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In this study, the copper nanoparticles (Cu NPs) reactivity for degradation of the reactive dye black 5 (RP5), picric acid (PA) and 2,4-D herbicide was evaluated. The RP5 degradation occurred by oxidative via, through hydroxyl radicals generated in situ, with active participation of Cu(I) and H2O2. The use of catalase confirmed the hydrogen peroxide formation in situ. Reduction degradation via electron transfer was also possible. On the other hand, PA had low degradation efficiency (less than 20%) under any conditions studied (similar to those used for RP5). High degradation efficiency for 2,4-D was achieved by the association of the Cu NPs/H2O2. Thus, the behavioral model of Cu NPs has been proven. This behavioral difference of the chemical species to be degraded in relation to the behavior of the Cu NPs was studied, evaluating its redox behavior by voltammetric analyzes. This study aided in the understanding and selection of the chemical species that can be degraded by these NPs.

Green synthesis of manganese oxide nanoparticles (NPs) was carried out by sol-gel method using Acacia Concinna fruit extract for removal of reactive dye. The effect of calcination temperature on its morphology was investigated. α-MnO2 and Mn3O4 NPs were synthesized at 400 °C and 900 °C respectively and were characterized by PXRD, SEM, TEM, FTIR, BET, Raman and TGA. As-synthesized MnO2 NPs were investigated for the adsorption of Reactive Blue 21 (RB-21) dye. The effect of pH, adsorbent dose, agitation speed, initial dye concentration and temperature on dye removal was explored. pHpzc was calculated from zeta potential study showing positive surface charge below pH 3.18 resulting in electrostatic force of attraction between adsorbate and adsorbent. Both linear and non-linear regression approaches were utilised for the fitting of kinetic models and adsorption isotherms. Adsorption data follows a pseudo second order kinetics and fits well with the Freundlich isotherm model. Thermodynamic parameters such as ΔHo, ΔSo and ΔGo were determined. The dye removal efficiency, in case of MnO2 NPs at pH 3.0 was obtained to be 98% whereas for Mn3O4, no such dye adsorption was observed. The mechanism of adsorption was studied theoretically confirming π-π interaction and H-bonding between the MnO2 and RB dye molecules.

The concept of natural organic matter of anthropogenic origin is introduced and its characteristics and interaction with chemical pollutants are investigated by adopting several distinct analytic methodologies. Scanning electron microscopy indicates that the used sample of anthropogenic organic matter (AOM) has an amphiphilic nature, which allows its supramolecular organization in water. Fourier transform infrared spectroscopy, in turn, gives a clear indication about the presence of polysaccharide markers, lipidic and amidic fractions, and suggests the absence of free organic acid. AOM sample and AOM mixed with dye sample were examined by the three-dimensional excitation-emission matrix fluorescence spectra and the nuclear magnetic resonance mono-dimensional spectra. The results highlighted the interactions occurring between the AOM and the reactive dye, selected as a representative chemical pollutant. Electron Spin Resonance confirms that the used AOM is able to completely include the dye in its structure. Overall, the obtained results indicate that the fate, transport, and toxicity of pollutants in the environment can be drastically influenced by the presence of AOM.

The electrochemical behavior of different carbon-based electrodes with and without nanoparticles of platinum electrochemically dispersed on their surface has been studied. Among others, reduced graphene oxide based electrodes was used to determine the best conditions for the decolorization/degradation of the reactive dye C.I. Reactive Orange 4 in sulfuric medium. Firstly, the electrochemical behavior was evaluated by cyclic voltammetry. Secondly, different electrolyses were performed using two cell configurations: cell with anodic and cathodic compartments separated (divided configuration) and without any separation (undivided configuration). The best results were obtained when reduced graphene oxide based anodes were used. The degree of decolorization was monitored by spectroscopic methods and high performance liquid chromatography. It was found that all of them followed pseudofirst order kinetics. When reduced graphene oxide-based electrodes coated with dispersed platinum by alternate current methods electrodes were used, the lowest energy consumption and the higher decolorization kinetics rate were obtained. Scanning Electronic Microscopy was used to observe the morphological surface differences., The authors wish to thank the Spanish Agencia Estatal de Investigacion (AEI) and European Union (FEDER funds) for the financial support (contract MAT2016-77742-C2-1-P). A.I. del Rio is grateful to the Spanish Ministerio de Ciencia y Tecnologia for her FPI fellowship. J. Molina is grateful to the Conselleria d'Educacio, Formacio i Ocupacio (Generalitat Valenciana) for the Programa VALi+D Postdoctoral Fellowship (APOSTD/2013/056). C. Garcia is grateful to the Conselleria d'Educacio, Formacio I Ocupacio (Generalitat Valenciana) for her Geronimo Forteza fellowship. The authors wish to acknowledge to Chemviron Carbon who kindly donated the 265 ZORFLEX (R) activated carbon fabric.

A thermal degradation pathway of the decolourisation of Reactive Cibacron Blue F3GA (RCB) in aqueous solution through catalytic thermolysis is established. Catalytic thermolysis is suitable for the removal of dyes from wastewater as it breaks down the complex dye molecules instead of only transferring them into another phase. RCB is a reactive dye that consists of three main groups, namely anthraquinone, benzene and triazine groups. Through catalytic thermolysis, the bonds that hold the three groups together were effectively broken and at the same time, the complex molecules degraded to form simple molecules of lower molecular weight. The degradation pathway and products were characterized and determined through UV-Vis, FT-IR and GCMS analysis. RCB dye molecule was successfully broken down into simpler molecules, namely, benzene derivatives, amines and triazine. The addition of copper sulphate, CuSO4, as a catalyst, hastens the thermal degradation of RCB by aiding in the breakdown of large, complex molecules. At pH 2 and catalyst mass loading of 5 g/L, an optimum colour removal of 66.14% was observed. The degradation rate of RCB is well explained by first order kinetics model.

A novel coagulant poly-ferric-titanium-silicate-sulfate (PFTS) was synthesized and employed to treat two typical kinds of dye wastewaters-disperse blue and reactive yellow. The results indicated that PFTS with a Si/Fe molar ratio of 0.02 exhibited superior coagulation performance, especially under alkaline condition. The residual turbidity after coagulation by PFTS was only half of that after coagulation by poly-ferric-titanium sulfate (T-PSF). The sludge volume index was also reduced by PFTS compared to T-PSF in reactive dye treatment. Through the structure and morphology investigation of PFTS, it was found that new bonds of Si-O-Fe, Si-O-Ti and Fe-OH (Si-OH) were formed, and multi-branched structures and expanded surface area were generated. Additionally, compared with T-PSF, the floc strength and the floc size were also enhanced by PFTS, which was attributed to the polymerization between polysilicic acid and Fe/Ti which formed multi-branched structures, and finally adsorption and bridging ability of the coagulant was improved. Furthermore, the floc formed in reactive yellow wastewater treatment was larger and looser than that formed in disperse blue wastewater, with poorer strength and recovery ability, which can also interpret the better coagulation efficiency in disperse dye water treatment. From the results of coagulant characterization, zeta potential and flocs properties, it can be inferred that charge neutralization by the positive charged hydrolysate of coagulant was identified as the critical effect in disperse dyes removal, while the sweep and adsorption of metal hydroxyl compound formed during the hydrolysis of coagulants were considered to play a key role in reactive dye removal.

The effluent discharged by the textile dyehouses has a seriously detrimental effect on the aquatic environment. Some dyestuffs produce toxic decomposition products and the metal complex dyes release toxic heavy metals to watercourses. Of the dyes used in the textile industry, effluents containing reactive dyes are the most difficult to treat because of their high water-solubility and poor absorption into the fibers. A range of treatments has been investigated for the decolorization of textile effluent and the adsorption seems to be one of the cheapest, effective and convenient treatments. In this review, the adsorbents investigated in the last decade for the treatment of textile effluent containing reactive dyes including modified clays, biomasses, chitin and its derivatives, and magnetic ion-exchanging particles have been critically reviewed and their reactive dye binding capacities have been compiled and compared. Moreover, the dye binding mechanism, dye sorption isotherm models and also the merits/demerits of various adsorbents are discussed. This review also includes the current challenges and the future directions for the development of adsorbents that meet these challenges. The adsorption capacities of adsorbents depend on various factors, such as the chemical structures of dyes, the ionic property, surface area, porosity of the adsorbents, and the operating conditions. It is evident from the literature survey that decolorization by the adsorption shows a great promise for the removal of color from dyehouse effluent. If biomasses want to compete with the established ion-exchange resins and activated carbon, their dye binding capacity will need to be substantially improved.

This study investigated the degradation of anthraquinone reactive dye C.I. Reactive Blue 19 (RB-19) with initial concentration of 100mg L(-1) in aqueous solution by ozone oxidation. The results of UV/VIS and FTIR spectra showed that the anthraquinone structures, nitrogen linkages and amino groups of RB-19 were destroyed under direct ozone reaction. The identification by LC-MS and GC-MS analyses indicated that some organic acids (e.g., phthalic acids) and 1,3-indanone could be the primary degradation products, respectively. The Microtox toxicity of the ozonated RB-19 solution initially increased but subsequently decreased when ozonation time increased. This detoxification accompanied biodegradability enhancement revealed by BOD/COD ratio increasing from 0.15 to 0.33 after 10min of ozonation.

Corynebacterium glutamicum , a lysine fermentation industry waste, showed promise for the removal of Reactive black 5 (RB5). Due to practical difficulties in solid–liquid separation, the free biomass was immobilized in two polymer matrices: calcium alginate and polysulfone. Initially, the optimization of biomass loading in polymeric beads and bead dosage were examined. Of the different combinations examined, 4% (with bead dosage of 2 g per 40 ml) and 14% (with bead dosage of 1 g per 40 ml) in the case of alginate and polysulfone beads, respectively, were identified as the optimal conditions. According to the Langmuir model, at pH 1, the maximum RB5 uptakes of 352, 282 and 291 mg g −1 were observed for free, alginate and polysulfone-immobilized biomass, respectively. According to the Weber–Morris model, intraparticle diffusion was found to be the potential rate limiting step for the immobilized beads. Regeneration experiments, with 0.01 M NaOH and Na 2 CO 3 as eluents, revealed that polysulfone beads exhibited invariable RB5 uptake capacity and very high mechanical stability even at the end of twentieth cycle, confirming the technical feasibility of the biosorption process for industrial applications.

The ozonation of synthetic wastewater containing azo dye, CI Reactive Black 5, was investigated using a microbubble generator and a conventional bubble contactor. The microbubble generator produced a milky and high intensity microbubble solution in which the bubbles had a mean diameter of less than 58 microm and a numerical density of more than 2.9 x 10(4) counts ml(-1) at a gas flow rate of less than 0.5 l min(-1). Compared with the bubble contactor, the total mass transfer coefficient was 1.8 times higher and the pseudo-first order rate constant was 3.2-3.6 times higher at the same initial dye concentration of 100 mg l(-1), 230 mg l(-1) and 530 mg l(-1) in the proposed microbubble system. The amount of total organic carbon removed per g of ozone consumed was about 1.3 times higher in the microbubble system than in the bubble contactor. The test using terephthalic acid as the chemical probe implied that more hydroxyl radicals were produced in the microbubble system, which contributed to the degradation of the dye molecules. The results suggested that in addition to the enhancement of mass transfer, microbubbles, which had higher inner pressure, could accelerate the formation of hydroxyl radicals and hence improve the oxidation of dye molecules.

A microbial consortia consisting of three bacteria isolated from tanning and textile wastewaters revealed high capacity to simultaneously bioaccumulate dye and Cr(VI). The identity of the bacteria were determined by 16S rRNA gene analysis to be closely related to Ochrobactrium sp., Salmonella enterica and Pseudomonas aeruginosa. Dependence of initial pH values and range of concentrations of the dye Reactive Black B (33.2-103.1 mg l(-1)) and Cr(VI) (19.9-127.6 mg l(-1)) were examined to find the effect of pH on the dye and Cr(VI) bioaccumulation. Optimal pH for growth of the consortia in media containing 35 mg l(-1) dye and 50 mg l(-1) Cr(VI) was determined to be around 8. The Cr(VI) bioaccumulation by the consortia was rapid in media containing molasses with or without reactive dye with a maximum Cr(VI) bioaccumulation yield ranging from 90% to 99% within a 2-4d period. A slightly lower yield for the dye bioaccumulation was measured with a maximum dye bioaccumulation of 80% at 59.3 mg l(-1) dye and 69.8 mg l(-1) Cr(VI). The highest specific Cr uptake value was obtained as 76.7 mg g(-1) at 117.1 mg l(-1) Cr(VI) and 50.8 mg l(-1) dye concentration. This ability to bioaccumulate dye and Cr(VI) was more efficient than the enriched sludge from which they were isolated.

In this study, an aqueous solution of purified, hydrolyzed C.I. Reactive Red 120 (RR 120, Color Index), was selected as a model to investigate the degradation pathways and to obtain additional information on the reaction intermediate formation. The dye was purified to avoid the influence of the impurities on the ozonation process and on the formation of oxidation by-products. To simulate the dye-bath effluents from dyeing processes with azo reactive dyes, a hydrolyzed form of the dye was chosen as a representative compound. High performance liquid chromatography/mass spectrometry and its tandem mass spectrometry was chosen to identify the decomposition pathways and reaction intermediate formation during the ozonation process. In addition total organic carbon and high performance ion chromatography analysis were employed to obtain further information on the reaction processes during ozonation. Purified, hydrolyzed RR 120 was decomposed under the direct nucleophilic attack by ozone resulting in oxidation and cleavage of azo group and aromatic ring, while the triazine group still remained in the solution even after prolonged oxidation time (120 min) due to its high resistance to ozonation. Phenol, 1,2-dihydroxysulfobezene, 1-hydroxysulfonbezene were detected as the degradation intermediates, which were further oxidized by O 3 and ·OH to other open-ring products and then eventually led to simple oxalic and formic acid identified by HPIC.

The electrochemical performance of pure Ti–Pt/β-PbO 2 electrodes, or doped with Fe and F (together or separately), in the oxidation of simulated wastewaters containing the Blue Reactive 19 dye (BR-19), using a filter-press reactor, was investigated and then compared with that of a boron-doped diamond electrode supported on a niobium substrate (Nb/BDD). The electrooxidation of the dye simulated wastewater (volume of 0.1 l, with a BR-19 initial concentration of 25 mg l −1 ) was carried out under the following conditions: current density of 50 mA cm −2 , volume flow rate of 2.4 l h −1 , temperature of 25 °C and electrode area of 5 cm 2 . The performances of the electrodes in the dye decolorization were quite similar, achieving 100% decolorization, and in some cases 90% decolorization was achieved by applying only ca. 0.3 A h l −1 (8 min of electrolysis). The reduction of the simulated wastewater organic load, monitored by its total organic carbon content (TOC), was greater for the Ti–Pt/β-PbO 2 –Fe,F electrode obtained from an electrodeposition bath containing 1 mM Fe 3+ and 30 mM F − . In this case, after 2 h of electrolysis the obtained TOC reduction was 95%, while for the pure β-PbO 2 and the Nb/BDD electrodes the reductions were 84% and 82%, respectively.

While synthetic polymeric sorbents effectively treat dye wastewaters by adsorption, the underlying mechanisms remain to be understood. This work determined the adsorption of an anionic dye by three polymers differing significantly in surface functionality. Surface functional groups of polymers were indicated in FTIR spectra and quantified by the Boehm titration. In reference to the commercial sorbent XAD-4 with a low degree of functionality, the laboratory synthesized NG-8 had primarily acidic functional groups, whereas its aminated product MN-8 had mainly basic amino groups. Electrophoresis determined the points of zero charge of 4.18, 3.23, and 4.51 for XAD-4, NG-8, and MN-8, respectively. The adsorption of Reactive Black 5 dye (RB5) by all the sorbents on a unit surface area basis increased with decreasing pH. At the same low pH (⩽4.40), the adsorption by NG-8 was similar to that by XAD-4, indicating little influence of protonated (neutral) surface functional groups. In contrast, the adsorption by NG-8 at pH 6.05 was 75% lower than that by XAD-4, resulting apparently from the strong electrostatic repulsion between RB5 and deprotonated (negative) groups. Amination substantially enhanced RB5 adsorption by eliminating acidic groups and creating a positive charge on the surface of MN-8. The adsorptive enhancement was also achieved in the presence of CaCl2, due presumably to the neutralization of negative surface charge by Ca2+ and the RB5-Ca2+ pairing. These results manifest the important role of surface functionality in the adsorption of dyes by synthetic polymers.

One kind of adsorbent with a high adsorption capacity for anionic dyes was prepared using ionically and chemically cross-linked chitosan beads. A batch system was applied to study the adsorption behavior of one acid dye (MY, metanil yellow) and one reactive dye (RB15, reactive blue 15) in aqueous solutions by the cross-linked chitosan beads. The adsorption capacities was 3.56 mmol g(-1) (1334 mg g(-1)) for dye MY and 0.56 mmol g(-1) (722 mg g(-1)) for dye RB15 at pH4, 30 degrees C. The Langmuir model agreed very well with the experimental data (R(2)>0.996). The kinetics of adsorption for a single dye and the kinetics of removal of ADMI color value in mixture solutions at different initial dye concentrations were evaluated by the nonlinear first-order and second-order models. The first-order kinetic model fits well with the dynamical adsorption behavior of a single dye for lower initial dye concentrations, while the second-order kinetic model fits well for higher initial dye concentrations. The competitive adsorption favored the dye RB15 in the mixture solution (initial conc. (mM): MY=1.34; RB15=1.36); while it favored the dye MY in the mixture solution (initial conc. (mM): MY=3.00; RB15=1.34) and the adsorption kinetics for dye RB15 has the tendency to shift to a slower first order model.

The oxidation of a reactive dye, Reactive Blue 4, RB4, (C.I. 61205), widely used in the textile industries to color natural fibers, was studied by electrochemical techniques. The oxidation on glassy carbon electrode and reticulated vitreous carbon electrode occurs in only one step at 2.0 < pH < 12 involving a two-electron transfer to the amine group leading to the imide derivative. Dye solution was not decolorized effectively in this electrolysis process. Nevertheless, the oxidation of this dye on Ti/SnO2/SbO(x) (3% mol)/RuO2 (1% mol) electrode showed 100% of decolorization and 60% of total organic carbon removal in Na2SO4 0.2 M at pH 2.2 and potential of +2.4V. Experiments on degradation photoelectrocatalytic were also carried out for RB4 degradation in Na2SO4 0.1 M, pH 12, using a Ti/TiO2 photoanode biased at +1.0 V and UV light. After 1h of electrolysis the results indicated total color removal and 37% of mineralization.

A two stage anaerobic/aerobic bacterial process was used to decolorize and partially mineralize a reactive vinyl sulfone diazo dye C.I. Reactive Black 5 (RB5) in a synthetic wastewater. Since the anchor group of reactive dyes reacts during the dyeing process, the effect the degree of hydrolysis of the vinyl sulfone dye had on decolorization, mineralization and toxicity in each stage was investigated. An overall color removal of approximately 65% was found for both the fully and partially hydrolyzed dye. Partial mineralization of the fully hydrolyzed RB5 was achieved in the two stage rotating disc reactors. While the anchor group metabolite p-aminobenzene-2-hydroxyethylsulfonic acid (p-ABHES) was mineralized, an oxidized form of the center metabolite (1,2-ketimino-7-amino-8-hydroxynaphthalene-3,6-disulfonic acid) remained in the aerobic stage effluent, causing the effluent to be colored although no RB5 was present. Partially hydrolyzed dye in the influent with vinyl forms of the anchor group caused cessation of biogas production and a reduction in decolorization efficiency in the anaerobic stage. No evidence for mineralization of the partially hydrolyzed dye or its metabolites was found. A method for evaluating dye mineralization using lumped parameters is presented.

In this study, Reactive Black 5 (RB5) was removed from synthetic wastewater using Fenton's oxidation (FO) process. Experiments were conducted on the samples containing 100 and 200 mg l(-1) of RB5 to remove the dye toxicity. Seventy-five milligram per litre of RB5 caused 25% toxicity on 24-h born daphnids whereas 100 mg l(-1) of RB5 displayed 100% toxicity on Daphnia magna. The study was performed in a systematic approach searching optimum values of FeSO(4) and H(2)O(2) concentrations, pH and temperature. Optimum pH and temperature for 100 mg l(-1) of RB5 were observed as 3.0 and 40 degrees C, respectively, using 100 mg l(-1) of FeSO(4) and 400 mg l(-1) of H(2)O(2) resulted in 71% chemical oxygen demand (COD) and 99% color removal. For 200 mg l(-1) of RB5, 84% COD removal was obtained using 225 mg l(-1) of FeSO(4) and 1000 mg l(-1) of H(2)O(2) yielding 0.05 molar ratio at pH 3.0 and 40 degrees C. Color removal was also more than 99%. The optimum conditions determined in accordance with the literature data. The H(2)O(2) requirement seems to be related to initial COD of the sample. FeSO(4)/H(2)O(2) ratios found were not changed for both concentrations. The temperature affected the COD removal significantly at high degrees. Toxicity was completely removed for each concentration of RB5 at optimum removal conditions.

Reactive brilliant red X3B, one recalcitrant textile dye, was decolorized in water by (Photo)-Fenton reactions and TiO(2) photocatalysis [Chemosphere 43 (2001) 1103]. Complementary to this study, the present work has shown the effectiveness of several Keggin-type heteropolyoxomatalates (POM) as a photocatalyst for X3B degradation in water at pH 1.0 under UV light (lambda/=320 nm) irradiation. Among four POMs, the relative activity was observed to be H(3)PW(12)O(40)z.Gt;H(4)SiW(12)O(40)H(4)GeW(12)O(40)H(3)PMo(12)O(40). The reaction was dependent of pH, light intensity and the catalyst loading, but not obviously of the molecular oxygen dissolved in water. Compared to the photocatalyst of TiO(2) (Degussa p25), H(3)PW(12)O(40) was less efficient for the dye bleaching and mineralization. The mechanism study reveals that hydroxyl radicals are involved in the degradation of X3B (and Rhodamine B) by POM photocatalysis.

Wet air oxidation of a prepared reactive dye solution was performed to assess the efficacy of CoAlPO(4)-5 and CeO(2) as catalysts in the reaction. Via adsorption and oxidation of dye, CoAlPO(4)-5 effectively decreased American Dye Manufacturers Institute and chemical oxygen demand (COD) values in the dye solution. At a reaction temperature of 135 degrees C and an applied pressure of 1.0 MPa, color and COD removal were as high as 95% and 90%, respectively, after 2 h. Active sites on the outer surface of CoAlPO(4)-5 are responsible for adsorption and decomposition of dye while active sites in the pores dominate further destruction and oxidation of intermediate products. Since the outer surface only represents a minor part of the total surface, the color removal does not increase appreciably with loading of CoAlPO(4)-5. The CeO(2) catalyst, calcined from cerium chloride under high thermal impact (type A CeO(2)) was very effective in removing color and COD from the solution. This catalyst demonstrated near 100% color removal at temperatures above 135 degrees C and the COD removal could be above 95% at 165 degrees C. With both CoAlPO(4)-5 and CeO(2) catalysts, COD rose and then fell back during the reaction, a feature typical of a consecutive reaction. In contrast to prepared CeO(2), a commercial CeO(2) did not exhibit any catalytic ability for the removal of color and COD. The durability of both CoAlPO(4)-5 and prepared CeO(2) is considered to be fair.

Pre-ozonation of 14 different reactive dyestuff hydrolysates at alkaline pH was investigated to assess possible relationships between ozone transfer efficiency, first order decolourization kinetics, release of initially complexed heavy metals and relative changes in the biodegradability of the partially oxidized dye waste samples. Biocompatibility of the raw (untreated) and ozonated dye hydrolysates was comparatively tracked through specific oxygen uptake rate measurements from which the respirometric inhibition of biological activated sludge imparted by raw and ozonated reactive dye wastewater with respect to synthetic domestic wastewater was determined. It could be demonstrated that preliminary ozonation of reactive azo dyes increases their biological compatibility more significantly than formazan copper complex, copper complex azo and phythalocyanine dyes as a consequence of heavy metal release associated with the cleavage of associated chromophoric groupings right at the initial stages of pre-ozonation.

Biosorption capacities and rates of different kinds of dried yeasts (Saccharomyces cerevisiae, Schizosaccharomyces pombe, Kluyveromyces marxianus, Candida sp., C. tropicalis, C. lipolytica, C. utilis, C. quilliermendii and C. membranaefaciens) for Remazol Blue reactive dye from aqueous solutions were compared under laboratory conditions as a function of initial pH and initial dye concentration. Optimum initial biosorption pH was determined as 2 for all the yeasts. All the yeast species showed comparable and very high dye sorption at 100 mg/l initial dye concentration. The equilibrium sorption capacity of the biomass increased with increasing initial dye concentration up to 400 mg/l for Candida sp. C. lipolytica and C. tropicalis; up to 300 mg/l for C. quilliermendii and C. utilis and up to 200 mg/l for S. cerevisiae, S. pombe, K. marxianus and C. membranaefaciens while the adsorption yield of dye showed the opposite trend for all the yeasts. Among the nine yeast species, C. lipolytica exhibited the highest dye uptake capacity (Q(0) = 250 mg/g). Both the Freundlich and Langmuir adsorption models were found suitable for describing the biosorption of the dye by all the Candida yeasts (except C. membranaefaciens). The results indicated that the dye uptake process followed the pseudo-second-order kinetics for each dye-yeast system.

The operational parameters and mechanism of mineralization of C.I. Reactive Yellow 84 (RY84), one of the azo dyes, in aqueous solution were investigated using sonolytic ozonation (US/O 3 oxidation). Of the pseudo-first-order degradation rate constants of TOC reduction, 9.0 × 10 −4 , 7.3 × 10 −3 and 1.8 × 10 −2 min −1 were observed with US, O 3 , and a combination of US and O 3 , respectively. These results illustrate that ozonation combined with sonolysis for removal of TOC is more efficient than ozonation alone or ultrasonic irradiation alone without considering the operating costs. With the initial pH value at 10.0, the ozone dose at 4.5 g h −1 , the energy density of ultrasound at 176 W l −1 , and the initial concentration of RY84 at 100 mg l −1 , the extent of mineralization measured as TOC loss was maximized. The variation of the concentrations of related ions (oxalate, formate, acetate, NO 3 - , NO 2 - , NH 4 + , Cl − , and SO 4 2 - ) during the reaction process was monitored. Other organic intermediates detected by GC/MS were N -methyleneaniline, phthalic acid, 4-hydroxyphthalic acid, isocyanatobenzene, aniline, 4-iminocyclohexa-2,5-dien-1-one, butene diacid and urea. Based on these findings, a tentative degradation pathway was proposed.

Selected results from the degradation of reactive-dye hydrolysates after UV irradiation, ozonation and sodium peroxodisulphate (NaPS) treatment are presented. Reactive dyes with representative chromophores and anchor groups were chosen for the research project. Different stages of oxidative decolourisation were examined and determined by water parameters for biological degradation (BOD). The paper focuses on toxicity tests with Pseudomonas putida to consider whether the oxidative treatments result in products with a risk for the environment. Tests were performed with the AQUALYTIC® Sensomat System, which measures biological oxygen demand (BOD). It was determined that the chosen oxidative treatments had as a rule no bearing on respiration of P. putida. Experiments with hydrolysates after short-term UV irradiation resulted in a slightly increased but not long-lasting toxicity in comparison with treatments with ozone or NaPS. Toxic effects were found in tests with hydrolysates of metalliferous dyes. During oxidative treatment, metals were liberated from the chromophores. This did cause complete inhibition of respiration of P. putida. Dye Blue E, a member of a dye class with chlorotriazine anchor groups, was itself found to be toxic, caused by the reactivity of the anchor group. The hydrolysate is only of minor toxicity.

A textile dye Reactive Black 5 was used in screening 25 fungal strains for their decolourising ability. The most promising strains were tested in a medium containing specific constituents of a dye bath in order to approach real application conditions. It was shown that the concentrations of the constituents had to be reduced to allow fungal growth. Decolourisation started in cultures of Geotrichum candidum but was not complete. Only Bjerkandera adusta was able to decolourise the black-blue colour through violet and red to pale yellow. After 17 days spectral absorption coefficients, α , at three wavelengths, 620, 525 and 436 nm almost reached the permitted values. A partly purified manganese peroxidase prepared from B. adusta was tested for decolourisation of several artificial dye baths. The constituents seemed not to be inhibitory to the enzyme and no dilution was necessary. Evaluation of decolourisation gave different results, depending on the method used. The most efficient decolourisation on a percentage basis was observed in the dye bath of the anthraquinone dye Reactive Blue 19, followed by the diazo dye Reactive Black 5. However, based on absorbance units, the largest reduction was achieved with the Reactive Black 5 and Acid Orange 7 dye baths. Comparing the α values after 120 h fungal and enzymatic treatments of Reactive Black 5 dye bath the enzyme showed about 1.5 times greater colour reduction than the fungus. Given the tolerance to the constituents and concentration of dye baths, the enzyme proved to be a promising tool for their treatment.

Basic oxygen furnace slag (BOF slag) is a solid waste arisen from the steel making process. FeO is one of the major components of BOF slag. The FeO-containing property of BOF slag makes it possible to catalyze the Fenton reaction. Reactive Black 5 (RB5) dye is chosen as the target compound in this study. This study has investigated the catalytic performance of BOF slag on the Fenton reaction to decompose RB5 in aqueous solution. A first-order kinetic model with respect to TOC was adopted to explain the mineralization of RB5 by the H 2 O 2 /BOF slag process. The experimental results in this study suggested that dosage with 1.49 × 10 −4 M min −1 H 2 O 2 and 12.5 g l −1 BOF slag in the solution at pH 2 provided the optimal operation conditions for the mineralization of RB5 yielding a 51.2% treatment efficiency at 100 min reaction time, and complete decoloration can be achieved within 30 min reaction time. The H 2 O 2 /Fe 2+ ratio was then determined to be 6.06:1.

Immobilized peroxidases from Momordica charantia were highly effective in decolorizing reactive textile dyes compared to its soluble counterpart. Dye solutions, 50-200 mg/l, were treated with soluble and immobilized bitter gourd peroxidases (specific activity of 99.0 EU per mg protein). The decolorization of dyes with soluble and immobilized enzyme was maximum in the range of pH 3.0-4.0. The effect of different temperatures on the dye decolorization was monitored and it was observed that all the dyes were maximally decolorized at 40 degrees C. In order to examine the operational stability of the immobilized preparation, the enzyme was repeatedly exploited for the decolorization of the dyes from fresh batch of dye solutions. Even after 10 cycles in each case the immobilized preparation retained nearly 50% of the initial enzyme activity. The immobilized enzyme exhibited more than 90% of the original activity while the soluble enzyme lost 33% of the initial activity when stored for 40 d at room temperature. Mixtures of three, four and eight dyes were prepared and treated with soluble and immobilized bitter gourd peroxidase. Each mixture was decolorized by more than 80% when treated with immobilized enzyme. Dyeing effluent collected from local dyers was treated with both types of enzyme preparations. Immobilized enzyme was capable of removing remarkably high concentration of color from the effluent. TOC content of soluble and immobilized enzyme treated individual dyes, mixture of dyes and dyeing effluent was determined and it was observed that higher TOC was removed after treatment with immobilized enzyme.

Alginate-immobilized Trametes versicolor decolorized Amaranth at similar rates in repeated batch culture when the dye was present in either (i) modified Kirk's medium containing 0.22 gl(-1) ammonium tartrate, (ii) the same buffer, thiamine, trace elements and glucose concentrations as in the modified Kirk's medium, or (iii) glucose alone at either 1, 5 or 10 gl(-1). With glucose alone (0.5 gl(-1)), Amaranth, Reactive Black 5, Reactive Blue 19 and Direct Black 22 had first-order decoloration rate constants of 0.56, 0.76, 0.52, and 0.15 h(-1), respectively. Mixtures of these dyes were also completely decolorized. After four successive decolorations, beads were kept in storage solutions for 48 d at 6 degrees C. CaCl2 (1g l(-1)) was the best storage solution as the beads were easier to handle and had the fastest decoloration rates after storage. Decoloration rates were faster with lower viscosity (less than 2000 cps) alginates and with softer beads which had a lower resistance to compression. Fungal colonization of the beads resulted in higher biomass concentrations with a corresponding higher decoloration rate but the beads became larger, had a lower resistance to compression and a higher percentage of bead breakage in a stirred tank reactor. Biomass, recovered from beads in which there was no growth, could be dispersed while the biomass from colonized beads formed a hollow, spherical shell due to growth on and near the bead surface and no growth in the bead interior. If alginate-immobilized T. versicolor is to be used in a stirred tank reactor, a high biomass loading during the immobilization phase and no fungal growth in the beads is recommended to have high decoloration rates and low bead breakage.

We tried to decolorize mixtures of four reactive textile dyes, including azo and anthraquinone dyes, by a white-rot basidiomycete Phanerochaete sordida . P. sordida decolorized dye mixtures (200 mg l −1 each) by 90% within 48 h in nitrogen-limited glucose–ammonium media. Decolorization of dye mixtures needed Mn 2+ and Tween 80 in the media. Manganese peroxidase (MnP) played a major role in dye decolorization by P. sordida . Decolorization of dye mixtures by P. sordida was partially inhibited by polyvinyl alcohol (PVA) that wastewaters from textile industries often contain. This was caused by an inhibitory effect of PVA on the decolorization of Reactive Red 120 (RR120) with MnP reaction system. Second addition of Tween 80 to the reaction mixtures in the presence of PVA improved the decolorization of RR120. These results suggest that PVA could interfere with lipid peroxidation or subsequent attack to the dye.

This study investigated Fenton and Fenton-like reactions at low iron concentration (≦10 mg l−1) to oxidize three commercial azo dyes, namely Red MX-5B, Reactive Black 5 and Orange G. In some local cases in Taiwan, wastewater color was found to be the only problem in meeting local effluent standards. This investigation reveals that both of these methods can remove the color of these dyes completely. Moreover they only produce little sludge in wastewater that meet local effluent standards and do not need to further treat. The effects of Fe2+, Fe3+, H2O2 and solution pH on dye decolorization are demonstrated in detail. The optimum pH for both Fenton and Fenton-like reactions in this study are about pH 2.5–3.0. Increasing the dose of ferric nitrate enhances the dye decolorization. The optimal levels of H2O2 required for the process are also examined. High levels of H2O2 appear to reduce dye decolorization. In addition, it is also found that decolorization of azo dyes undergoes a faster reaction rate than mineralization of azo dyes.

Degradation of 20 different dyes in aqueous solutions by the Fenton process was performed. These dyes include 6 types: acidic, reactive, direct, cationic, disperse and vat dyes. The former four types of dyes were decolorized and their TOC values were decreased greatly, while the color and TOC removals of the latter two types were lower. The catalytic activities of four metal ions on the degradation efficiencies of Vat Blue BO, which was chosen as a model dye because of its lowest color and TOC removals, were compared in the dark and under the ultraviolet light irradiation. The catalytic ability of different metals was Fe2+>Cu2+>Mn2+>Ag+ in the dark, and the same sequence was obtained under irradiation condition with greater degradation efficiency. Furthermore, the efficiencies of three oxidation processes, including H2O2/UV, Fe2+/H2O2 and Fe2+/H2O2/UV were compared. The results showed that the oxidation by Fe2+/H2O2/UV was the strongest, and even greater than the arithmetic sum of the other two processes, which suggests the synergistic effect of ultraviolet and ferrous ions on the degradation reaction.

A kinetic model for the decolorization of C.I. Reactive Black 5 by the combination of hydrogen peroxide and UV radiation was developed based on experimental results and known chemical and photochemical reactions. The observed kinetic reaction coefficient was determined and correlated as a function of hydrogen peroxide concentration and UV intensity. The validity of the rate expression was tested experimentally in a parameterization study. The decolorization rate follows pseudo-first order kinetics with respect to dye concentration. The rate increases linearly with UV intensity and nonlinearly with increasing hydrogen peroxide concentration, going from a linear relationship at low H(2)O(2) concentrations to a maximum as hydrogen peroxide concentration continues to increase. The decolorization rate expression derived from the proposed reaction mechanism was reconciled with that used for correlating the experimental data.

A batch system was applied to study the adsorption of reactive dye (reactive red 189) from aqueous solutions by cross-linked chitosan beads. The ionic cross-linking reagent sodium tripolyphosphate was used to obtain more rigid chitosan beads. To stabilize chitosan in acid solutions, chemical cross-linking reagent epichlorohydrin (ECH), glutaraldehyde and ethylene glycol diglycidyl ether was used and ECH shows a higher adsorption capacity. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms at different particle sizes and isotherm constants were determined. The Langmuir model agrees very well with experimental data and its calculated maximum monolayer adsorption capacity has very large value of 1802-1840 (g/kg) at pH 3.0, 30 degrees C. The kinetics of the adsorption with respect to the initial dye concentration, temperature, pH, ionic strength, and wet/dry beads were investigated. The pseudo-first-order, second-order kinetic models and intraparticle diffusion model were used to describe the kinetic data and the rate constants were evaluated. The dynamical data fit well with the second-order kinetic model, except for the dry beads fitting better with the first-order model. The adsorption capacity increases largely with decreasing solution pH or with increasing initial dye concentration. Thermodynamic parameters such as change in free energy (deltaG(0)), enthalpy (deltaH(0)), entropy (deltaS(0)) and activation energy were also determined. The adsorption mechanism is shown to be the electrostatic interactions between the dye and chitosan beads. The desorption data shows that the removal percent of dye RR 189 from the cross-linked chitosan beads is 63% in NaOH solutions at pH 10.0, 30 degrees C. The desorbed chitosan beads can be reused to adsorb the dye and to reach the same capacity as that before desorption.

The toxicity of 17 selected process effluents, 11 reactive dyestuffs and 8 auxiliaries from a textile dyeing and finishing mill in Ayazaga, Istanbul, Turkey was evaluated by bioluminescence test using bacteria Vibrio fischeri in LUMIStox 300. The EC20 and EC50 for auxiliaries, the EC20 for dyestuffs were determined. For selected process effluents GL-values, the dilution level at which a wastewater sample causes less than 20% inhibition, were examined. Our results demonstrate that the toxicity assessment with luminescent bacteria is effective and of practical use for chemicals applied in textile finishing industry with the limitation of the deep dark-colored dye bath samples and for the related effluents. Inhibition effects of numerous dyestuffs as well as auxiliaries to luminescent bacteria differed considerably with a range 5-600 mg 1(-1) for EC20 and 9-6930 mg 1(-1) for EC50, respectively. Among 17 effluents, 1 sample exhibited high toxicity (GL = 100), 7 showed moderate toxicity (GL = 12 32), and 9 had a GL-value

This work reports the semiconductor-assisted photochemical degradation of reactive dyes. In an oxygenated-UV-ZnO system almost total decolorization of Remazol Brilliant Blue R, Remazol Black B, Reactive Blue 221 and Reactive Blue 222 was observed in reaction times of about 60 min. Extending the photochemical treatment up to 120 min, mineralization higher than 80% for all the dyes was observed. During the same period, the residual acute toxicity was significantly reduced only for Remazol Black B. A systematic optimization study carried out by factorial design showed that for the reactive dyes tested, the ZnO semiconductor exhibits a better efficiency than that observed with anatase TiO2. A synergistic effect in the coupled TiO2-ZnO system was not observed.