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Development in Wastewater Treatment Research and Processes Innovative Microbe Based Applications For Removal Maulin P Shah Full Chapter PDF
Development in Wastewater Treatment Research and Processes Innovative Microbe Based Applications For Removal Maulin P Shah Full Chapter PDF
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Development in
Wastewater Treatment
Research and
Processes
This page intentionally left blank
Development in
Wastewater Treatment
Research and
Processes
Innovative Microbe-Based
Applications for Removal of
Chemicals and Metals in
Wastewater Treatment Plants
Edited by
Maulin P. Shah
Senior Environmental Microbiologist, Environmental Microbiology
Lab, Bharuch, Gujarat, India
Susana Rodriguez-Couto
Department of Separation Science, LUT School of Engineering
Science, LUT University, Mikkeli, Finland
Notices
Knowledge and best practice in this field are constantly changing. As new research and
experience broaden our understanding, changes in research methods, professional
practices, or medical treatment may become necessary.
Practitioners and researchers must always rely on their own experience and knowledge in
evaluating and using any information, methods, compounds, or experiments described
herein. In using such information or methods they should be mindful of their own safety
and the safety of others, including parties for whom they have a professional
responsibility.
To the fullest extent of the law, neither the Publisher nor the authors, contributors, or
editors, assume any liability for any injury and/or damage to persons or property as a
matter of products liability, negligence or otherwise, or from any use or operation of any
methods, products, instructions, or ideas contained in the material herein.
8 Detoxification............................................................... 253
9 Different types of bioremediators for heavy metals ............. 256
9.1 Algae...................................................................257
9.2 Fungi...................................................................258
9.3 Bacteria ...............................................................258
10 Integrated system .......................................................... 259
11 Conclusion and future perspectives................................... 260
References ................................................................... 261
CHAPTER 12 Membrane proteins mediated microbial-
electrochemical remediation technology............. 265
Jesús Pérez-Garcı´a, Javier Bacame-Valenzuela,
Diana Mayra Sánchez López,
José de Jesús Gómez-Guzmán,
Martha Leticia Jiménez González,
Luis Ortiz-Frade and Yolanda Reyes-Vidal
1 Introduction ................................................................. 265
2 Microbial electrochemistry ............................................. 267
2.1 Microbial-electrochemical systems for
bioremediation ..................................................... 268
3 Membrane protein complex in electrogenic bacteria for
bioremediation ............................................................. 270
3.1 Respiratory complexes of Shewanella oneidensis and
heavy metals biodegradation................................... 270
3.2 Redox mediators of Pseudomonas aeruginosa in
environmental bioremediation ................................. 272
3.3 Geobacter sulfurreducens cytochromes and
nanowires in heavy metals reduction ........................ 272
4 Biological enzymes for environmental bioremediation......... 273
4.1 Oxidoreductases ................................................... 274
4.2 Peroxidases.......................................................... 274
4.3 Oxygenases.......................................................... 275
4.4 Monooxygenases .................................................. 275
4.5 Methane oxygenase (MMO) ................................... 276
4.6 Laccases.............................................................. 276
5 Electrochemical characterization of redox enzymes ............ 277
5.1 Cyclic voltammetry............................................... 277
5.2 Electrochemical impedance spectroscopy (EIS).......... 278
5.3 Coupled spectroscopic and electrochemical
techniques ........................................................... 279
6 Perspectives ................................................................. 281
References ................................................................... 282
Contents xiii
Index...................................................................................................461
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Contributors
Kunwali Das
Department of Microbiology, Tripura University (A Central University), Agartala,
Tripura, India
Moazam Ali
Department of Clinical Medicine and Surgery, University of Agriculture,
Faisalabad, Punjab, Pakistan
Jayshree Annamalai
Centre for Environmental Studies, Department of Civil Engineering, Anna
University, CEG Campus, Chennai, Tamil Nadu, India
Ambreen Ashar
Department of Chemistry, Government College Women University, Faisalabad,
Punjab, Pakistan
Javier Bacame-Valenzuela
Center of Research and Technological Development in Electrochemistry,
Querétaro Technology Park, Pedro Escobedo, Querétaro, México; CONACYT-
Center of Research and Technological Development in Electrochemistry,
Querétaro Technology Park, Pedro Escobedo, Querétaro, México
Pujaita Banerjee
Department of Life Sciences, Presidency University, Kolkata, West Bengal, India
Sudeshna Banerjee
Department of Microbiology, Amity University, Lucknow, Uttar Pradesh, India
Sanchayita Basu
Department of Microbiology, Tripura University (A Central University), Agartala,
Tripura, India
Manaswini Behera
School of Infrastructure, Indian Institute of Technology Bhubaneswar,
Bhubaneswar, Odisha, India
Hiren N. Bhalani
College of Agriculture, Junagadh Agricultural University, Junagadh, Gujarat,
India
Navneeta Bharadvaja
Plant Biotechnology Laboratory, Department of Biotechnology, Delhi
Technological University, New Delhi, Delhi, India
Devikaben Bharatbhai Vishani
Department of Microbiology, Parul Institute of Applied Sciences, Parul University,
Vadodara, Gujarat, India
xix
xx Contributors
Deepti Bhardwaj
Plant Biotechnology Laboratory, Department of Biotechnology, Delhi
Technological University, New Delhi, Delhi, India
Pinal Bhatt
Department of Microbiology, Parul Institute of Applied Sciences, Parul University,
Vadodara, Gujarat, India
Joyani Bhattacharjee
Department of Biotechnology, Haldia Institute of Technology, Haldia, West
Bengal, India
Arunima Bhattacharjee
Department of Microbiology, Tripura University (A Central University), Agartala,
Tripura, India
Sourish Bhattacharya
Process Design and Engineering Cell, CSIR Central Salt and Marine Chemicals
Research Institute, Bhavnagar, Gujarat, India
Zeeshan Ahmad Bhutta
The Royal (Dick) School of Veterinary Studies, University of Edinburgh, Easter
Bush Campus, Midlothian, Scotland, United Kingdom
Pitam Chakrabarti
Department of Biotechnology, Haldia Institute of Technology, Haldia, West
Bengal, India
Vivek Chauhan
Department of Biotechnology, Himachal Pradesh University, Summer Hill,
Himachal Pradesh, India
Suraj Chetri
Department of Zoology, Cotton University, Guwahati, Assam, India
Mohita Chugh
Plant Biotechnology Laboratory, Department of Biotechnology, Delhi
Technological University, New Delhi, Delhi, India
Anjali Dahiya
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati,
Assam, India
Sagar Daki
Process Design and Engineering Cell, CSIR Central Salt and Marine Chemicals
Research Institute, Bhavnagar, Gujarat, India
José de Jesús Gómez-Guzmán
Center of Research and Technological Development in Electrochemistry,
Querétaro Technology Park, Pedro Escobedo, Querétaro, México
Contributors xxi
Subhasish Dutta
Department of Biotechnology, Haldia Institute of Technology, Haldia, West
Bengal, India
Salman Farissi
Department of Environmental Science, School of Earth Science Systems, Central
University of Kerala, Kasaragod, Kerala, India
Janhavi Gadkari
Department of Microbiology, Parul Institute of Applied Sciences, Parul University,
Vadodara, Gujarat, India
Priya Gautam
Department of Biotechnology, Himachal Pradesh University, Summer Hill,
Himachal Pradesh, India
Bhaswati Ghosh
Department of Microbiology, Sarsuna College, University of Calcutta, Kolkata,
West Bengal, India
Martha Leticia Jiménez González
Center of Research and Technological Development in Electrochemistry,
Querétaro Technology Park, Pedro Escobedo, Querétaro, México
Rishee K. Kalaria
ASPEE Shakilam Biotechnology Institute, Navsari Agricultural University, Surat,
Gujarat, India
Ayesha Kanwal
Institute of Biochemistry, Biotechnology and Bioinformatics, The Islamia
University of Bahawalpur, Bahawalpur, Punjab, Pakistan
Shamsher S. Kanwar
Department of Biotechnology, Himachal Pradesh University, Summer Hill,
Himachal Pradesh, India
Priya Khadgawat
Department of Genetics, University of Delhi, New Delhi, Delhi, India
Khushbu
Department of Applied Chemistry, Delhi Technological University, New Delhi,
Delhi, India
Veena Gayathri Krishnaswamy
Department of Biotechnology Stella Maris College (Autonomous), Affiliated to
University of Madras, Chennai, Tamil Nadu, India
Deepak Kumar
Amity Institute of Biotechnology, Amity University Haryana, Gurugram, Haryana,
India
xxii Contributors
Lakhan Kumar
Plant Biotechnology Laboratory, Department of Biotechnology, Delhi
Technological University, New Delhi, Delhi, India
Ashutosh Kumar
Department of Microbiology, Tripura University (A Central University), Agartala,
Tripura, India
Sangeeta Kumari
Amity Institute of Biotechnology, Amity University Haryana, Gurugram, Haryana,
India
Sidak Minocha
Department of Genetics, University of Delhi, New Delhi, Delhi, India
Muthukumar Muthuchamy
Department of Environmental Science, School of Earth Science Systems, Central
University of Kerala, Kasaragod, Kerala, India
Anbazhagi Muthukumar
Department of Environmental Science, School of Earth Science Systems, Central
University of Kerala, Kasaragod, Kerala, India
Iqra Muzammil
Department of Clinical Medicine and Surgery, University of Agriculture,
Faisalabad, Punjab, Pakistan
Luis Ortiz-Frade
Center of Research and Technological Development in Electrochemistry,
Querétaro Technology Park, Pedro Escobedo, Querétaro, México
Ashok Pandey
CSIR-Indian Institute of Toxicological Research, Lucknow, Uttar Praesh, India
Shubhangi Parmar
Process Design and Engineering Cell, CSIR Central Salt and Marine Chemicals
Research Institute, Bhavnagar, Gujarat, India
Hiren K. Patel
School of Sciences, P P Savani University, Surat, Gujarat, India
Bhisma K. Patel
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati,
Assam, India
S.M. Paul Khurana
Amity Institute of Biotechnology, Amity University Haryana, Gurugram, Haryana,
India
Contributors xxiii
Jesús Pérez-Garcı́a
Center of Research and Technological Development in Electrochemistry,
Querétaro Technology Park, Pedro Escobedo, Querétaro, México
Sneha Ramesh
Department of Environmental Science, School of Earth Science Systems, Central
University of Kerala, Kasaragod, Kerala, India
Sathish Raam Ravichandran
Department of Chemical Engineering, Kongu Engineering College, Erode, Tamil
Nadu, India
Aryama Raychaudhuri
School of Infrastructure, Indian Institute of Technology Bhubaneswar,
Bhubaneswar, Odisha, India
Yolanda Reyes-Vidal
Center of Research and Technological Development in Electrochemistry,
Querétaro Technology Park, Pedro Escobedo, Querétaro, México; CONACYT-
Center of Research and Technological Development in Electrochemistry,
Querétaro Technology Park, Pedro Escobedo, Querétaro, México
Dipanjan Roy
Department of Agricultural Biotechnology, Ramkrishna Mission Vivekananda
Educational and Research Institute (RKMVERI), Kolkata, West Bengal, India
Ashish Kumar Sahoo
Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati,
Assam, India
Mothil Sengottian
Department of Chemical Engineering, Kongu Engineering College, Erode, Tamil
Nadu, India
Aveepsa Sengupta
Department of Microbiology, Tripura University (A Central University), Agartala,
Tripura, India
Bipin Kumar Sharma
Department of Microbiology, Tripura University (A Central University), Agartala,
Tripura, India
Muhammad Shoaib
Institute of Microbiology, University of Agriculture, Faisalabad, Punjab, Pakistan;
Key Laboratory of New Animal Drug Project, Gansu Province, Key Laboratory of
Veterinary Pharmaceutical Development, Ministry of Agriculture, Lanzhou
Institute of Husbandry and Pharmaceutical Sciences of CAAS, Lanzhou, China
xxiv Contributors
Anupama Shrivastav
Department of Microbiology, Parul Institute of Applied Sciences, Parul University,
Vadodara, Gujarat, India
Pragati Singh
Department of Microbiology, Tripura University (A Central University), Agartala,
Tripura, India
Rajalakshmi Sridharan
Department of Biotechnology Stella Maris College (Autonomous), Affiliated to
University of Madras, Chennai, Tamil Nadu, India
Diana Mayra Sánchez López
Center of Research and Technological Development in Electrochemistry,
Querétaro Technology Park, Pedro Escobedo, Querétaro, México
Sabeela Beevi Ummalyma
Institute of Bioresources and Sustainable Development (IBSD), An Autonomous
Institute Under Department of Biotechnology, Government of India, Takyelpat,
Imphal, Manipur, India
Divyesh K. Vasava
College of Agriculture, Junagadh Agricultural University, Junagadh, Gujarat,
India
Chitra Devi Venkatachalam
Department of Food Technology, Kongu Engineering College, Erode, Tamil Nadu,
India
Sivakumar Venkatachalam
Department of Chemical Engineering, AC Tech Campus, Anna University,
Chennai, Tamil Nadu, India
CHAPTER
A comparative study
between physicochemical
and biological methods for
effective removal of textile
1
dye from wastewater
Subhasish Dutta, Joyani Bhattacharjee
Department of Biotechnology, Haldia Institute of Technology, Haldia, West Bengal, India
1. Introduction
One of the major sources of pollution in nature is industrial wastewater. Due to high
global development, various chemical agents like dyes, pigments, and other aro-
matic compounds are used in industries such as textile, printing, pharmaceuticals,
and plastics to generate products with better results (Khan and et al., 2020). Various
studies have confirmed that an average sized textile industry consumes around 1.6
million liters of water per day for the production of about 8000 kg of fabric. A
research from World Bank has said around 17%e20% of textile industry water
pollution comes from dyeing and finishing treatments that are applied to the fabric.
The processes included in the main steps of textile industry are resizing, dyeing,
printing and some finishing steps. The finishing steps are softening, cross-linking
and waterproofing and they require a huge amount of water supply (Nemr, 2012;
Bhatia et al., 2017). Large amount of effluents are generated from dyeing and the
finishing processes. Dyeing can be defined as the process of applying colors to
the fabrics which are resistant to the effect of light, water, and soap. Tannin and
lignin are considered examples of coloring agents. For various other processes to
be carried out in the textile industry, a particular mixture is made out of chemicals,
dye stuffs, and water. Once the process is completely done this mixture is released
into various water bodies (Anjaneyulu et al., 2005). The presence of suspended solid
particles, high chemical oxygen demand (COD), synthetic dyes, and heavy metals
such as lead, mercury, and cadmium have been considered to increase the toxicity
of water. These textile effluents alter the color and composition of the water bodies
making it very hazardous for the marine ecosystem (Nguyen and Ruey-Shin, 2013).
Dyes have high thermal and photo stability which helps them to persist for an
extended period of time in the water environment if left untreated. The dark color
imparted by these toxic chemicals reduces the sunlight penetration thus hampering
photosynthesis. They also inhibit the growth and activity of microorganisms.
The effluents generated from these textile industries are not only considered to be
toxic for the aquatic ecosystem but they are also enriched by the presence of various
carcinogenic and mutagenic substances which are harmful to human beings too. For
instance, the very famous azo dye, which is one of the main components of textile
industry, is very much responsible for bladder cancer in humans (Ramachandran
et al., 2013). They also cause severe damage to kidney, brain, reproductive system.
Therefore, in this chapter an effort has been made in discussing the preexisting phys-
iochemical methods to remove toxicity from textile effluents and their inefficiencies
and cost effectiveness, with special focus on biological methods which have been
found beneficial.
Based on the presence of chromophoric groups, dyes can be classified into more
than 20e30 groups. Out of which most important ones are nitro dyes, nitroso dyes,
azo dyes, trimethyl ethane dyes, phthalein dyes, indigo dyes, anthraquinone dyes,
and sulfur dye (Benkhaya et al., 2020; Ramachandran et al., 2013).
3. Physical methods
Physical methods can be defined as a straight forward method to remove toxic efflu-
ents from wastewater by the application of forces such as gravitation, electrical
3. Physical methods 5
Modified from El Harfi, S., El Harfi, A., 2017. Classifications, properties and applications of textile dyes: a
review. Appl. J. Environ. Eng. Sci. 3 (3), 00000e00003 and Singh, P.K., Ram, L.S., 2017. Bio-removal
of azo dyes: a review. Int. J. Appl. Sci. Biotechnol. 5 (2), 108e126.
attraction, and van der Waal’s force. Of all the three methodologies (physical, chem-
ical, and biological), physical method is the most used one as it is much simpler, effi-
cient, and the least amount of chemicals and biological organisms are used (Vanitha
et al., 2018).
3.1 Adsorption
Of all the available physical methods, adsorption has been proven to be the most effi-
cient and widely used technology to treat waste water effluents (Anjaneyulu et al.,
2005). Adsorption can be defined as a physicochemical mass transfer process where
6 CHAPTER 1 A comparative study between physicochemical and biological
elements are concentrated on the surface of the adsorbent (solid or liquid). This pro-
cess happens in the interface of either two similar or different states for example,
liquid-liquid, gas-liquid, and solid-liquid (Natarajan et al., 2018). The process of
adsorption has been considered as one of the most feasible equilibrium separation
techniques to remove toxic effluents from water bodies due to its economic effi-
ciency and also due to the production of high quality products (Natarajan et al.,
2018). To perform adsorption, no pretreatment is required. Often, it is used as a post-
treatment for various other conventional methods as the process doesn’t produce
additional toxic matters as a result in the end (Vanitha et al., 2018). The surface
on which the process of adsorption takes place is called adsorbent and the adsorbates
are the molecules that get adhered to the surface of adsorbent. If the process of
adsorption is characterized by low heat generation and is reversible in nature, it is
called physisorption (physical adsorption). If the process is characterized by
high heat generation and is irreversible in nature with chemical force acting
between adsorbate and adsorbent, it is called chemisorptions (chemical adsorption)
(Natarajan et al., 2018).
Factors affecting adsorption: There are certain physicochemical factors associ-
ated with adsorption such as temperature, pH, solution concentration, nature of
adsorbate (molecular structure, size, and weight), surface charge, and time duration
of contact (Vanitha et al., 2018; Saini, 2017).
Due to the rising popularity of the adsorption process, a vast range of adsorbents
are used nowadays. Few of them are chitin, almond peels, fly ashes, baggase, acti-
vated carbon, sugarcane, etc.
substances like biomass, waste materials, and so forth (Vanitha et al., 2018). Acti-
vated carbon particle comes in different shapes and sizes. Powdered activated carbon
(PAC) is very fine in structure thus they can stay suspended for longer while and
making it difficult to be reused. Adding a little quantity of polyaluminum chloride
can enhance the decolorization rate making it easier to collect the sludge from
settling tank and reuse them. In case of granular activated carbon (GAC), it is easier
to replace the GAC packed bed with fresh amount of carbon particles when
exhausted (Nguyen and Ruey-Shin, 2013).
3.2.1 Irradiation
This is the simplest yet effective technique to remove textile dye effluents from
waste water. This process requires a large amount of UV radiation and constant dis-
solved oxygen supply. Titanium dioxide acts as a catalyst in the process. On treating
a secondary effluent with irradiation of gamma ray it was found that there was a
reduction of 64% COD, 34% TOC, and 88% of color (Anjaneyulu et al., 2005;
Robinson et al., 2001).
4. Membrane technology
Membrane technology can be considered as one of the most effective and cost-
efficient methods which not only help in decolorization but also in reduction of
BOD and COD of wastewater. The main advantage of membrane technology is
that the drench can be further reused. This kind of technology is immensely useful
in places where there is shortage of water (Buckley, 1992). On the basis of classifi-
cation of dye and degree of separation of effluents, this process can be classified into
four types.
4.1 Microfiltration
This is one of the oldest yet most capable ways of removing suspended particles hav-
ing aperture approximately 0.1e1 mm. Through this process of microfiltration wide
range of contaminants such as suspended particles, yeast cells, large pathogens, and
so forth can be separated. Microfiltration is usually performed prior to reverse
osmosis and nanofiltration (Buckley, 1992; Anis et al., 2019).
5. Chemical methods 9
4.3 Nanofiltration
The process of nanofiltration also known as charged filtration is performed after
adsorption to minimize the polarization concentration happening during the filtra-
tion process. It has the advantage of both reverse osmosis and ultrafiltration (UF),
i.e., application of moderate pressure like UF and separations of solutions like
reverse osmosis. Commercially available nanofiltration membrane have been used
to treat cotton textile dye effluents (Buckley, 1992; Xu and Lebrun, 1999).
4.4 Ultrafiltration
UF can be considered as a one-step removal of secondary effluents. UF can be
considered as an RO pretreatment. In many cases UF membranes have been found
using hollow fiber geometry (Xu and Lebrun, 1999).
From the experiment conducted by Paz’dzior et al. for the removal of azo dye by
the amalgamation of nanofiltration with biological methods, it was concluded that
almost 90% color removal was evident and pure colorless filtrate was obtained hav-
ing adequate quantity of salt and alkali concentration. Due to the formation of cleav-
age of Reactive Red 120, orthanilic acid was released. In an aerobic reactor, this acid
was further degraded whereas in the sequencing batch reactor, the aromatic amine
was not degenerated using the microbial culture (Pazdzior et al., 2009).
_
Zy11a et al. performed an experiment with real wastewater collected from two
textile plants. On applying nanofiltration on these textile effluents it was found
that there was significant deterioration in the COD and textile colors. The further
concentrated product in the nanofiltration was made to undergo anoxic biological
treatment. It was observed that there was approximately 50% reduction in the
COD. It was also inferred that the filtrate received from nanofiltration could be
_
used as process water for the rest of the process (Zy11a et al., 2006).
5. Chemical methods
Chemical methods of dye removal can be defined as a collection of certain conven-
tional methods performed by utilizing chemical theories to remove textile dye
10 CHAPTER 1 A comparative study between physicochemical and biological
effluents. This method requires specific set of equipments and high electrical energy
to work efficiently. Usually chemical technologies have been proven to have success
rate of 88%e99% (Vanitha et al., 2018).
5.2 Ozonation
This is one of the most effective chemical processes for nearly complete removal of
textile dye effluents from waste water. Ozone is an excellent oxidizing agent
compared to chlorine, hydrogen peroxide, and other oxidizing agents due to its
high instability. The proportion of ozone to be used in the process is directly propor-
tional to the amount of color and residual COD to be removed. The end product of
ozonation can be easily discharged in the water bodies easily due to the lesser
amount of color and COD present. Ozone can be applied in gaseous state thus vol-
ume of the sludge is not increased (Vanitha et al., 2018). In an experiment conducted
by Lin et al., three strengths of waste water effluent were collected low, medium and
high. The COD and color content of the effluents were observed to intensify from
low to high in the three containers. For low strength, it was inferred that only ozon-
ation was sufficient for decolorization and to remove turbidity. But for medium and
high strength, ozonation was found to be effective for the removal of color but not
5. Chemical methods 11
for turbidity reduction. Thus, coagulation with aluminum sulfate or PAC was neces-
sary. Even with the amalgamation of chemical coagulation with ozonation, approx-
imately 70% COD could be reduced (Lin and Lin., 1993).
5.3 Cucurbitiril
These are cyclic oligomer molecules made up of glycoluril and formaldehyde.
Glycoluril is formed from glyoxal and urea. The monomers are held together by
methylene bridges. The origin of the name cucurbitiril is from the Latin word
Cucurbita maxima which is the scientific name for pumpkin, for its pumpkin like
structure. The uril part of cucurbitiril emphasizes on the presence of urea. It was
inferred that cucurbitiril has extremely good sorption capacity for several textile
dyes. It also forms host-guest relation with aromatic compounds thus removing
the toxicity for adsorption. Another mechanism is based on formation of insoluble
cucurbitiril dye-cation aggregate as adsorption occurs at a faster rate (Robinson
et al., 2001; Nagy et al., 2009) (Fig. 1.1).
FIGURE 1.1
Structure of cucurbitiril (https://pubchem.ncbi.nlm.nih.gov/compound/Cucurbit_8_uril).
12 CHAPTER 1 A comparative study between physicochemical and biological
the brightness of the product. The chloride molecule attacks the amino group of the
dye, thus accelerating an azo bonding cleavage. This method is not applied for azo
dyes. In an experiment conducted by Massoudinejad et al. it was concluded that
combining chemical oxidation method with sodium hypochlorite solution gives rele-
vant standard to biological method. It was also noticed that imported chorine was
about 3.65 times more efficient than Iranian native chlorine (Robinson et al.,
2001; Massoudinejad et al., 2015).
5.5.1 Photocatalysis
Photo catalysis can be defined as a process by which a photo reaction is accelerated
in the presence of catalyst. This method degrades the dye molecule into water and
carbon dioxide by the action of UV rays in the presence of catalyst H2O2. Depending
on the product to be catalyzed and the length of the reaction, various byproducts are
formed. No sludge production is associated with the process. UV light on degrading
reaction with H2O2, forms two hydroxyl radicals which help in the further chemical
processes (Robinson et al., 2001).
Photo catalytic removals of organic pollutants have been found to be one of the
most effective ways. Ag/Cl can be considered as high performing photo catalysts
that can be used for degradation. Zhao et al. in his experiment successfully prepared
Ag/AgCl nanoparticles biochemically from the metabolin of living fungi. These
nanoparticles were found to be 3e5 nm in size, spherical in shape. On studying these
particles under microscope it was found that these particles show visible light driven
photo catalytic performance. This biochemical invention helped in the degradation
of a carcinogenic RhB (Zhao et al., 2015).
6. Advanced oxidation process 13
pH can be easily oxidized. It has been studied that sulfate radicals are selective in
nature thus can be used properly to oxidize specific functional groups responsible
for toxicity of wastewater (Lutze et al., 2015).
7. Biological methods
Various physicochemical methods such as oxidation, ozonation, membrane technol-
ogy, coagulation flocculation, and AOPs have been administered to reduce the COD
level and to remove the toxic effluents which are released from textile effluents in
various water bodies. But these processes have some limitations such as costing,
equipments and sludge formation in the end. Many of these processes even work
in situ for only small scale effluents. Thus biological methods have been used as
alternating techniques to remove large scale effluents using living microorganisms
in much cost-efficient and simpler way (Table 1.2).
Table 1.2 Factors affecting biological method of dye removal (Rauf and
Ashraf, 2012; Wesenberg et al., 2003).
Serial
no. Factor Affect
1 Oxygen Dye degradation can occur under aerobic and anaerobic
conditions. Under anaerobic condition, reductive enzyme
activity is higher. Under aerobic conditions, carbon sources
like glucose, starch, acetate affect the decolorization process.
2 Ph The enzymatic activity depends on the pH and on the acid-
base behavior of the substrate and amino acid side chain. The
optimum pH for color removal is often neural or slightly
alkaline. The rate of color removal decreases with acidic pH
values.
3 Temperature This is one of the most impactful parameters. With an increase
in temperature, the rate of color removal increases too. The
temperature required for maximum color removal is nearly
around 35 to 45 C, which is also optimum for cell growth.
4 Dye structure The more dye concentration, the more is the amount of
and toxicity. Dye structure varies in different dyes. Dyes with
concentration simple structure and low molecular weight give out higher rate
of color removal and the process is more difficult with dyes of
high molecular weight.
5 Redox Enzyme mediated degradation is a versatile process efficient
mediator process. The redox mediator is required to maintain the redox
equilibrium. The more redox potential, the faster the molecule
is reduced.
7. Biological methods 15
can be defined as a process which prevents cell washing outs and also allows higher
cell density to be maintained in the continuous reactor. Immobilization upgrades the
catalytic stability thus increasing the concentration of degradation of textile dyes. It
has been studied that immobilization results in increased uptake of nutrients due to
the availability of nutrients at the solid-liquid interface. On comparing the immobi-
lized cells of Pseudomonas putinda P8 to the free cells P. putinda, the immobilized
cells have been found to be more efficient in degrading catechol. Immobilization
method using biomass has been found to be really beneficial. It is performed under
aseptic conditions within the bioreactors (Puvaneswari et al., 2006).
62.5 kDa. They are secreted in multiple isoforms. MnPs generally oxidize Mn2þ to
Mn3þ which then is stabilized by chelating compound such as oxalic acid which is
also secreted by the fungi itself. The chelated Mn3þ thus formed is highly reactive
and acts as a diffusible redox mediator. Thus, MnPs oxidizes and depolymerizes
lignin and also xenobiotics like nitroaminotoluenes and toxic textile dyes. The
stability of MnP can be enhanced by immobilizing with sodium alginate, gelatin
or chitosan as carriers and glutaraldehyde as cross-linking (Wesenberg et al.,
2003; Asgher et al., 2008).
7.6.3 Laccases
These are N-glycosylated extracellular blue multicopper oxidases having molecular
mass around 58e90 kDa. The optimum pH and temperature vary from around 2 to
10 and 40e65 C respectively. Two strains of laccase isoenzymes LacI and LacII
have been found in Physisporinus rivulosus T241i, Trametestrogii, Cerrena unicolor
137 and Panustigrinus. Laccases along with oxidizing aphenolic and methoxyphe-
nolic acids, it also decarboxylizes them and attacks their methoxy groups (Asgher
et al., 2008).
Small molecule mediators are low molecular weight highly diffusible redox sub-
stances which help in the interaction between lignin and LME. Due to the random
polymer nature of lignin and bulk of LME, the interaction becomes highly problem-
atic thus these mediators come in action. A few examples of native mediators are P.
chrysosporium, Armillaria mellea, and so forth (Wesenberg et al., 2003).
Most of the dye stuffs that are used in the industries are extensively harmful to
any living being. These dye effluents are highly carcinogenic in nature. White-rot
fungi are used for the purpose of degradation of these harmful dye effluents.
White-rot fungi are preferred over prokaryotic cells due to the presence of LME
system which is nonspecific in nature, thus can degrade a wide range of dyes. P.
chrysosporium and Trametes versicolor are the most used ones. There are other use-
ful WRF too, they are Phellinus gilvus. DIchomitussqualens. Irpex flavus, Gano-
derma sp., etc. The degrading mechanism of dyes varies from the structure and
reactivity of different dyes. For instance, the decolorization of Reactive Blue 15
by chrysosporium follows first order kinetics with respect to initial dye concentra-
tion. Here, MnP plays a major role in decolorization (Asgher et al., 2008).
In an experiment conducted by Kapdan et al. he prepared four separate white-rot
fungi cultures to decolorize five kinds of textile dyes. The strains of white-rot fungi
taken were P. chrysosporium MUCL, P. chrysosporium 671.71, Coriolus versicolor
MUCL, and C. versicolor. The dye stuffs taken were Everzol Yellow 4 GL (Reactive-
monoazo), Everzol Red RBN (Reactive-monoazo), Drimaren Orange K-GL
(Reactive-disazo), Everdirect Supra Yellow PG (Direct-disazo) and Everzol
Turquoise Blue G (Reactive-phtalocyanin). He concluded that the culture of P.
chrysosporium or C. versicolor were highly effective in total removal of dye color
effluents. But, the high incubation temperature around 37 C was marked to be disad-
vantage for the process. Because of lower incubation temperature around 28 C
requirement for C. versicolor cultures, C. versicolor MUCL culture seems to be
more suitable than P. chrysosporium culture for practical applications (Kapdan
et al., 2000).
References 19
8. Conclusion
Different textile industries generate different forms of textile dyes. In this research
article, various physicochemical methods, their advantages and limitations, and
various biological processes with their advantages, have been discussed (Bhatia
et al., 2017). The various physicochemical methods were found to be costly and
reactive only when the effluent volume was less. Many of these processes produced
large volumes of sludge in the end thus not being effective in removal of toxicity
(Ramachandran et al., 2013). Due to the ineffectiveness of the conventional
physicochemical processes, biological processes have been discussed which were
considered to be more ecofriendly and effective for the removal of textile dyes
(Ramachandran et al., 2013). Bioremediation methods use naturally occurring
microbes which are economically friendly and even cost-efficient. Processes like
biosorption is an amalgamation of physical and biological method has been
discussed as an emerging technique which can be used to degrade textile effluent
(Bhatia et al., 2017).
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Con queste spedizioni Augusto compieva nelle Alpi un’opera, le cui
conseguenze durano ancora: apriva quella famosa catena di
montagne alla civiltà. L’opera era grande: ma nel pensiero di
Augusto doveva servire di preparazione ad un’opera ancora più
vasta, destinata ad avere le conseguenze più grandi nella storia
della civiltà. Gli anni che seguono il 16 a. C., e nei quali Augusto, per
le necessità della guerra, visse in Gallia o vicino alla Gallia, sono
anni decisivi nella storia del mondo antico; perchè in questi anni
Augusto e il governo romano si accorsero definitivamente che la
Gallia, la barbara, fredda e povera Gallia della tradizione, era una
provincia ricchissima, il vero Egitto dell’Occidente, che Roma aveva
interesse a difendere quanto le più ricche provincie dell’Oriente. Le
conseguenze di questa scoperta dovevano essere immense; poichè,
se fino ad allora Roma aveva guardato quasi soltanto all’Oriente,
come alla sede della ricchezza e della cultura, ed era stata sempre
in pericolo di inorientarsi, mutandosi in un impero asiatico, da questi
anni essa diventa potenza mezzo asiatica e mezzo europea, nel cui
impero la Gallia fa contrappeso all’Egitto o alla Siria, e l’Italia si trova
ben posta in mezzo, per essere l’arbitra e la dominatrice dell’Oriente
e dell’Occidente. A partire da questo momento, in cui la civiltà greco-
latina valica le Alpi e si addentra nel continente europeo, incomincia
la vera storia dell’Europa, che sino allora, fuorchè nelle sue coste
meridionali, era stata barbara; e l’impero romano diventa un impero
misto, orientale e occidentale, sotto l’egemonia dell’Italia. Senza la
Gallia, Roma non avrebbe potuto a lungo essere la capitale di un
impero, le cui province più importanti e i maggiori interessi erano in
Asia ed in Africa, e l’Italia sarebbe stata presto o tardi assorbita dalle
sue conquiste asiatiche ed africane. Insomma l’unità dell’impero
mediterraneo di Roma e la egemonia dell’Italia in quello
dipendevano dal possesso e dallo sviluppo della Gallia. Senonchè,
se queste dovevano essere le conseguenze lontane della conquista
di Cesare, l’arricchimento della Gallia generava un altro effetto
immediato; ed era quello di obbligare Roma a difenderla contro i
Germani, sempre inquieti, sempre bellicosi e più pronti ad assaltar la
Gallia ora che non la difendeva più la sua vecchia aristocrazia
militare. Perciò il pericolo germanico non minacciava più, come ai
tempi di Cesare, la Gallia sola, ma l’impero romano tutto quanto. Ma
che altro mezzo c’era di assicurare la Gallia contro le invasioni dei
Germani, se non conquistare la Germania? Anche questa era una
catena. Dal commovimento delle province d’Occidente, dalla
crescente prosperità della Gallia, Augusto fu tratto in questi anni a
sostituire alla conquista della Persia, vecchio sogno romano, la
conquista della Germania, a cui nessuno aveva ancora pensato sul
serio. Roma diventava potenza occidentale ed europea.
Prima però di accingersi a tanto passo, Augusto volle toglier via dalla
Gallia qualsiasi possibilità di agitazione antiromana. Vi sussistevano
ancora le divisioni territoriali, che Cesare avea trovate e conservate.
I popoli più potenti, come gli Edui e gli Arverni, conservavano
ancora, quali alleati di Roma, la loro clientela di piccole civitates che
essi governavano direttamente. Ma ora che la Gallia era divenuta un
paese industrioso e pacifico, queste clientele, fuorchè a conservare
privilegi invecchiati e a giustificare pretese di egemonie fittizie, non
potevano servire che come strumenti di nuove coalizioni nazionali:
erano dunque o inutili o pericolose.
Augusto sottomise tutte queste civitates di clienti e di popoli alleati,
direttamente, all’autorità di Roma; inoltre, fondandosi sui resultati del
censimento, distribuì tutta la Gallia in 60 civitates, all’incirca eguali di
grandezza e pari in diritto tra loro. Ma crescendo così il compito e la
responsabilità del governatore romano in Gallia, tripartì il paese in
Aquitania, Lugdunensis e Belgica (le Tres Galliae), di cui ciascuna
avrebbe avuto a capo un luogotenente del governatore generale
della provincia. Senonchè in questa ripartizione Augusto non tenne
più conto delle diversità o affinità etniche e delle secolari unioni
storiche del paese, se non per mescolare in ciascuna delle tre gli
elementi diversi — celtici, iberici, celto-germanici — di cui la Gallia si
componeva; per spegnere in quelle mescolanze il vecchio spirito
nazionale e tradizionale; per intralciare gli accordi fra tribù affini; e
per piegare il paese denazionalizzato verso gli scopi della politica
romana.
Augusto inoltre volle, prima di incominciare la sua grande impresa,
riordinare, come faceva mestieri, l’esercito, regolando con una legge
le più importanti condizioni del servizio, fin ad allora regolate da
consuetudini poco certe. La ferma durerebbe 16 anni per i legionari;
12 anni per la guardia dell’imperator, i pretoriani. Fu stabilito inoltre
che, finito il servizio gli uni e gli altri sarebbero ricompensati, non con
terre, ma con una somma di danaro, di cui ci è ignoto l’ammontare.
Ciò fatto, preparativi adeguati all’impresa furono incominciati; e fu
elaborato un piano di invasione molto ingegnoso, nel quale è
verosimile riconoscere la mano di Agrippa. Si tenterebbe di invadere
l’impervia Germania dal mare del Nord per le due grandi linee fluviali
dell’Ems e del Weser; due eserciti entrerebbero per questi fiumi nel
cuore della Germania, costruirebbero sull’uno e sull’altro dei grandi
campi trincerati, destinati a servire come basi di operazione, per
condurre a termine la conquista dell’interno; nel tempo stesso un
altro esercito, varcato il Reno, avanzerebbe alla volta dell’Ems;
l’esercito sbarcato sull’Ems, avanzando lentamente, cercherebbe di
dar la mano a quello che verrebbe dal Reno, come a quello che
verrebbe dal Weser: e così mediante larghe vie, fiancheggiate da
fortificazioni, si sarebbero collegati insieme il Reno all’Ems, l’Ems al
Weser e forse anche all’Elba. Ottimo piano, che proteggeva da molti
e grandi rischi gli eserciti invasori. Ma poichè in tal guisa le flottiglie
fluviali romane sarebbero esposte troppo tempo al tempestoso mare
del Nord, Augusto volle aprire un canale tra il Reno e l’Yssel, di
guisa che la flotta romana sarebbe potuta penetrare sicuramente
nello Zuidereee (lago Flevo) e di là nel mare del Nord.
Ma al momento di porre mano a questa spedizione, preparata con
tanta cura, un gran lutto colpì l’impero. Augusto aveva senza
difficoltà ottenuto dal senato il prolungamento per altri cinque anni
dei poteri suoi e di Agrippa, scadenti alla fin dell’anno 13; continuava
alacremente i preparativi per la guerra di Germania, quando al
principio dell’anno 12, nel mese di marzo, pochi giorni dopo che
Augusto era stato eletto anche pontifex maximus in sostituzione di
Lepido morto, e proprio quando la invasione della Germania stava
per cominciare, Agrippa moriva in Campania. La perdita era funesta:
sia perchè Augusto, che aveva voluto spartire con lui il carico e la
responsabilità del potere fu costretto ad assumere di nuovo da solo il
governo della repubblica; sia perchè spariva, proprio al momento in
cui Roma stava per intraprendere una spedizione di capitale
importanza, l’uomo di guerra più sperimentato su cui fare
assegnamento. La morte di Agrippa sembrò infatti indurre Augusto a
rinviare l’impresa germanica. Lì per lì Augusto si restrinse a spedir
Tiberio nella Pannonia, che si era ribellata, e soltanto nella seconda
metà dell’anno si risolvè a riprendere il disegno della guerra in
Germania, incaricandone Druso, che era allora un giovane
propretore di 26 anni. Eseguendo il piano lungamente preparato da
Agrippa, Druso, con una parte delle truppe, discese il corso del
Reno, entrò nello Zuidersee, penetrando così nel cuore del paese
dei Frisoni (la moderna Olanda): di lì uscì con la flotta nel Mare del
Nord ed imboccò l’Ems, sbarcando, a un certo punto del corso del
fiume, una parte delle sue forze. Quindi ridiscendeva il fiume, e
tentava, come sembra, di ripetere sul Weser l’operazione già
compiuta sull’Ems, ma senza riuscirvi, questa volta; anzi scampando
a stento a un naufragio. Alla fine dell’anno 12, egli era di ritorno in
Gallia.
Queste operazioni non erano che il prologo della vera campagna,
che doveva incominciare l’anno seguente e che doveva consistere,
secondo il piano di Augusto, in una lenta, metodica e graduale
invasione. Nella primavera dell’11, Druso doveva con un esercito
risalire la valle della Lippe sulla riva destra, mirando a ricongiungersi
nell’alta valle con le altre forze romane sbarcate sulle rive dell’Ems,
che a loro volta risalirebbero la valle di questo fiume. Alla confluenza
della Lippe con un fiume, che gli storici antichi chiamano Aliso,
doveva fondare una grande fortezza e collegarla al Reno con una
strada e una catena di fortezze minori. Era questo il compito
tracciato a Druso per quell’anno. Druso risalì vittoriosamente la valle
della Lippe e si ricongiunse felicemente con l’esercito che aveva
risalito l’Ems: ma appena operata la congiunzione, osò fare uno
strappo al prudente piano di Augusto e di Agrippa. Le popolazioni
germaniche essendo in guerra tra loro, egli giudicò che l’ardimento
poteva fruttar questa volta assai più che un lungo e prudente
guerreggiare. Raccolse in fretta dei viveri, attraversò il paese dei
Sicambri che era deserto perchè i maschi adulti si erano gettati sul
paese dei Catti; invase il territorio dei Tencteri che si sottomisero;
indi, come attingendo nuovo coraggio dalla propria audacia, avanzò
nel paese dei Catti e costrinse questi e i Sicambri con cui essi
combattevano, a riconoscere la signoria romana. Ma la mancanza di
vettovaglie e la sterilità del paese lo costrinsero presto a ritirarsi
verso la Lippe. Senonchè nel ritorno cadde in un’imboscata, e per
poco non fu annientato insieme col suo esercito. Sfuggito per
miracolo a tanto rischio, e giunto di nuovo alla Lippe, riprese il piano
di Augusto; e ordinò la costruzione del castellum, al quale si sarebbe
dato il nome di Aliso; quindi, tornato in Gallia, decise di erigere un
altro castellum sul Reno, probabilmente quello che doveva un giorno
essere Coblenza.
Il terzo anno della guerra — l’anno 10 a. C. — sembra essere
passato abbastanza tranquillo, senza grandi eventi. È probabile i
Germani non si mossero, e che i Romani continuarono alacremente
a costruire i due castelli, incominciati l’anno prima. Certo è che
Druso potè in quell’anno venire a Roma; e a Roma brigare e
ottenere il consolato per l’anno 9. Ma prima della fine dell’anno, e
senza aver avuto il tempo di prendere possesso dell’altissima carica,
Druso fu costretto a lasciar Roma e a tornare frettolosamente in
Germania, ove Sicambri, Svevi e Cherusci tentavano di collegarsi
per fare guerra insieme alla Gallia. E l’anno seguente, il 9, la guerra
mutò carattere. Sia che Druso avesse convinto Augusto della
necessità di atterrire con un grande colpo i Germani; sia che di
questa necessità l’avessero convinto gli ambiziosi progetti dei
Sicambri, degli Svevi e dei Cherusci, in quell’anno la Germania fu
invasa davvero e a fondo. Druso si spinse, combattendo, non
sappiamo per quali vie e con quante forze, prima fino al Weser, e poi
fino all’Elba. L’ardita mossa riuscì, perchè i Germani non osarono
attaccarlo in massa. Druso potè scorrazzar da padrone nella
Germania, sino ai primi di agosto, quando, la stagione incalzando, si
volse al ritorno. Ma nel ritorno cadde da cavallo, si ruppe una
gamba; e dopo pochi giorni moriva, in seguito a questa ferita.
La morte di Druso era una disgrazia per la repubblica. Augusto
perdeva, dopo Agrippa, un altro collaboratore fidato, mentre nel
senato e nella aristocrazia cresceva la riluttanza ad assumere le
grandi cariche, e diminuiva il numero degli uomini capaci. I giovani
soprattutto erano restii ad uscir di Roma, a passare lunghi anni nelle
province, ad imparare il duro mestiere della milizia e del comando.
Pare che di nuovo Augusto pensasse di ritirarsi a vita privata sul
finire dell’anno 8, quando i suoi poteri quinquennali scadrebbero.
Erano 20 anni ormai, dalla restaurazione della repubblica, che egli
governava Roma come princeps e avrebbe avuto diritto di riposarsi.
Ma chi poteva occupare il suo posto? Non si sarebbe tutta
l’amministrazione dell’Impero sfasciata, se fosse sparito l’uomo, il
quale pensava a tutto ciò, cui il senato e i magistrati repubblicani non
provvedevano? Il potere personale di Augusto era la necessaria
correzione della decadenza dell’aristocrazia. Gli fu forza quindi,
volente o nolente, di accettare un nuovo prolungamento del suo
potere per 10 anni, e per provvedere alla Germania richiamò l’altro
suo figliastro, Tiberio, che da tre anni combatteva nella Pannonia e
nella Dalmazia; e gli diede l’incarico di terminare la conquista della
Germania. Tiberio era diventato suo genero; poichè nell’11 era stato
costretto da Augusto a ripudiare la moglie, che era figlia di Agrippa,
e a sposare la vedova di Agrippa, che era sua figlia Giulia. Ma
Tiberio non ebbe, l’anno 8, che a passare il Reno alla testa di un
esercito; e tutta la Germania, si arrese. La marcia di Druso dava i
suoi frutti. In soli quattro anni, la Germania era, o almeno pareva,
conquistata dal Reno all’Elba, e la grande impresa, tentata per la
prima volta da Cesare, condotta a compimento dal figlio suo.
Note al Capitolo Ottavo.
43. Si legge nella lex de imperio Vespasiani (C. I. L. VI, 930, 17-19): utique
quaecunque ex usu reipubblicae majestate divinarum huma[na]rum
publicarum privatarumque rerum esse censebit, ei agere facere jus
potestasque sit ita uti divo Augusto.... Le ragioni per cui crediamo
doversi riportare a questo momento il conferimento di questa autorità
quasi illimitata, si trovano esposte in G. Ferrero, Grandezza e
Decadenza di Roma, IV, p. 188.
44. Dion. Cass., 54, 12. Ferrero, Grandezza e Decadenza di Roma, IV, p.
293.
CAPITOLO NONO
LA SUCCESSIONE DI AUGUSTO
47. Sulla catastrofe di Varo le opere più recenti sono Gailly de Taurines,
Les legions de Varus, Paris, 1911; e W. A. Oldfather and H. Vernon
Canter, The defeat of Varus and the German frontier Policy of
Augustus, in University of Illinois Studies, 1915.
CAPITOLO DECIMO
TIBERIO [48]
(14-37 d. C.)