Developments in new processes for colour

removal from effluent

M Joshi and R Purwar

INTRODUCTION component aromatic amines. Twenty two of these

amines are recognised as potential human carcinogens
Dyes are highly dispersible aesthetic pollutants, which
and several of them have shown carcinogenic potential
contribute to aquatic toxicity. It is difficult to treat, as most
in experimental animals according to a survey of azo-
dyes are highly stable molecules which resist degradation
colorants in Denmark [4].
by light, chemical, biological and other treatments.
Dyes can also significantly affect photosynthetic
Removing colour from textile effluent prior to it being
activity in aquatic life due to reduced light penetration
discharged into sewers is currently a major challenge to
and may also be toxic to certain forms of aquatic life
environmental as well as textile scientists.
[5,6]. In general, it is indicated that ionic dyes do not
This paper reviews the various textile wastewater
have any significant bioaccumulation potential but
decolorisation techniques being applied and researched
non-ionic dyes and pigments do have a potential risk
to remove colour from textile wastewater. The recent
for bioaccumulation [4].
developments in the promising areas of bioadsorbents,
The environmental impact of heavy metals in
hydrogen peroxide-based oxidation techniques and the use
wastewater effluent is also an important issue because
of microbial cultures for decolorisation are highlighted.
a significant number of dyestuffs are metallised dyes.
Commonly-employed metals are chromium, cobalt,
Background
nickel and copper, all of which are designated as
Textile industries consume large volumes of water and
priority pollutants by the US Environmental Protection
chemicals for the wet processing of textiles. A major
Agency [3].
contribution to colour in textile wastewater is usually
the dyeing and the washing operations. Wastewater is
During dyeing, most of the dye is exhausted on the fibre
extremely variable in composition due to large numbers of
but the unfi xed dye goes into the wastewater. The biggest
dyes and other chemicals used in processing. The problem
problem relates to the dyeing of cotton with reactive and
is further made complex by the more than 10 000 dyestuffs
vat dyes because of low levels of exhaustion and fixation, as
commercially available.
shown in Table 1 [7]. However various developments have
Although dyes constitute a small portion of the total
been carried out in recent years to increase the fi xation
waste discharged in textile processing, colour removal
level of reactive dyes [8,9].
from effluent is a major problem for the textile industry for
Practically, the most important textiles dyes can be
several reasons:
classified into acid, basic, direct, disperse, metal complex,
The presence of even a small fraction of dye in water is
reactive, sulphur and vat. Acidic and basic dyes are
highly visible (due to the high tinctorial value of dyes)
water soluble dyes with coloured anionic and cationic
and affects the aesthetic merit of streams and other
moieties, respectively. Direct dyes are anionic in nature
water resources.
and substantive to cellulose when applied from an aqueous
Most dyes have complex aromatic structures resistant
bath containing an electrolyte. The majority of direct dyes
to light, biological activity, ozone and other degradative
belong to bis, tris and poly azo classes, the remainder being
environments and hence not readily removed by typical
monoazo, stilbene, oxazine, thiazole and phthalocyanine
waste treatment processes.
compounds. Disperse dyes are water insoluble dyes and
Most of the modern textile dye ranges which meet
consumer performance requirements have very low
levels of toxicity as demonstrated by data provided Table 1 Exhaustion range of various dye classes
by the dye manufacturers. However, a small number
of classical dyes prepared from amines (now known Degree of Loss to
to be carcinogenic) and which do not meet modern Dye class Fibre fi xation (%) effluent (%)
textile market requirements, could cause concern
because of possible mutagenic, carcinogenic and/or Acid Polyamide 8095 520
Basic Acrylic 95100 05
allergenic effects [13]. Such dyes can have acute and/ Direct Cellulose 7095 530
or chronic effects on exposed organisms depending on Disperse Polyester 90100 010
exposure time and dye concentration. The highest rates Metal complex Wool 9098 210
of toxicity were found amongst basic and diazo dyes. Reactive Cellulose 5090 1050
Sulphur Cellulose 6090 1040
The azo linkage of azo dyes, but not of azo pigments, Vat Cellulose 8095 520
may undergo metabolic cleavage resulting in free

58 Rev. Prog. Color., 34 (2004)

r3308_Joshi.indd 1 25/11/2004 12:01:27

 are usually applied from fine aqueous dispersion. Reactive
dyes include molecules with fibre-reactive groups, such as
mono, dichlorotriazinyl and chloroethyl sulphonyl. Dyes
are bound to the fibre either through covalent or ionic
bonding, van der Waals forces or impregnation of colloidal
dye particles into the fibre.
The above classification of dyes is based on their dyeing
mode or main structural moieties, both of which are
generally inadequate for their environmental evaluation
purposes. The colour of water polluted with organic
colorants reduces with the cleavage of C=C or N=N double
bonds or heterocyclic and aromatic ring cleavage and the
absorption of light by associated molecules shifts from
visible to ultraviolet (UV) or infrared regions.
The effectiveness of different decoloration techniques
for the removal of various dyes also depends on the dye
class (the chromophore) as well as its varying substituent
groups (auxochromes). Generally, highly water soluble
dyes (i.e. reactive, acid and other anionic dyes) are more
difficult to remove by conventional techniques than poorly
soluble dyes (i.e. vat and disperse dyes). Anthraquinone-
based dyes are most resistant to degradation due to their
fused aromatic structures and remain coloured for a long
time. The water solubility and molecular size of a dye also
affects the adsorption of dye on activated sludge and other
adsorbents such as activated carbon. Dyes having fewer
sulphonic acid groups and higher molecular weight (both
features reduce water solubility) show better adsorption
on activated sludge. Low adsorption occurs for acid and
reactive dyes, high adsorption occurs with basic and direct
dyes and high to medium for disperse dyes. The presence
of hydroxy, nitro and azo groups in dye structure increases
the amount of dye removed by this process.
The susceptibility to degradation by oxidation, i.e.
hydrogen peroxide/UV, also varies for different dye classes.
Acid dyes may be degraded but with an increase in the
number of azo groups effective decoloration decreases.
While direct, metal complex and disperse dyes may be
decoloured quickly, reactive dyes take a longer time.
For vat dyes the decoloration is only 50% or less. It is in
this respect that for the large number and variety of dyes
currently available commercially and new dyes being
added to the list, the problem of colour removal from
effluent becomes more and more challenging.
The economic and efficient removal of polluting dyes
from textile effluent is also important because government
legislation on effluent limits of colour is becoming more
and more stringent all over the world. During the past two
decades, much research activity has been reported in the
literature on various colour removal techniques [10,11].
The present paper reviews widely used decolorisation
techniques and highlights the recent developments in new
processes for colour removal from textile effluent.
COLOUR REMOVAL TECHNIQUES
Most current practices for wastewater decolorisation
treatment strategies fall into three main classes: physical
or physicochemical, chemical and biological. These
techniques depend on physical dye separation, breakdown
of dyes or decolorisation by adsorption/biodegradation,
respectively.
r3308_Joshi.indd 2
Physical or physicochemical techniques
Coagulation/flocculation
Over the years, coagulation has been the most economically
feasible method for colour removal [11], however it does not
treat all dye types effectively [12]. Sulphur and disperse
dyes coagulate well and settle easily, while acid, direct, vat
and reactive dyes coagulate well but the resulting flock is
of a poor quality and does not settle easily. Cationic dyes do
not coagulate at all. Several studies have been reported in
the literature on the use of different coagulants for textile
wastewater treatment [1214]. The coagulant dose required
depends on the type of effluent, concentration of dye and
other processing aids used. In the presence of surfactants,
the dosing of chemicals has to be significantly increased to
achieve satisfactory colour removal. A major disadvantage
of using coagulation and flocculation is the generation
of large amounts of toxic sludge creating many handling
and disposal problems. The other major drawback is that
this scheme is not able to reduce the total dissolved solids
(TDS), rather the TDS levels are enhanced during treatment
and hence pose a lot of problems in water recycling and
reuse.
Synthetic organic coagulants are highly charged cationic
polyelectrolytes and promote precipitation of dye residues
forming small insoluble colour particles which are later
removed using a suitable solid/liquid separation process.
These often completely eliminate the need for the large
amounts of aluminium- or iron-based salts traditionally
used. The mechanism of dye removal is electrostatic
attraction between the oppositely-charged soluble dye and
polymer molecules [10].
Adsorption
Adsorption is an effective method for lowering the
concentration of dissolved organics in an effluent and
several adsorbents have been used for removal of colour
from textile effluent.
Activated carbon is one of the more popular adsorbents
used for dyes [11,15]. However, the carbon adsorption
of dyes is neither efficient nor economical when used
alone, although when used in combination with polymer
flocculation, chemical coagulation or biodegradation, it
becomes a very useful polishing step for efficient dye
removal. One of the main reasons for the observed poor
adsorption is the polar nature of dyes versus the non-polar
nature of carbon. Factors, such as choice of activated
carbon, temperature, pH, contact time and dosage, must
be taken into consideration for optimum removal of dyes
from wastewater. Activated carbon, although reasonably
effective at removing dyes from aqueous streams, needs
either regeneration or disposal, once it is fully loaded.
The other limitations are the high cost and 1015% loss of
adsorbent on reactivation.
Many inexpensive inorganic adsorbents have been
evaluated as potential adsorbents for dyes, which include
peat [5], flyash [16], bentonite [17], calcium metasilicate
[18], activated alumina [19], clay, bauxite [20], dolomite [21]
and anion clay hydrotalcite [22]. The use of high surface
area silica, cinder and clays has also been tried for a range
of dyes [23]. Silica was found to be reasonably effective for
treating effluent containing basic dyes.
Rev. Prog. Color., 34 (2004) 59
25/11/2004 12:01:32
 Macrosorb is a range of inorganic synthetic particulate
clay absorbents developed by Crosfields and Unilever
Research engineered for optimum absorption of large
negatively charged polar molecules, i.e. dyes, organo
halides, pesticides, etc. [10]. These absorbents have very
high capacities and can remove these contaminants from
process water down to extremely low levels and are then
removed by gravity settlement in the form of pumpable
sludge. This offers the prospect of being able to meet not
only any current or envisaged consent limits but also
of water reuse. Similarly, Arcasorb D is a proprietary
biological adsorbent from Archaeus Technology Group,
which removes soluble dyes (in particular reactive dyes)
and other contaminants from textile waste streams [10].
The main mechanism involved in removal of colour and
other contaminants from effluent streams by Macrosorb
and Arcasorb D are believed to be physical adsorption and
anion exchange.
Since most dyes are chemically either anionic or
cationic, they could in theory be removed on ion exchange
resins [6,10,2426]. However, such resins have not been
widely used for the treatment of dye-containing effluent,
mainly due to the fact that ion exchange resins cannot
accommodate a wide range of dyes, i.e. they are not
effective for disperse dyes, and some have to be regenerated
using organic solvents once they are saturated, which adds
to the cost.
Cucurbiturial, a cyclic polymer of glycoluril and
formaldehyde, showed extraordinary good sorption
capacity for various types of textile dyes [27]. It is known
to form hostguest complexes with aromatic compounds
and this may be the mechanism for dye adsorption. High
cost is a disadvantage.
In recent years, many investigations have been
undertaken to evaluate inexpensive alternative materials
of biological origin (bioadsorbents) as potential adsorbents
for dyes, which include chitin, chitosan [10,28], sawdust
[29,30], carbonised wool, [31] activated sludge [32], wood
bark, rice husk, cotton waste [33], apple pomade, wheat
straw [34] and barley husk [35].
Biomass: Due to its low cost and widespread availability,
biomass has been extensively investigated for removing
colour, with promising results [36]. In this case, biomass
refers to dead plant and animal matter such as agriculture,
forest, fermentation and shellfish by-products or wastes.
Biomass can be used for the decolorisation of textile
wastewater by the use of adsorption and ion exchange
mechanisms. Unfortunately, without prior chemical
modification these materials uniformly have very low
adsorption capacities for anionic dyes. There have been
several studies reported on chemical modification of
celluloses and ligno-celluloses extracted from cotton waste,
sawdust and corn stalks, etc. [37].
Microbial biomass: The uptake or accumulation of chemicals
by microbial biomass has been termed biosorption. Dead
bacteria, yeast and fungi have all been used for the purpose
of decolorising dye-containing effluent [38]. Depending on
the dye and the species of microorganisms used different
binding rates and capacities were found. The use of biomass
has its advantages, especially if the effluent is very toxic.
60 Rev. Prog. Color., 34 (2004)
r3308_Joshi.indd 3
Biomass adsorption is effective when conditions are not
favourable for the growth of microbial populations.
Microbial biomass that is the by-product of industrial
fermentation processes can serve as a dye adsorbent as the
microbes contain chitin and chitosan in their cell walls.
The biosorption of reactive dyes on Aeromonas biomass
[39] and oven-dried Rhizopus arrhizus biomass [40], and
the basic dye Methylene Blue (CI Basic Blue 9; 1) on dried
Spirodela polyrrhiza biomass [41], have been reported.
Removal of an anionic disazo direct dye, Congo Red (CI
Direct Red 28; 2), from an aqueous solution by biosorption
on dead fungus, Aspergillus niger, has also recently been
investigated [42].
N
(H3C)2N S N(CH3)2
ZnCl3
1
NaO3S
N H2N
N N
NH2 N
2 SO3Na
Chitin and chitosan: Chitin is a polysaccharide very
similar in structure to cellulose, being composed of poly-
2-acetamido-2-dioxy-D -glucose. Chitosan, a deacetylated
chitin, is a natural biopolymer extracted from the shells
of arthropods [10]. Due to its unique molecular structure,
chitosan has an extremely high affinity for many classes of
dyes, including disperse, direct, reactive, acid, vat, sulphur
and naphthol. The only class for which chitosan has a
low affi nity is basic dyes. There have been several studies
reported on the use of chitin and chitosan for removal
of dyes [4346]. Knorr was the fi rst to examine the dye
binding properties of chitin and chitosan and found that
chitosan had better dye-uptake properties than chitin [43].
McKay et al. did extensive work on chitin and reported
adsorption equilibrium studies [44], batch and column
studies [45], and kinetic studies and mass transfer models
[46] for the adsorption of various dyestuffs on chitin.
More recently, Qin [47] investigated the possibility of
using chitosan fibre, which has amino groups and therefore
has the advantage of more adsorption capacity and much
easier desorption. A moderately crosslinked chitosan
fibre [48] allows the fibres to be used at low pH which
improves the dye binding capacity without solubilising the
chitosan.
Unmodified lignocellulose: McKay and Prasad examined
wood bark, rice husk and cotton waste for their ability to
bind Congo Red (a divalent anion) and observed negligible
amounts of adsorption [33]. McKay and Poots showed that
wood as adsorbent can adsorb acid dyes successfully but
long contact times are required to reach equilibrium [49].
Similarly, McKay et al. reported wood shavings to have a
capacity for Congo Red of 0.001 mol/kg [50]. The binding
of CI Acid Blue 25 (3) to sugarcane bagasse is slow and the
25/11/2004 12:01:32
 capacity only 0.05 mol/kg. Maize (corn) [51] also bound CI
Acid Blue 25 slowly, requiring more than 3 h to reach the
equilibrium, and to an extent of 0.1 mol/kg.
O NH2
SO3Na
O N
H A low cost adsorbent can be prepared by quaternisation
3
Chemically-modified cellulose and lignocellulose: Hwang
and Chen reported a series of adsorbents prepared from
the reaction of polyamide-epichlorohydrin (PAE) resin
and cellulose [52]. This material, composed of 1030%
cellulose, has a high adsorption capacity for acid, direct
and reactive dyes. The apparent adsorption capacity of
PAEcellulose is pH-dependent (similar to chitosan) and
dye adsorption is very slow, requiring three days at 30 C
to reach equilibrium.
Youssef described the chemical modification of cellulose
(cotton) with the N-methylol derivatives of tris- and bis(2-
carbamoylethyl)ethylamine to enhance acid dye adsorption
[53]. Equilibrium with the dye was reached within 30 min,
indicating excellent kinetics.
Cellulose and phosphorylated cellulose with different
phosphorus content, as cationic dye absorbers for
decolorisation of coloured wastewater, have been reported
by Kammel [54]. Abo-Shosha et al. prepared cellulose/
glycidyl methacrylate/acrylic acid cation exchange
composite which was used to remove some basic dyes from
textile effluent [55]. The cellulose derived from sugarcane
bagasse was derivatised to its carbamoyl derivative and
used as a direct dye adsorbent [56]. However, it was
observed that the dye binding capacity of the untreated
cellulose was higher than its derivative.
Quaternary ammonium groups can be introduced
into cellulose and lignocellulosic materials introducing
a permanent positive charge to the substrate, making the
materials very effective acidic dye adsorbents. Gangneux
et al. demonstrated that quaternised cellulose has an
exchange capacity of 0.60.7 equiv./kg for acid, direct and
reactive dyes [57]. The equilibrium adsorption of the dye
was achieved in less than 2 h. While quaternised cellulose
has most of the desired performance characteristics (high
capacity, rapid kinetics, etc.), it fails to retain the most
important attribute low cost.
of lignocellulosic materials such as corn cob [58], sawdust
[59], sugarcane bagasse [60] and polysaccharides [61].
These materials have the exchange capacities in the range
of 0.350.85 equiv./kg. The dye adsorption and desorption
characteristics of quaternised lignocelluloses is quite
comparable to the cationic materials prepared from pure
cellulose.
Thus, relat ively i nexpensive, moderately hig h
capacity, anionic dye adsorbents could be prepared from
lignocellulose biomass, however none of these adsorbents
have any commercial importance. Table 2 summarises
the main advantages and disadvantages of different
bioadsorbents reported for removal of a variety of dyes from
textile wastewater, including Congo Red (2), CI Acid Blue
25 (3), Acid Orange II (CI Acid Orange 7; 4), CI Acid Orange
25 (5), Lanasyn Black (CI Acid Black 172; 6), CI Acid Red
1 (7), CI Acid Yellow 114 (no structure provided), Reactive
Yellow (CI Reactive Yellow 2; 8), CI Direct Blue 86 (9) and
CI Acid Blue 13 (10).
Membrane separation
The use of reverse osmosis and nanofi ltration membranes
to separate out water soluble dyes from textile effluent
is well documented in the literature [10,11,6267]. There
are four developed membrane separation processes,
namely microfiltration, ultrafiltration, reverse osmosis
and electrodialysis. The first three of these processes
differ principally in the size of particles separated by the
membrane. The microfiltration process has membrane
pore diameters from 0.1 m (100 nm) to 10 m, where as

Table 2 Summary of bioadsorbents

Adsorption capacity (mol/kg)

Biomass Monovalent dye Divalent dye Major drawback

Chitin 0.45 (CI Acid Blue 25) 0.13 (CI Acid Red 1) Slow kinetics
Chitosan 0.45 (CI Acid Red 1) Slow kinetics
Crosslinked chitosan 4.50 (Acid Orange II) pH sensitive
Fungal biomass 0.05 (Acid Orange II) 0.11 (Acid Red 114) Slow kinetics
Bacterial biomass 0.08 (Reactive Yellow) a
Sugarcane bagasse 0.05 (CI Acid Orange 25) Low capacity
Sawdust 0.001 (Congo Red) Low Capacity
Maize cob 0.10 (CI Acid Blue 25) Low capacity
Peat moss 0.13 (Lanasyn Black) Low capacity
Rice hull 0.14 (Lanasyn Black) Low capacity
PAEcellulose Slow kinetics
Carbamoylcellulose 1.0 (CI Direct Blue 86) Low capacity
Quaternised-cellulose 0.601.10b 0.013 (CI Acid Blue 13) Expensive
Quaternised-lignocellulose 0.0350.85b None

a Trivalent anion
b Adsorption capacity units = equiv./kg

Rev. Prog. Color., 34 (2004) 61

r3308_Joshi.indd 4 25/11/2004 12:01:33

 SO3H HO
OH
N
HO N N HO3S N
NaO3S N
N N OH
N H
O
O2N
5 6

4
SO3Na SO3Na
Cl
CH3 H H O
H H NaO3S N N Cl
N
N O N O N N
N
N N N
N H H3C
NaO3S SO3Na Cl
8
7
(H3C)2N N(CH3)2

NaO3S

N SO3

N N
N Cu N
N N N
H5C2
N

9 SO3Na
SO3Na
10

ultrafi ltration refers to membranes with pore diameters in
the range of 2100 nm. In reverse osmosis, the membranes
pores are very small in the range of 0.52.0 nm in diameter,
and are within the range of thermal motion of the polymer
chains.
When ultrafiltration membranes have similar pore sizes
to those used in reverse osmosis, the process is referred
to as nanofiltration. Ultrafiltration involves separation of
solutes of molecular weight (MW) between 1000100 000,
while below MW 1000, nanofiltration and reverse osmosis
come into play. The operational pressures for reverse
osmosis are high in the range of 1001000 psi, whereas
ultrafiltration systems operate at pressures in the range
of 10100 psi. Whilst ultrafiltration separates colloidal
materials and dissolved macromolecules such as proteins,
nanofiltration can separate organic molecules of MW > 350
and even polyvalent ions, while allowing smaller ions to
pass through. Reverse osmosis membranes, however, retain
even the smallest ions (e.g. Na+, Cl) allowing the passage
of pure water only and find use mainly in the desalination
of sea water.
Ultrafiltration has been successfully applied for
recycling high molecular weight and insoluble dyes (e.g.
indigo and disperse dyes), auxiliary chemicals (polyvinyl
alcohol) and water [68,69]. However, this process does
not remove low molecular weight and soluble dyes (acid,
direct, reactive, basic, etc.) though efficient colour removal
has been achieved by nanofi ltration and reverse osmosis
[7072]. Hydrolysed reactive dyes, the most problematic
to remove by other conventional techniques of colour
removal, have been successfully removed from textile
effluent using nanofiltration and reverse osmosis processes
[7375]. Nanofi ltration has been demonstrated to separate
reactive dyes of MW 400 from textile plant effluent and also
give a sharp reduction in chemical oxygen demand (COD)
(up to 94% in cross flow cell).
The membranes used have excellent thermal, chemical
and mechanical stability, allowing operation at high
flux rates, and, being resistant to wider ranges of pH,
temperature and solvents, are found to be suitable for
separation of organic dyes from textile effluent. Reverse
osmosis and ultrafiltration membranes, made out of a
variety of polymers like polyamides [76], poly(phthalazine
ether sulphone ketone) [77], styrene copolymer [78],
polyacrylonitrile, polysulphones [79], polycarbonate and
fluorocarbon-based polymers, have been used for textile
applications. The use of polymeric membranes is limited
to temperatures below 70 C, pressures <67 MPa and pH
range 212 (maximum). Ceramic membranes withstand
higher mechanical forces and tolerate rough effluent
conditions such as temperatures higher than 100 C and pH
greater than 12. Inorganic membranes have longer lifetimes
but are fragile and require frequent back pulsing.
Membranes are packaged in modules that control the
pressure, feed stream velocity and turbulence in order to
reduce concentration polarisation (fouling) effects. There
are four basic kinds of modules namely plate and frame,
tubular, spiral wound and hollow fibre modules [80]. Spiral
wound modules provide a relatively high packing density
(<1000 m2/m3) and allow for a compact design, but they

62 Rev. Prog. Color., 34 (2004)

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 are intolerant of particulates. A prefiltration step to remove
fibres, grease, etc. in early process effluent is essential to
avoid clogging of the flow channels. Tubular membrane
modules seem to be most appropriate for dye removal from
textile effluent [81]. This is because they are relatively
insensitive to clogging and more effectively cleaned
during backwash procedures. However, packing densities
are very low (<100 m2/m3) and feed flow rates per unit
membrane are high. Nowak et al. reported the suitability
of capillary membrane modules (ultra- and nano-filtration)
for decolorisation of both simulated and actual dye effluent
and found 9299% retention for direct dyes of various MW
461878 [82].
Membrane processes, especially nanofiltration and
reverse osmosis, in combination with other treatments (e.g.
electro flocculation/ozonation) have been successfully used
to treat water to a quality required for recycle and reuse
[83,84]. Reductions of fresh water use of the order of 60%
can be achieved by integration of membrane technology
into continuous washing/rinsing processes. Compared with
other separation processes, the space requirements of these
processes are low and modular construction and design
allows relatively easy expansion.
The major problem faced in the application of membrane
technology for effluent treatment is the high cost of
membranes and other membrane filtration equipment
depending on the size of plant, the operating condition and
associated water pretreatment costs besides the problem
of lowered productivity with time due to deposition
of precipitated dyestuff leading to membrane fouling.
Micro- and ultra-fi ltration have been recommended as
suitable pretreatment steps for nanofi ltration and reverse
osmosis processes to minimise the fouling problems [83].
An electric field-enhanced nanofi ltration of direct dye
effluent reported 100% dye rejection and the electric
field was found to reduce fouling [66].The disposal of the
concentrates from the membrane processes is another
major problem. There have been several attempts to solve
this difficulty by oxidative degradation of the membrane
concentrates by Fentons reagent [85] and ozonation of
membrane concentrated secondary effluent [86].
Chemical techniques
Chemical oxidation
Many dyes are effectively decolorised using chemical
oxidising agents and seem to hold potential for future use
in the textile industry. Many studies on usage of different
oxidising agents, i.e. chlorination, chlorine dioxide
treatment, ozonation, hydrogen peroxide with other salts
(Fentons reagent), permanganate, etc. have been reported
in the literature and summarised in Table 3 [87].
Chlorination: Chlorination has been evaluated for its
effectiveness in colour removal [88]. High concentrations
of chlorine are required for efficient colour removal but
a significant amount remains as residual chlorine in the
treated effluent. Chlorine is reported to be more effective for
dye decolorisation at pH 3.5 than pH 7.0 or 10.0. Chlorine
can be used for the rapid decolorisation of acid and reactive
dyes but not direct and disperse dyes (even at large doses).
Instead, rather persistent yellow decomposition products
are formed. Recently an electrolytic process based on
chlorine generation was adapted to wastewater containing
textile dyes [89]. Although decolorisation using sodium
hypochlorite is inexpensive and effective, dechlorination
of wastewater is necessary in order to prevent toxic effects
in the ensuing biological processes. Moreover, chlorine is
viewed with increasing disfavour because it has potential
for generating toxic chlorinated compounds, i.e. absorbable
organohalides (AOX), that are harmful to humans and the
environment.
Ozonation: Ozone is a more powerful oxidant than chlorine
and other oxidising agents (i.e. oxidation potentials for
O3 2.07, Cl2 1.36, H2O2 1.78) and offers a mechanism

Table 3 Summary of chemical oxidation techniques

Method Comments

Sodium hypochlorite Effective on decolorisation, cheaper than other oxidants and easily applicable (2040 C, 530
min); risk of halogenated hydrocarbon (AOX) increase and bacterial toxicity; can only be used
with small amounts of wastewater
Hydrogen peroxide Environmentally friendly; not effective on all dyes as oxidation potential is not very high
Fentons reagent More effective than hydrogen peroxide on different classes of dyes; wastewater may be reused
following this treatment and removes heavy metals; causes severe sludge problems
Ozone Useful in the decolorisation of water-soluble dyes; does not sufficiently decrease COD and
turbidity; acids, aldehydes and ketones are reaction products; recommended that coagulation
and ozone can be used prior to biological treatment
UV irradiation Photocatalytic reactions of some organic species in aqueous solutions are feasible; removes
heavy metals; sludge and harmful UV scattering problems
Gamma irradiation New technique
UV irradiation/hydrogen peroxide Increased rate and strength of oxidation, but the cost of producing UV irradiation does not
compensate for the increase; environmentally friendly, apart from some UV scattering
UV irradiation/ozone Increased rate and strength of oxidation, but the cost incurred by the UV irradiation does not
compensate for this increase; environmentally friendly, apart from UV and ozone scattering;
wastewater may be reused since reaction products could be carbon dioxide, water, nitrogen,
etc.

Rev. Prog. Color., 34 (2004) 63

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 SO3Na
H N N N
N O
H3C
11
SO3Na
EtO N N
Scheme 1
for oxidising dye wastewater without producing harmful
chlorinated organics [11]. Ozone reacts with dye molecules
in two ways, below pH 56, ozone is present mostly as O3
and reacts, selectively, with double bonds in dye molecules.
At higher pH, i.e. above 8, ozone rapidly decomposes
forming hydroxyl free radicals that react non-selectively
with organic compounds. Ozone fading of dyes occurs by
the oxidative cleavage of the conjugated system of the dye
molecule, in this case Crysophenine (CI Direct Yellow 12;
11) (Scheme 1). Ozone is useful for removing many toxic
chemicals from wastewater, as it is capable of decomposing
detergents, chlorinated hydrocarbons, phenols, pesticides
and aromatic hydrocarbons. It is reported that biological
treatment followed by 10 min ozone oxidation reduced the
overall toxicity significantly (92%) [90].
Ozone treatment has been successfully used to remove
colour from dyeing wastewater [9193], with some classes
of dye responding more readily to oxidation by ozone
than others. Reactive dyes are degraded to the greatest
extent and ozonation is moderately successful when
treating wastewater-containing sulphur, azoic and basic
dyes [10]. However disperse dyes have poor response
to ozonation. The dosage applied to the dye-containing
effluent is dependent on total colour and residual COD to be
removed with no residues or sludge formation and no toxic
metabolites [94]. Ozonation may decrease COD and increase
the biodegradability of the waste stream but produces little
reduction in total organic carbon (TOC). Cost and efficiency
are barriers associated with ozonation. Another major
drawback is its short life (half-life being 20 min) requiring
continuous ozonation. Improvement of ozone diffusion by
means of membrane contractor (higher gas/liquid contact
surface) in order to further reduce operating costs has been
recently reported [95].
Additionally, since ozone is hazardous it requires an
ozone destruction unit to prevent ozone from escaping from
the process and damaging the environment.
64 Rev. Prog. Color., 34 (2004)
r3308_Joshi.indd 7
NaO3S
N H
N
CH3
N N
H H
CHO + HOOC N N OEt
NaO3S
OHC N N OEt + H2O2
NaO3S
Other oxidising agents
Hydrogen peroxide: Activated hydrogen peroxide is an
important oxidising agent used for decolorisation by
chemical means and removes the dye from the effluent by
oxidation resulting in aromatic ring cleavage of the dye
molecules. This agent needs to be activated by some means
for example, UV light, inorganic salts, i.e. iron(II), ozone or
ultrasound. The methods of chemical decolorisation vary
depending on the way in which the hydrogen peroxide is
activated.
Fentons reagent: Fentons reagent is a suitable chemical
means of treating wastewater which is resistant to
biological treatment or poisonous to live biomass. In acid
solution with iron(II) as a catalyst, peroxide vigorously
forms hydroxyl ions and radicals (Eqn 1), which are used
to remove the dye from the wastewater [96].
H2O2 + Fe2+ Fe3+ + OH + OH (1)
This reagent is capable of treating soluble (reactive) and
insoluble (vat and disperse) dyes and achieves consent
conditions for both the concentrated and dilute waste
investigated [10]. The vigorous oxidation also reduces
the COD of the effluent. Neutralisation of the effluent
after treatment causes precipitation of the iron oxide and
hydroxide, which removes any remaining insoluble dyes
from the effluent by adsorption and/or flocculation. One of
the major disadvantages of this method is sludge generation
through flocculation of the reagent and dye molecule. The
sludge, which contains the concentrated impurities, still
requires disposal and the performance depends on fi nal
floc formation and its settling quality. In a comparative
study on the oxidation of disperse dyes by electrochemical
processes, ozone, hypochlorite and Fentons reagent, the
best results were obtained with the Fenton process [97].
25/11/2004 12:01:35
 Hydrogen peroxide/UV: Decolorisation of dyes using UV/
peroxide photochemical oxidation has been investigated
[98103]. This method degrades dye molecules to carbon
dioxide and water by UV treatment in the presence of
hydrogen peroxide [98,99], with degradation being caused
by the production of a high concentration of hydroxyl
radicals. UV light activates the destruction of hydrogen
peroxide into two hydroxyl radicals (Eqn 2). This causes
chemical oxidation of organic material.
2 OH
UV
H2O2 (2)
The rate of dye removal is influenced by the intensity
of the UV radiation, pH, dye structure and the dye
bath composition [100]. This may be set up in a bath or
continuous column unit [101]. Depending on the initial
material, additional by-products such as halides, metals,
inorganic acids, organic aldehydes and organic acids may
be produced [98]. There are advantages of photochemical
treatment of dye-containing effluent, i.e. no sludge is
produced and foul odours are greatly reduced.
Hydrogen peroxide/ozone: Advanced techniques using
a combination of ozone and hydrogen peroxide make it
possible to remove odour, colour, COD, TOC and AOX. The
resultant products are often easily biodegradable [102].
Decolorisation by means of ozone/peroxide combination is
applicable for direct, metal complex or blue disperse dyes,
but there are some problems with decolorisation of acid
dyes, red disperse dyes and their mixtures [100].
Hydrogen peroxide/peroxidase: Peroxidase can also be used
as an activator for hydrogen peroxide for decolorisation
purposes. Morita et al. studied decolorisation of acid dye
using three types of peroxidases as peroxide activators
[104]. The decolorisation rate increases with increasing
peroxidase concentration and temperature of the medium
and was greatest at pH 9.5.
Hydrogen peroxide/UV/ultrasound: Fung et al. studied the
decolorisation and degradation kinetics of reactive dye
wastewater by a UV/ultrasonic/peroxide system [105]. It
was observed that ultrasound in combination with UV
dramatically improves the initial reaction rate and the
overall dye removal efficiency. Ultrasound may increase
the oxygen uptake and transfer rates and these enhance the
oxidation processes due to the hydroxyl radicals. Sonication
thus accelerates decolorisation and mineralization of the
dye [106,107].
Irradiation
Gamma radiation-induced oxidation [87,107] decolorises
refractory dyes that withstand many of the conventional
textile waste treatment processes. The rate of reaction
is controlled by the radiation dose and the availability
of oxygen in the solution. It proved to be an effective
technique for removal of reactive, acid and disperse
dyes as well as toxic organic compounds, i.e. benzene,
toluene, chlorophenols, by oxidising them into more
easily biodegradable compounds. Both COD and AOX
were decreased and 90% of colour in the wastewater
r3308_Joshi.indd 8
was eliminated. However, very high cost is the major
disadvantage.
The solar radiation-assisted photocatalytic degradation
of various dyes, such as Methylene Blue, Remazol Brilliant
Blue R and Orange G, using nano-titanium dioxide as
the catalyst has been recently reported [108]. This can be
highly economical compared with the processes using
artificial UV radiation, which require substantial electrical
power input.
Wet air oxidation is another process by which the
effluent could be effectively disposed after decolorisation
[109].
Chemical reduction
For many dyes, particularly azo dyes, chemical reduction is
an effective decolorisation technique. Chemical reduction
of azo dyes causes cleavage of the azo bond, generating
lower molecular weight non-chromophoric aromatic
amines that are more amenable to subsequent aerobic
biological treatment than the parent dye structure. In
addition, certain reactive dyes are adsorbed better onto
activated carbon when pretreated with a reducing agent
[110]. Chemical reduction, based on bisulphite-catalylsed
sodium borohydride along with a cationic agent, has been
applied to water-soluble direct, acid and reactive dyes
containing azo or other reducible groups and to copper
based metallized dyes [11]. Using this process colour
reduction of >90% was possible. The other most commonly
used chemical reducing agents are sodium hydrosulphite,
thiourea dioxide and tin(II) chloride. When evaluating
the chemical decolorisation of wastewater containing azo
dyes using reducing agents, it is important to investigate
the potential reversal of the reaction upon exposure to
oxygen, since colour may reappear upon discharging the
wastewater to the environment.
Electrochemical decolorisation
Elect rochem ica l tech n iques, i.e. elect rod ia lysis /
electrochemical ion oxidation, combine the oxidation of
the dye and the other polluting contaminants by means
of the electrolytic process with the physico-chemical
precipitation of the sludge. Electroflocculation is the
combination of an oxidation, flocculation and flotation.
Electrochemical ion generation is a proven technology for
removing colour, biological oxygen demand (BOD), COD,
TOC, solids (suspended and dissolved) and heavy metals
such as chromium, copper, zinc from textile waste water
[11,111].
The system most commonly utilises an electrochemical
cell with steel electrodes .The positively charged sites of
the electrodes (anodes) produce ferrous ions. At negative
sites (the cathodes) the water decomposes into hydrogen
gas and hydroxyl ions. The overall reaction results in the
formation of hydrous iron oxide, ferrous hydroxide and
ferric oxyhydroxide. The electrodes are slowly consumed
as the metal hydroxide is generated. The process water
then enters a degassing tank; pH is adjusted <7 or >11 for
satisfactory Fe2+ precipitation. The use of an aluminium
cell or combined iron/aluminium cells is also reported
in the literature. Trivalent iron and aluminium flocculate
oxidised substances because of electrostatic interaction
Rev. Prog. Color., 34 (2004) 65
25/11/2004 12:01:35
 and coprecipitation. Recently, use of titanium or titanium/
platinum/iridium electrode, as anodes have also been
reported [112]. The efficiency of the process depends on
several parameters, i.e. difference of potential, nature of
electrodes, pH, salt concentration of solution, number of
electrodes, distance between them, stirring and current
intensity, etc. [113].
Electrochemical technology is reported to remove acid,
disperse and metal complex dyes effectively [114,115]. If
metal complex dyes are present, dye solubilising and charge
are the most important factors for successful removal of
heavy metals. The pH has to be adjusted to maximise dye
insolubility. Lin and Chen have reported that the addition
of a small amount of hydrogen peroxide (200 mg/l) elevates
the efficiency of electrochemical treatment process by as
much as 100% [116]. This is due to in situ generation of the
hydroxyl radical (Fentons reagent) when an iron electrode
is used, leading to rapid oxidation of Fe2+ to Fe3+.
Thus, electrof locculation is a promising method
for producing recyclable process water as there is no
simultaneous addition of anions such as sulphate or
chloride. This is in contrast to conventional chemical
precipitation methods that introduce either chloride
or sulphate ions both of which increase the TDS of the
effluent. Moreover, evidence of salt content (sulphate and
chloride) reduction was found, which makes the treatment
even more interesting for recycling from a technical point
of view.
Biological treatment
Biological digestion involves the aerobic (presence of
oxygen) or anaerobic (absence of oxygen) degradation of
organic substances by microorganisms and has been widely
researched and reviewed [11,117].
Aerobic treatment
Aerobic biological treatment using activated sludge is
one of the most commonly used treatment methods
for textile dyeing eff luent. Normally, this process
removes the biodegradable components of the effluent
(i.e. carbohydrates, waxes and the readily degradable
auxiliary compounds), although more complex xenobiotic
compounds (dyes, surfactants) may not be degraded to
a significant extent in many cases. Dyes, being resistant
to biodegradation, have a very low rate of removal ratio
for BOD to COD (BOD/COD is less than 0.1) and thus
are difficult to remove through biodegradation in the
biological treatment stage. Another problem with aerobic
biological treatment of dye wastewater, is the difficulty
in acclimatising the microorganisms to the substrate due
to constant product changes and batch dyeing operations.
Several studies on aerobic biological treatment of textile
dye wastewater [118,119] indicate that little biodegradation
of dyes actually occurs and that the primary removal
mechanism involves adsorption to activated sludge.
The adsorption properties of activated sludge are similar
to that of activated carbon and are mainly dependent on
dye properties (molecular structure and type, number and
position of substituents in the dye molecule). Adsorption is
increased in the presence of hydroxy, nitro and azo groups
but decreased by sulphonic acid groups [118]. The factors
inhibiting permeation of the dye through the microbial cell
66 Rev. Prog. Color., 34 (2004)
r3308_Joshi.indd 9
membrane (e.g. increased or decreased water solubility and
increased molecular weight) reduce the efficiency of the
biological system. A study on the removal of dyes by an
activated sludge process indicates that low adsorption on
sludge occurs with acid and reactive dyes, high adsorption
occurs with basic and direct dyes and high to medium
adsorption occurs with disperse dyes [120].
Churchley et al. carried out a chemometric analysis
to fi nd out the level of bioelimination of water-soluble
dyes [121]. This analysis was conducted to correlate
bioelimination with chemical structure/functionality. It
was found that the level of bioelimination is proportional
to the size/charge ratio of the dye. In the case of acid and
direct dyes, bioelimination varied from 0 to 95% for the
series of dyes studied, while in the case of reactive dyes,
the level of bioelimination varied from 0 to only 25%. To
maximise the bioelimination of reactive dyes, large, planar
triazine based dyes should be used.
In an activated sludge tank, water is mixed and aerated
with a suspension of microorganisms. A high population of
microorganisms is generally maintained that permits rapid
breakdown of organics. A large bacterial population creates
a secondary waste treatment concern in the form of bio
solids or bacteria. These bacteria, often called sludge, must
be disposed of and this increases overall waste treatment
costs.
Immobilised microbe reactors claim better contact
between the microbial population and the waste, without
concomitant production of excessive bio solids [122]. This
is done through the use of a solid but porous matrix (beads)
to which a tailored microbial consortium of organisms
has been attached. This allows for a greater number of
organisms to be available for waste degradation without
the need for a suspended population and protection from
shocks for the bacterial population in the interiors of the
porous beads.
Although aerobic digestion of textile effluent removes
6070% of organic waste, the toxicity level is hardly
reduced due to the presence of organic matter which cannot
be degraded and requires tertiary treatments to remove
the toxicity. Efforts have also been reported to tailor the
activated sludge to accommodate textile effluent more
effectively by sludge seeding and sludge conditioning. Both
methods aim to produce a biased microbial community,
dominated by species that are more suited to digesting a
specific waste type [123].
The PACT (Powdered Activated Carbon Treatment)
system patented by DuPont is a combined powdered
activated carbonactivated sludge system [10]. It consists
of adding powdered-activated carbon to an activated sludge
system. The carbon dosage depends on the wastewater
characteristics and can be added at any stage to the waste
stream, i.e. before treatment, to the recycled sludge or to
the aeration tank itself. It can effectively treat effluent with
COD in the range of 5050 000 mg/l. A few of the other
advantages of the PACT system include improved organics
removal, control of odours, colour removal and metals
removal. It is also resistant to shock loads.
Anaerobic treatment
Anaerobic biological reduction of azo dyes has been
investigated from many perspectives, i.e. chemical
25/11/2004 12:01:36
 degradation (treatment) and colour removal. Anaerobic
reducing conditions found in the environment include
sediments at the bottom of streams of certain sections
of landfills where there is no oxygen. Anaerobic
bioremediation of azo and other soluble dyes to undergo
decolorisation by breaking them into corresponding
amines has been widely researched (Scheme 2) [124126].
However, the intentional generation of amines that are
more toxic than the dye itself is not appealing from an
environmental perspective. The decolorisation occurs due
to azo reduction.
NaO3S
N N
N H
CI Acid Yellow 36
O3SNa
H
NH2 + H2N N
3-aminobenzene-sulphonic acid
N-phenyl-1,4-diaminobenzene
Scheme 2
Azo dyes act as an oxidising agent for reduced flavin
nucleotides of the microbial electron chain and are reduced
and undergo decolorisation concurrently with reoxidation
of the reduced flavin nucleotides. In order for this to occur,
additional carbon is required for decolorisation to proceed
at a viable rate and this is converted to methane, hydrogen
sulphide and carbon dioxide. This additional carbon source
may be a limiting factor commercially.
In many conditions, decolorisation of reactive azo dyes
under anaerobic conditions is due to the action of an
azo reductase enzyme [127]. Goncalves et al. studied the
removal of colour from textile effluent using a laboratory
upflow anaerobic sludge blanket reactor [128]. Several
commercial dyes were selected to study the effect of dye
structure on colour removal. The average removal efficiency
for acid dyes using this method was between 80 and 90%
and that observed for the direct dye was 81%.
The breakdown of azo dyes to their corresponding
amines accomplishes two goals: (a) decolorisation of
wastewater; and (b) preparation of the wastewater for
subsequent aerobic biological treatment, since the aromatic
amines released by anaerobic digestion of azo dyes are
effectively treated by aerobic treatment processes. Hence,
the literature reveals that an anaerobicaerobic treatment
sequence has been found more effective method of
treatment of textile wastewater [129].
Anaerobic processes usually occupy less space, treat
waste up 30 000 mg/l COD, have lower recurring costs and
produce less sludge. If complete mineralisation occurs,
conversion of organic contaminants into methane and
oxygen leads to production of biogas which is a major
attraction because of heat, power and reduced energy costs.
r3308_Joshi.indd 10
However, the toxicity of certain dyes inhibits complete
mineralisation.
Anaerobicaerobic treatment
The anaerobicaerobic sequence produced significantly
greater colour reduction (88 vs 28%) and TOC reduction (90
vs 79%) when compared to aerobic treatment alone [129].
A similar process has been recently reported, namely
the AB (adsorption/biooxidation) process [130] which is
a modified two-stage activated sludge design and uses
physical, biochemical and biological reaction mechanisms
to reduce a very wide spectrum of organic pollutants.
The fi rst stage is the adsorption stage (A) with anaerobic
conditions with a very high food-to-microorganism ratio
fostering growth of bacteria and a short retention time,
followed by a second stage for biological oxidation (B)
(aerobic activated sludge system). The microbial ecosystems
in the two stages are kept distinctly separate enabling job
sharing and better efficiency of the process. This patented
process reduces colour, COD and BOD very effectively,
while being largely resistant to shock loads and pH
fluctuations.
Decolorisation using cultures of bacteria, fungi, algae and
yeast
Microbial decolorisation and degradation of dyes is seen
as a cost effective and ecofriendly method for removing
them from textile effluent. Recent fundamental work has
revealed the existence of a wide variety of microorganisms
capable of undertaking decolorisation of an equally wide
range of dyes, and has been reviewed by Banat et al. [131].
Bacterial cultures: Numerous bacteria capable of dye
decolorisation have been reported [131]. Efforts to isolate
bacterial cultures capable of degrading azo dyes started
in the 1970s with reports of Bacillus subtilis [132], then
Aeromonas hydriphila [133] followed by Bacillus cereus
[134]. Isolating such microbes proved to be a difficult task
and extended periods of adaptation in chemostat conditions
were needed to isolate the strain capable of decolorisation.
An azo reductase enzyme was responsible for the initial
degradation of the Acid Orange II azo dye by these strains
and substituting any of the groups near the azo groups
chemical structure hindered the degradation.
An upsurge in interest in these bacterial cultures took
place in the 1990s and Haug et al. described a bacterial
consortium capable of mineralising the sulphonated azo
dye CI Mordant Yellow 3 (12) [135]. An alteration from
anaerobic to aerobic conditions was required for complete
degradation in such mixed bacterial cultures. Several other
strains have been reported which can decolorise copper
complex azo dyes, reactive dyes including anthraquinone,
phthalocyanine and azo through adsorption of dyes to
the cellular biomass without any degradation [136]. In a
COONa
N OH
N
NaO3S
12
Rev. Prog. Color., 34 (2004) 67
25/11/2004 12:01:37
 NaO3SOCH2CH2O2S SO2CH2CH2OSO3Na
H H
N NH2 O N NaO3SOCH2CH2O2S
N N
NaO3S SO3Na
13
recent study, Aeromonas hydrophila [137] has demonstrated
the greatest capability for colour removal from various
textile dyes including azo, anthraquinone and indigo
dyes. The colour removal was best in anaerobic culture
and decolorisation appeared to proceed primarily by
biological degradation. The significance of the toxicological
perspective in the decolorisation of reactive dyes by
P. luteola has been reported [138]. The toxicity series of
the three dyes used was found to be Reactive Acid Yellow
(RAY) > Reactive Black B (CI Reactive Black 5; 13) > CI
Reactive Red 22 (14). The less toxic of these dyes (e.g. 14)
undergoes decolorisation more easily. A relatively higher
toxicity to P. luteola was shown due to the presence of two
azo-bonds in the other two dyes. Biosorption accounts for
decolorisation of the more toxic dye (RAY). Because of this
chronic toxicity of the dye to cells, a failure to preserve
cellular viability leads to the occurrence of biosorption
instead of decolorisation.
Algae: A few species of algae such as Chlorella and
Oscillatoria [131] are capable of degrading azo dyes to their
aromatic amines through an induced form of azo reductase
and further metabolise the aromatic amines to simple
organic compounds or carbon dioxide. These algae species
utilise azo dyes as their source of carbon and nitrogen.
Such algae can be used for the stabilisation of ponds as
they can play a role in aromatic amines removal.
Fungi: Several fungal systems including the white rot
fungi, i.e. Phanerochaete chrysosporuim in particular,
have been the subject of intense research related to the
biodegradation of a wide range of recalcitrant xenobiotic
compounds including azo dyes [131,136,139,140]. White
rot fungi are those organisms that are capable of degrading
lignin, the structural polymer found in woody plants. They
have been found to degrade dyes using enzymes such as
lignin peroxidase (LiP), manganese-dependent peroxidases
(MnP), glucose-1-oxidase and glucose-2-oxidase along with
laccase and a phenol oxidase enzyme.
Azo dyes, the largest class of commercial dyes, are not
easily degraded by microorganisms but can be degraded
by these enzymes. Commercial azo, triarylmethane,
anthraquinonic and indigoid textile dyes are efficiently
decolorized with enzyme preparations from a range of
fungal species [141].
The enzymes MnP and LiP belong to the class of
peroxidases that oxidise their substrates by two consecutive,
one-electron oxidation steps with an intermediate cation
radical. While MnP only attacks phenolic substrates using
Mn2+/Mn3+ as an intermediate redox couple, LiP with
a higher redox potential prefers non-phenolic methoxy-
68 Rev. Prog. Color., 34 (2004)
r3308_Joshi.indd 11
OCH3
N O
N
14 SO3Na
substituted lignin subunits as substrates [141]. Laccases have
very broad substrate specificity with respect to the electron
donor. They catalyse the removal of a hydrogen atom from
the hydroxy group of ortho- and para-substituted mono-
and poly-phenolic substrates and from aromatic amines
by one-electron abstraction to form free radicals capable
of undergoing further depolymerisation, repolymerisation,
demethylation or quinone formation [141].
The colour removal achieved with these enzymatic
treatments range from 4099% depending on the dyes
complexity, nitrogen availability, activity of the culture,
presence of other auxiliaries in the effluent, concentration
of dye, retention time etc. The nature of substitutents on
the dyes (e.g. benzene rings) influences enzyme activity.
Electron donating methyl and methoxy substituents
seemed to enhance enzymatic degradation, while electron
withdrawing chloro, fluoro and nitro substituents inhibited
oxidation by the enzyme laccase.
White rot fungi (P. chrysoporuim) is also capable of
degrading dioxins, polychlorinated biphenyl and other
chloro-organics thus rendering effluent less toxic [142].
The presence of salts and other textile dyeing auxiliaries
have a potential inhibitory effect on enzymatic action.
Higher salt concentrations decrease the decolorisation
efficiency by up to 80% and even lead to partial
precipitation of proteins caused by increased surface
tension and hydrophobic interactions. Enzymes such as
laccase, containing three copper-binding sites per protein
molecule or one copper, one iron and two zinc atoms
per protein molecule, is inactivated by copper and iron.
Chelating agents and anionic detergents seem to partially
denature proteins (enzymes) and almost 70% loss of
activity is reported [140].
Some of the drawbacks of enzymatic decolorisation
include:
substrate specificity of some enzymes, hence selection
of appropriate enzymes for continuously varying
composition of textile effluent may be an arduous
task;
the rate of reaction, which can be slow unless
conditions of pH and temperature are optimal;
commercial production of these specific enzymes is
very difficult; and
the presence of salts and other auxiliaries in
the effluent has an inhibitory effect on enzymatic
activity.
Thus knowledge not only about substrate specificity but
also about the effect of auxiliaries is important for selecting
suitable enzymes for dye decolorisation under industrial
conditions.
25/11/2004 12:01:37
 Yeast: Yeasts such as Klyveromyces marxianus have been
used in the decolorisation of dyes. In one study, levels of
Remazol Black B were reduced by 7898% [141]. Zissi et al.
showed that Bacillus subtilis could be used to breakdown
p-aminoazobenzene, a specific azo dye [143]. Further
research using mesophilic and thermophilic microbes has
also shown yeasts to be applicable in the degradation and
decolorisation of dyes.
Future trends: The advantages of mixed cultures are
apparent as some strains can collectively carry out complex
bioremediatation tasks that no individual strain can
achieve independently. Similar bacterial cultures have
been reported [144].
Future investigations would focus on the immobilisation
of selected enzymes to form the base for industrial
application of enzymatic decolorisation [145,146]. Banat
et al. have reported cheap support media for biofilm
development for active textile dye decolorisation
using gravel, calcium alginate beads, polystyrene and
polyurethane foam chips, nylon webs, inert polyethylene
chips, porous volcanic rocks etc. [147].
One of the routes still to be explored is the use of
thermotolerant or thermophilic microorganisms in
decolorisation systems. This would be an advantage as
many textile and other dye effluent is produced at relatively
high temperatures (5060 C), even after the cooling or heat
exchange steps.
The literature thus suggests a great potential for
microbial decolorisation systems for achieving total colour
removal, occasionally with only hours of exposure. Such
biological processes could be adopted as a pretreatment
decolorisation step combined with the conventional
treatment systems to reduce the BOD and COD as an
effective alternative for use in textile dyeing industries.
SUMMARY
The majority of colour removal techniques work either
by concentrating the colour into sludge or by the partial
or complete breakdown of the dye molecule. In principle,
decolorisation is achievable using one or a combination
of different methods depending on the wastewater
characteristics. Each technique has a specific application as
well as distinct advantages and disadvantages and has to be
evaluated according to cost, application and performance
in relation to the desired goal.
With rapid changes in dyes and stricter consent limits,
conventional coagulation/flocculation methods alone do
not give completely satisfactory treatments, especially with
highly soluble reactive dyes. Moreover, large quantities
of sludge generation containing all the toxic compounds
present in the effluent are likely to increase disposal costs
substantially. Low cost bioadsorbents have been extensively
investigated for the treatment of waste containing dyes as
an alternative to high cost activated carbon. However
specificity to remove certain contaminates, slow kinetics,
regeneration and f low problems have limited the
commercial success of these adsorbents at the industrial
scale. Membrane systems provide a means to recover water
and other auxiliaries for total treatment or stand-alone
r3308_Joshi.indd 12
processes for scouring or dyebath liquor separation. The
major limitations are the economic feasibility because of
high costs and the treatment of concentrate streams, which
are highly concentrated.
In the light of an integrated approach to waste treatment,
it is likely that destruction technologies will gain favour
at the expense of technologies that just transfer the
pollutant from liquid to solid phase for disposal or form a
liquid concentrate for further treatment. The established
destruction technologies are based on chemical, bio and
electrochemical oxidation techniques. These lead to either
partial oxidation of the dye destroying the conjugated
bonding system in the chromophore, thus removing colour
or total oxidation to form carbon dioxide and inorganic ions
which is the most ideal. However, total oxidation using
these reagents may not be economically viable. The problem
associated with partial oxidation lies in the unknown
nature of the products formed and the risk that some
of these may be even more harmful to the environment
than the initial components of the effluent. These mostly
reduce carbon loading of the effluent but can increase the
concentration of inorganic content.
Enzymatic microbial decolorisation of textile dyeing
effluent is a very promising and innovative area of
investigation. It eliminates the need for inorganic oxidising
agents such as ozone or precipitating agents such as
polymeric flocculants, which potentially could lead to
higher toxicity in wastewater and generate additional solid
waste. Microbial decolorisation using enzymes degrades
the aromatic ring structure to carbon dioxide, molecular
nitrogen and water, which may result in less toxicity.
However, the specificity of enzymes, slow rate of reaction
(unless pH and temperature are optimal) and difficulty
of commercial production of enzymes may be limitations
which need to be overcome by more intense research in the
field of biotechnology.
The problem of colour in effluent can be reduced to
an extent by adopting right-fi rst-time approaches, proper
work practices and waste minimisation programmes. Dyes
showing a high level of exhaustion and fixation on the fibre
have been, and will continue to be, the prime targets of
research and development activity in the future.
Although developments in this field are ongoing, in
future the standards will be enforced with increasing
severity by the regulators and newer dyes more resistant
to photo and biodegradation will be in the market. Thus,
there remains an urgent and immediate need to evolve
more effective, widely applicable and commercially viable
techniques of colour removal from textile effluent.
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3. H S Freeman, D Hinks and J Esancy, Physico-chemical
Principles of Colour Chemistry, Eds A T Peters and H S
Freeman (London: Chapman & Hall, 1996) 254.
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Dr Mangala Joshi and Dr R Purwar work in the
Department of Textile Technology, Indian Institute
of Technology, Hauz Khas, New Delhi 110016, India
(email: mangala@netearth.iitd.ac.in).
Rev. Prog. Color., 34 (2004) 71
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