in a concentration of

64% in 11 samples with values above the LOQ, PCB 180 in 45%, PCB 118 in 45%,
PCB 138 in 18% and PCB 28, PCB 52 and PCB 101 in 9% of the samples. In 2018,
in 7 samples analyzed with values above the LOQ were found PCB 153 in 57%,
PCB 180 in 43%, PCB 138 and PCB 52 in 29% of the samples. For the rest of the
samples which represent a percentage of 71%, there wasn’t detected a contamination
with article indicated PCBs.
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SIMULTANEOUS DETERMINATION OF PROCAINE

HYDROCHLORIDE, PROCAINAMIDE HYDROCHLORIDE AND
LIDOCAINE BY MOLECULAR ABSORPTION SPECTROMETRY
Nicoleta Mirela Marin, Gheorghe Batrinescu, Mihai Nita-Lazar, Luoana Florentina Pascu,
Carol Blaziu Lehr
National Research and Development Institute for Industrial Ecology, Drumul Podu Dambovitei
no 71-73, Bucharest, nicoleta_mirela02@yahoo.com, Romania
Abstract
Two spectrometric methods have been developed for quantitative simultaneous
determination of procaine hydrochloride (PH·HCl), procainamide hydrochloride
(PHA·HCl) and lidocaine (Lid) from synthetic mixture. The methods employed are
first derivative spectrometry, using zero crossing method and multicomponent
analysis which is based on the additivity law. Using first derivative spectrometry,
the wavelength selected for the quantitative determination of PH·HCl was 237 nm
for Lid was 242 nm and for PHA·HCl was 290 nm in mixture. The method is linear
when the concentration ranged between 6.62-9.93 µg/mL for PH·HCl, 6.43-9.64 for
PHA·HCl and 5.56-8.35 for Lid. The multicomponent analysis is a direct method
and involves the absorbance measurements of at three different wavelengths. The
molar absorption coefficients values were calculated at each wavelength and the
concentration of PH·HCl, PHA·HCl and Lid from mixture was determined by
solving matrix using Cramer's rule. The recovery of each compound in mixture was
calculated and it is 101.4 % for PH·HCl, 100.4 % for PHA·HCl and 98.4 % for Lid.
Keywords: first derivative spectrometry, multicomponent analysis, procaine

hydrochloride, procainamide hydrochloride, lidocaine
Introduction
Procaine hydrochloride (PH·HCl), procainamide hydrochloride (PHA·HCl) and
lidocaine (Lid) are chemicals compounds with local anesthetics properties. Those
compounds can be divided into two groups: the amino-amides (PHA∙HCl) and
amino-esters (Lid and PH∙HCl). The PH∙HCl (2-diethyaminoethyl-4-amino benzoate
hydrochloride) is the active substance in Romanian medical products Gerovital H 3
and Aslavital, used in anti-aging treatments. PHA∙HCl (4-amino-N-(2-
diethylaminoethyl) benzamide hydrochloride) is an antiarrhythmic drug used to treat
ventricular arrhythmias. Lidocaine (4-amino-N-(2-diethylaminoethyl) benzamide) is
a local anesthetic widely used for major pain during epidural, peripheral and central
spinal anesthesia (Qin et al. 2010; Quiroz et al. 2019; Kumar et al. 2012). In spite of
the fact that numerous methods, such as UV-VIS (Tamarh et al. 2012; Kumar et al.
2012), RP- HPLC (Qin et al. 2010; Lian et al. 2019; Jadac et al. 2012) and LC-
MS/MS (Manna et al. 2019; Lian et al. 2019) have been reported to determine these
compounds. The aim of this article was to develop two simple, rapid, accurate and
precise methods for simultaneous quantitative determination of PH·HCl, PHA·HCl
and Lid from the synthetic mixture. The chemical structure of those compose are
presented in Figure 1.
Lidocaine
Procaine Procainamide
hydrochloride hydrochloride
Figure 1. Structures of PH·HCl, PHA·HCl and Lid

Chemicals
All chemicals and solvents used in this study have the analytical grades. The
PH∙HCl (99%), PHA∙HCl (99%) and Lid (97.5%) were purchased from Across
Organics Company and the methanol was obtained from Sigma-Aldrich.
Apparatus
The measurements were carried out using a Jasco V 530 double beam spectrometer
coupled to a PC computer, running the Jasco software. All spectra measurements
have been made in quartz cells of 1 cm path-length. The spectra were recording for
wavelengths in range of 200-400 nm at a scanning speed of 100 nm∙min-1. Microsoft
office excel 2007 was used for linear regression analysis.
Stock solution and working solutions
The stock solutions of 1 mM were obtained by dissolving the suitable quantity of
procaine hydrochloride, procainamide hydrochloride or lidocaine in 5 mL methanol
then filled up to 25 mL in volumetric flask mark with distilled water.
Working solutions The 0.04 mM working solution were prepared from a volume of
1mL stock solution of PH∙HCl, PHA∙HCl or Lid in 25 mL volumetric flask. For
validation method have been prepared different solution by diluting the stock
solution in distilled water.
Mixture solution A volume of 1 mL from 1mM stock solution of each compound
was quantitatively transferred in 25 mL volumetric flask and filled up to mark with
distilled water.
Procedures
The UV spectra of all the solutions are recorded in the range of 200-400 nm. The
zero order spectra of each solution was detected against a blank solution which did
not contain the studied compounds. First derivative spectrum has been obtained
using the Jasco software.

The quantitative determination of organic compounds with whose structure ensures
the existence of UV-VIS spectrum is easy to measure if is only one species in the
mixture. In addition, if the sample to be analyzed contains several organic
compounds and whose spectra is overlaped, depending on their structure, specific
method called derived spectrometry (Badea et al. 2002; Badea & Vladescu 2015;

Moldovan & Alexandrescu 2004; Zimmer & Czarnecki 2010) or multicomponent

analysis can be developed to detected of them.
In our experiment the absorption spectra of PH·HCl (11.04 µg/mL), PHA·HCl
(10.72 µg/mL) and Lid (9.28 µg/mL) as well as their mixture (11.04 - 10.72 - 9.28
µg/mL) showed a high degree of overlapping in the range of 200-350 nm which
made impossible to simultaneously determinate the PH·HCl, PHA·HCl and Lid
(Figure 2).
This issue of quantification the PH·HCl, PHA·HCl and Lid was solved by using the
first derivative spectrometry (Figure 3). The results showed that at 237 and 279 nm,
242 and 290 nm or 258 and 284 nm the derivative signals of the PHA·HCl, PH·HCl
and Lid passed through zero. Therefore, based on zero crossing first derivative
spectrometry principle at 242 nm, 290 nm and 237 nm were selected the optimum
working wavelengths for the quantitative determination of Lid, PHA·HCl and
PH·HCl from the mixture without the need of prior separation before analysis.
Figure 2. Absorption spectra of: 1. PH·HCl (11.04 µg/mL), 2. PHA·HCl (10.72

µg/mL), 3. Lid (9.28 µg/mL) and 4. mixture of PH∙HCl, PHA·HCl and Lid (11.04 -
10.72 - 9.28 µg/mL)
Validation of the derivative method

The first derivative method developed in this study was validated in accordance with
ICH guideline. Therefore, the validation steps were linearity, limits of detection and
quantification, accuracy and precision (Badea et al. 2012, Cruceru et al. 2011, ICH
Q2(R1) 2015).
The linearity of method was verified on five working solutions prepared for every
compound. The concentrations of working solutions were ranged from 6.62-9.93
µg/mL for PH·HCl, 6.43-9.64 µg/mL for PHA·HCl and 5.56-8.35 µg/mL for Lid.
The parameters of linearity showed that the intercept values are small and the
correlation coefficient is close to one for all the studied compounds (Table 1) which
suggests can the Lambert Beer law is verified.

Figure 3. First derivative spectra of 1. PH·HCl (11.04 µg/mL), 2. PHA·HCl (10.72

µg/mL), 3. Lid (9.28 µg/mL)
Table 1. Results obtained for linearity, LOD and LOQ studies
Linearity
Regression LOD LOQ Λ
Compound range R2
equations µg/mL µg/mL nm
(µg/mL)
y=0.0018x +
PH·HCl 6.62-9.93 0.9975 0.01 0.06 231
0.0004
y=0.0020x +
PHA·HCl 6.43-9.64 0.9961 0.01 0.04 302
0.0015
y=0.0002x +
Lid 5.56-8.35 0.9955 0.07 2.78 274
0.0001
Detection and quantification limits were established as 3:1 and 10:1 signal to noise
ratio. The LODs and LOQs determined and are presented in Table 1.
Accuracy has been determined by calculating the recovery of PH·HCl, PHA·HCl
and Lid from stock solutions. For this purpose different solutions have been
prepared in triplicate at three levels of concentration, covering the range 80%, 100%
and 120%. Results determined from experimental studies are shown in Table 2.
Retrieval yields were ranged between 99.4 and 101% results that corresponds to the
criterion for this validation parameter.
The precision was estimated by repeatability and intermediate precision which is
evaluated by determination of the relative standard deviation (RSD, %). The results
are presented in Table 3. The RSD values calculated are less than 2% for each
compound.

Table 2. Results obtained for accuracy

Compound Conc. Added Found1 Recovery1 Average RSD
range (µg/mL) (µg/mL) [% ± sd] recovery1 %
(µg/mL)
PH·HCl 80% 6.62 6.675±0.008 100.8±0.115
100% 8.28 8.311±0.007 100.4±0.083 100.8 0.384
120% 9.93 10.049±0.015 101.1±0.148
PHA·HCl 80% 6.43 6.568±0.011 102±0.017
100% 8.04 7.942±0.038 98.8±0.474 100.5 1.619
120% 9.64 9.722±0.010 101±0.107
Lid 80% 5.56 5.504±0.016 99±0.291
100% 6.96 6.891±0.030 99±0.428 99.4 0.706
120% 8.35 8.368±0.045 100.2±0.541
1each result represents mean calculated for three determinations ± standard deviation
Table 3. Values of precision calculated

Compound Added Found Found RSD%
(µg·mL-1) intraday 1 interday 1 Intraday Interday
(µg·mL-1) (µg·mL-1) (after one day)
PH·HCl 8.28 8.366 8.333 0.28 0.29
PHA·HCl 8.04 8.001 8.005 0.14 0.26
Lid 6.96 6.932 6.955 0.74 0.66
1each result represents mean calculated for six determinations
Multicomponent analysis using molecular absorption spectrometry in visible range

The present paper used the performances of multicomponent analysis can involve to
solving n equations and n unknown systems, but in the same time the choosing
adequate of wavelengths to determined accurate experimental results (Samah et al
2016).
Development of the multicomponent method in this study, the additivity law is
employed for quantitative simultaneous determination of PH·HCl, PHA·HCl and
Lid in the mixture. In order to calculate the concentration of these compounds, a
mathematical system equal to the number of analytes was employed, and in
consequence we have three equations. The matrix methodology was used to solve
the system of equations with three unknowns and Cramer's rule have been involved
to the matrix developed. The result obtained represents the concentration of
PH·HCl, PHA·HCl and Lid from the mixture. The absorption spectra of these
compounds and their mixture were presented in Figure 1. The measurement of
absorbances was carried out at three different wavelengths of 222 nm (λmax of
PH·HCl), 217 nm (λmax of PAH·HCl) and 216 nm (λmax of Lid) and the molar
absorption coefficient values were calculated. The found concentrations of PH·HCl,
PHA·HCl and Lid obtained by solving the equations system is illustrated in Table 4.
Moreover, the recovery of each compound was calculated and the results detected
were presented in Table 4.

Table 4. Results obtained when the multicomponent method was applied on the
mixture sample
Compound Added Found Recovery
(µg·mL-1) (µg·mL-1) %
PH·HCl 11.31 11.53 101.4
PHA·HCl 11.36 11.41 100.4
Lid 9.28 9.13 98.4
Conclusions
The first derivative spectrometry and multicomponent analysis methods could be
used with very good results for quantitative simultaneous determination of PH·HCl,
PHA·HCl and Lid from synthetic mixture. The first derivative method was validated
by checking the linearity, limit of detection and limit of quantification, accuracy and
precision. The multicomponent method was found to be simple, sensitive, accurate
and represents a better alternative to the other methods for the determination of
PH·HCl, PHA·HCl and Lid from synthetic mixture.
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SOME CONSIDERATIONS ON INDOOR AND OUTDOOR IMPACTS

OF DIFFERENT WAYS OF PM RELEASE AND ODOUR EMISSION
IN INDUSTRIAL SECTORS
Elena Cristina Rada1

1
Department of Theoretical and Applied Sciences, Insubria University of Varese, Via G.B.
Vico 46, I-21100, Varese, Italy; elena.rada@uninsubria.it
Abstract
In the industrial sectors, the ways of release pollutants into the atmosphere can vary
significantly. We can find various combinations of primary conveyed emissions,
secondary conveyed releases, diffused emissions, depending on the characteristics of
the industrial plant. When an environmental impact assessment is performed,
discussion concerns mainly the impact on the public health, whilst the occupational
impact of these releases is moved to other contexts. The present paper zooms on
selected case studies in order to understand the consequences of different way of
pollutant release on the outdoor and indoor air quality at the site of the plant (within
the fence). Two kinds of pollutants were selected: particulate matter and odoriferous
substances. Results demonstrate that the industrial sector is unbalanced: the
regulations in force in EU give different attention to the impact of the releases to the
atmosphere depending on the industrial sector. In particular, in some sectors the
impact of diffused emissions is underestimated because of a raw management of
their control. Some preliminary proposals are put forwards for a better management
of the emissions to the atmosphere in potentially critical cases. These proposals are
based on the concept that conveyed solutions for pollutant release must be preferred,
with the care of designing the related stacks with an optimised combination of stack
height, conveyed gas velocity, temperature at the exit. The opposition to this
approach is basically related to the additional costs. This article demonstrate that
these extra-costs are due in many cases. Their economic sustainability is discussed
too.
Keywords: economic sustainability, emissions, impact, industrial, odour,

particulate matter
Introduction
In the European Union (EU), the regulation concerning emissions to the atmosphere
from industrial plants evolved during the last decades. The present article wants to
contribute to a critical analysis of the reached level, in order to verify which kind of
improvements should be studied for guaranteeing a balanced approach. Sometimes
the literature has pointed out potential criticalities for specific cases and concerning
a variety of pollutants: e.g., unconventional release of PCDD/Fs (Rada et al., 2011)
and significant release of NOx (Ragazzi et al., 2015), both at outdoor level.
Sometimes the criticalities concern indoor conditions that could affect the attention
at occupational level, when talking about CO2 accumulation (Ragazzi et al., 2017).

In the case of the present article, the interest is towards the ways of release
pollutants into the atmosphere, as they can vary significantly. When zooming on the
environmental impact of the concerned plants, the discussion refers mainly on the
impact on the public health, whilst the occupational impact of the related emissions
is moved to other contexts. The present paper zooms first on selected case studies
developed with the participation of the Author. The aim is to understand the
consequences of different way of pollutant release on the outdoor and indoor air
quality at the site of the plants (thus, also within their fence). Two pollutants were
selected: particulate matter (PM) and odour (odoriferous substances). Both of them
are a mix of compounds that can affect the human health or the human wellbeing
both in the short and in the long term. The discussion, presented together with the
results, wants to contribute to an enhancement of the approach of emission control,
taking into account some potential criticalities that concern not only the population
exposure but also the occupational one.

The pollutants selected for this article (particulate matter and odour) are topical in
the frame of the international literature. Indeed, their relevance is demonstrated by
the growing yearly production of related articles in the Scopus® database, in the last
decade.
The methodology adopted in the present article is the following:
classify the main ways of release of pollutants into the atmosphere, in
industrial plants;
find industrial activities that could have potential criticalities (both on the
territory and at occupational level) in releasing pollutants by those
modalities, specifically for particulate matter and odour;
find literature that allows zooming on those criticalities;
discuss about technical solutions to decrease the impact on environment
and health; valorise existing methodologies and studies for a first
quantification of the effects of those solutions, when this is needed;
discuss about the sustainability of the costs for implementing those
solutions.
As reported above, the literature analysis and the discussion start from the scientific
production of the Author to be enlarged to the literature of the sector in order to
verify if the criticalities pointed out have reached a common point of view.

Looking at the typical industrial activities, often they show three kinds of options,
alone or in combination, to release pollutants into the atmosphere, in a context of EU
authorisation:
release of off-gas from a main stack;
release of emissions, both conveyed (into secondary stacks) and areal (e.g.
from a biofilter) that are considered having a lower impact;
evacuation of indoor air from sections of the plant where pollutants are
generated from secondary activities.
Among the wide variety of industrial activities that are authorised in the EU, four of
them were selected for the analysis reported in the present article:

bio-drying of residual municipal solid waste (RMSW); this process (Rada

et al., 2012; Velis et al 2009) aims to modify the characteristics of the
MSW that remains as result of the activation of selective collection (SC),
that is the RMSW; the performed modifications allow an easier post-
treatment to extract non-combustible recyclable materials (glass, metals,
inert) in order to generate a fuel that can substitute coal in a few industrial
plants; often (e.g. in Italy) the process air is treated and released from a
biofilter;
composting of source separated food waste (Cadena et al., 2009); this
process aims to valorise source separated food waste in order to generate a
product (compost) to be used on agricultural lands; also in this case the
treated process air is typically released from a biofilter; however, the
potential criticalities are different from the case of bio-drying because the
amount of putrescible volatile solids consumed per unit of input are higher
in case of composing. Thus, composting can have a higher impact in terms
of odour;
RMSW incineration (Thorin 2012); in this case the aim is the generation
of energy from the valorisation of the fractions of MSW that are not
suitable for material recycling (in the virtuous contexts where selective
collection has been optimised); typically, the pollutant releases are from
primary and secondary stacks.
Steel making plants (Tupkary 2017); the technology for producing steel
can vary a lot in the sector; in the present article, the case of electric arc
furnaces is analysed, focusing on the variety of releases into the
atmosphere that characterise these plants.
These activities cover all the modalities of release to the atmosphere listed above.
Two of them are based on biological processes at low temperature; the remaining
two are high temperature processes.
The potential criticalities (both on the territory and at occupational level) that
characterise the above-mentioned activities concern many kinds of pollutants. The
present article focuses on particulate matter and odour, as explained below:
bio-drying is based on a strong aeration of the RMSW; thus, one of the
potential criticalities is related to the extraction of particulate matter from
the biological reactor through the evacuation of the exhausted air; the
common adoption of a biofilter to decrease the pollutants loads generates
an areal release at low height, low velocity, low temperature, thus low
dilution into the atmosphere; the verifications of the consequent impact are
related typically to the impact on the territory; in the present article, the
effects of the accumulation of particulate matter in the area of the plant are
discussed also in terms of impact on the workers, that could be under-
estimated;
also composting is based on a strong aeration; in this case the aeration
concerns food waste; in this sector, it is well known that the main
criticality is related to the generation of odour mostly from the biological
reactor; again, the typical adoption of a biofilter to decrease the pollutants
loads generates an areal release at low height, low velocity, low
temperature, thus low dilution into the atmosphere; again, the impact is
typically studied in terms of effects on the territory; in the present article,
the impact of odours in the area of the plant are discussed also in terms of
exposure of the workers, as this aspect could be under-esetimated;
RMSW incineration is widely studied in terms of environmental and
health impact on the territory; these analyses helped to modify the
characteristics of the process and to favour its evolution in the last
decades. However, today the main concern is the main stack and its role in
the pollutants impact. In the present article, some aspects both on
particulate matter and odour are discussed in terms of workers’ exposure;
steel making plants are widely studied too, because of the fate of the
pollutants already present in the input, because of the high flowrate sent to
the main stack after treatment, because of the potential process stage
where the roof of the plant is open and, finally, because of the evacuation
of air (polluted) from the windows of the industrial building. In the present
article, some considerations on particulate matter are discussed in terms of
workers’ exposure.
The literature selected as a starting point to zoom on the above-mentioned
criticalities is the following:
RMSW bio-drying: here the quantification of the phenomena can be made
adapting an approach available in the literature for a case study (Rada &
Ragazzi 2011). If we assume, as first approximation, that the released
particulate matter from the biofilter of the case study has a diffusive
behaviour similar to a gas and if we use an emitted particulate matter
concentration equal to 5 mg/m3, results show that only at a few hundreds
of meters from the plant the concentration decreases of one order of
magnitude. Apart from the non-negligible incidence of dust on the
territory, the reduced dispersion causes an accumulation of dust that can
be relevant for the workers’ exposure. In practice, the workers operate in a
deformed half-bubble of pollutants locally accumulated (deformation
depends on the wind). The fact that the particulate matter has a
granulometry that gives a behaviour only partially equivalent to a gas
means that the highest granulometric classes tend to settle closer to the
plant, increasing the relevance of the phenomenon;
food waste composting: the quantification of the phenomena can be based
on an approach available in the literature (Rada & Ragazzi 2013).
conventional biofilters are authorised in EU with emission odour units in a
range typically around 250-300 o.u./m3. The cited case-study demonstrates
that the impact of the odorigenous emissions of a conventional biofilter
could be negligible only at more than 1 km from the plant. Again, apart
from the non-negligible incidence of odours on the territory, the reduced
dispersion accumulates the odorigenous compounds at levels that can be
relevant for the workers’ exposure. Again, the workers operate in a
deformed half-bubble of compounds locally accumulated, with
uncomfortable conditions of work;
RMSW incineration: a first quantification of the phenomena can be based
on an approach available in the literature (Schiavon et al., 2019).
Secondary emissions of particulate matter from an incinerator are typically
authorised without analysing their incidence at ground level. On the
contrary, the less stringent emission limits for secondary sources and their
lower height of emission can give a contribution of dust at ground level

that can be higher than the one from the main stack, as demonstrated in the
cited study (the impact of the secondary contributions are double than the
one from the main stack, in that case). Another anomaly can come from
the authorisation of the release of odorigenous compounds when the
incineration activities are stopped for maintenance and the waste pit is
full: the air extracted from the building of the pit is typically sent to
combustion, but this is the case of maintenance with no combustion
performed. In this case, a simple deodorisation system (e.g. activated
carbon filters) with low height release could be critical, creating at least
discomfort among the staff working at the plant;
steel making plants: a first quantification of the phenomena can be based
on studies concerning not only the modelling of the pollutant diffusion to
the atmosphere, but also the use of deposimeters and soil characterisation
(Rada et al., 2016a; Rada et al., 2016b). This mixed approach comes from
the need to verify the role of secondary and diffused emissions that can be
significant for conventional plants. Zooming on the selected case, results
show that the role of the main stack is expected to have a negligible effect
on the territory, including the internal area of the plant; however, a remark
must be done on the way of managing the authorisation to the release of
heavy metals, as the limit to be complied with at the stack is a generic sum
of concentrations, not dependent on the single toxicity of the heavy
metals. On the contrary, in a conventional plant, secondary and diffused
emissions are expected to create a deformed half-bubble of pollutants,
including particulate matter, that can affect the quality of the air within the
gate of the plant and for hundreds of meters in the surroundings.
For each of the selected criticalities, the technical sector offers solutions that
mitigate the problems pointed out, as explained below:
in case of RMSW bio-drying, two options can be comparatively analysed
starting from a methodology described in literature (Ragazzi et al., 2014);
the comparison can be made in terms of positioning of the conventional
biofilter: on the ground vs on the roof of the plant there described.
Calculations have been regenerated for the present article considering a
concentration of particulate matter after biofiltration (assumed as a first
approximation as having a behaviour of a gas) equal to 2.5 mg/m3; results
showed a significant decrease (up to 5 times) of dust deposition in the area
within the gate of the plant and in the closest surroundings; thus, the “roof
option” gives a contribution to protect the workers operating at the plant.
More technological solutions are potentially available; they are discussed
in the next section, related to composting, because of some similarities;
food waste composting is evolving towards anaerobic digestion plus post-
composting, specifically in countries where the generation of electricity
from renewable sources receives public incentives; if this is the case, the
odorigenous impact is reduced thanks to the introduction of the sealed
reactor of anaerobic digestion; if the approach of direct composting must
be confirmed, a solution different from what discussed above for bio-
drying could be the introduction of an additional exhaust air treatment step
as non-thermal plasma (Schiavon et al., 2015) to decrease the odoigenous
load reaching the biofilter; however, also in this case the adoption of an
open biofilter on the roof of the plant can reduce the incidence of the plant
locally; a solution alternative to biofiltering, named biotrickling filter, is
expected to enlarge the viable options but it is not yet optimized for a real
scale in the composting sector. Based on a compact bioreactor, the
exhausted air after treatment is conveyed at a stack guaranteeing a good
pollutant dilution into the atmosphere (Schiavon et al., 2016). Another
conveyed system, named regenerative thermal oxidation (RTO) is already
available in real scale, but it is based on the controversial use of methane
to get high temperature (before heat recovery) to thermally oxidize the
undesired compounds (Rada & Ragazzi, 2011). Non-thermal plasma,
biotrickling filter and RTO can be of interest not only for composting but
also for RMSW bio-drying;
As pointed out above, in the sector of RMSW incineration there is a need
to pay more attention to the role of secondary emissions.
Designing/modifying the height of release of these emissions can give
important results in terms of reduction of the internal impact in the area of
the plant. It must be also remembered that indoor air in the office section
is affected by the outdoor air quality, thus advantages can be obtained also
for the staff of the plant;
A solution to prevent RMSW incineration to give odour problem when
combustion is not performed for plant maintenance, but the waste pit is
full, is the adoption of a fan to force the contaminated air of the pit to exit
through the main stack. Its height guarantees generally some orders of
magnitude of dilution;
steel making plants are complex infrastructures; in spite of that, an
important solution to decrease their impact, when not yet performed, is
conceptually simple: maximise the conveying and treatment of polluted
streams before their release into the atmosphere in order to increase the
dilution effect. Low height releases must be avoided. Moreover,
conveying makes easier a correct monitoring of discharged flowrates and
concentrations.
The considerations reported above demonstrate that the incidence of the underlined
criticalities on the impact of the plants could be not negligible. In spite of that, the
solutions presented above are not considered compulsory neither for authorisation
pathways nor in most of the literature of the sector (e.g., referring to the Scopus®
database). An explanation could be the extra-costs for their implementation. To this
concern, some considerations can be made:
In the sector of MSW, many tenders are based on criteria that ask to
choose the cheapest offer; that causes a cut of all not specifically requested
from the regulation in force; a bonus in the evaluation of the offers
showing more attention to the health of population and workers, beyond
the regulation in force, should be included;
When the initiative for the construction of a plant is totally private, it is the
authorisation pathway that must guarantee and enhanced approach in the
prevention of effects on health and environment. Thus, the presence in EU
of plants that can release pollutants in non-conveyed (cheap) conditions
means that a lot must be done yet for having really modern regulations.
Conclusions
The present article analysed two industrial activities at low temperature and two at
high temperature. Results showed that some local impact criticalities in terms of
particulate matter and odour are not temperature depending. The central role belongs
to the modality of release: conveyed or diffused. Moreover, secondary emissions
could be underestimated when the attention is fully concentrated on the main stack
of a plant. Some potential criticalities have been found also thanks to an analysis of
the literature of the sector, adapted to the new vision of the impact proposed in the
present article: workers, and staff in general, operate on the site; thus, plant designs
and authorisations should avoid solutions that accumulate pollutants within the gate
of the plants. In some cases, the technical options available in the sector have to
complete their evolution to the real scale; however, the most important solution to
mitigate the impact of the analysed cases is based on emissions adequately conveyed
to a stack. Of course, the modifications could be expensive, but talking about health
of population and workers, the criteria to consider economically sustainable a
solution should be seen with more attention to protect.
References
Cadena, E., Colon, J., Sanchez, A., Font, X., Artola, A., 2009, ‘A methodology to
determine gaseous emissions in a composting plant’, Waste Management, 29,
2799-2807.
Rada, E.C., Lodi, M., Teoldi, F., Ragazzi, M., Rossi, B., 2016a, ‘Characterization of
fine and ultrafine particles in air near a steel making plant: An Italian case’,
Management of Environmental Quality: An International Journal, 27, 4, 350-
363.
Rada, E.C., Ragazzi, M., Tubino, M., Gambaro, A., Torretta, C., Argiriadis, E.,
Vecchiato, M., Rossi, B., Tava, M., 2016b, ‘Characterization of metals in air
and soil near a steel making plant in the North part of Italy’, Management of
Environmental Quality: An International Journal, 27, 4, 441-451.
Rada E.C., Ragazzi M., 2011, ‘Municipal Solid Waste bio-drying: odor problems of
three configurations’, Waste-to-Resources 2011: IV International Symposium
MBT and MRF, 24th-26th May, Hannover, Germany
Rada E.C., Ragazzi M., 2013, ‘Odorous impact from composting plant: biofilter
versus RTO’ In: Proceedings of the 13th International Conference on
Environmental Science & Technollogy, Greece
Rada E.C., Ragazzi M., Badea A., 2012, ‘MSW bio-drying: design criteria from a 10
years research’, UPB Scientific Bulletin, Series D: Mechanical Engineering,
74, 3, 209-216
Rada, E.C., Ragazzi, M., Zardi, D., Laiti, L., Ferrari, A., 2011, ‘PCDD/F
enviromental impact from municipal solid waste bio-drying plant’,
Chemosphere, 84, 3, 289-295.
Ragazzi, M., Rada, E.C., 2012, ‘Multi-step approach for comparing the local air
pollution contributions of conventional and innovative MSW thermo-chemical
treatments’, Chemosphere, 89, 6, 694-701.
Ragazzi, M., Rada, E.C., Ferrentino, R., 2015, ‘Analysis of real-scale experiences of
novel sewage sludge treatments in an Italian pilot region’, Desalination and
Water Treatment, 55, 3, 783-790.

Ragazzi M., Rada E.C., Schiavon, M., Torretta V., 2014, ‘Unconventional
parameters for a correct design of waste biostabilization plant in agricultural
areas’, Mitteilungen Klosterneuburg, 64, 6, 1-13.
Ragazzi, M., Rada, E.C., Zanoni, S., Passamani, G., Dalla Valle, L., 2017,
‘Particulate matter and carbon dioxide monitoring in indoor places’,
International Journal of Sustainable Development and Planning, 12, 6, 1032-
1042.
Schiavon, M., Adami, L., Torretta, V., Tubino, M., ‘Environmental balance of an
innovative waste to energy plant: the role of secondary emissions’, In:
8th International Conference on Energy and Sustainability: 3-5 July 2019,
Coimbra, Portugal
Schiavon, M., Ragazzi, M., Rada, E.C., Torretta, V., 2016, ‘Air pollution control
through biotrickling filters: a review considering operational aspects and
expected performance’, Critical Reviews in Biotechnology, 36, 6, 1143-1155.
Schiavon, M., Ragazzi, M., Torretta, V., Rada, E.C., 2016, ‘Comparison between
conventional biofilters and biotrickling filters applied to waste bio-drying in
terms of atmospheric dispersion and air quality’, Environmental Technology,
37, 8, 975-982.
Schiavon, M., Scapinello, M., Tosi, P., Ragazzi, M., Torretta, V., Rada, E.C., 2015,
‘Potential of non-thermal plasmas for helping the biodegradation of volatile
organic compounds (VOCs) released by waste management plants’, Journal of
Cleaner Production, 104, 211-219.
Thorin, E., 2012, ‘Waste to energy – A review’. Suzhou, In: Proceedings of the
International Conference on Applied Energy, ICAE
Tupkary R.J., 2017, ‘Modern Steel Making Handbook’, Mercury Learning &
Information, 1st Edition.
Velis, C.A., Longhurst, P.J., Drew, G.H., Smith, R., Pollard, S.J., 2009, ‘Biodrying
for mechanical-biological treatment of wastes: a review of process science and
engineering’, Bioresources Technologies, 100, 11, 2747-2761.

THE COMPARISON OF DESTRUCTION DEGREE BETWEEN

DIFFERENT TYPES OF MICROORGANISMS UNDER GAS/CAVITATION
CONDITIONS
Koval Iryna Z.
Lviv Polytechnic National University, Department of Physical, Analytical and General

Chemistry, Bandera str., 12, 79013, Lviv, irynazk@gmail.com, Ukraine
Abstract
Comparison of values of destruction degree of microorganisms of different types
(Micrococcus luteus, Pseudomonas fluorescens, Bacillus cereus, Sarcina lutea
bacterias and Saccharomyces yeasts) under the simultaneous treatment of water by
cavitation and gas is carried out. Has been determined the nature of the gas in which
the cells were most actively destroyed by comparing the values of destruction
degree. The greatest effectiveness of microorganisms destruction was achieved with
the Ar/US-action, regardless of the type of microorganisms, their morphological
characteristics and their initial amount per unit volume of water. Morphological
features have an influence only on the duration of cavitation treatment of water.
Keywords: bubbling, cavitation, destruction degree, gas, microorganisms
Introduction
Microbiological contamination of water is one of the contamination factors of
natural water and sewage, with which scientists are fighting till today (Ashbolt 2015,
Pachepsky et al 2018). Various scientists have proposed many methods of
microbiological water purification, but they mainly determine the total number of
destroyed microbes, without specifying their genus. Much attention should be given
to the identification of the aquatic microbiota and to establish varieties of
microorganisms in the process of water decontamination. This task and its disclosure
are set out in this paper. Here is the proposed cavitation method of water
disinfection from microorganisms of a particular type. But the effect of cavitation on
different types of microorganisms is uneven, which indicates the specificity of the
cavitation field effect on microscopic organisms (Koval 2018, Badve et al 2015, Jain
2019). However, experimentally argued data that would confirm this fact in the
literature are absent. Therefore, the study of this work is aimed at assessing the
destruction degree of microorganisms of various types with simultaneous action of
gas bubbling and cavitation.

Model waters were used for investigations to which microorganisms were added,
namely Micrococcus luteus, Pseudomonas fluorescens, Bacillus cereus, Sarcina
lutea bacterias and Saccharomyces yeasts. The purification process lasted 2 hours.
Previous studies have shown that microorganisms number is not changed during two
hours in the control experiments without cavitation and gas action in all investigated
waters medium, that is enough for the experiment.
Сavitation processes in the aquatic medium were generated by ultrasonic (US)

action (UZDN-2T) with the frequency of 22 kHz, power of 35 W was used. Gas
bubbling into the water is an additional factor for intensification of the cavitation
process, namely oxygen, carbon dioxide, argon and helium. All experiments were
carried out under T = 298±1 K, P = 0.1 MPa.
The number of living cells was determined after the treatment by colony counting on
a nutrient medium – meat and peptone agar. Calculated colonies were expressed as
colony forming units per cubic centimeter.

Destruction degrees of microorganisms (Dd) after gas/US treatment equals to
number of microorganisms (NM) concerning to initial number of microorganisms
(NM0) landed at 100% and expressed in percentage are presented in Table 1.
One may compare Bacillus destruction within a cavitation field for different gases
being bubbled into its dispersion and so determine the gaseous atmosphere in which
this process is most effective (Figure. 1).
Figure 1. Dynamics of Dd changes of Bacillus cereus in time. Conditions: NM0 =

7·104 CFU/сm3, Т=298±1К.
Bacillary Ps. fluorescent type bacteria, unlike B. cereus microbial cells, are unable
to form spores, they were investigated for their response to gas/cavitation treatment
(Figure. 2).

Figure 2. Dynamics of Dd changes of Pseudomonas fluorescens in time. Conditions:

NМ0 = 9.5·104 - for О2/US; NМ0 = 9.7·103 - for СО2/US; NМ0 = 1.8·103 – for
Ar/US; Т=298±1К.
It should be noted that during the first stage of being subjected to Не/US effect
(t=1800 s) an increase in NM was observed as a result of intensive disaggregation of
microbial cells found in the effluent water, whilst active microorganism destruction
proper (tНе/US=1800÷7200s) was only observed at the second stage. Therefore, in
determining Dd values NМмах was considered instead of the NМ0. For that reason, in
this particular instance the comparison between the effect of helium and other gases
in a cavitational field is inappropriate (this is not shown in the Figure. 2).
The destruction effectiveness order for Sacch. Cerevisiae when subjected to various
gas/cavitation combinations is presented on Figure 3.
Figure 3. Dynamics of Dd changes of Saccharomyces cerevisiae in time.

Conditions: NМ0 = (4.2÷5.2) ·103 CFU/сm3 – for Не/US and СО2/US and NМ0 =
(1.9÷2.07) ·104 CFU/сm3 – for О2/US and Ar/US; Т=298±1К.

Table 1. Destruction degrees of investigated microorgamisms

Investigated Destruction degrees (Dd) after t = 7200 s, %
microorgamisms Ar/US Не/US О2/US CО2/US
Bacteria
Bacillus cereus 97.4 86.9 88.6 82.9
Micrococcus luteus 90.3 69.8 - -
Sarcina lutea 97.0 95.3 - -
Pseudomonas
94.4 42.4 59.3 80.0
fluorescens
Yeast
Saccharomyces
99.52 97.62 80.77 80.0
cerevisiae
The process of water decontamination, depending on the cells size, is considered in

the previous work (Koval 2018). The above data (Table 1) describes the ambiguity
of the effect of gas nature on the efficiency of organisms destruction under
cavitation influence. Hence, Ar/US-action demonstrated the best results, regardless
of the microorganism’s type. The value of destruction degree depends on
morphological features of the cells.
Conclusions
The ratios of the number of microorganisms concerning to initial number of
microorganisms are calculated. The highest values of destruction degrees of
microorganisms have been established under Ar/US action, unlike Не/US, О2/US,
CO2/US regardless morphological features of the cells, type of microorganisms and
initial concentration of the cells in the investigated water. While the value of
destruction degree depends on morphological features of the cells as yeast cells were
more likely to be destroyed under gas/cavitation conditions, compared with the
destruction of bacterial cells that is explained by the morphological characteristics of
the cells.
References
Ashbolt, NJ 2015, 'Microbial Contamination of Drinking Water and Human Health
from Community Water Systems', Current Environmental Health Reports, vol.
2, no. 1, pp.95-106.
Badve Mandar, P, Bhagat Mihir, N & Pandit Aniruddha, B 2015, 'Microbial
disinfection of seawater using hydrodynamic cavitation', Separation and
Purification Technology, vol. 151, pp. 31-38.
Jain, P, Bhandari, VM, Balapure, K, Jena, J & Killedar, DJ 2019, 'Hydrodynamic
cavitation using vortex diode: An efficient approach for elimination of
pathogenic bacteria from water', Journal of Environmental Management, vol.
242, pp. 210-219.
Koval, IZ 2018, 'Destruction cavitation action on the microbial cells sizes',
International Symposium The environment and the Industry, pp. 362-365.
Pachepsky, YA, Allende, A, Boithias, L, Cho, K, Jamieson, R, Hofstra, N & Molina,
M 2018, 'Microbial Water Quality: Monitoring and Modelling', Journal of
Environmental Quality, vol. 47, pp. 931-938.

UNIVERSAL SCREENING OF PRIVATE WELLS WATER QUALITY IN

THE MUNTENIA REGION, ROMANIA
Gina Vasile Scaeteanu1, Roxana Maria Madjar1*, George Adrian Peticila2
1
University of Agronomic Sciences and Veterinary Medicine, Faculty of Agriculture, 59
Blvd. Marasti, 011464, Bucharest, *rmadjar@yahoo.com, Romania
2
University of Agronomic Sciences and Veterinary Medicine, Faculty of Horticulture, 59
Blvd. Marasti, 011464, Bucharest, Romania.
Abstract
Drinking water quality is an actual and stringent problem and the presence of nitrate
and nitrite ions above limits imposed by legislation may produce
methemoglobinemy and different types of cancer. Because nitrate is odourless,
colourless and tasteless is undetectable without tests and well water is recommended
to be evaluated from this point of view, especially when in the proximity of the
wells are activities which may contribute to water contamination. The present
research was carried out with aim to achieve nitrate and nitrite levels from wells
located in three areas from Muntenia region: Chiajna (Ilfov), Letca Noua (Giurgiu)
and Manastirea (Calarasi). The obtained results evidenced that 10 from 14 analysed
wells contain nitrate levels were over imposed limit, one of them located in
Manastirea (Calarasi) being even 4 times higher. Regarding nitrite, water from one
sampling point is over 0.5 mg/L, all the rest being lower and much lower than
imposed limit.
Keywords: health, nitrate, nitrite, pollution, well water
Introduction
Over last decades, nitrate levels in groundwater have gradually increased in many
European countries and the main factors responsible for this situation are
represented by the use of nitrogenous fertilizers, intensive agriculture and disposal
of wastes mainly from animal farming (WHO, 2016).
Beside methemoglobinemy, the most common manifestation derived from excessive
nitrate exposure, literature presents some other negative health effects associated
with nitrates: various types of cancer (Dourson & Baily 1990; Mirvish 1991;
Prakasa & Puttanna 2000; Gulis et al 2002), central nervous system defects
(Dourson & Baily 1990; Mirvish 1991), hypertrophy of the thyroid (Vermeer et al
1998).
In Romania there were developed projects concerning nutrient control in order to
minimize pollution effects, especially nitrate pollution. Thus, Integrated Nutrient
Pollution Control Project was intended to implement EU Nitrate Directive for nitrate
vulnerable zones by application some specific measures in order to contribute to
reduction of nitrate pollution. Some legislative regulations for Romania sustain
reducing water pollution caused or induced by nitrates from agricultural sources and
preventing further pollution (Council Directive 91/676/EEC). Application and
implementation of Council Directive 91/676/EEC is depicted in a report from the
Commission to the Council and The European Parliament which is based on the
information provided by Member States for 2012-2015 period of time concerning
water quality, designation of nitrate vulnerable zones, action programs.
In Romania and European Union, the guideline values for nitrate and nitrite are 50
mg/L and 0.5 mg/L, respectively. As nitrate and nitrite may occur simultaneously in
drinking water and having in view the cumulative hazardous effect of their presence,
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 aim of the research was to evaluate the nitrate and nitrite levels of water
collected from private wells located in three areas from Muntenia region, as it
follows: Chiajna (Ilfov), Letca Noua (Giurgiu) and Manastirea (Calarasi). The
results were compared with quality standards for drinking water imposed by Council
Directive 98/83/EC and also with Romanian legislation and discussed as a
constituent part of our previous researches on this topic.
Experimental
Evaluation of the nitrate and nitrite levels for water collected from private wells
located in Chiajna (Ilfov), Letca Noua (Giurgiu) and Manastirea (Calarasi) was
performed according to the procedures described below. The research was carried
out during 2018-2019 and for each area were selected several sampling points which
are sources of drinking water and/or are used for domestic usage (cooking,
washing), as it follows: 6 points (A1-A6) for Chiajna, 4 points for Letca Noua (B1-
B4) and 4 points for Manastirea (C1-C4).
Sampling depths for investigated points are: a) for Chiajna - 22 m (A1), 70 m (A2),
13 m (A3), 32,5 m (A4), 8 m (A5), 19 m (A6); b) for Letca Noua - 20 m (B1), 18 m
(B2), 14 m (B3), 13 m; c) for Manastirea - 5 m (C1), 6 m (C2), 6m (C3), 5m (C4).
The results represent the average of the determinations. Water samples were
collected in pre-cleaned polyethene bottles, preserved at 4ºC and the analyses were
conducted within 48 hours of collection. The samples were allowed to stay until they
reached room temperature before analysis.
Nitrate ions concentrations were quantified by spectrophotometric means using 2,4-
disulphonic acid in basic medium when it was obtained yellow nitroderivatives that
have absorption maxima at 420 nm. The nitrite levels were determined
spectrophotometrically as well, using Griess reagent. After diazotation reaction
between sulphanilic acid and nitrites followed by coupling with naphthylamine, it
was obtained a pink azoic compound with absorption maxima at 540 nm.
Spectrophotometric measurements were carried out using Metertek SP830 Plus
apparatus.

For tested samples, the nitrate and nitrite levels present large variations that are
depicted in Table 1, Figure 1 and Figure 2. For Chiajna, nitrate levels are within
10.94 and 128.02 mg/L, with an average for investigated area of 66.75 mg/L. In the
case of A3, A5 and A6, the nitrate levels exceeded maximum admitted level,
meanwhile in the case of A4 found concentration was near reference value.
Related to nitrite levels, as average, the obtained value (0.295 mg/L) is lower than
imposed concentration (0.5 mg/L), but for A5, found concentration exceeded the
limit. Concerning relation imposed by Council Directive 98/83/EC, for A3, A5 and
A6 sampling points was encountered the same alarming situation. Thus, the results
obtained for the relation [NO3-]/50 + [NO2-]/3 are over limit in the case of A3, A5
and A6 sampling points. In this context, water provided by A3, A5 and A6 wells is
not suitable to be consumed and its use for any domestic purpose also must be
forbidden.
Table 1. Nitrate and nitrite contents for well water from Chiajna, Letca Noua and
Manastirea
Nr. crt. Well NO3-, mg/L NO2-, mg/L [NO3-]/50 + [NO2-]/3
Chiajna, Ilfov
1. A1 12.66 0.106 0.288
2. A2 10.94 0.162 0.272
3. A3 99.12 0.361 2.102
4. A4 46.12 0.090 0.952
5. A5 128.02 0.565 2.748
6. A6 103.66 0.487 2.235
Average 66.75 0.295 1.432
Letca Noua, Giurgiu
1. B1 34.73 0.080 0.721
2. B2 103.32 0.175 2.124
3. B3 126.87 0.480 2.697
4. B4 105.75 0.229 2.191
Average 92.66 0.241 1.933
Manastirea, Calarasi
1. C1 208.79 0.169 4.232
2. C2 75.75 0.102 1.549
3. C3 95.46 0.084 1.937
4. C4 103.08 0.145 2.110
Average 120.77 0.125 2.457
MAL* 50 0.5 ≤1
*According to Council Directive 98/83/EC and to Law no. 458/2002 (2011)
value below MAL value that exceed MAL
In the case of Letca Noua area, nitrate levels exceeded maximum admitted level
(MAL) for three sampling points (B2, B3 and B4), even of 2.53 times (Table 1,
Figure 1). Consequently, relation imposed by Council Directive 98/83/EC has led to
values higher than limit for the same sampling points: 2.124 mg/L (B2), 2.697 mg/L
(B3), 2.191 mg/L (B4). Only B1 sampling point presented a value below limit
(0.721 mg/L). Nitrite levels are below 0.5 mg/L, the highest found concentration
being encountered for B3 (0.480 mg/L) (Table 1, Figure 2).
Nitrate concentrations found for well water samples collected from Manastirea,
Calarasi are all over maximum admitted level of 1.5 to 4 times higher, with an
average of 120.77 mg/L (Table 1, Figure 1). In contrast to nitrate levels, nitrite
levels for C1-C4 sampling points are below 0.5 mg/L (Table 1, Figure 2). All the
results of the relation [NO3-]/50 + [NO2-]/3 are higher than imposed value, the
increasing order being C2 < C3 < C4 < C1.
Figure 1. Nitrate levels determined for well water collected from Chiajna (A1-A6),
Letca Noua (B1-B4) and Manastirea (C1-C4)
The obtained results are of great concern having in view that 71.42% from all
analyzed water samples contain nitrates over MAL, one of them being 4 times
higher than limit. As average, well water collected from Chiajna, Ilfov present the
lowest nitrate levels (66.75 mg/L), followed by those collected from Letca Noua,
Giurgiu (92.66 mg/L) and from Manastirea, Calarasi (120.77 mg/L).
This situation appeared mainly due to agricultural practices associated with nitrogen
fertilisation adopted by locals. Beside this evident explanation which is sustained by
the position of wells in the proximity of the greenhouses and solariums, it could be
taken into consideration also, the improper position of the wells near septic fosses
and livestock facilities.
The obtained levels of nitrate in investigated areas correlated with literature data
regarding relation between nitrate and methemoglobinemy (Fan et al 1987) must
represent a serious threat and consumption of water from these sources must be
suspended. Also, having in view the agricultural potential of Giurgiu and Calarasi
areas, nitrate levels must be monitored strictly and the environmental risk which
arises from nitrate presence is necessary to be estimated.

Figure 2. Nitrite levels determined for well water collected from Chiajna (A1-A6),
Letca Noua (B1-B4) and Manastirea (C1-C4)
Regarding nitrite, 92.85% from investigated water samples correspond to limit

imposed by legislation, only one sample which originates from Chiajna has nitrite
concentration slightly above limit (0.565 mg/L).
Integration of the obtained results into our previous researches

There are many studies that deal with nitrate levels found in well water collected
from different areas in Romania. Extreme values were reported for well water from
Ozun village (Covasna) when nitrate levels exceeded the limit value even 3 times,
meanwhile nitrite concentrations were within safe limit (Raduly & Farkas 2017).
Nitrate levels over 300 mg/L were also reported for water collected from wells
located in Salaj (Martonos & Sabo 2017).
The results presented in this paper represent a constituent part of our previous
researches on this topic. Accordingly, the results depicted in Table 2 and Figure 3
indicate that the highest nitrate levels were found in Matca (279.57 mg/L, as
average), followed by Sahateni (248.9 mg/L, as average). These results are not
totally unexpected having in view that Matca is the most important vegetable area
from Galati and high nitrate levels in soil were reported (Lacatus et al 2016).
The lowest nitrate levels, even below MAL (as average), were found in Prahova
County, followed by Ilfov County.
Literature studies show that drinking water with nitrate levels between 41-100 mg/L
present risks for adults and young livestock, meanwhile concentrations over 100
mg/L indicate that water should not be used for drinking either by humans or
livestock (Daniels & Mesner 2010). A study concerning methemoglobinemy in
Romania indicates that 20% of cases appeared when nitrate levels in well water were
between 0 and 20 mg/L, meanwhile 58% of cases were associated with nitrate levels
between 101 and 500 mg/L (Tudor & Staicu 2009).

Table 2. Nitrate levels in well water from different areas (mg/L)

Nr. Sampling Sampling NO3- Average Reference
crt area points NO3- content
1 Buzau, 8 48.2 - 540.80 248.90 Pele et al 2010
Sahateni
2 Calarasi, 4 75.74 - 208.78 120.77 this study
Manastirea
3 Constanta, 5 19.55-235.56 103.02 Vasile Scaeteanu
Cobadin & Madjar 2018
4 Galati, 7 149 - 452 279.57 Pele et al 2010
Matca
5 Giurgiu, 4 34.73 - 126.87 92.66 this study
Letca Noua
6 Ilfov, 6 10.94 - 128.02 66.75 this study
Chiajna
7 Ilfov, 8 44.70 - 66.58 49.78 Pele et al 2010
Clinceni
8 Prahova, 4 20.33 - 87.09 45.83 Vasile Scaeteanu
Fantanele et al 2014
9 Prahova, 7 8.53 - 49.22 33.31 Vasile Scaeteanu
Maneciu- & Madjar 2017
Ungureni
Figure 3. Representation of average nitrate contents found in well water from

various areas
Conclusions
The research consisting in evaluation of nitrate and nitrite levels for drinking water
collected from private wells located in Muntenia region (Chiajna - Ilfov, Letca Noua
- Giurgiu and Manastirea - Calarasi), provided some conclusions.
Three from six investigated wells from Chiajna contain water with nitrate levels
over MAL, with an average of 66.75 mg/L.
Nitrate levels form Letca Noua are higher than those found in Chiajna, with an
average of 92.66 mg/L. All samples collected from Manastirea are over MAL, one
of them being 4 times higher;
Regarding nitrite concentration, water from one sampling point is over 0.5 mg/L, all
the rest being lower and much lower than imposed limit.
On the basis of these alarming results (71.42% of all analyzed water samples contain
nitrates over MAL), it must be taken into consideration the alternative to find other
water sources for drinking and further monitoring and surveillance of water from
these points need to be enhanced.
Controlling nitrate levels is very difficult, having in view that nitrate vulnerable
areas are agricultural ones. The best manner is prevention by adopting a good
management for agricultural practices, for fertilizer and manure applications and by
avoiding storage of animal manures near well water sources.
References
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against pollution caused by nitrates from agricultural sources (91/676/EEC).
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***Law 458/2002 (2011) regarding drinking water quality.
***Ministerul Apelor si Padurilor, Controlul Integrat al Poluarii cu Nutrienti.
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***Official Journal of the European Communities, Council Directive 98/83/EC of 3
November 1998 on the quality of water intended for human consumption.
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in plastic houses cutivated with vegetable crops and active substance
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from private wells located in Constanta County and risk implications for
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Industry - SIMI 2018, Proceedings Book, pp. 333-340.
Vasile Scaeteanu, 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.
Dourson, M, Stern, B, Griffin, S & Baily, K 1990, 'Impact of risk-related concerns
on U.S. Environmental Protection Agency programs. Nitrate Contamination',
NATO ASI Series vol. G30, Editors. Bogardi, I & Kuzelka RD, Springer
Verlag, Berlin Heidelberg, pp. 477-487.
Mirvish, SS 1991, 'The significance for human health of nitrate, nitrate and N-
nitroso compounds. Nitrate Contamination', NATO ASI Series vol. G30, eds. I.
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Prakasa, R & Puttanna K 2000, 'Nitrates, agriculture and environment', Current
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Nitrosamine formation after intake of nitrate at the ADI level in combination
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459-463.
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Environmental Research, vol. 88, no. 3, pp. 182-187.

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INTERNATIONAL SYMPOSIUM “THE ENVIRONMENT AND THE INDUSTRY”,

SIMI 2019, PROCEEDINGS BOOK

22nd INTERNATIONAL SYMPOSIUM

22nd International Symposium “The Environment and the Industry” –

Ph.D. Chem. Luoana Florentina PASCU

Graphic design Alina TANASESCU

Publisher: National Research and Development Institute for Industrial

2017 SYMPOSIUM PROCEEDINGS IS INDEXED IN WEB OF SCIENCE –

2015, 2016, 2017, 2018

Symposium Proceedings are

under Honorary Patronage of:

under Coordination of:

We wish you a pleasant and fruitful stay in Bucharest.

Ph.D. Chem. Luoana Florentina Pascu

Nicolae Hurduc - Minister of Research and Innovation

Acad. Ioan Aurel Pop – President of Romanian

Acad. Marius Andruh – President of „Chemical Sciences Section” of

the Romanian Academy

Emeritus Prof. Dr. Eng. Sorin Rosca – President of Romanian

Prof.Dr.Eng. Vladimir Rojanschi – President of Romanian

Environment Assoc. 1998

Felix Stroe – President of Romanian Water Association

Emeritus Prof. Dr. Eng. Gheorghita Jinescu (Vice-President of

Romanian Society of Chemistry, Romania)

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

Sustainable Environmental Technologies

Pollution Assessment & Management System

A NEW APPROACH TO DETERMINE THE DISCHARGE 17

REMEDIATION OF POPS POLLUTED SITES IN REPUBLIC OF 90

Pollution Assessment & Management Systems

A FINITE ELEMENT METHOD FOR ENVIRONMENTAL AND 122

EVALUATION OF ASH RELATED PROBLEMS DURING 184

WASTE MANAGEMENT SYSTEM IN ROMANIA – STATUS 293

Pollution Control and Monitoring

NEW TOOLS FOR ASSESSMENT OF WASTEWATER 302

Papers developed within the project ”Promotion, identification and development of

SUSTAINABLE ENVIRONMENTAL TECHNOLOGIES

A NEW APPROACH TO DETERMINE THE DISCHARGE PASSING OVER

Ali Yildiz, Alpaslan Yarar, Ali İhsan Marti, Öznur Kocaer

Konya Technical University Civil Engineering Department, Konya, ayarar@ktun.edu.tr,

Keywords: analytical study, experimental investigation, Ogee Spillway

Section Sustainable Environmental Technologies 17

driven by him to improve accuracy of the design and structural optimization of

Materials and Methods

Figure 1. Discharge coefficient for vertical-faced ogee spillway (USBR 1987)

Section Sustainable Environmental Technologies 18

Figure 2. Discharge coefficient for various total head (USBR, 1987)

Section Sustainable Environmental Technologies 19

Figure 4. Discharge-Total head relation curve

Results and Discussion

Figure 5. Comparison of analytical and experimental results

Table 1. Results from analytical calculations and physical modeling

Section Sustainable Environmental Technologies 21

Figure 6. Comparison of analytical and experimental results

Table 2. Results got from new formula and physical modeling

Section Sustainable Environmental Technologies 22

Section Sustainable Environmental Technologies 23

CONVERSION OF LIGNOCELLULOSIC AGRICULTURAL WASTES

Keywords: activated carbon, adsorption, antibiotic, carbonization, lignocellulosic

Materials and Methods

Results and Discussion

Table 1a. Characterization of raw and thermally activated solids

Table 1b. Characterization of chemically and thermally activated solids