Journal of Environmental Management 182 (2016) 351e366

Contents lists available at ScienceDirect

Journal of Environmental Management

journal homepage: www.elsevier.com/locate/jenvman

Review

A critical review on textile wastewater treatments: Possible

approaches
Chandrakant R. Holkar, Ananda J. Jadhav, Dipak V. Pinjari*, Naresh M. Mahamuni,
Aniruddha B. Pandit
Chemical Engineering Department, Institute of Chemical Technology Mumbai, N. P. Road, Matunga (E), Mumbai, 400019, India

a r t i c l e i n f o a b s t r a c t

Article history: Waste water is a major environmental impediment for the growth of the textile industry besides the
Received 3 March 2016 other minor issues like solid waste and resource waste management. Textile industry uses many kinds of
Received in revised form synthetic dyes and discharge large amounts of highly colored wastewater as the uptake of these dyes by
14 July 2016
fabrics is very poor. This highly colored textile wastewater severely affects photosynthetic function in
Accepted 28 July 2016
plant. It also has an impact on aquatic life due to low light penetration and oxygen consumption. It may
also be lethal to certain forms of marine life due to the occurrence of component metals and chlorine
present in the synthetic dyes. So, this textile wastewater must be treated before their discharge. In this
Keywords:
Textile wastewater
article, different treatment methods to treat the textile wastewater have been presented along with cost
Cavitation per unit volume of treated water. Treatment methods discussed in this paper involve oxidation methods
Ozone (cavitation, photocatalytic oxidation, ozone, H2O2, fentons process), physical methods (adsorption and
H2O2 filtration), biological methods (fungi, algae, bacteria, microbial fuel cell). This review article will also
Bacteria recommend the possible remedial measures to treat different types of effluent generated from each
Microbial fuel cell textile operation.
Cost analysis © 2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
2. Textile operations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
2.1. Sizing and desizing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
2.2. Bleaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
2.3. Mercerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
2.4. Dyeing and printing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
2.5. Finishing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
3. The textile industry standards for water pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
4. Treatment processes for textile wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
4.1. Physical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
4.2. Oxidation methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
4.3. Biological methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
4.3.1. Fungal cultures for degradation of dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
4.3.2. Algae for degradation dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
4.3.3. Pure culture and mixed culture for degradation of dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
4.3.4. Microbial fuel cell: sustainable technology for textile wastewater treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
5. Factors affecting bacterial degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
6. Biological and physicochemical combination processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
7. Cost of textile wastewater treatment techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362

* Corresponding author.
E-mail address: dv.pinjari@ictmumbai.edu.in (D.V. Pinjari).

http://dx.doi.org/10.1016/j.jenvman.2016.07.090
0301-4797/© 2016 Elsevier Ltd. All rights reserved.
352 C.R. Holkar et al. / Journal of Environmental Management 182 (2016) 351e366

8. Conclusion and recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362

Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363

1. Introduction 2. Textile operations

Industrialization plays an important role in the development of Textile industries prepare fibers; transform fibers into yarn and
any country. Textile industry is a vital and quickly emerging in- alter the yarn into fabric and then these fabrics goes through
dustrial segment in India. The textile industry uses different re- several stages of wet processing. Some of the stages in wet pro-
sources/raw materials such as cotton, woolen and synthetic fibers. cessing of textile fabrics are revealed in Fig. 1 (Vigo, 2013) and are
Cotton based textile industries are considered in this study. The discussed in detail in the subsequent sections.
textile industries can also be classified into two groups viz dry and
wet fabric industry. Solid wastes are generated in dry fabric in-
dustry while liquid wastes are generated in wet fabric industries. 2.1. Sizing and desizing
All textile industries in the later category are considered in this
study. Processing operation such as desizing, scouring, bleaching, Textile wet processes like dyeing and printing are affected by
mercerizing, dying, printing and finishing stages are included in the existence of sizing chemicals in the fabric. For instance, the
wet fabric processing industry. During fabric formation, the water occurrence of starch hampers the diffusion of the dye molecule into
utilization and waste water generation from a wet processing the yarn/fabric, which needs the elimination of starch preceding to
textile industry depends upon the operations. dyeing and then printing. Enzymatic or dilute mineral acid hydro-
The textile industry is a main creator of effluent wastewater due lysis or oxidation is used to remove such a sizing chemicals. Such a
to a more consumption of water for its different wet processing hydrolysis or oxidation processes convert starch into simple water
operations. These effluent wastewater contains chemicals like soluble products (Fu and Lu, 2014). Effluent from desizing has a
acids, alkalis, dyes, hydrogen peroxide, starch, surfactants more biological oxygen demand (BOD) in the range of
dispersing agents and soaps of metals (Paul et al., 2012). So, in 300e450 ppm and pH of 4-5- (Magdum et al., 2013) that renders it
terms of its environmental impact, the textile industry is estimated out of use. An oxidation by hydrogen peroxide can be used for the
to use more water than any other industry, globally and almost all degradation of starch into CO2 and H2O. Alternatively, the problem
wastewater discharged is highly polluted. Average sized textiles of starch can also be eased by using enzymes that covert it into
mills consume water about 200 L per kg of fabric processed per day ethanol. Distillation is used to recover this ethanol which can be
(Wang et al., 2011; Kant, 2012). According to the World Bank esti- used as a fuel, thus reducing the ultimate biological oxygen demand
mation, textile dyeing and finishing treatment given to a fabric (BOD) load on the treatment (Sarayu and Sandhya, 2012).
generates around 17 to 20 percent of industrial waste water (Kant,
2012).
In India, the textiles industry consumes around 80% of the total 2.2. Bleaching
production of 1, 30,000 tons of dyestuff, due to high demand for
polyester and cotton, globally (Naik et al., 2013). These dyes in Natural color substance in the fabric is responsible for the
wastewater severely affect photosynthetic function in plant. They creamy look to the fabric. In order to get a white fabric which en-
also have an impact on aquatic life due to low light penetration and ables the production of bright shades, it is essential to remove
oxygen consumption. They may also be lethal to certain forms of natural color matter from the fabric by the process of bleaching. In
marine life due to the occurrence of component metals and chlo- earlier days, hypochlorite was being used as bleaching agents. Now
rine. Suspended particles can choke fish gills and kill them. They days, hypochlorite is exchanged by another bleaching agents such
also decrease the capacity of algae to make food and oxygen. Dyes as H2O2 and peracetic acid. Peracetic acid is an environmentally
are also detected to hinder with certain municipal wastewater benign alternative to hypochlorite bleaching agent. Higher luster
treatment operations such as ultraviolet decontamination etc. along with less yarn destruction of the processed fabric is the one
(Mazumber, 2011). major benefits of peracetic acid (Abdel-Halim and Al-Deyab, 2013;
At present, aromatic and heterocyclic dyes are used in textile Liang and Wang, 2015).
industry. The complicated and stable structure of dye is posing a
greater difficulty in degradation when present not only in textile
2.3. Mercerization
wastewater but also in any kind of complex matrix (Ding et al.,
2010). The mineralization of dyes, organic compounds and hence
Mercerization of cotton fabrics are carried out after bleaching to
the toxicity of the wastewater generated by textile industry and
give a shine and advance dye uptake. Basically, it is done by treating
dyes manufacturing industry is a main challenge and an ecological
cotton fabric with a high concentration (about 18e24% by weight)
concern. Hence, understanding and emerging real textile waste-
of sodium hydroxide. In this process, cotton fabric goes through the
water treatment is ecologically noteworthy.
longitudinal shrinkage during impregnation in the NaOH solution.
Therefore, the main aim of this paper is to provide a complete
Here, this longitudinal shrinkage can be avoided by elongating the
survey about different wet processing steps in cotton textile in-
fabric or holding the fabric under tension. The excess caustic is
dustry and the cost of methods implemented for the treatment of
washed off after 1e3 min, while holding the cotton fabric under
the dyes in textile wastewater. This review also explains the critical
stress. Then, the material gains the preferred properties of luster,
study of the most generally used methods (chemical, physical and
easy dye uptake and improved absorbency. Membrane techniques
biological) of dye removal from textile industrial effluents.
or multiple effect evaporators can be used to recover the sodium
hydroxide in the wash water (Fu et al., 2013; Lee et al., 2014).
 C.R. Holkar et al. / Journal of Environmental Management 182 (2016) 351e366
Fig. 1. A flow diagram for several steps involved in wet processing of fabric.
2.4. Dyeing and printing
Dyeing is the treatment of fabric or yarn with a dye to impart
color. Chromophore groups such as azo (eN]Ne), carbonyl (eC]
O), nitro (eN]O), quinoid groups and auxochrome groups like
amine, carboxyl, sulphonate and hydroxyl in the dyes are respon-
sible for the color (Waring and Hallas, 2013). Azo and anthraqui-
none are the most important groups. These chromophores also
cause contamination rendering unacceptable color to the textile
wastewater. Fig. 2 depicts the main types of dyes used for dyeing
different kinds of fibers (Waring and Hallas, 2013).
The important reactions involved in printing process are similar
to those in dyeing process. In case of dyeing, dye is applied in a
solution form, while in printing; dye is applied in a thick paste form
of the dye to prevent its spread. Printing effluent also contains
waste components similar to dyeing effluent (Ratthore et al., 2014).
2.5. Finishing
Here, fabrics are exposed to a several types of finishing pro-
cesses. Finishing process is used to improve definite properties in
the fabric. Specific properties like softening, waterproofing, anti-
bacterial and UV protective are imparted to fabric in the process of
finishing. The finishing processes also contribute to water pollution.
List of some water pollutants that may be produced at different
stage of wet processing is depicted in Fig. 3 (Kant, 2012).
3. The textile industry standards for water pollutants
There are stringent requirements for the discharge of the textile
wastewater as it is unsafe to the environment and societies. The
standards of the wastewater discharge (Table 1 (Paul et al., 2012)
have far too many parameters due to the variation in the raw
Fig. 2. Dyes for different fibers.
353
materials used, different types of dyes and equipment. These
standards are established by the national environmental protection
department of Central Pollution Control Board (CPCB) depending
upon the local surroundings and environmental safety necessities
which are unfixed.
In case of textile wastewater, metal ions, dyes and its color are of
the first concern due to their harmfulness to environment and
people. In recent times, the recovery and reuse of wastewater has
received considerable attention because of the scarcity of water.
The interest today is not in technologies for color removal but in
technologies that can produce reusable water, remove toxicity,
mineralize aromatic compounds or recover the dyes, recover the
salt, do not produce toxic sludge, possibly do not produce sludge at
all. Technologies for color removal were important 30 years ago and
are well known today. Hence, wastewater treatment processes for
the mineralization of dyes are discussed in the subsequent sections
rather than that for color removal.
4. Treatment processes for textile wastewater
The textile wastewater has a high color, high BOD/COD and salt
(Total Dissolved Solids, TDS) load. The textile wastewater generated
from cotton dyeing industry is extremely polluted due to presence
of reactive dyes which are not readily amenable to biological
treatment. Color water causes scarcity in the light which is essential
for the development of the aquatic organisms. As result, it leads to
an imbalance in the environment. To reduce the treatment cost of
the river water which is used the purpose of drinking; it should not
have any color and toxic compounds. So, before discharge of textile
wastewater into river, many treatment processes (Fig. 4) including
physical, chemical, biochemical, hybrid treatment processes have
been developed to treat it in an economic and efficient way. These
technologies are verified to be highly effectual for the treatment of
354 C.R. Holkar et al. / Journal of Environmental Management 182 (2016) 351e366

Fig. 3. List of some of the pollutant generated at each level of textile wet processing.

Table 1 the low decolorisation efficiency and large generation of resultant

Indian Textile industry standards for water pollutants.
Sr.No. Parameters
1 pH
2 BOD
3 COD
4 TDS
5 Sulphide
6 Chloride
7 Calcium
8 Magnesium
textile wastewater. (Kumar and Bhat, 2012).
4.1. Physical methods
Coagulationeflocculation based physical methods are useful for
the decolorisation of wastewater containing disperse dyes. They
also have low decolorisation efficiency for the wastewater having
reactive and vat dyes. These techniques also limit their use due to
sludge (Liang et al., 2014; Yeap et al., 2014).
Standards Adsorption approaches have attracted significant attention due
to their greater decolorisation efficiency for wastewater containing
6.9
30 ppm a variety of dyes. High affinity, capability for the compounds and
250 ppm adsorbent regeneration ability are the main characteristics which
2000 ppm need to be considered during the selection of an adsorbent for color
2 ppm
removal (Jadhav and Srivastava, 2013). Activated carbon is an
500 ppm
75 ppm
effective adsorbent for a wide range of dyes. But, its high price and
50 ppm difficulty in its regeneration limits the application for decolorisa-
tion (Gala
n et al., 2013). For economically practicable application of
the adsorption method, some researchers used a low cost adsor-
bent material such as peat, bentonite clay, fly ash and polymeric
resins. Some scientists also tried many biotic resources like wheat
residue, treated ginger waster, ground nut shell charcoal, date
stones and potato plant waste for the decolorisation of textile
wastewater. Various adsorbents along with the dye are summa-
rized in Table 2. However, an applications of these adsorbents have
been restricted by the several problems such as its regeneration
and/or dumping, sludge generation and high price of the adsorbent

Fig. 4. Treatment methods for the degradation of dyes in textile wastewater.

 C.R. Holkar et al. / Journal of Environmental Management 182 (2016) 351e366
Table 2
Various adsorbent for adsorption of dye.
Sr. No. Adsorbent
1 Symphoricarpusalbus, Modified with sodium diethyldithiocarbamate
2. Modified wheat residue (MWR)
3. Capsicum annuum seeds
4. Immobilized eggshell with a polymer mixture of alginate and polyvinyl alcohol
5. Treated ginger waste (TGW)
6 Ground nut shells charcoal (GNC), and Eichhornia charcoal (EC)
7. Pistachio hull powder (PHP)
8. Date Stones (DS) and Palm-Trees Waste (PTW)
9. Potato plant waste
10. Straw based absorbent
11. Waste tea activated carbon (WTAC)
(Gupta et al., 2011a,b). Therefore, adsorbents should be applied to
processes that have low concentrations of pollutants or when the
adsorbent has a low cost or can be easily regenerated.
Filtration techniques like ultrafiltration (UF), nanofiltration (NF)
and reverse osmosis (RO) have been used to recover and reuse a
water. For the choice of the filter and its permeability, it is necessary
to consider the content and the temperature of textile wastewater
essential for the separation method. In textile industry, an appli-
cation of membranes delivers exciting potential for the recycle of
hydrolysed reactive dyes and auxiliaries used during dyeing which
concurrently decrease the biological oxygen demand (BOD),
chemical oxygen demand (COD) and color from the textile waste-
water (Chollom et al., 2015). But, membranes also have a significant
disadvantages such as its cost of initial investment, possible fouling
of membrane and the generation of another wastes containing
water insoluble dyes (e.g. indigo dye) and starch which need
further treatment (Koyuncu and Güney, 2013).
4.2. Oxidation methods
These are the most usually used methods of degradation of dyes
by chemical means due to its easiness of application. These
oxidation technologies can be categorized as advanced oxidation
processes (AOP) and chemical oxidation. These processes have the
ability to degrade the toxic initial and their byproduct chemicals,
dyes, pesticides, etc. either partly or completely under ambient
conditions. These oxidation technologies can be used individually
as well as in synergism with each other. This synergism is termed as
the hybrid advanced oxidation process (AOP) technologies.
Advanced oxidation processes (AOP) are the processes in which
hydroxyl radicals are produced in adequate amounts. These hy-
droxyl radicals are powerful oxidizing agents. These oxidizing
agents have an oxidation potential of 2.33 V and shows faster rates
of oxidation reactions as compared conventional oxidants such as
hydrogen peroxide or potassium permanganate. Hydroxyl radicals
react with most dyes with high rate reaction constants (Asghar
et al., 2015). These hydroxyl radicals are also be able to oxidize
majority of the complex organic and inorganic chemicals present in
the textile effluent water. These AOP processes contain cavitation,
generated either by means of ultrasonic irradiation termed as
acoustic cavitation (Jadhav et al., 2015) or via constrictions like
orifice, venturi, etc. in the hydraulic devices termed as hydrody-
namic cavitation. These AOP processes also involve photocatalytic
oxidation (use of sun light for activation of semiconductor catalyst)
and Fenton chemistry (reaction between Fe3þ ions and H2O2).
Fentons reagent is an appropriate chemical (mostly an iron salt)
which promote oxidation of complex organic pollutant (by pro-
moting H2O2 decomposition), which are resistant to biological
degradation. It has also been shown to be operative in degrading
both soluble and insoluble dyes. One main drawback of Fenton
355
Dye Reference
Reactive dye (RR45), (Kara et al., 2012)
Anionic dye (Reactive red-24, RR-24) (Zhong et al., 2011)
Reactive Blue 49 (Tunali Akar et al., 2011)
C.I. Remazol reactive red 198 (Elkady et al., 2011)
Crystal violet (CV) dye (Kumar and Ahmad, 2011)
Dye basic blue 9 (BB9) (Sumanjit et al. 2012)
Methylene blue (MB) (Moussavi and Khosravi, 2011)
Methylene Blue (MB) (Belala et al., 2011)
Methylene blue & malachite green dye (Gupta et al., 2011a)
Methylene blue (Zhang et al., 2011)
Acid blue 25 (AB25) dye (Auta and Hameed, 2011)
method is the iron sludge generation due to combined flocculation
of the reagent and the dye molecules (Babuponnusami and
Muthukumar 2014).
Chemical oxidation methods use oxidizing agents like O3 and
H2O2. Ozone and H2O2 forms strong non-selective hydroxyl radicals
at high pH values. These radicles due to this high oxidation po-
tential can effectively break down the conjugated double bonds of
dye chromophores as well as other functional groups such as the
complex aromatic rings of dyes. Subsequent formation of smaller
non-chromophoric molecules decreases the color of the effluents
(Tehrani-Bagha et al., 2010). These methods are useful for double-
bonded dye molecules. These oxidizing agents have a low rate of
degradation as equated to the AOP processes due to less production
of hydroxyl radicals (Asghar et al., 2015). One major benefit of the
ozonation is that ozone can be used in its gaseous state and
consequently does not raise the volume of the wastewater and does
not result into sludge generation. However, the major disadvantage
of using ozone is that it may form toxic byproducts even from
biodegradable dyes in wastewater (Miralles-Cuevas et al., 2016).
The disadvantages of ozonation is the cost, as constant ozona-
tion is essential due to its short half-life of 10 min in water at pH 7
(Gosavi and Sharma, 2014). This short half life time can be sup-
plementary reduced due to the presence of dye. The stability of
ozone is also affected by the presence of salts, pH, and the tem-
perature. Ozone decomposition is faster under alkaline condition of
pH > 8.5. So, the continuous monitoring of the textile effluent pH is
required (Tian et al., 2014; Zhang et al., 2014). Degradation of the
dye is also possible by the combined treatment of UV light and the
H2O2 due to the production of high concentrations of hydroxyl
radicals. This combined method of UV light and the H2O2 is ad-
vantageous for dye-containing textile effluent due to no sludge
production and reduction in foul odors. Here, UV light is used to
activate the decomposition of H2O2 into hydroxyl radicals. These
hydroxyl radicals cause the chemical oxidation of dye or organic
material, mineralizing the same to CO2 and H2O. The parameters
such as UV radiation intensity, pH, structure of dye molecule and
the dye bath composition need to be optimized to get a more rate of
dye removal (Soares et al., 2013; Yen, 2015). Thus, free radicals can
be generated by the combination of ozone with hydrogen peroxide.
In other way, free radicals can also be produced by the action of
ozone or hydrogen peroxide in presence of the energy dissipating
components. Here, UV, sun light or ultrasound are the energy
dissipating components (Saharan et al., 2014). These hybrid tech-
niques have lesser treatment times as related to any one of the
individual methods but are also associated with higher energy cost
(Bagal and Gogate, 2014).
Table 3 shows some of the typical applications of oxidation
process to the treatment of textile waste water. It also illustrates the
type of oxidation process used for treatment, the dyes and the
significant results of the work. It can also be observed from Table 3,
356 C.R. Holkar et al. / Journal of Environmental Management 182 (2016) 351e366

Table 3
Different oxidation method for degradation of dyes.

Sr. No. Type of oxidation process Conditions Results Reference

1 UV/H2O2 Azo dye Reactive Green 19 (RG19), ✓ Complete decolorization in about 20 min. (Zuorro and
Optimum condition of UV radiation ✓ 63% Total organic carbon (TOC) removal in 90 min. Lavecchia, 2014)
1500 mW cm2 H2O2 and pH conditions
(ch ¼ 30 mM, pH ¼ 6.5)
2 Combinations of TiO2/UV/H2O2 Azo dye  Amaranth (AM), Optimum ✓ The decolorization efficiencies were 17%, 26%, 38% (Gupta et al.,
condition of TiO2 (0.16 g/L) and UV and 64% in the runs UV, UV þ H2O2, UV þ TiO2 2012)
radiation of 10 mW/cm2 at wavelength of and (UV þ TiO2þ H2O2) after approximately
254 nm ✓ 100 min illumination periods, respectively.
3 Hydrogen peroxide in subcritical water Reactive Red 120(100e300 mg/L), ✓ The experimental temperature connected to the rate (Daskalaki
Temperature of 150e200  C, H2O2(0.5e1 w/ of H2O2 conversion to hydroxyl radicals. et al., 2011)
v), ✓ 0.5% w/v H2O2 was the optimum for degradation of
RR120 at all dyes concentrations and temperatures.
✓ At the most ‘intense’ conditions of 200  C and 1% w/v
H2O2.
✓ A maximum of 64% TOC removal.
4. Acoustic cavitation (generated using Orange acid-II (OA-II) and brilliant green ✓ In the case of acoustic and hydrodynamic cavitation, (Gogate and
ultra-sonic horn) and hydrodynamic (BG) degradation was in the range of 50e60% depending Bhosale, 2013)
cavitation (generated using single hole on the dye and type of cavitation used.
orifice) in combination with different ✓ The most effective decolorization of both dye effluent
chemical oxidants like H2O2, Na2S2O8 by the combination of hydrodynamic cavitation and
and NaOCl, chemical oxidation as compared to chemical
oxidation and acoustic cavitation based combination.
5. Hydrodynamic cavitational with the Rhodamine B (10 ppm) inlet pressure (2.9 ✓ 99.9% decolorization of Rhodamine using a (Mishra and
presence of H2O2, CCl4 and Fenton's e5.8 atm), temperature (30 and 40  C) and combination of cavitation and H2O2 as well as a Gogate, 2010)
reagent pH (2.5e11) H2O2 (10e200 mg/l) combination of cavitation with Fenton chemistry.
✓ 82% degradation by the combination of cavitation
with CCl4.
6. Hydrodynamic cavitation using orifice Orange-G dye [OG] concentration ranging ✓ Acidic medium (lower pH) for the degradation of OG (Saharan et al.,
plate, circular venturi and slit venture from 30 to 150 mM pH of 2e13 using HC. 2013)
✓ The slit venturi results in to almost 50% greater
degradation rate and cavitational yield among all
three cavitating devices studied for the same amount
of energy delivered.
7. Hydrodynamic cavitation in presence of Reactive Red 120 dye (RR120) (34 m M) pH 2 ✓ Acidic medium found to be favourable for the higher (Saharan et al.,
hydrogen peroxide e9 pressure 3e5 bar degradation. 2011)
✓ The addition of H2O2 increases the degradation rate
as additional hydroxyl radicals available for the
oxidation of dye.
✓ No further enhancement in decolorisation after
optimum concentration of H2O2.

that more work is done on a lab scale and great considerable work
should be focused on the design approaches for the scale up.
A summary of the several physical/oxidation methods used for
the textile wastewater treatment discussed in above section tells
that cavitation is one of the recent technologies for textile waste
water treatment but only a few studies have been reported in this
regards. The cavitation technology can be suitable for lowering the
toxicity levels of the effluent stream, reduction of COD to TOC ratio
and enhancement of Biodegradation Index (BI) (BOD5 to COD ratio)
as well as color reduction. Thus, cavitation technique is an energy
efficient option and can be used as pretreatment method in com-
bination with other advanced oxidation processes or biological
methods (Mishra and Gogate, 2010; Saharan et al., 2011, 2013). As
far as cost is concerned cavitation technology requires overall lower
costs of treatment as compared to other method (Gogate and
Bhosale, 2013).
4.3. Biological methods
The biological process removes only the dissolved matter in
textile wastewater. The removal efficiency is influenced by the ratio
of organic load/dye and the microorganism load, its temperature,
and oxygen concentration in the system. On the basis of oxygen
requirement, biological methods can be classified into aerobic,
anaerobic and anoxic or facultative or a combination of these. An
aerobic methods use microbes for the treatment of the textile
wastewater in presence of oxygen while an anaerobic methods use
microbes to treat it in absence of oxygen. The combination of
anaerobic and aerobic method is typically implemented in real
practice which use an anaerobic process to treat textile wastewater
of chemical oxygen demand (COD), followed by the use of aerobic
polishing treatment to treat the resulting textile wastewater of low
COD (Wang et al., 2011). Generation of “methanogenic biogas” by
anaerobic process is possible only if the wastewater has a rather
high COD, higher than 3 g/L, which is the case for desizing waste-
water containing more biodegradable organic compounds such as
polyvinyl alcohol (PVA) or starch (Rongrong et al., 2011). Thus,
anaerobic treatment results in the generation of methanogenic bio-
gas having some calorific value. Part of the energy generated by its
combustion then can be used for aerobic polishing step. In these
biological methods, microorganisms adapt themselves to textile
dyes and new resilient strains grow naturally out of survival
requirement, which then convert several dyes into less hazardous
forms. In this system, the biodegradation mechanism for recalci-
trant dyes is based on the stroke of the enzymes such as laccase,
lignin peroxidase, NADH-DCIP reductase, tyrosinase, hexane oxi-
dase and aminopyrine N-demethylase (Solís et al., 2012).
The biological methods for the complete degradation of textile
wastewater have benefits such as: (a) eco-friendly, (b) cost-
competitive, (c) less sludge production, (d) giving non-hazardous
metabolites or full mineralization (e) less consumption of water
(higher concentration or less dilution requirement) compared to
 C.R. Holkar et al. / Journal of Environmental Management 182 (2016) 351e366 357

physical/oxidation methods (Hayat et al., 2015).
The efficiency of biological methods for degradation depends on
the adaptability of the selected microbes and the activity of en-
zymes. Therefore, a large number of microorganisms and enzymes
have been isolated and tried for the degradation of several dyes.
The isolation of potent microbes and its use for degradation is an
interesting biological aspect of textile wastewater treatment. A
wide range of microorganisms such as bacteria, fungi and algae are
able to degrade a wide variety of dyes present in the textile
wastewater.
4.3.1. Fungal cultures for degradation of dyes
A fungal culture has an ability to acclimate its metabolism to
changing environmental conditions. This ability is a vital for their
existence. Here, intra and extracellular enzymes help in metabolic
activity. These enzymes have ability to degrade various dyes pre-
sent in the textile wastewater. Due to these enzymes, fungal cul-
tures seem to be suitable for the degradation of dyes in textile
wastewater. These enzymes are lignin peroxidase (LiP), manganese
peroxidase (MnP) and laccase (Chander, 2014; Chen and Yien Ting,
2015a). Mostly, white rot fungal cultures have been used for the
removal of azo dyes Current reports on degradation of dyes by fungi
are indicated in Table 4.
White rot fungi Coriolopsis sp (Chen and Yien Ting, 2015a),
Penicillium simplicissimum(Chen and Yien Ting, 2015b) and white rot
fungus Pleurotus eryngii (Hadibarata et al., 2013) showed degrada-
tion along with the COD removal.
However, degradation of dyes in the textile wastewater by
white-rot fungi has some intrinsic disadvantages like the long
growth phase and the requirement of nitrogen restrictive envi-
ronments, unreliable enzyme production and large reactor size due
to the long holding time for complete degradation (Anastasi et al.,
2011). The main problem with using fungi alone is that the
system is not stable and after 20e30 days bacteria will start
growing and the fungi will no longer dominate the system and
degrade the dyes (Jonstrup et al., 2013).
4.3.2. Algae for degradation dyes
Algae are omnipresent and are getting an increasing consider-
ation in the area of degradation of textile wastewater. Several
species of algae which have been successfully used are reported in
Table 5. A review of literature recommends that degradation of dyes
by algae occurs through three different mechanisms such as 1)
consumption of dyes for their growth, 2) transformation of dyes to
non-colored intermediates or CO2 and H2O, 3) chromophores
adsorption on algae. Biosorption and biodegradation are very
different phenomena. Biosorption implies moving the dye from the
water phase to the solid phase (the bioadsorbent) while biodeg-
radation means that enzymes are actually breaking bonds that
constitute the chemical structure of the dye, so that the dye is
transformed into other chemical compounds. The literature also
recommends that Green macroalgae Cladophora species (Khataee
et al., 2011a) have capability to degrade mainly azo dyes due to
presence of azoreductase enzyme Meng et al (Meng et al., 2014).
studied azo dye (acid red 27) decolorization by Shewanella algae
(SAL) in the presence of high concentrations of NaCl and different
quinones or humic acids. This study showed that mediated decol-
orization of acid red 27 results into less phytotoxic aromatic
amines. Khataee et al.(Khataee et al., 2013) also reported the
biodegradation of C.I. Basic Red 46 (BR46) solution using the green
macroalga Enteromorpha sp. under optimum conditions with a
reaction time of 5 h, a temperature of 25  C, alga biomass of 2 g and
initial dye concentration of 15 mg/L. Thus, algal biomass plays a
significant part in the elimination of azo dyes in the textile
wastewater by biodegradation. Furthermore, bio-sorption process
using algal waste for color removal can be a practical alternative for

Table 4
Recent reports on fungal cultures capable of dye degradation.

Sr.No. Fungi Dye Results Reference

1 White rot fungus Pleurotus Naphthalene
eryngii
2 white rot fungus Coriolopsis
sp. (1c3), isolated from
compost
3 Penicillium simplicissimum
isolated from indoor
wastewater sample
4 Aspergillus niger
5 Lichen Permelia perlata
Triphenylmethane dyes (Crystal
Violet (CV), Methyl Violet (MV),
Cotton Blue (CB) and Malachite
Green (MG)
Triphenylmethane dyes (Crystal
Violet (CV), Methyl Violet (MV),
Cotton Blue (CB) and Malachite
Green (MG)
Remazol Brilliant Blue R (RBBR) and ✓ Recombinant and native laccases showed similar decolorisation (40
Acid Red 299 (NY1)
Disperse dye Solvent Red 24
✓ Naphthalene degradation by Pleurotus eryngii. (Hadibarata
✓ Use of naphthalene as carbon source instead of limited carbon et al., 2013)
source.
✓ 1,4-Naphthaquinone, benzoic acid and catechol are metabolites as
result of naphthalene biodegradation.
✓ 94%, 97% and 91% decolorisation was observed for Crystal Violet (CV; (Chen and Yien Ting,
100 mg/l), Methyl Violet (MV; 100 mg/l) and Cotton Blue (CB; 50 mg/ 2015a)
l), with within 7, 7 and 1 day(s) respectively.
✓ 52% decolorization was observed for Malachite Green (MG; 100 mg/l)
for after 9 day.
✓ Laccase, lignin peroxidase and NADH-DCIP reductase activities
responsible for possible occurrence of biodegradation of TPM dyes.
✓ Decolorisation of 95%, 98% and 82% was observed for Crystal Violet (Chen and Yien Ting,
(CV; 100 mg/l), Methyl Violet (MV; 100 mg/l) and Cotton Blue (CB; 2015b)
50 mg/l), with within 14, 13 and 1 day(s) respectively.
✓ 54% decolorization was observed for Malachite Green (MG; 100 mg/l)
for after 14 days.
✓ Biodegradation of Triphenylmethane dyes was due to Lignin
peroxidase and NADH-DCIP reductase activities using 2 g/l biomass
and 100 ppm dye.
(Benghazi et al.,
e60%) for Remazol Brilliant Blue R within 200 min. 2014)
✓ In case of Acid Red 299 (NY1), recombinant laccases (30%
decolorisation) showed faster decolorisation as compared to native
laccases (13% decolorisation) within 40 min.
✓ Laccase and Manganese peroxidase was responsible for (Kulkarni et al.,
bioransformation. 2014)
✓ 100% decolorisation was observed within 24 h under pH and
temperature of 8 and 50 C, respectively.
✓ metabolites obtained after biotrasformation were naphthalen-1-
yldiazene, naphthalene, 1-(2-methylphenyl)-2-phenyldiazene and
diphenyldiazene
358 C.R. Holkar et al. / Journal of Environmental Management 182 (2016) 351e366
Table 5
Reports on algae for dye removal.
Sr.No. Algae Dye
1 Brown alga, Stoechospermummarginatum. Acid orange II (AO7) dye
2 Xanthophyta alga, Vaucheria species Triphenylmethane dye, Malachite Green (MG)
3 Green macroalga Enteromorpha sp. C.I. Basic Red 46 (BR46)
4 Shewanella algae (SAL) Acid red 27 (AR27)
5 Green macroalgae Cladophora species Malachite Green (MG)
the expensive material such as activated carbon (Kumar et al.,
2015).
4.3.3. Pure culture and mixed culture for degradation of dyes
Generally, aerobes, anaerobes and facultative anaerobes (able to
grow either with or without oxygen) are used for the degradation of
dyes. All aerobic processes produce sludge as compared to anaer-
obic and facultative treatment. Bacterial degradation of mainly azo
dyes is due to the reductive breakage of azo bonds (eN]Ne) by
azo-reductase enzymes under anaerobic condition. This breakage
of azo bonds (eN]Ne) effects in the formation of possibly color-
less toxic-intermediates which are further treated by aerobic or
anaerobic method (Palani et al., 2012). Moreover, bacterial (Pseu-
domonas sp.SUK1) degradation of C.I Disperse Red 78 is 37% higher
compared to fungal system (Aspergillus ochraceus NCIM-1146)
with respect to the degradation of dyes (Lade et al., 2012). In
recent times, a significant research on the field of degradation of
textile wastewater containing dyes has been done by using single
bacterium culture such as Alcaligenes faecalis PMS-1 (Shah et al.,
2012), Enterobacter sp. EC3 (Wang et al., 2009), Enterobacter sp. F
NCIM 5545 (Holkar et al., 2014) and isolated Pseudomonas sp. SUK1
under anaerobic environments (Kalyani et al., 2009). Numerous
studies telling the removal of dyes from textile wastewater facili-
tated by single bacterium culture and their outcomes are shortened
in Table 6. The use of single bacterium culture for treatment of
textile wastewater confirms reproducibility. Here, the detailed
mechanisms of biodegradation due to single strain can be deter-
mined by using the knowledge of molecular biology as well as
biotechnology. Then, biochemistry knowledge can be used to pro-
duce improved strains with better enzyme activities. But individual
bacterium culture usually does not degrade azo dyes fully and the
intermediate compounds may be frequently toxic aromatic com-
pounds, which require further decomposition (Khan et al., 2014).
It has been observed that bacterial consortia are mainly bene-
ficial as they can conjointly carry out degradation tasks that no
single bacterium culture can begin effectively (Saroj et al., 2015). In
mixed culture system, the degree of biodegradation and minerali-
zation of dyes is higher due to the synergism of metabolic activities
of a bacterial community. In a mixed culture system, the single
bacterium culture may attack at a different site of dye molecule or
may consume intermediate metabolites formed by another existing
bacterium culture for supplementary degradation of dyes. But the
disadvantages are that bacterial consortia just provide an average
macroscopic observation about biodegradation, the results of
degradation are also not reproducible and effective explanation for
the biodegradation system is quite complicated. Thus, the degra-
dation of azo dyes from wastewater by bacteria consortia has been
attracted a considerable interest due to higher degree of biodeg-
radation. Some studies regarding the biodegradation of dyes in
textile wastewater using microbial consortia are also reported in
Table 6.
It can be understood from Table 6 that extensive research has
been done to decide the role of the various bacteria groups in the
degradation of azo based water soluble dyes. These studies have not
reported degradation pathway through enzyme assay and
Mechanism Reference
Adsorption (Kousha et al., 2012)
Adsorption (Khataee et al., 2011b)
Biodegradation (Khataee et al., 2013)
Biodegradation (Meng et al., 2014)
Biodegradation (Khataee et al., 2011a)
phytotoxicity studies of degraded compounds, which need to be
studied in future. Few studies have been reported on the anthra-
quinone based dyes. Recently, Holkar et al. (Holkar et al., 2014)
reported 90% degradation of anthraquinone based Reactive blue 19
within 24 h while Wang et al. (Wang et al., 2009) reported 92%
degradation of anthraquinone based Reactive black 5 within 120 h
under anaerobic condition. So, in future it is necessary to carry out
more work that will try to emphasis the kinetics of degradation of
anthraquinone based dyes with the help of bacterial processes. It is
also important to focus on the point that most of the work has been
done on the synthetic wastewater and may or may not give
reproducibility when applied to real wastewater containing a
different kind of compounds like surfactant, salts, desizing agent
and finishing agents. Thus, it is necessary to apply these works for
the degradation of interested dye in real wastewater using reported
single bacterium or bacterial consortia.
4.3.4. Microbial fuel cell: sustainable technology for textile
wastewater treatment
In a microbial fuel cell (MFC) system, the electrochemically
active microorganisms oxidize various organic compounds of
textile wastewater in the anode chamber and generate protons and
electrons that transport to the cathode chamber to reduce oxygen
to water. Most MFCs have a membrane to separate the compart-
ments of the anode and the cathode (Li et al., 2014). The electricity
generated can be easily harvested by an external resistor placed
between the anode and the cathode. The progress in the compo-
nents of MFCs like electrodes membranes and microorganisms is
still in the initial stage. The main disadvantage of MFC is its appli-
cation on large scale due to the lower production of power and
higher cost MFC materials. Over the past decade, tremendous work
has been made to improve the power production of MFCs. Recent
papers have reported different configurations, membrane materials
and electrode materials (cathodes and anodes), microbial com-
munity and textile wastewater containing azo dyes used for elec-
tricity generation using MFC (Pant et al., 2010; Solanki et al., 2013;
Patade et al., 2016). Nevertheless, the membrane (Nafion), anode
(i.e. carbon cloth and carbon paper) and cathode (Platinum) ma-
terials used are expensive and fragile. MFCs with high power
output, low cost electrode and membrane materials and good
scalability should be developed to realize the real-world applica-
tion for treatment of different effluents like desizing, bleaching,
dyeing and printing effluent.
In recent years, most of the work is being done on the use of
activated and modified carbon nanofibres as an anode. However,
they have a high internal resistance which may be due to film
formation or large pore size. Power can further be improved if this
limitation is surpassed in future. Multiwall carbon nanotubes
(MWCNT)-SnO2 coating on granular carbon electrode (GCE) was
used which showcased that nanotubes improve stability, power
and reduce charge transfer resistance. Majority of materials used
for anodes are made up of carbon which have high resistivity (Mink
et al., 2012; Karra et al., 2013; Mehdinia et al., 2014). In future, this
resistivity can be minimized by the use of edged metal collectors
like Cu TiO2, Ni, Si. So, the use of carbon based composites along
 C.R. Holkar et al. / Journal of Environmental Management 182 (2016) 351e366 359

Table 6
Pure or mixed bacterial cultures for degradation of dyes in textile wastewater (TOC: Total Organic Carbon and COD: Chemical Oxygen Demand, NR: Not Reported).

Bacterial strain Dye & Condition (pH, T( C), Time % % Enzyme References
concentration agitator TOC Decolorization

Proteus mirabilis LAG, Reactive Blue 13 pH ¼ 7, 35  C, anoxic, 5 h NR 84% Azoreductase and veratryl (Olukanni
(RB13), (100 mg/ static alcohol oxidase, laccase et al.,
l) 2010)
Kocuriarosea(MTCC 1532) Methyl orange Static, pH ¼ 6.8, 30  C 24 h NR 100 Azoreductase and NADH-DCIP (Parshetti
(50 mgl1) reductase et al.,
2010)
Alcaligenes faecalis PMS-1 Reactive Orange static anoxic condition, 24 h NR 100 Veratryl Alcohol Oxidase, (Shah
13 pH ¼ 7 37  C Tyrosinase and NADHeDCIP et al.,
reductase enzymes 2012)
Enterobacter sp.F NCIM 5545 Reactive Blue 19 anaerobic condition, 24 h NR 90 NR (Holkar
pH ¼ 7 37  C et al.,
2014)
Bacillus cereus B. megaterium Azo dye Red 3BN Shake, pH ¼ 7.2e6 144 h NR 93.64 NR (Kumar
(100 mg/l) and Bhat,
2012)
Microbial consortium DAS Reactive Orange pH ¼ 7 30  C, static. 48-h 75 100 Laccase and reductase enzyme (Kurade
16 (RO16) COD et al.,
dye(100 mg/l) 2012)
Consortium-GR, consisting of Proteus vulgaris NCIM- Azo dye Scarlet R Static anoxic,pH ¼ 6.6 3 h >90 NR Riboflavin reductase and (Jadhav
2027 (PV) and Micrococcus glutamicus NCIM-2168 30 mg/l 30  C NADHeDCIP reductase et al.,
(MG), 2010)
Mixed consortium (Alcaligenesfaecalis, Sphingomonas sp. Dye Direct Blue- Static, 37  C, 24 h NA 95.45 NA (Jain et al.,
EBD, Bacillus subtilis, Bacillus thuringiensis and 15(250 mg/l) 2012)
Enterobactercancerogenus)
Novel microbial consortia ‘Bx’ Blue Bezaktiv S- Aerobic sequencing 24 h 95- 88e97 NA (Khouni
GLD 150 dye, batch reactor(ASBR), 98 et al.,
15 mg/l pH ¼ 7, 30  C COD 2012)

with cheap electrocatalyst i.e. Cu, TiO2, Ni, Si looks like a promising
anode material but more detailed work needs to be done in this
aspect.
Recent discovery on cathode also focuses on the use of nano-
fibres/nanotubes of carbon to increase surface. Co3O4/nanocarbon
composite was examined by Song et al., 2015 which almost
matched the performance of Pt/C in all aspects like columbic effi-
ciency, current at reduction peak and power density (Song et al.,
2015). As of now, nanofibres of carbon can be expected to match
the performance of Pt/C electrode or even perform better if suitable
blending catalysts are found. So, more work needs to be done for
modification of carbon nanofiber based cathode by use of more
efficient and cheaper catalyst for MFC. Use of nanofibre composites
along with cheap catalyst like Cobalt, Iron and Manganese dioxide,
Silver and Palladium looks like a promising cathode material but
more detailed work needs to be done in this aspect before any
claims can be made.
Scope of MFC for commercial use is highly dependent on
membranes which have low resistance, high selectivity and are
cheap with long term stability. Membranes are used in MFC to
ensure transport of ions from one chamber to the other. High ionic
conductivities (1 S cm1) associated with the liquid KOH, phos-
phoric acid have been used along with the thick sheets of mem-
branes such as Aromatic Sulphonic Acid sulfonated poly(sulfones),
sulfonated poly (ether ketones) (Ayyaru and Dharmalingam, 2014;
Prabhu and Sangeetha, 2014). Moreover, electricity production
have also been accomplished by making materials like ceramic and
earthen pot more porous to ensure lower resistance (Daud et al.,
2015). It will be a major development of MFC if cheap mem-
branes like above can affect proton transfer in presence of other
cations due to size difference. However, the issue of selectivity still
remains. Cation species present in textile waste water such as Kþ,
Naþ, Ca2þ, NHþ 4 , and Mg
2þ
are able to cross the Nafion membrane
like protons. Considering that the concentration of these cation
species is higher in MFCs than the proton concentration, an accu-
mulation of these cation species are produced in the cathode
chamber causing an increase in the pH in the previous chamber and
a decrease of the pH in the anodic chamber. As a result of this, MFCs
efficiency is reduced by decreasing microorganism activity and
decrease of the thermodynamic cell potential (Hern
andez-
Ferna
ndez et al., 2015). Hence, one work that can be done is to
ensure that only protons and no other cations can be transported by
modifying pore size of membranes. Different approaches i.e. use of
cation exchange membranes (CEM) or anion exchange membranes
(AEM) have also been suggested to solve the problem of the pH
gradient on both sides of the membrane (Pandit et al., 2012; Leong
et al., 2013). The ionic liquid (IL) membranes can open up this field
of improvement in MFCs. Here, the ionic nature of ionic liquids can
assure the selective transport of only protons and no other cations
through the membrane. This may result in the improvement of MFC
efficiency as microbial activity in anode chamber is not affected due
to no transport of cations present in the textile wastewater across
the membrane. Thus, it is possible to extract energy from textile
wastewater which is 5 times as much as the energy consumed to
treat the wastewater (Xie et al., 2011).
5. Factors affecting bacterial degradation
Oxygen, temperature, pH, concentration of dye, structure of dye,
concentration of carbon and nitrogen sources, amount of electron
donor as well as redox mediator are various physicochemical
operational parameters which directly control the bacterial
degradation. Thus, to get a more effective and faster the bacterial
degradation, it is necessary to determine the consequence of and
every parameter on the bio-degradation. Table 7 summarizes
possible range of operational parameters for a better bio-
degradation.
6. Biological and physicochemical combination processes
Biological method does not constantly deliver reasonable results
of the treatment of real textile wastewater, as some of the dye
360 C.R. Holkar et al. / Journal of Environmental Management 182 (2016) 351e366

Table 7
Effect of different parameters on bacterial degradation.

Parameters Effect of parameter on bacterial degradation

Oxygen ✓ Superior degradation under strictly anaerobic conditions due to higher reductive enzyme activities(Cervantes and Dos Santos, 2011).
✓ Requirement of a minor amount of oxygen for the oxidative enzymes those are responsible for the azo dye degradation.
✓ Oxygen requirement for degradation of the intermediates formed during the reduction reaction of azo dyes, such as the simple aromatic
compounds such as naphthalene sulphonic acid, aniline, phenol, phthalic acid, sodium benzoate (Parshetti et al., 2010; Olukanni et al.,
2010; Jain et al., 2012)
✓ Use of the anaerobic process following aerobic treatment (Saratale et al., 2009; Olukanni et al., 2010).
Carbon and nitrogen ✓ No degradation of dyes by bacteria without any supplementation of carbon or nitrogen sources.
sources ✓ Azo dye degradation by microbial consortia as well as single bacterium cultures normally needs various carbon sources (glucose, starch,
fructose, maltose, lactose, sodium acetate) with concentration of 1 g/L and the organic nitrogen sources (0.5 g/L), such as peptone,
ammonium nitrate, urea, yeast extract. (Ponraj et al., 2011; Garg et al., 2012; Jain et al., 2012; Shah et al., 2013)
✓ Glucose, starch and fructose serves as superior co-substrates.
✓ Effective degradation only for yeast extract.
Temperature ✓ The degradation of azo dyes increases by 50e70% up to the optimal temperature of 37  C.
✓ Marginal reduction in the degradation activity by 80e90% at higher temperature greater than or equal to 42  C due to the loss of cell
sustainability or the loss of activity of an enzyme responsible for degradation (Holkar et al., 2014).
✓ For certain whole bacterial cell (Dermacoccus abyssi MT1.1T strain) preparations, the azoreductase enzyme can persist active up to temperatures
of 60  C, over period of one hour (Lang et al., 2014).
pH ✓ The optimum pH for degradation is between 3.0 and 10.0(Ayed et al., 2011).
✓ The degradation rate is higher at the optimum pH of 7(Anjaneya et al., 2011).
✓ The degradation rate decreases rapidly under strongly acidic or strongly alkaline pH (Ayed et al., 2011).
Dye concentration ✓ Bacterial cultures exhibit good degradation for the dye concentration in range of 50e400 ppm.
✓ Higher concentration of dye slowly decreases the degradation efficiency due to the toxicity of dyes on the individual bacteria or insufficient
biomass to dye concentration (Holkar et al., 2014; Phugare et al., 2011).
✓ Reactive azo dyes having sulfonic acid (SO3H) groups inhibits the growth of microbes at higher concentration of dyes (Kalyani et al., 2009).
Dye structure ✓ Higher degradation rate for dyes (e.g. crystal violet, malachite green and ethyl violet) with molecular weights less than 500 g/mol and simpler
molecular weight.
✓ Lower degradation rate in the case of dyes having electron extracting groups such as eSO3H, eSO2 and NH2 in the para position of the aromatic,
relative to the azo bond and for dyes (e.g. Reactive Blue 19, Reactive Blue 13, Reactive Orange 16 and Reactive Orange 7) with the molecular
weight higher than 500 g/mol (Lade et al., 2012; Holkar et al., 2014).
✓ Faster degradation for monoazo dyes as likened to diazo and triazo dyes (Garcia-Segura et al., 2011).
Redox mediator ✓ Lower rate of transfer of reducing equivalents from a primary electron donor to a terminal electron acceptor (azo dye in the anaerobic azo dye
reduction process.
✓ Use of redox mediators with concentration in the range of 0.005e0.02 mM enhances the transfer of reducing equivalents to the terminal
electron acceptor (Sun et al., 2013).
✓ Flavin-based compounds (flavin adenide dinucleotide (FAD) and flavin adenide mononucleotide (FMN)) and quinone-based compounds
(anthraquinone-2,6-disulfonate (AQDS), anthraquinone-2-sulfonate (AQS), riboflavin (vitamin B2), cyanocobalamin (vitamin B12) and lawsone
(2-hydroxy-1,4-naphthoquinone)) have been extensively reported as redox mediators (Saratale et al., 2011; Sun et al., 2013).

molecules or other components created by textile industry at
different stages of wet processing are hazardous or unaffected by to
biological methods (Oller et al., 2011). In case of chemical oxidation,
total mineralization of some of the dye molecules in textile
wastewater is not always possible and may be generally expensive
due to additional energy (e.g. UV radiation) and chemical reagents
(e.g. Fe3þ and H2O2 and oxidizers) (Blanco et al. 2012; Lotito et al.,
2012; Hayat et al., 2015).
Therefore, the only feasible option for constant results is to use
these oxidation methods as a pre-treatment and biological as a
post-treatment or a vice-versa to alter the biodegradability of pri-
marily stable dye molecules. Then, this biodegradable in-
termediates obtained after pre-treatment would be further
degraded by a post-treatment at a significantly lower cost (Blanco
et al., 2014; Fu et al., 2011). Here, the pre-treatment is used for
the partial oxidation of the non-biodegradable part to give biode-
gradable compounds depending upon the components in the
textile wastewater. It is necessary to reduce the needless spending
on chemicals and energy to lower the operating cost of pretreat-
ment. This indicates that the mineralization percentage should be
minimum the pre-treatment stage. Conversely, the pre-treatment
time should not be too small. Otherwise, the intermediates ob-
tained after pretreatment may still be basically similar to the initial
dye molecules (Paul et al., 2013; Yahiaoui et al., 2014). Different
combinations of chemical oxidation methods and biological
methods have been described in Table 8. Some of these studies
contain oxidation by ozonation (Lotito et al., 2012; He et al., 2013)
H2O2 (Blanco et al. 2012), photolysis (Basha et al., 2011), photo-
fenton (Blanco et al., 2014), photo electrochemical process and
electron-beam treatment (Basha et al., 2011).
Table 8 also reviews recent research on the combining oxidation
method and biological method for the degradation of dyes in textile
wastewater. Here, chemical oxidation method is used as a pre-
treatment or post-treatment. It also highlights the efforts in
applying chemical oxidation process as a pre-treatment as well as
the actual cases in which the combination approach is used in an
alternative sequence i.e. first removing the biodegradable compo-
nent of the textile wastewater by biological method and then
removing the refractory components (non-hazardous) by the post-
treatment of advanced oxidation process (AOP) or chemical
oxidation (Basha et al., 2011; Azizi et al., 2015).
Selection of the greatest combination for the textile wastewater
treatment is a difficult task. The combinations of one or more
oxidation methods along with biological methods depend on the
component of the textile wastewater, quality criteria to be required
and the cost of treatment. When chemical oxidation method is used
as a pretreatment or post treatment in a combination sequence,
sometimes its effect is minor and even dangerous to the charac-
teristics of the original textile wastewater (Punzi et al., 2015). The
most general reasons for this are:
 Formation of stable compounds that are not biodegradable as
compared to initial dye molecules (Paul et al., 2013).
 Unnecessary use of oxidant like O3 and H2O2 which are known
as biocides (Punzi et al., 2015) and their residual concentration.
To know the effect of the working conditions (treatment time,
concentration of oxidant, catalyst type and temperature) on the
 C.R. Holkar et al. / Journal of Environmental Management 182 (2016) 351e366 361

Table 8
Combined biological and chemical process for textile wastewater treatment.

Sr.No. Type of effluent Combined biological and chemical Results Reference

process

1. Printing wastewater
2. Textile wastewater(apparent color
purple red, colority 500e1000 times,
turbidity 80e300 nephelometric
turbidity units (NTU), pH 10e12.2, SS
120e220 mg/L, COD 536e1356 mg/L
and temperature 25e33  C)
3. Textile effluents from cotton mills (COD Integrated ozone-BAFs (ozone
of 82e120 mg/L, BOD5 of 12.6e23.1 mg/ biological aerated filters) and
L, suspended solids (SSs) of 38e52 mg/ membrane filtration
L).
4. Textile wastewater (Total Organic
Carbon (TOC) ¼ 390 mg/L, Chemical
Oxygen Demand (COD) ¼ 1560 mg/L
and Escherichia coli ¼ 80,000 CFU/mL
5. Procion blue (Reactive dye) synthetic
wastewater (COD of 82e2000 mg/L,
BOD5 of 281 mg/L and pH ¼ 10.5)
6. Reactive Red-120 (RR-120)
7. Azo dye AR18
Ozonation followed by Sequencing
batch biofilter granular reactor(SBBGR)
Anoxic filter bed and biological wriggle ✓ Effluent COD concentration of the AFB, BWB, O3-BAF (Fu et al., 2011)
bed-ozone biological aerated filter
(AFB-BWB-O3-BAF) process for two
month
photo-Fenton oxidation and the
combination of aerobic sequencing
batch reactor (SBR) þ photo-Fenton
processes
Combined electrochemical (for 4 h),
microbial (using bacteria
i.e.Pseudomonas putida and Bacillus
cereus and fungal strains i.e. Pleurotus ✓ After microbial treatment, COD reductions were 59%
ostreatus, Fusarium oxysporum and
Trichoderma viridae), post
electrochemical (for 5 h) and
photocatalytic methods (for 5 h)
Low dose irradiation (0, 0.5 and 1 kGy ✓ Irradiation of 0, 0.5 and 1 kGy doses a pretreatment (Paul et al., 2013)
doses) pretreatment followed by on the
microbial (Pseudomonas sp. SUK1)
decolouration
SBR and enhanced Fenton process as
post treatment
✓ Optimization in terms of organic load and ozone (Lotito et al., 2012)
concentration.
✓ Ozone concentration and the COD removal ratio was
lower than 0.75
✓ Chemical oxidation and biological treatment
permitted a more effective use of ozone.
✓ High surfactant and color removal.
were 704.8 mg/L, 294.6 mg/L and 128.8 mg/L, with
Hydraulic retention time (HRT) being 8.1e7.7 h, 9.2 h
and 5.45 h, respectively.
✓ HRT affected the COD removal efficiency of the AFB-
BWB-O3-BAF process, which was increased from
74.1% to 84.1% with increase in HRT
✓ After treatment, effluent with COD <45 mg/L, BOD5 (He et al., 2013)
<7.6 mg/L, SS < 15 mg/L were obtained.
✓ Complete removal of polyvinyl alcohol (PVA)
✓ 79% COD and 75% TOC reduction were obtained after (Blanco et al., 2014)
single photo-Fenton process ([Fe (II)] ¼ 216 mg/L;
[H2O2] ¼ 4950 mg/L; pH ¼ 2.7 and T ¼ 35  C)
✓ Aerobic SBR under 1 day hydraulic retention time
(HRT), gave 75% TOC reduction after 25 cycles.
✓ COD and TOC reductions of 97 and 95% respectively
was obtained, when photo-Fenton process as a pol-
ishing step coupled under: ([Fe (II)] ¼ 66.5 mg/L;
[H2O2] ¼ 1518 mg/L; T ¼ 25  C and pH ¼ 2.7)
conditions.
✓ Bio-degradability index (BI) of 0.48 was obtained (Basha et al., 2011)
after electrochemical pretreatment by the applied
charge of 3.84 A h.
and 39% respectively for the effluent containing the
bacterial strain and fungal strain.
✓ 81% and 65% COD reduction was obtained by post
electrochemical process of effluent containing the
bacterial strain and fungal strain respectively.
✓ Overall 95% and 80% COD reduction was obtained
after photocatalytic process (0.5 g/L TiO2) of
effluent containing the bacterial strain and fungal
strain respectively.
resulted in to 27%, 56% and 66% decolouration of
150 ppm RR-120 dye solution respectively after 24 h
microbial treatment.
✓ About 70%, 88% and 90% TOC removal was observed
after pretreatment by applying 0, 0.5 and 1 kGy
doses, respectively and 96 h microbial treatment.
✓ Enzymes i.e. laccase, tyrosinase, azoreductase and
NADH-2,6-dichlorophenol indophenol reductase
were responsible for decolorisation.
✓ Fenton process was enhanced by using H2O2 and (Azizi et al., 2015)
zero valent iron (ZVI) with ultrasonic irradiation.
✓ About 99% of dye, 97% of COD was removed.

original effluent properties in the pretreatment scheme, a sys-
tematic study is needed. There is a requirement to find the research
methodologies which considers the above effects. Such a study
must implement analytical tools to estimate the effect of the
chemical oxidation process as a pre-treatment or post-treatment
on harmfulness and ratio of BOD to COD i.e. biodegradability in-
dex. Thus, the effect of pretreatment or post treatment should not
be only evaluated by ratio of BOD to COD but also toxicity of in-
termediates obtained after treatment as toxicity may give very low
COD but cause big damages (Punzi et al., 2015).
Brief review of a several combinations of chemical and biological
for dealing with the textile wastewater is shown in Table 8 and it
reveals that whether the oxidation methods or the biological
methods are first in a sequence of treatment, the ultimate aim of
decreasing costs will be similar to the reducing oxidation method
and exploiting the efficiency of the biological method, as a conse-
quence of the large cost difference of these two methods. The total
cost of biological effluent treatment plant (ETP) is 70e80% lower
than that of the chemical ETP (0.33e0.5 USD/m3 of treated water)
(Miah, 2012). Thus, an appropriate methods must be combined to
give the textile wastewater treatment technique with the best
overall commercial and environmental performance.
The main inferences arrived at from the literature presented in
Table 8 are that further work/study should be focused on the
degradation kinetics and reactor modeling of the combination
processes. There is also a need to check the effect of chemical
oxidation or advanced oxidation process (AOP) as a pretreatment of
segregated recalcitrant streams from each stage of wet processing
362 C.R. Holkar et al. / Journal of Environmental Management 182 (2016) 351e366
before subjecting to biological treatment of the textile wastewater.
Such a pretreatment may lead to a substantial enhancement in
biodegradability of the textile effluent. Furthermore, better cost-
effective prototypes must be established to evaluate, how the cost
of these combined chemical-biological processes vary with respect
to specific textile wastewater properties, the overall degradation
efficiency and cost of the chemical oxidation or AOPs against bio-
logical method.
7. Cost of textile wastewater treatment techniques
In recent time, the researches on water pollution control for the
textile industry are mostly focused on only qualitative explanation
and the related scientific methods. They do not have quantifiable
analysis of water pollution-control cost for textile industry to
justify and support economic decisions. Hence, it is also necessary
to give an importance to focus on the effluent treatment cost
analysis. Methods for the water pollution-control, regional distri-
bution and the type of textile industry are all key factors which
influence cost of water pollution control (Rodrigues et al., 2014).
This section adopts literature collection to identify the cost for the
textile wastewater pollution control techniques. In Table 9, possible
operating cost for textile wastewater treatment techniques have
been reported. Table 9 indicates that cost analysis have been done
on very few treatments. These studies show that combined fenton
and biological based treatment has lower cost as compared to
combined ozone and biological treatment. But fenton based treat-
ment produces more sludge as compared to ozone based treatment
and its disposal will also need the additional cost. In addition, the
wastewater used for the treatment is different and hence these two
treatments should not be compared. In future, there is a need to
carry out study which will focus on the cost analysis of more and
more treatments like advanced oxidation processes, photo catalyst,
combined treatments and microbial fuel cell used for actual textile
wastewater.
To get the lower operating cost of combination techniques for
degradation of organic matter in textile wastewater, the minerali-
zation percentage should be minimum in the pre-treatment or
Table 9
Cost of textile wastewater treatment techniques.
Sr.No. Process for treatment of textile Treatment cost ($/m3) (the
wastewater sludge disposal cost and
labor cost are excluded)
1 Color removal by Fetons process 0.4 USD per m3
followed by COD removal by activated
sludge
2 Fetons oxidation for the color and COD 0.59 USD per m3
removal from biologically pretreated
textile wastewater (Textile factory in
Turkey)
3 Fe3þ/H2O2 for the color and COD 0.57 USD per m3
removal from biologically pretreated
textile wastewater(Textile factory in
Turkey)
4 Ozonation for the color and COD 4.94 USD per m3
removal from biologically pretreated
textile wastewater(Textile factory in
Turkey)
5 Ozonation and H2O2 (peroxone) for the 5.02 USD per m3
color and COD removal from
biologically pretreated textile
wastewater(Textile factory in Turkey)
6 Fetons process followed by coagulation 3.5 USD per m3 (cost of
(polyaluminium chloride) followed by sludge disposal 1.5 USD per
ion exchange process applied to textile m3)
wastewater
post-treatment stage to reduce the needless spending of chemicals
and energy (Vergili et al., 2012; Rodrigues et al., 2014). To optimize
the costs, first the most expensive treatment parts should be
identified and then those parts should be minimized or substituted
with cheaper or more effective solutions. For example reuse of
catalyst and exploitation of the hydrogen peroxide already present
in the bleaching effluent. Fig. 5 recommends the different steps
which need to be followed for a possible selection of combination
of advanced oxidation process/biological treatment for textile
wastewater. Cost of all these possible combinations and the toxicity
of intermediates obtained after treatment should be compared
with each other. Then, the combination having low cost and giving
low toxicity should be used for the treatment of dyes in textile
wastewater. This Fig. 5 shows the essential chemical and biological
analysis which must be used in textile wastewater treatment
sequence. This also depicts the different conditions that may be
encountered, depending upon the components of the textile
wastewater.
8. Conclusion and recommendations
Aim of the Effluent Treatment Plants (ETP) in textile industry is
to implement technologies giving minimum or zero water pollu-
tion. These effluents treatment plants (ETP) in textile industry are
the most accepted approaches towards reaching environmental
safety. However, unfortunately, no particular treatment method-
ology is appropriate or universally adoptable for all kinds of textile
effluents. Therefore, the treatment of textile wastewater is done by
a combination of several methods, which contain physical, chemi-
cal and biological method depending on the type and quantum of
pollution load. This review has discussed several methods that can
be adopted to treat the dye in textile wastewater and to reduce the
pollution load.
Physical and oxidation methods are effective for the degradation
of dye in textile wastewater only if the textile effluent volume is
small. This bounds the usage of physical and chemical methods.
Cost of membrane filtration limits its application. These are true
even in lab-scale studies. Hence, they are not used in the large-scale
Color/COD removal References
✓ Complete decolorisation. (Vandevivere et al., 1998)
✓ Final COD of 80 ppm after activated sludge process.
✓ For the Fenton process, 78% and 95% COD and color removal (Solmaz et al., 2006)
efficiencies respectively.
✓ For the Fenton e like process, 64% and 71% COD and color (Solmaz et al., 2006)
removal efficiencies respectively.
✓ 43% COD and 97% color removal by ozonation. (Solmaz et al., 2006)
✓ 54% COD and 99% color removal by ozonation. (Solmaz et al., 2006)
✓ In this study, chemical coagulation (8% COD removal) and ion (Üstün et al., 2007)
exchange processes (51% COD removal and final COD 50 mg/
l) were applied after pre-treatment by Fenton oxidation
process (29% COD removal) to the textile wastewater.
 C.R. Holkar et al. / Journal of Environmental Management 182 (2016) 351e366
Fig. 5. Strategy for the combination of AOP/chemical oxidation and biological process for textile wastewater treatment.
studies.
Effluent treatment plants (ETP) utilizing biological methods,
rather than chemical methods claim that their preference is due to
low production of inorganic sludge, low working costs and com-
plete mineralization/stabilization of dye in biological method.
Normally, textile waste water parameters after biological treatment
are not in compliance with the textile wastewater discharge stan-
dards. So to meet wastewater discharge and to reduce the effect of
toxic or inhibitory compounds on bacteria, firstly, recalcitrant
organic compounds and dyes should be oxidized by chemical
oxidation or advanced oxidation method to convert it to biode-
gradable constituents before subjecting the wastewater to bacterial
treatment is preferred. Cavitation can be used to destroy microbial
life in water, if any. The treated water after removal of microbes can
be recycled for the purpose of cleaning. Now onwards, more re-
searchers should focus on the kinetic study of decolorisation/
degradation and modeling of bioreactor for the combination pro-
cesses of AOP or chemical oxidation as a pre-treatment or post-
treatment of segregated recalcitrant streams from each stage of
wet processing before or after subjecting to biological treatment of
the textile wastewater. The researches on pollution control for the
textile industry should also focus on quantitative description of
combination processes instead of only qualitative discussion.
Extensive research has been done to decide the role of the
various bacteria groups in the degradation of azo based water
soluble dyes. Few studies have been reported on the anthraquinone
based reactive dye. So, in future it is necessary to carryout work that
will try to emphasis the degradation of anthraquinone based dyes
with the help of integrated solutions (AOP and biological combi-
nation processes). Such a work may enhance the biodegradability of
textile industry wastewater containing anthraquinone based water
soluble dyes used for dyeing. The success of the work related to low
cost materials for MFC will have a positive impact on the local
363
textile wastewater treatment plant through application of MFC
technology, energy recovery from wastewater and (possible)
reduction of energy consumption by effluent treatment plant.
Acknowledgment
Authors would like to acknowledge Department of Science and
Technology (DST), Government of India for providing essential
financial support to conduct the research work.
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