Bioresource Technology 77 (2001) 247±255

Review paper

Remediation of dyes in textile e‚uent: a critical review on current
treatment technologies with a proposed alternative
Tim Robinson, Geo€ McMullan, Roger Marchant, Poonam Nigam *
Biotechnology Research Group, School of Applied Biological and Chemical Sciences, University of Ulster, Coleraine, BT52 1SA, UK
Accepted 29 May 2000

Abstract
The control of water pollution has become of increasing importance in recent years. The release of dyes into the environment
constitutes only a small proportion of water pollution, but dyes are visible in small quantities due to their brilliance. Tightening
government legislation is forcing textile industries to treat their waste e‚uent to an increasingly high standard. Currently, removal
of dyes from e‚uents is by physio-chemical means. Such methods are often very costly and although the dyes are removed, accumulation of concentrated sludge creates a disposal problem. There is a need to ®nd alternative treatments that are e€ective in
removing dyes from large volumes of e‚uents and are low in cost, such as biological or combination systems. This article reviews the
current available technologies and suggests an e€ective, cheaper alternative for dye removal and decolourisation applicable on large
scale. Ó 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Textile dyes; Dye decolourisation; Chemical, physical and biological treatments; White-rot fungi; Solid state fermentation (SSF)

1. Introduction
Textile industries consume large volumes of water
and chemicals for wet processing of textiles. The
chemical reagents used are very diverse in chemical
composition, ranging from inorganic compounds to
polymers and organic products (Mishra and Tripathy,
1993; Banat et al., 1996; Juang et al., 1996). The presence of very low concentrations of dyes in e‚uent is
highly visible and undesirable (Nigam et al., 2000).
There are more than 100,000 commercially available
dyes with over 7  105 ton of dye-stu€ produced annually (Meyer, 1981; Zollinger, 1987). Due to their chemical structure, dyes are resistant to fading on exposure to
light, water and many chemicals (Poots and McKay,
1976a; McKay, 1979). Many dyes are dicult to decolourise due to their complex structure and synthetic
origin. There are many structural varieties, such as,
acidic, basic, disperse, azo, diazo, anthroquinone based
and metal complex dyes. Decolouration of textile dye
e‚uent does not occur when treated aerobically by
municipal sewerage systems (Willmott et al., 1998).

*

Corresponding author. Tel.: +28-7032-4053; fax: +28-7032-4906.
E-mail address: p.nigam@ulst.ac.uk (P. Nigam).

Through the formation, in 1974 of the Ecological and
Toxicological Association of the Dyestu€s Manufacturing Industry (ETAD), aims were established to
minimise environmental damage, protect users and
consumers and to co-operate fully with government and
public concerns over the toxicological impact of their
products (Anliker, 1979). Over 90% of some 4000 dyes
tested in an ETAD survey had LD50 values greater than
2  103 mg=kg. The highest rates of toxicity were found
amongst basic and diazo direct dyes (Shore, 1996).
In Great Britain, such matters are regulated by the
Environment Agency (EA) for England and Wales, and
the Scottish Environment Protection Agency (SEPTA),
(Willmott et al., 1998). Government legislation is becoming more and more stringent, especially in the more
developed countries, regarding the removal of dyes from
industrial e‚uents. Environmental policy in UK, since
September 1997, has stated that zero synthetic chemicals
should be released into the marine environment. Enforcement of this law will continue to ensure that textile
industries treat their dye-containing e‚uent to the required standard. European Community (EC) regulations are also becoming more stringent (OÕNeill et al.,
1999).
There are many structural varieties of dyes that fall
into either the cationic, nonionic or anionic type.
Anionic dyes are the direct, acid and reactive dyes

0960-8524/01/$ - see front matter Ó 2001 Elsevier Science Ltd. All rights reserved.
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1997). The main oxidising agent is 2. 1988). . usually hydrogen peroxide (H2 O2 ).and nitro-compounds are reduced in sediments. ultra violet light. Oxidation by ozone is capable of degrading chlorinated hydrocarbons. 2. Ozonation The use of ozone was ®rst pioneered in the early 1970s. and it is a very good oxidising agent due to its high instability (oxidation potential. but such disposal is seen by some to be far from environmentally friendly. Chemical oxidation removes the dye from the dye-containing e‚uent by oxidation resulting in aromatic ring cleavage of the dye molecules (Raghavacharya.1. 1998). This review illustrates the critical study of the most widely used methods of dye removal from dye-containing industrial e‚uents. yielding mediocre results (Raghavacharya. direct. Acid. but the resulting ¯oc is of poor quality and does not settle well. (1978) illustrated their reduction in the intestinal environment. physical and biological. Oxidative processes This is the most commonly used method of decolourisation by chemical means. watersoluble reactive and acid dyes are the most problematic. dependent on biological activity. were found to be inecient in the removal of these dyes (Moran et al. This agent needs to be activated by some means.1.78). Brightly coloured. phenols. still requires disposal. pesticides and aro- 2. another oxidising agent (1. Chemical methods 2. This is mainly due to its simplicity of application. Municipal aerobic treatment systems. It has conventionally been incinerated to produce power. as they tend to pass through conventional treatment systems una€ected (Willmott et al. Many methods of chemical decolourisation vary depending on the way in which the H2 O2 is activated (Slokar and Le Marechal. Concern arises. mordant and reactive dyes usually coagulate. and similarly Chung et al. Anthroquinone-based dyes are most resistant to degradation due to their fused aromatic ring structure. vat. 1993). as many dyes are made from known carcinogens such as benzidine and other aromatic compounds (Baughman and Perenich. 2. Chemical separation uses the action of sorption or bonding to remove dissolved dyes from wastewater and has been shown to be e€ective in decolourising both soluble and insoluble dyes (Pak and Chang. 1997). The sludge. One major disadvantage of this method is sludge generation through the ¯occulation of the reagent and the dye molecules.1.2. 1997). The ability of some disperse dyes to bioaccumulate has also been demonstrated (Baughman and Perenich. Robinson et al. Nonionic dyes refer to disperse dyes because they do not ionise in an aqueous medium. The performance is dependent on the ®nal ¯oc formation and its settling quality. These methods have been discussed under three categories: chemical. Weber and Wolfe (1987) demonstrated that azo. although cationic dyes do not coagulate at all... and H2 O2 (1. 1988).36).1. H2 O2 ±Fe(II) salts (Fentons reagent) Fentons reagent is a suitable chemical means of treating wastewaters which are resistant to biological treatment or are poisonous to live biomass (Slokar and Le Marechal. 1997).07) compared to chlorine. 1999). 1997). / Bioresource Technology 77 (2001) 247±255 Table 1 Advantages and disadvantages of the current methods of dye removal from industrial e‚uents Physical/chemical methods Advantages Disadvantages Fentons reagent Sludge generation Ozonation Photochemical NaOCl Cucurbituril Electrochemical destruction Activated carbon Peat E€ective decolourisation of both soluble and insoluble dyes Applied in gaseous state: no alteration of volume No sludge production Initiates and accelerates azo-bond cleavage Good sorption capacity for various dyes Breakdown compounds are non-hazardous Good removal of wide variety of dyes Good adsorbent due to cellular structure Wood chips Silica gel Membrane ®ltration Ion exchange Irradiation Electrokinetic coagulation Good sorption capacity for acid dyes E€ective for basic dye removal Removes all dye types Regeneration: no adsorbent loss E€ective oxidation at lab scale Economically feasible Short half-life (20 min) Formation of by-products Release of aromatic amines High cost High cost of electricity Very expensive Speci®c surface areas for adsorption are lower than activated carbon Requires long retention times Side reactions prevent commercial application Concentrated sludge production Not e€ective for all dyes Requires a lot of dissolved O2 High sludge production (Mishra and Tripathy. Currently the main methods of textile dye treatment are by physical and chemical means (Table 1) with research concentrating on cheaper e€ective alternatives. resulting in the formation of toxic amines. which contains the concentrated impurities. for example.248 T.

2. The use of Cl for dye removal is becoming less frequent due to the negative e€ects it has when released into waterways (Slokar and Le Marechal. One major advantage is that ozone can be applied in its gaseous state and therefore does not increase the volume of wastewater and sludge. 1989) or with a membrane ®ltration technique (Lopez et al. 1999). ozone decomposition is accelerated. It initiates and accelerates azobond cleavage. Photochemical This method degrades dye molecules to CO2 and H2 O (Yang et al. resulting in reduced colouration (Peralto-Zamora et al. Pelegrini et al. 1997). 2. 1999). / Bioresource Technology 77 (2001) 247±255 matic hydrocarbons (Lin and Lin. 1997) and no toxic metabolites (Gahr et al. Ozonation leaves the e‚uent with no colour and low COD suitable for discharge into environmental waterways (Xu and Lebrun. These smaller molecules may have increased carcinogenic or toxic properties.. 1999).1. and then rediscovered in the 1980s by Freeman et al. indicates that a urea monomer is also part of this compound... Decolouration occurs in a relatively short time. may be produced (Yang et al. Better results can be achieved using irradiation (Gro€ and Byung. There is little or no consumption of chemicals and no sludge build up. 1997) and the release of aromatic amines which are carcinogenic. Sodium hypochloride (NaOCl) This method attacks at the amino group of the dye molecule by the Cl‡ .. 1999). Cucurbituril Cucurbituril was ®rst mentioned by Behrand et al. 1994. because its structure is shaped like a pumpkin (a member of the plant family Cucurbitaceae). 3. cucurbituril would need to be incorporated into ®xed bed sorption ®lters (Karcher et al. One of the major drawbacks with ozonation is cost. 1995) and this may be the mechanism for reactive dye adsorption... which was developed in the mid 1990s. An increase in decolouration is seen with an increase in Cl concentration. Chromophore groups in the dyes are generally organic compounds with conjugated double bonds that can be broken down forming smaller molecules. 1996). UV light may be used to activate chemicals.. 1998. Adsorption Adsorption techniques have gained favour recently due to their eciency in the removal of pollutants too stable for conventional methods. 1999) by UV treatment in the presence of H2 O2 . This method shows a preference for double-bonded dye molecules (Slokar and Le Marechal. 1997). 1993.1. It is a cyclic polymer of glycoluril and formaldehyde (Karcher et al. A disadvantage of ozonation is its short half-life. and so careful monitoring of the e‚uent pH is required (Slokar and Le Marechal.3. Robinson et al. 1999a. 2. such as. This may be set-up in a batch or continuous column unit (Namboodri and Walsh. pH. Buschmann (1992) showed extraordinarily good sorption capacity of cucurbituril for various types of textile dyes. and so ozonation may be used alongside a physical method to prevent this. and the cost of electricity used is comparable to the price of chemicals. It shows ecient and economical removal of dyes and a high eciency for colour removal and degradation of recalcitrant pollutants (Ogutveren and Kaparal. with stability being a€ected by the presence of salts. so named. 1998). There are advantages of photochemical treatment of dye-containing e‚uent. The dosage applied to the dye-containing e‚uent is dependent on the total colour and residual COD to be removed with no residue or sludge formation (Ince and Gonenc. Like many other chemical methods.. This method is unsuitable for disperse dyes. Electrochemical destruction This is a relatively new technique. Degradation is caused by the production of high concentrations of hydroxyl radicals.6. Adsorption produces a . Cucurbituril is known to form host-guest complexes with aromatic compounds (Mock. metals. (1981). The uril. 1999b). To be industrially feasible. inorganic acids.1. 1999). typically being 20 min. It has some signi®cant advantages for use as an e€ective method for dye removal. and temperature. This time can be further shortened if dyes are present. pH.. The breakdown metabolites are generally not hazardous leaving it safe for treated wastewaters to be released back into water ways.. dye structure and the dye bath composition (Slokar and Le Marechal. 1999). and the rate of dye removal is in¯uenced by the intensity of the UV radiation.1. 1997).T.4. UV light activates the destruction of H2 O2 into two hydroxy radicals H2 O2 ‡ hv ! 2OH This causes the chemical oxidation of organic material.b). organic aldehydes and organic acids. additional by-products. In alkaline conditions. no sludge is produced and foul odours are greatly reduced. 249 2. Another proposed mechanism is based on hydrophobic interactions or the formation of insoluble cucurbiturildye-cation aggregates since adsorption occurs reasonably fast. such as H2 O2 . Peralto-Zamora et al. halides. Physical treatments 3. Cucurbituril.5. cost is a major disadvantage. Xu and Lebrun. 1994). Depending on initial materials and the extent of the decolourisation treatment.1. or otherwise toxic molecules (Banat et al. 1999). (1905). Relatively high ¯ow rates cause a direct decrease in dye removal. continuous ozonation is required due to its short half-line (Xu and Lebrun.

Spent peat may be burned and utilised for steam raising. to separate dye continuously from e‚uent (Mishra and Tripathy. direct. it has a much larger surface area. an adverse chemical environment. 3. 3. The dissolved oxygen is consumed very rapidly and so a constant and adequate supply is required. pigment and reactive dyes (Raghavacharya. and the ion exchange method is not very e€ective for disperse dyes (Mishra and Tripathy. 1:1 (Gupta et al. 1991..6. dye/ sorbent interaction. 1998).1. unlike activated carbon. Adsorbed wood is conventionally burnt to generate power although there is potential for SSF of the dyeadsorbed wood chips.1. 3. It has some special features unrivalled by other methods.1. Nigam et al. Membrane ®ltration This method has the ability to clarify. Rao et al. temperature. 1997). Silica gel An e€ective material for removing basic dyes. 1999). Other materials The use of these substrates such as natural clay. 2000). 2000) and longer contact times are required (Poots and McKay. and is in¯uenced by many physio-chemical factors. Ion exchange Ion exchange has not been widely used for the treatment of dye-containing e‚uents. Performance is dependent on the type of carbon used and the characteristics of the wastewater. resistance to temperature. rice hulls etc.7. and hence has a better capacity for adsorption. The concentrated residue left after separation poses disposal problems. 1997). and eciency of dye removal becomes unpredictable and dependent on massive doses of carbon. which makes water re-use a dicult task. but it is unable to reduce the dissolved solid content. Nasser and El-Geundi. Peat requires no activation. most importantly. and contact time (Kumar et al.. mainly due to the opinion that ion exchangers cannot accommodate a wide range of dyes (Slokar and Le Marechal. 1976b). This has an e€ect on cost. 1990). 1989. 1976a). Irradiation Sucient quantities of dissolved oxygen are required for organic substances to be broken down e€ectively by radiation. Wastewater is passed over the ion exchange resin until the available exchange sites are saturated. such as. mordant. 3.. for protein enrichment.. like many other dye-removal treatments. where it is widely available. is well suited for one particular waste system and ine€ective in another.. This combination may be substituted for activated carbon. and microbial attack.1. reclamation of solvent after use and the removal of soluble dyes. dispersed.1. potentially. Fly ash and coal (mixture) A high ¯y ash concentration increases the adsorption rates of the mixture due to increasing the surface area available for adsorption. Advantages of this method include no loss of adsorbent on regeneration. Activated carbon This is the most commonly used method of dye removal by adsorption (Nasser and El-Geundi. 3.5.8. vat. sorbent surface area. with a ratio of ¯y ash:coal. Removal rates can be improved by using massive doses. Decolourisation is a result of two mechanisms: adsorption and ion exchange (Slokar and Le Marechal. 1997.250 T. such as air binding and air fouling with particulate matter. 3. 1993. They are economically attractive for dye removal. concentrate and.. Peat may be seen as a viable adsorbent in countries such as Ireland and UK.1..2. as substrate in SSF. and membrane replacement are its disadvantages. compared to activated charcoal. Dye-containing e‚uent may . 3. A major disadvantage is cost. Reactivation results in 10±15% loss of the sorbent. It has the ability to adsorb transition metals and polar organic compounds from dye-containing e‚uents. Due to activated carbonÕs powdered nature. Activated carbon. The carbon also has to be reactivated otherwise disposal of the concentrates has to be considered. and also costs much less (Poots and McKay. These materials are so cheap regeneration is not necessary and the potential exists for dye-adsorbed materials to be used as substrates in solid state fermentation (SSF) for protein enrichment. and high capital cost and the possibility of clogging. Wood chips They show a good adsorption capacity for acid dyes although due to their hardness. although side reactions.9.1.1. 3. it is not as good as other available sorbents (Nigam et al. for dye removal is advantageous mainly due to their widespread availability and cheapness.1. particle size. This method of ®ltration is suitable for water recycling within a textile dye plant if the e‚uent contains low concentration of dyes. and is a process which is economically feasible (Choy et al. although regeneration or re-use results in a steep reduction in performance. with many comparing well in certain situations (Nawar and Doma. 1991) and is very e€ective for adsorbing cationic. and acid dyes and to a slightly lesser extent.4. Both cation and anion dyes can be removed from dye-containing e‚uent this way. 3. 1999).3. Organic solvents are expensive. Robinson et al. Peat The cellular structure of peat makes it an ideal choice as an adsorbent. 1994). / Bioresource Technology 77 (2001) 247±255 high quality product. Activated carbon is expensive. 1993). pH. Xu and Lebrun.1. prevents it being used commercially. corn cobs. or.

soluble. Germany. 1993). along with laccase. which isolated a strain of Sphingomonas capable of using redox mediators generated during the aerobic metabolism of 2-naphthalenesulfonate to facilitate a 20-fold increase in its ability to reduce the sulfonated azo dye amaranth (Keck et al. Although white-rot fungi have been shown to decolourise dyes in liquid fermentations. Azo dyes. 1994). 1994. The ability to utilise these fungi in their natural environment means that they are more likely to be more e€ective in SSF. Electrokinetic coagulation This is an economically feasible method of dye removal. 1997). known as azo reductases. Under aerobic conditions azo dyes are not readily metabolised although Kulla (1981). such as anoxic sediments. / Bioresource Technology 77 (2001) 247±255 251 be treated in a dual-tube bubbling rector. This is mainly due Mixed bacterial cultures from a wide variety of habitats have also been shown to decolourise the diazolinked chromophore of dye molecules in 15 days (Knapp and Newby.1. These microbial systems have the drawback of requiring a fermentation process. 1995). is Phanerochaete chrysosporium. 1992. Ogawa and Yatome (1990) also demonstrated the use of bacteria for azo dye biodegradation. White-rot fungi are able to degrade dyes using enzymes. Kirby. many bacteria gratuitously reduce azo dyes reportedly by the activity of unspeci®c. Other microbial cultures 4. manganese dependent peroxidases (MnP). the structural polymer found in woody plants (Barr and Aust. using free growing cells or in the form of bio®lms on various support materials. This method showed that some dyes and phenolic molecules can be oxidised e€ectively at a laboratory scale only (Hosono et al.. 1996. such as. sordida to treat creosote contaminated soil. These are the same enzymes used for the lignin degradation (Lonergan. allowing excellent removal of direct dyes from wastewaters. 1996. chrysosporium had the ability to decolourise arti®cial textile e‚uent by up to 99% within 7 days. The ability of bacteria to metabolise azo dyes has been investigated by a number of research groups. 1995). Phlebia tremellosa and Coriolus versicolor have also been shown to decolourise dye-containing e‚uent (Banat et al. the intermediates formed by these degradative steps resulted in disruption of metabolic pathways and the dyes were not actually mineralised. Barr and Aust. 1992.. Kirby (1999) has shown that P.2. Reddy.T. Thurston. Biological treatments 4. reported the ability of Pseudomonas strains to aerobically degrade certain azo dyes. 3. Inonotus hispidus. with the high cost of the ferrous sulphate and ferric chloride. 1995). chrysosporium (Paszczynski and Crawford. Nigam and Marchant (1995) and Nigam et al. and possibly carcinogenic to animals. Production of large amounts of sludge occurs.. and a phenoloxidase enzyme (Archibald and Roy. (1996) demonstrated that a mixture of dyes were decolourised by anaerobic bacteria in 24±30 h. 1995). This fungus is capable of degrading dioxins. Taken together both pieces of evidence point to the existence of a reducing activity which is not dependent on the intracellular availability of the azo dye (Keck et al.1. Unfortunately. mutagenic. 1994.2-dihydroxynaphthalene and were able to anaerobically shuttle reduction equivalents from the bacterial cells to the extracellular azo dye. Kirby.. It involves the addition of ferrous sulphate and ferric chloride. Increasingly literature evidence suggests that additional processes may also be involved in azo dye reduction. the largest class of commercially produced dyes. . polychlorinated biphenyls (PCBs) and other chloro-organics (Chao and Lee. 1999). Other enzymes used for this purpose include H2 O2 -producing enzymes. (1993) also showed the potential of using P. 1994). Hirschioporus larincinus. Other fungi such as. 4.. This hypothesis was supported by work at the University of Stuttgart. cytoplasmic reductases. Schliephake and Lonergan. In addition many highly charged and high molecular-sized sulfonated and polymeric azo dyes are unlikely to pass the cell membrane. 1993). However. such as lignin peroxidases (LiP). The optimum coagulant concentration is dependent on the static charge of the dye in solution and diculty in removing the sludge formed as part of the coagulation is a problem (Mishra and Tripathy.10. are not readily degraded by micro-organisms but these can be degraded by P. 1997). The most widely studied white-rot fungus. 1999). and are therefore unable to cope with larger volumes of textile e‚uents. Under anaerobic conditions. enzyme production has also been shown to be unreliable. Robinson et al. It has been reported that many bacteria reduce a variety of sulfonated and non-sulfonated azo dyes under anaerobic conditions without speci®city of any signi®cance. glucose-1-oxidase and glucose-2-oxidase. Decolourisation by white-rot fungi White-rot fungi are those organisms that are able to degrade lignin. Reddy. means that it is not a widely used method. 1994. These enzymes are reported to result in the production of colourless aromatic amines which may be toxic. These redox mediators were found to be decomposition products of 1. and this results in high disposal costs (Gahr et al. poor results with acid dyes. Davis et al. to the unfamiliar environment of liquid fermentations. in regards to xenobiotic degradation.

is incapable of removing dyes from e‚uent on a continuous basis. 1989.. Biogas can be reused to provide heat and power. a speci®c azo dye. 1998). Therefore. exhibited a relatively high anity for heavy metals (Riordan et al. marxianus was capable of decolourising Remazol Black B by 78±98%. Dead bacteria. Robinson et al. releasing electrons. The electrons react with the dye reducing the azo bonds. Riordan and McHale. 4. Biosorption capacities showed that this type of biomass had a signi®cantly high anity for dye removal. 1997). such as Klyveromyces marxianus. Bustard and McHale. Azo dyes are soluble in solution. are unable to be used by large-scale industry. This additional carbon supplementation may be a limiting factor when this technology is scaled-up. 1996. especially if the dye-containing e‚uent is very toxic. are capable of decolourising dyes. This is likely to be due to an increase in surface area caused by cell rupture during autoclaving (Polman and Brekenridge.. 1996). and methods.. 1997. K. and ultimately causing decolourisation (Carliell et al. anaerobic breakdown yields methane and hydrogen sulphide (Carliell et al. 1996). In order for this to occur. 1996. Tsezos and Bell. 1996). Anaerobic degradation of textile dyes yields only azo reduction. This decolourisation involves an oxidation±reduction reaction with hydrogen rather than free molecular oxygen in aerobic systems. 1996). apart from the decolourisation of soluble dyes. Zhou and Zimmerman (1993) used actinomyces as an adsorbent for decolourisation of e‚uents containing anthroquinone. (1997) showed that Bacillus subtilis could be used to break down p-aminoazobenzene. and are not removed via conventional biological treatments. 1992. 4.. Typically. and therefore their interactions with micro-organisms depend on the chemistry of a particular dye and the speci®c chemistry of the microbial biomass (Polman and Brekenridge. 1997).. Anaerobic bioremediation allows azo and other water-soluble dyes to be decolourised. 5.. A major advantage of this anaerobic system. 1995).. to small-scale in situ removal. such as membrane ®ltration and cucurbituril. Azo dye acts as an oxidising agent for the reduced ¯avin nucleotides of the microbial electron chain and is reduced and decolourised concurrently with reoxidation of the reduced ¯avin nucleotides. careful monitoring is required before treated wastewater is released into waterways. It can be said that certain dyes have a particular anity for binding with microbial species. and so widened the spectrum of use for biomass (Bustard et al. Kumar et al. This is due to the time period of a few days required for decolourisation-fermentation processes. This additional carbon is converted to methane and carbon dioxide. and will reduce energy costs. (1999) showed that K. phalocyanine and azo dyes. 1996. Biomass adsorption is e€ective when conditions are not always favourable for the growth and maintenance of the microbial population (Modak and Natarajan. Depending on the dye and the species of micro-organism used di€erent binding rates and capacities will be observed. Anaerobic textile-dye bioremediation systems Azo dyes make up 60±70% of all textile dyestu€s (Carliell et al. A limiting factor of these methods is cost. 1998).. This is true even in lab-scale studies.. Conclusions and suggestion for dye removal Physical and chemical methods of dye removal are e€ective only if the e‚uent volume is small.. It has been shown that azo. It had been observed that biomass derived from the thermotolerant ethanol-producing yeast strain. marxianus IMB3. in this case. Banat et al. 1996). The use of biomass has its advantages. Textile dyes vary greatly in their chemistries. 1995). in liquid state fermentations.252 T. Zissi et al. Hu (1992) demonstrated the ability of bacterial cells to adsorb reactive dyes. Mineralisation does not occur. In lab-scale studies glucose has been added to provide a source of carbon. therefore. yeast and fungi have all been used for the purpose of decolourising dye-containing e‚uents. 1996). These electrons cascade down the electron transport chain to a ®nal electron acceptor.4. 1994). Biosorption tends to occur reasonably quickly: a few minutes in algae to a few hours in bacteria (Hu.3.and nitro-components are reduced in the sediments and in the intestinal environment. the azo-reactive dye. Biological activity. is the production of biogas. additional carbon is required in order for decolourisation to proceed at a viable rate. In order for this . 1998). Reactive dyes have been identi®ed as the most problematic compounds in textile dye e‚uents (Carliell et al. / Bioresource Technology 77 (2001) 247±255 Subsequently this group found that their isolate Sphingomonas sp strain BN6 possessed both cytoplasmic and membrane-bound azo-reductase activities (Kudlich et al. Adsorption by living/dead microbial biomass The uptake or accumulation of chemicals by microbial mass has been termed biosorption (Hu. Banat et al. Further research using mesophilic and thermophilic microbes has also shown them to degrade and decolourise dyes (Nigam et al. Adsorption by biomass occurs by ion exchange. 1998.. Yeasts. resulting in the regeneration of the parent toxic amines (Banat et al. This limits the use of physio-chemical methods.

. Biotechnol. Singh.. Textile e‚uent decolourisation and dye-adsorbed agricultural residue biodegradation (Nigam et al. Microbiol.J. Toxicol.L.. W.. 19... N. J.. S.. E. D. 1994. Buckley. 7. Porter. can be used to remove dyes from solution.H. Bustard. 1989) and the suggested alternative incorporates the adsorption method with decolourisation by means of SSF by white-rot fungi..L. R. 21. USA. J. Naidoo. adsorption o€ers the alternative of splitting up these two steps (Barr and Aust. D. Soc.. 339.. 10....A. 30. it is in a more treatable form. Fig. D. E.A. 7367±7368. 351±353.A.. Smyth. P. Nigam et al. Acta 193. The fermented mass can then be recycled. McKay.. R.. which have good adsorption capacities. McHale. Recy.. G. McMullan. Marchant. Ecotox. 427±430. Ecotoxicology of dyestu€s ± a joint e€ort by industry. Gahr. W.. Annal.A.J. Field evaluation of the lignin-degrading fungus Phanerochaete sordida to treat creosote-contaminated soil. Sci.M. Environ. 2572± 2576. G. 28. Lee. K. Nigam. Naidoo.T. N.. C.. Agricultural waste residues such as. 183±199. Carliell. Inorg.W. I. Resour. C. Chem. Microbial decolourisation of reactive azo dye under anaerobic conditions. 320±328. S. 547±551. 1999.A.. 1978. 1±137. Chem..D.. 1 outlines how the proposed alternative can be approached. 1±16. Anaerobic decolourisation of reactive dyes in conventional sewage treatment processes. Buckely.Y. 225±233.. Roy. Environ. Hermanutz. Water S. Barclay. G. Senior. A. / Bioresource Technology 77 (2001) 247±255 253 re-used.M.. Veber Condensation procucte aus Glycoloril und Furmaldehyd. G.. Behrand..A.F. Chao. 20. R. 1992. Microbiol. Environ. Indianapolis. McMullan. 1994. Meehan. McHale. Chung. Glasser. Environ. Barclay. Meyer. C. 556±559. M. C. 27. Degradation of the adsorbed dye can then be carried out by SSF whilst simultaneously enriching the protein content of the substrate by the presence of fungal-biomass. E. will degrade the dye and simultaneously enrich the nutritional value of the waste. Adsorption methods allow the dye to be dealt with on a solid substrate. D. I. Carliell. 2000).L. pp. 103. Cucurbituril as a ligand for the complexation of cations in aqueous solutions.A. K.T. to be a viable option for industry. Liebig. 61±69.M. R.. In: Proceedings of the Industrial Waste Technical Conference.. 558±562. Archibald. 59±74. Cucurbituril. 1998. Technol.... 1988... P. J. A. 1905. 93±97. Microbial decolorization of textile-dye-containing e‚uents: a review. 217±227. 341±345.P.M. increasing the surface area and dried to increase adsorbency. 1979.W. Environ. 1995. Bustard. Marchant. F.A. Technol. 35. Ozonation ± an important technique to comply with new German law for textile wastewater treatment. Chem. 1994. C. 3. Buckely. allowing the decolourised water to be reclaimed and Anliker. Chim. Senior.. 1996. Water S. utilised as fertiliser or soil conditioner. R. Bioresour. R.. 1998.J. Safe. Bioprocesss Eng. Kirby. The use of adsorption techniques o€ers much potential in the treatment of dye-containing e‚uents (Nawar and Doma. the dye-containing e‚uent must be held in large tanks.P... Shih. J. 58.. B... Technol. World J..M. N. Bioprocess Eng. Biosorption of textile dyes by biomass derived from Klyveromyces marxianus IMB3. Decoloration of azo dyes by three whiterot fungi: in¯uence of carbon source. Marchant. S.. 1994). 1993. M.. Sci.. Nigam. wheat straw or rice hulls. Biosorpion of heavy metals by distillery-derived biomass. Appl. Conserv. Freeman. Mock. M.K. 27.. Rather than attempting to remove the dye and degrade it at the same time. Appl. Production of marganic chelates by laccase from the lignin degrading fungus Trametes versicolor. Microbiol. Baughman. W. S.. J. Carliell.. F. 57±71. Perenich. Buschmann. 58. Am.L. Microbial decolorization of textile dyes present in textile industries e‚uent. Environ.. Robinson et al. Banat. W..... Aust.. Fulk. left to stand for 48 h.. F. 1981. 23. Lamar. M.. 1. 1496±1499.E. P. 255±263.J. Mechanisms white rot fungi use to degrade pollutants. Barclay. Fate of dyes in aquatic systems: I Solubility and partitioning of some hydrophobic dyes and related compounds. . 22. D. 1.M.F. Davis.. H. Water Sci. Banat. W. C. Reduction of azo dyes by intestinal anaerobes. Singh. 1999.. Barr. 1997. The substrate can then be added to the dye-containing e‚uent. N. 1992.. References Fig. Mulholland. The isolation of thermophilic bacterial cultures capable of textile dyes decolorization..A. McMullan. Once the dye has been adsorbed onto the agricultural substrate. 2000). 1994. This fermented substrate then has the potential to be used as soil conditioner or fertiliser (Fig.A.. The residues must be milled.A. Nigam. S. Egan. Banat.P. Water S. G. Environ. F. which is a renewable agricultural resource. C. Sorption of acid dyes from e‚uents using activated carbon.. Rusche.. Choy. I. Mulholland. 1996. 19. G. this presents problems due to the sheer site size required. Opperman. SSF of the dye-adsorbed waste. and can then be treated through SSF.T. Technol. Evans. T. Int. Treatment of exhausted reactive dye bath e‚uent using anaerobic digestion: laboratory and full scale trials.

Ogawa. Keck. E€ects of sewage treatment on textile e‚uent. diazo and reactive dyes. Reddy. Selection of the substratum for composing bio®lm system of textile decolourizing bacteria. 214±217. 63. A. 2000.A. Fib. R.. Bull. 115±121. R. Am.. Kornmuller. G. M. 68. McKay. 320±328.. 561±566. Treatment of textile waste e‚uents by ozonation and chemical coagulation. Meyer.. H. Technol. Water Res.. Shore. M. Bioremediation of textile industry wastewater by white rot fungi. Arai. 1999.S. Chem. A.S. Mishra. J. Water Res. Kunz. 1199±1203. Doma. C.S. Microbiol. World 32.. Chem. R. Cook.T. Reduction of azo dyes by redox mediators originating in the naphthalenesulfonic acid degradation pathway of Sphingomonas sp. 1999. Ricco. 1999. 1995. W. Potential for bioremediation of xenobiotic compounds by the white-rot fungus Phanerochaete chrysosporium.. 385±387. Biotechnol. Bioprocess Eng. A.. Water Sci. A... Removal of dyes from e‚uents using low cost agricultural by-products. University of Ulster. Lett. Nuesch. 44.... 1979. McKay. Technol. Electrochemically assisted photocatalytic degradation of reactive dyes.. Moran. J. 11. Lourenco. M. Textile wastewater reuse: ozonation of membrane concentrated secondary e‚uent. OÕNeill. J. 1998. Biotechnol. Lett. Biodegradation of azo dyes in multistage rotating biological contractor immobilized by assimilating bacteria. 271±279... 257±264. Hosono. Lett. 1±16. R. 371±385.. Hall. 1997.V. 40. 3684±3690.R. 387±399. W.. 1993. Schliephake. Colourage 40.H... 17. Lin. Environ. K.H. Shimizu.. Microbial process for the decolorization of textile e‚uent containing azo. Kornmuller.J. Biotechnol. Biotechnol. Rep. Tripathy. pp. Colour.. T. Treatability of a textile azo dye by UV/H2 O2 . 1997.. 72. Singh.... J.. Nasser. Colour in textile e‚uents ± sources. 189± 195. Progr.. Removal of lead from solution using non-living residual brewery yeast. Technol. Juang..R. Reyers. discharge consents and simulation: a review. 18. Water Res.. Waste colour removal from textile e‚uents. Chem. Klein. 74. 1998. Advances in direct dyes. N..... Aizawa. 113. White-rot-fungi ± an environmental panacea? Environ.G.P. A. 29±36.. M. 31±35. 1999. 368±379. P. Lonergan. Water Sci. Tot. Pelegrini. 35±38. 63. 277±280. A. S.. A. 3691±3694.K.. J. M. M. 10.. Lin. J. 24. J.R. 38±42. 1996. Indian J. Health A 31. P. (Eds.. 1993. I. T. 1009±1018.M. Dutta.J.A. Sci. Sridhari. Appl. M..L. In: Leisinger. Proc. K.... Technol.. Text. R.. Environ. 10. Ultraviolet light/hydrogen peroxide system for decolorizing spent reactive dye bath waste water.D.. Hawkes.. R. Poots. Water Res. Contam... Kulla. K. Technol. Riordan. Comparative cost of colour removal from textile e‚uents using natural adsorbents. 1990. Kaparal. pp. 1995.J.. N.G. Kirby. 1997. S. U. D. A. Natarajan. Appl. Bhavani.M. Sugiyama. Chem. March. 1989.I. Metall. Colour removal from textile e‚uents by electrochemical destruction. Byung. R.P. 1996.K. London. Decoloration and degradation of azo dye in aqueous solution of supersaturated with oxygen by irradiation of high-energy electron beams.. Singh. Marchant. 1996. 325±338. strain BN6 and e€ect of arti®cial redox mediators on the rate of azo dye reduction. A. Newby.J. 872±876. S. 34. Textile wastes.. 12. Bioresour. Res. P. Colour removal from a dye stu€ industry e‚uent using activated carbon.. Water Sci. C. S. A.M. 272±274. U. P. The removal of acid dye from e‚uent using natural adsorbents ± II Wood.).S. Lin. The microbiological decolorization of an industrial e‚uent containing a diazo-linked chromophore. 21. 27. Chemosphere 38. Biotechnol. Curr. Technol. 1067± 1070. Polman. 99± 105. Biodegradation of synthetic organic colorants. A. Krishnaiah.. 219±226. 1997. measurement. R. 1976a.R.. Bustard. Hu. N. R. R. 1992. Lonergan. 1993.S. Microbial degradation of xerobiotics and recalcitrant compounds. R. Banat. Paszczynski.. 1995.). 19. Trends in color removal from textile mill e‚uents. London.C. 28. de Andrade. C. Stolz. Rad. Walsh. Modak. Duran. E€ects of alkaline-earth cations on the removal of reactive dyes with cucurbituril. 1±24. 1996. V. Pelegrini.254 T. P.. Coleraine. 1991.. D. El-Geundi. Gupta. J. 40. 50..K. 1997. 1±29. 83±90. T.B. Laccase variation during dye decolourisation in a 200 L packed-bed bioreactor. 1995. C. 175. 425±433.R. Environ. Hawkes. Knapp. 40.. Chem.. N. Sci.P.N. 15±25. 1995... Health A 29.. Kudlich. Marchant. Biotechnol. A. I.. T. Jekel. V. Hu. K. M. Pinheiro.S. Tex... Academic Press. The potential for white rot fungi in the treatment of pollutants.. 1996. Environ. 19. Rep...M.H. Sci. R. Opt. The removal of acid dye from e‚uent using natural adsorbents ± I Peat. G. Knackmuss.N. S. 357±366. 45±50. M. App. Colour removal from industrial e‚uents ± a comparative review of available technologies.. C.. Water Sci. Curr. G. Ogutveren. de Capos Moleiro. 6. 1995. Nawar. 18. 1989. (Eds. Water Res. Pak. A. McHale. H. Karcher. T. 1999.. D.. Localization of the enzyme system involved in anaerobic reduction of azo dyes by Sphingomonas sp. 1994. Use of chitin and chitosan in lobster shell wastes for colour removal from aqueous solutions.. UK. C. A. 79.-J. G.. Hutter. 1990...C. J. Removal of chrome dye from aqueous solutions by mixed adsorbents: ¯y ash and coal. Yatome. Marchant. 1992.. J. F.L. Cucurbituril. Mattes.P. FEMS Symposium 12. Brekenridge. 1996.. Putt. Yamamoto.. 881±886. H. M. Kumar.. J. M. R. Process Biochem.. R. D.E. Decolorizing dye wastewater with low temperature catalytic oxidation. Jekel. Biomass-mediated binding and recovery of textile dyes from waste e‚uents. H.... Technol. Cook. 13±19. Removal of reactive dyes from aqueous solution by di€erent bacterial genera. McHale. 993±996. 1997. Dyes. C.. Dyes.. Peralto-Zamora. G. Sorption of reactive dyes by Aeromonas biomass. Tseng.A. In: Leisinger. Poots.L. 1976b. F. Mock. Colour. 1994. DPhil Thesis. FEMS Symposium. Gonenc. 1. G. Iso. J. Biosorption of metals using non-living biomass ± a review. Robinson et al. 1981. Am..T. Gomez de Morales. Rozzi. Biotechnol. Chem. Technol.L.... Karcher.M.. 1999b. Environ. A critical review of the treatments for decolourization of textile e‚uent. J.. Colorage 40. Nigam. Microbial degradation of xenobiotic and recalcitrant compounds.. Possino. Di Pinto. 31. strain BN6. A. Indian J. G. 835±852. Microbiol. 1981. Hunter. 1743±1748. C. WPCF 61. Removal of reactive dyes by sorption/complexion with cucurbituril. Nigam. T. Removal of uranium from solution using residual brewery yeast: combined biosorption and precipitation. Prasad.A.. K. Keck. Ciannarella. November. Kudlich. J. Environ. Chang. K. Soc... 435±442.. P. Rao. A comparative study of ozonation. N..D. Technol. Environ. Lopez.. Riordan. 1999.. G. Klein.. Stolz.C. A. C. Eng. Wu. W. Biotechnol. Crawford.. enzymatic and photochemical processes. 26. R. A. / Bioresource Technology 77 (2001) 247±255 Gro€. V. Ashutush. Technol..L. N. Reyes. 27. P... Delee. Degradation of reactive dyes I. Water Sci. S. Nuesch.M... 22. 179±185. Peralto-Zamora. J. R.. .M. 2.L.. Top. Aerobic bacterial degradation of azo dyes... 1061± 1066.J. 44. Acta hydrochim. W. 89±95...... 1996.. D. Banat. Dyers.. I. 1807±1809. Ince. K. S.. Namboodri. Toxicol. Singh. C. 53±54. Appl. Min... Academic Press. McKay... Duran. Howell. K.. Physical removal of textile dyes and solid state fermentation of dyeadsorbed agricultural residues. P... 25±34. Nigam. J.. 7. Catal B-Environ. M. M. 1999a.C. Raghavacharya. Armour.

Microbiol. 19±26. Yang. Colour Chemistry-Synthesis.. 38±41. Tsezos. G. Willmott. Nelson. Thurston. N. The biotechnology approach to colour removal from textile e‚uent... Technol. Zhou. Color. 255 Xu. Ind. 1998.F. 27±35. J. 30. 2501±2519.. E. / Bioresource Technology 77 (2001) 247±255 Slokar.E... Treatment of textile dye plant e‚uent by nano®ltration membrane. Chem.. pp.M.L.T. Text. 19. D. J. Lebrun. Wolfe.T. Bell. 911±920. 1989. 1987. C. 92±100. Lyberatus... Y. 335±356. JSDC 114. 49±55. 1993. Bahorsky. Sci..P. 6. Separ. 23. Biodegradation of paminoazobenzene by Bacillus subtilis under aerobic conditions. . Zollinger. S. 1998. Microbiology 140. 1987. 561±568. Properties of Organic Dyes and Pigments. M. Lett. 1994. Zimmerman.. Weber. Guthrie. Chem. W. 1999. Comparison of the biosorption and desorption of hazardous organic pollutants by live and dead biomass. M. Decolorization of industrial e‚uents containing reactive dyes by actinomyces. Wyatt II. J. Biot.. New York..M. VCH Publishers.. G. Pavlou. Water Res. FEMS 107. 1997. R.. Zissi.. 1997. H. Le Marechal. N. Microbiol. Environ. The structure and function of fungal laccases. Toxicol. W.. A. Y.. Kinetics studies of reduction of aromatic azo compounds in anaerobic sediment/water systems. 34. W. 157±162. Decolorization of dyes using UV/H2 O2 photochemical oxidation... Dyes Pigments 37. Methods of decoloration of textile wastewaters.. Robinson et al. Y.