MOLECULARLY IMPRINTED POLYMERS FOR SOME REACTIVE DYES

Depending upon their structure, azo- and anthraquinonic dyes are the two major classes and together represent 90% of all organic colorants. Adsorption of dye molecules onto a sorbent can be an effective, low-cost method of color removal. Most of the techniques used for removal of dyes are of high production cost, and the regeneration also makes them uneconomical. There is much interest in the development of cheaper and effective newer materials for use as adsorbents. Molecular imprinting is a new kind of materials that can be alternative adsorbents. In this study, molecularly imprinted polymers of three textile dyes (Cibacron Orange P-4R, Cibacron Red P-4B, Cibacron Black PSG) were prepared. Methacrylic acid was used as a monomer for red and orange dyes and acrylamide was used for black dye. Methanol:acetonitrile was used as a porogen. The selective recognition ability of the molecularly imprinted polymers was studied by an equilibrium–adsorption batch method. The adsorption data are for Cibacron Black PSG 65% and nonimprinted polymer (NIP) 25%; Cibacron Red P-4B 72% and NIP 18%; and Cibacron Orange P-4R 45% and NIP 10%, respectively. Dye-imprinted polymers were used as a solid-phase extraction material for selective adsorption from wastewater of textile factory.     

Biosorption of textile dyes by biomass derived from Kluyveromyces marxianus IMB3

Since it had previously been found that biomass derived from the thermotolerant ethanol-producing yeast strain Kluyveromyces marxianus IMB3 exhibited a relatively high affinity for heavy metals it was decided to determine whether or not it might be capable of textile dye biosorption. To this end, biosorption isotherm analysis was carried out using the biomass together with commonly-used textile dyes including Remazol Black B, Remazol Turquoise Blue, Remazol Red, Remazol Golden Yellow and Cibacron Orange. Although the dyes Remazol Black B, Remazol Turquoise Blue and Remazol Red adhered to the Langmuir model, the remaining dyes failed to do so. The observed biosorption capacities at equilibrium dye concentrations of 100?mg/l were compared and it was found that the biomass exhibited a significant affinity for each dye. The potential use of this biosorptive material in the bioremediation of textile processing effluents is discussed.     

Effect of pretreatments of three waste residues,wheat straw,corncobs and barley husks on dye adsorption

The removal of dyes (Cibacron Yellow C-2R, Cibacron Red C-2G, Cibacron Blue C-R, Remazol Black B and Remazol Red RB) from an aqueous solution has been discussed by adsorption which was examined on three different low cost pretreated agricultural residues viz., wheat straw, corncob and barley husk. The pretreatments were carried out in order to delignify, or to increase the surface area of the sorbents, and to study their effect on the rate and effective adsorption of dyes. Steam, alkali, ammonia steeping and milling were the pretreatments employed and compared with the untreated sorbents. A higher percentage of dye removal was achieved at a faster rate by the milled samples proving milling to be a better and more cost effective treatment, except for barley husk which had a higher percentage removal for the control.     

Oxidation and removal of industrial textile dyes by a novel peroxidase extracted from post-harvest lentil (Lens culinaris L.) stubble

The degradation and removal of a series of dyes used in the textile industry for polyester/wool (PES/WO) blends and present in effluents, such as Green, Ash-Grey, Black, Navy Blue, Red and Yellow Domalan, and Orange and Red Bemacid, by catalytic action, in the presence of H₂O₂, of extracts of a novel peroxidase from postharvest lentil stubble was investigated. The extracts of this peroxidase (LSP) were effective in degrading these lastgeneration textile dyes, especially Green Domalan, Orange Bemacid, Grey and Black Domalan. A sensitivity study was carried out for Green Domalan biodegradation to determine the effects of process parameters such as pH, H₂O₂, enzyme and dye concentrations, contact and centrifugation times, and temperature. Standard ecotoxicity studies performed with Vibrio fischeri revealed that the dye solutions treated with peroxidase and H₂O₂ were less ecotoxic than the untreated ones.     

Accumulation of Acid Orange 7, Acid Red 18 and Reactive Black 5 by growing Schizophyllum commune

The effect of Acid Orange 7, Acid Red 18 and Reactive Black 5 on the growth and decolorization properties of Schizophyllum commune was studied with respect to the initial pH varying from 1 to 6 and initial dye concentration (10-100 mg/L). The optimum pH value was found to be 2 for both growth and color removal of these azo dyes. Increasing the concentration of azo dyes inhibited the growth of S. commune. It was observed that S. commune was capable of removing Acid Orange 7, Acid Red 18 and Reactive Black 5 with a maximum specific uptake capacity of 44.23, 127.53 and 180.17 (mg/g) respectively for an initial concentration of 100 mg/L of the dye. Higher decolorization was observed at lower concentrations for all the dyes. Finally it was found that the percentage decolorization was more in the case of Reactive Black 5 dye compared to the other two dyes used in the present investigation.     

Studies on desorption of individual textile dyes and a synthetic dye effluent from dye-adsorbed agricultural residues using solvents

Two solvents, A and B (A: methanol, chloroform, water in the ratio 1:1:1; B: 50% methanol), were used to extract textile dyes adsorbed onto substrates for the purpose of future analyses of the amount of dyes degraded through solid state fermentation (SSF) using white rot fungi. Barley husk, apple pommace and corncob were separately soaked in five different dye solutions and a synthetic textile effluent. A maximum value of 93% desorption of Cibacron Red from corncob was achieved using solvent A. Barley husk was the only substrate from which the synthetic textile effluent could be desorbed, with 82% being recovered using solvent A.     

Starch/polyaniline nanocomposite for enhanced removal of reactive dyes from synthetic effluent

Starch/polyaniline nanocomposite was synthesized by chemical oxidative polymerization of aniline and was subsequently analyzed for dye removal from aqueous solution. Batch experiment results showed that nanocomposite removed 99% of Reactive Black 5, 98% of Reactive Violet 4, and decolorized 87% of dye bath effluent. The Toth isotherm model better described single component equilibrium adsorption, whereas the modified Freundlich model showed satisfactory fit for dye bath. In kinetic modeling, single system followed pseudo-second-order and dye bath followed the modified pseudo-first-order model. Fourier transform infrared spectroscopy pattern of the nanocomposite showed the participation of aromatic, amino, hydroxyl, and carboxyl groups. The results indicate that starch/polyaniline nanocomposite can be used as an effective adsorbent for removal of dyes from textile effluents.     

Binding of textile azo dyes byMyrothecium verrucaria

Summary A strain ofMyrothecium verrucaria that showed a high capacity for rapid decolorization of textile dye solutions was isolated from soil. As much as 70%, 86%, and 95% of Orange II, 10B (blue) and RS (red) dyes (color index no. 15510, 20470, 23635), respectively, were adsorbed from solutions of approximately 0.2 g dye per liter in 5 h by approximately 4.5 g dry weight of cells per liter of dye solution. Intact cells showed a higher adsorption capacity than disrupted cells for Orange II and RS but not for 10B. Dye bound to cells was recoverable by extraction with methanol and methanol-treated cells were able to be recycled, albeit with a slightly diminished dye-binding capacity. The Tween detergents were shown to reduce dye adsorption. Dyes strongly bound to the fungal biomass required sonication in dH₂O or in Triton X-100 or extraction with methanol for their removal. These results suggest that hydrophobic/hydrophilic interactions are important in dye binding.     

Removal of disperse dyes from textile wastewater using bio-sludge

Granular activated carbon (GAC) did not show any significant adsorption ability on the disperse dyes, while resting (living) bio-sludge of a domestic wastewater treatment plant showed high adsorption abilities on both disperse dyes and organic matter. The dye adsorption ability of bio-sludge increased by approximately 30% through acclimatization with disperse dyes, and it decreased by autoclaving. The deteriorated bio-sludge could be reused after being washed with 0.1N NaOH solution. Disperse Red 60 was more easily adsorbed onto the bio-sludge than Disperse Blue 60. The Disperse Red 60, COD, and BOD5 adsorption capacities of acclimatized, resting bio-sludge were 40.0+/-0.1, 450+/-12, and 300+/-10mg/g of bio-sludge, respectively. The GAC-SBR system could be applied to treat textile wastewater (TWW) containing disperse dyes with high dye, BOD5, COD, and TKN removal efficiencies of 93.0+/-1.1%, 88.0+/-3.1%, 92.2+/-2.7% and 51.5+/-7.0%, respectively without any excess bio-sludge production under an organic loading of 0.18 kg BOD5/m3-d. Furthermore, the removal efficiencies increased with the addition of glucose into the system. The dye, BOD5, COD, and TKN removal efficiencies of the GAC-SBR system with TWW containing 0.89 g/L glucose were 94.6+/-0.7%, 94.4+/-0.6%, 94.4+/-0.8% and 59.3+/-8.5%, respectively, under an SRT of 67+/-0.4 days.     

Decolorization of reactive dyes by mixed cultures isolated from textile effluent under anaerobic conditions

In the present study mixed cultures that could grew in the molasses media were isolated from textile dye effluent and its decolorization activity was studied in a batch system under anaerobic conditions, in order to determine the optimal conditions required for the highest decolorization activity. The optimum pH value for decolorization was determined as 8 for all the dyes tested. In the experiment with pH 8 dye decolorizations by mixed cultures were investigated at about 96.2–1031.3 mg l⁻¹ initial dye concentrations. The highest dye removal rates of mixed cultures were 94.9% for Reactive Red RB, 91.0% for Reactive Black B and 63.6% for Remazol Blue at 953.2, 864.9 and 1031.3 mg l⁻¹ initial dye concentrations respectively within 24 h incubation period. When the Reactive Red RB was used, approximately 82–98% total color removal was obtained at between 96.2 and 953.2 mg l⁻¹ initial dye concentrations after 12 h of incubation at 35 °C. These results show that our enriched mixed cultures have the potential to serve as an excellent biomass for the use in reactive dye removal from wastewaters under anaerobic conditions.     

Use of immobilised Chlorella vulgaris for the removal of colour from textile dyes

Discharge of textile wastewater containing toxic dyes can adversely affect the aquatic ecosystems and human health. The objective of the present study was to investigate the potential use of immobilised Chlorella vulgaris UMACC 001 in removing colour from textile dyes (Supranol Red 3BW, Lanaset Red 2GA and Levafix Navy Blue EBNA) and textile wastewater (TW). Two immobilisation matrices were used, namely 1% κ-carragenan and 2% sodium alginate. Of the three dyes tested, the highest percentage of colour removal was from Lanaset Red 2GA. The cultures immobilised in 2% alginate attained the highest percentage of colour removal (44.0%) from the dye at an initial concentration of 7.25 mg L⁻¹. Immobilised cultures in alginate also removed higher percentage of colour (48.9%)from the TW, than the suspension cultures (34.9%). Aeration did not enhance the percentage of colour removal but increased the colour intensity of the wastewater instead. C. vulgaris immobilised in alginate will be useful for final polishing of textile wastewater after undergoing primary treatment before discharge.     

Decoloration of textile dyes by Trametes versicolor and its effect on dye toxicity

Amaranth, Tropaeolin O, Reactive Blue 15, Congo Red, and Reactive Black 5 were completely decolorized with no dye sorption by Trametes versicolor. Cibacron Brilliant Red 3G-P, Cibacron Brilliant Yellow 3B-A, and Remazol Brilliant Blue R were partially decolorized with some dye sorbed to the biomass. The Microtox assay before decoloration showed that Amaranth and Tropaeolin O were not toxic [the percent concentration to decrease 20% of the luminescence of Vibrio fischeri (EC₂₀) was greater than 100%]; Cibacron Brilliant Yellow 3B-A, Reactive Blue 15 and Cibacron Brilliant Red 3G-P were moderately non-toxic (100% > EC₂₀ > 75%); Remazol Brilliant Blue R was toxic (75% > EC₂₀ > 50%); and Congo Red and Reactive Black 5 were moderately toxic (50% > EC₂₀ > 25%). After decoloration the toxicity of the solutions containing Amaranth, Tropaeolin O and Reactive Black 5 was unchanged; Reactive Blue 15, Remazol Brilliant Blue R and Cibacron Brilliant Red 3G-P decreased to non-toxic levels; and Cibacron Brilliant Yellow 3B-A and Congo Red became very toxic (EC₂₀ < 25%).     

Modeling the discoloration of a mixture of reactive textile dyes by commercial laccase

Degradation of a mixture of three reactive textile dyes (Reactive Black 5, Reactive Yellow 15 and Reactive Red 239), simulating a real textile effluent, by commercial laccase, was investigated in a batch reactor. The discoloration was appraised as a percentage of the absorbance reduction at the wavelength of maximum absorbance for each dye and as total color removal based in all visible spectrum. A significantly high discoloration was achieved in both cases, indicating the applicability of this method for textile wastewater treatment. Mathematical models were developed to simulate the kinetics of laccase catalyzed degradation of reactive dyes in mixtures. Like in single dye degradation, some of the reactions present an unusual kinetic behavior, corresponding to the activation of the laccase-mediator system. The kinetic constants of the models were estimated by minimizing the difference between the predicted and the experimental time courses. Although not perfect, the ability of the models in representing the experimental results suggests that they could be used in design and simulation applications.     

Bilirubin removal from human plasma by Cibacron Blue F3GA using immobilized microporous affinity membranous capillary method

A novel affinity sorbent system for direct bilirubin removal from human plasma was developed. These new adsorbents comprise Cibacron Blue F3GA as the specific ligand, and microporous membranous poly(tetrafluoroethylene) capillary (modified by coating with a hydrophilic layer of poly(vinyl alcohol) after activation) as the carrier matrix. The affinity adsorbents carrying 126.5 micromol Cibacron Blue F3GA/g polymer was then used to remove bilirubin in a flow-injection system. Non-specific adsorption on the poly(vinyl alcohol) coated capillary remains low, and higher affinity adsorption capacity, of up to 76.2 mg/g polymer was obtained after dye immobilization. The bilirubin adsorption capacity of the affinity capillary decreased with increase in the recirculation rate of plasma. The adsorption capacity increased with increase the temperature while decreased with increase the ionic strength. The maximum adsorption was only observed in neutral solution (pH 6-7). The adsorption isotherm fitted the Langmuir model well. These new adsorbents have higher velocity of mass transfer, better adsorption capacity, less fouling, longer service life and good reusability. The results of blood tests suggested the dye affinity capillary has good blood compatibility.     

The significance of azo-reduction in the mutagenesis and carcinogenesis of azo dyes

Azo dyes are widely used in textile, printing, cosmetic, drug and food-processing industries. They are also used extensively in laboratories as either biological stains or pH indicators. The extent of such use is related to the degree of industrialization. Since intestinal cancer is more common in highly industrialized countries, a possible connection may exist between the increase in the number of cancer cases and the use of azo dyes. Azo dyes can be reduced to aromatic amines by the intestinal microflora. The mutagenicity of a number of azo dyes is reviewed in this paper. They include Trypan Blue, Ponceau 3R, Pinceau 2R, Methyl Red, Methyl Yellow, Methyl Orange, Lithol Red, Orange I, Orange II, 4-Phenylazo-Naphthylamine, Sudan I, Sudan IV, Acid Alizarin Violet N, Fast Garnet GBC, Allura Red, Ponceau SX, Sunset Yellow, Tartrazine, Citrus Red No. 2, Orange B, Yellow AB, Carmoisine, Mercury Orange, Ponceau S, Versatint Blue, Phenylazophenol, Evan's Blue and their degraded aromatic amines. The significance of azo reduction in the mutagenesis and carcinogenesis of azo dyes is discussed.     

Monoazo and diazo dye decolourisation studies in a methanogenic UASB reactor

Mixed anaerobic bacterial consortia have been show to reduce azo dyes and batch decolourisation tests have also demonstrated that predominantly methanogenic cultures also perform azo bond cleavage. The anaerobic treatment of wool dyeing effluents, which contain acetic acid, could thus be improved with a better knowledge of methanogenic dye degradation. Therefore, the decolourisation of two azo textile dyes, a monoazo dye (Acid Orange 7, AO7) and a diazo dye (Direct Red 254, DR254), was investigated in a methanogenic laboratory-scale Upflow Anaerobic Sludge Blanket (UASB), fed with acetate as primary carbon source. As dye concentration was increased a decrease in total COD removal was observed, but the acetate load removal (90%) remained almost constant. A colour removal level higher than 88% was achieved for both dyes at a HRT of 24h. The identification by HPLC analysis of sulfanilic acid, a dye reduction metabolite, in the treated effluent, confirmed that the decolourisation process was due mainly to azo bond reduction. Although, HPLC chromatograms showed that 1-amino-2-naphthol, the other AO7 cleavage metabolite, was removed, aeration batch assays demonstrated that this could be due to auto-oxidation and not biological mineralization. At a HRT of 8h, a more extensive reductive biotransformation was observed for DR254 (82%) than for AO7 (56%). In order to explain this behaviour, the influence of the dye aggregation process and chemical structure of the dye molecules are discussed in the present work.     

Intraparticle diffusion processes during acid dye adsorption onto chitosan

The adsorption of five acid dyes onto chitosan was studied. The equilibrium capacities based on the Langmuir analysis were 1.54, 2.66, 1.11, 1.25 and 1.03 mmol/g chitosan for Orange 10 (AO10), Acid Orange 12 (AO12), Acid Red 18 (AR18), Acid Red 73 (AR73) and Acid Green 25 (AG25) respectively. The batch adsorption rate for the five systems based on an intraparticle diffusion rate parameter derived from the plots of dye adsorbed versus the square root of time indicated that the adsorption mechanism was predominantly intraparticle diffusion but there was also a dependence on pore size as the dye diffuses through macropore, mesopore and micropore respectively.     

Removal of basic and reactive dyes using ethylenediamine modified rice hull

Wastewaters from textile industries may contain a variety of dyes that have to be removed before their discharge into waterways. Rice hull, an agricultural by-product, was modified using ethylenediamine to introduce active sites on its surface to enable it to function as a sorbent for both basic and reactive dyes. The sorption characteristics of Basic Blue 3 (BB3) and Reactive Orange 16 (RO16) by ethylenediamine modified rice hull (MRH) were studied under various experimental conditions. Sorption was pH and concentration dependent. Simultaneous removal of BB3 and RO16 occurred at pH greater than 4. The kinetics of dye sorption fitted a pseudo-second order rate expression. Increase in agitation rate had no effect on the sorption of BB3 but increased uptake of RO16 on MRH. Decreasing particle size increased the uptake of dyes in binary dye solutions. Equilibrium data could be fitted into both the Langmuir and Freundlich isotherms. Maximum sorption capacities calculated from the Langmuir model are 14.68 and 60.24 mg/g for BB3 and RO16, respectively in binary dye solutions. This corresponds to an enhancement of 4.5 and 2.4 fold, respectively, compared to single dye solutions. MRH therefore has the potential of being used as an efficient sorbent for the removal of both dyes in textile wastewaters.     

Decolorization of Some Reactive Textile Dyes by White Rot Fungi Isolated in Pakistan

Summary Four white-rot fungi isolated in Pakistan were used for decolorization of widely used reactive textile dyestuffs. Phanerochaete chrysosporium, Coriolus versicolor, Ganoderma lucidum and Pleurotus ostreatus were grown in defined nutrient media for decolorization of Drimarene Orange K-GL, Remazol Brilliant Yellow 3GL, Procion BluePX-5R and Cibacron Blue P-3RGR for 10 days in shake flasks. Samples were removed every day, centrifuged and the absorbances of the supernatants were read to determine percentage decolorization. It was observed that P. chrysosporium and C. versicolor could effectively decolorize Remazol Brilliant Yellow 3GL, Procion BluePX-5R and Cibacron Blue P-3RGR. Drimarene Orange K-GL was completely decolorized (0.2 g/l after 8 days) only by P.chrysosporium, followed by P. ostreatus (0.17 g/l after 10 days). P. ostreatus also showed good decolorization efficiencies (0.19–0.2 g/l) on all dyes except Remazol Brilliant Yellow (0.07 g/l after 10 days). G. lucidum did not decolorize any of the dyestuffs to an appreciable extent except Remazol Brilliant Yellow (0.2 g/l after 8 days).     

An integrated process of textile dye removal and hydrogen evolution using cyanobacterium,Phormidium valderianum

The work deals with the removal of textile dyes from wastewater using cyanobacteria and integrating the dye removal ability of the organism with the ability to produce hydrogen. Phormidium valderianum, a marine cyanobacterium, has been shown to remove more than 90% of textile dyes Acid red, Acid red 119 and Direct black 155 from the solutions in the pH range higher than 11. Presence of phenolic compounds and metal chelators drastically reduced the dye adsorption capacity of the organisms. The mechanism involved in the dye adsorption has been investigated. Hydrogen production by cells grown in presence of dyes in any phase of their growth was found to be less in comparison to that of control (grown without dye). A laboratory scale reactor was designed to integrate the hydrogen production and dye removal ability of P. valderianum.