Influence of organic and inorganic compounds on oxidoreductive decolorization of sulfonated azo dye C.I. Reactive Orange 16

An isolated bacterial strain is placed in the branch of the Bacillus genus on the basis of 16S rRNA sequence and biochemical characteristics. It decolorized an individual and mixture of dyes, including reactive, disperse and direct. Bacillus sp. ADR showed 88% decolorization of sulfonated azo dye C.I. Reactive Orange 16 (100 mg L⁻¹) with 2.62 mg of dye decolorized g⁻¹ dry cells h⁻¹ as specific decolorization rate along with 50% reduction in COD under static condition. The optimum pH and temperature for the decolorization was 7–8 and 30–40 °C, respectively. It was found to tolerate the sulfonated azo dye concentration up to 1.0 g L⁻¹. Significant induction in the activity of an extracellular phenol oxidase and NADH–DCIP reductase enzymes during decolorization of C.I. Reactive Orange 16 suggest their involvement in the decolorization. The metal salt (CaCl₂), stabilizers (3,4-dimethoxy benzyl alcohol and o-tolidine) and electron donors (sodium acetate, sodium formate, sodium succinate, sodium citrate and sodium pyruvate) enhanced the C.I. Reactive Orange 16 decolorization rate of Bacillus sp. ADR. The 6-nitroso naphthol and dihydroperoxy benzene were final products obtained after decolorization of C.I. Reactive Orange 16 as characterized using FTIR and GC–MS.     

Ecofriendly biodegradation and detoxification of Reactive Red 2 textile dye by newly isolated Pseudomonas sp. SUK1

The aim of this work is to evaluate textile dyes degradation by novel bacterial strain isolated from the waste disposal sites of local textile industries. Detailed taxonomic studies identified the organisms as Pseudomonas species and designated as strain Pseudomonas sp. SUK1. The isolate was able to decolorize sulfonated azo dye (Reactive Red 2) in a wide range (up to 5 g l(-1)), at temperature 30 degrees C, and pH range 6.2-7.5 in static condition. This isolate also showed decolorization of the media containing a mixture of dyes. Measurements of COD were done at regular intervals to have an idea of mineralization, showing 52% reduction in the COD within 24h. Induction in the activity of lignin peroxidase and azoreductase was observed during decolorization of Reactive Red 2 in the batch culture, which represented their role in degradation. The biodegradation was monitored by UV-vis, IR spectroscopy, HPLC. The final product, 2-naphthol was characterized by GC-mass spectroscopy. The phytotoxicity study revealed the degradation of Reactive Red 2 into non-toxic product by Pseudomonas sp. SUK1.     

Decolorization of different dyes by a newly isolated white-rot fungi strain Ganoderma sp.En3 and cloning and functional analysis of its laccase gene

A laccase-producing white-rot fungi strain Ganoderma sp.En3 was newly isolated from the forest of Tzu-chin Mountain in China. Ganoderma sp.En3 had a strong ability of decolorizing four synthetic dyes, two simulated dye bath effluents and the real textile dye effluent. Induction in the activity of laccase during the decolorization process indicated that laccase played an important role in the efficient decolorization of different dyes by this fungus. Phytotoxicity study with respect to Triticum aestivum and Oryza sativa demonstrated that Ganoderma sp.En3 was able to detoxify four synthetic dyes, two simulated dye effluents and the real textile dye effluent. The laccase gene lac-En3-1 and its corresponding full-length cDNA were then cloned and characterized from Ganoderma sp.En3. The deduced protein sequence of LAC-En3-1 contained four copper-binding conserved domains of typical laccase protein. The functionality of lac-En3-1 gene encoding active laccase was verified by expressing this gene in the yeast Pichia pastoris successfully. The recombinant laccase produced by the yeast transformant could decolorize the synthetic dyes, simulated dye effluents and the real textile dye effluent. The ability of decolorizing different dyes was positively related to the laccase activity. In addition, the 5′-flanking sequence upstream of the start codon ATG in lac-En3-1 gene was obtained. Many putative cis-acting responsive elements were predicted in the promoter region of lac-En3-1.     

Degradation of immobilized azo dyes by Klebsiella sp. UAP-b5 isolated from maize bioadsorbent

The degradation of two immobilized dyes by Klebsiella sp. UAP-b5 was studied. In batch experiments, the azo dyestuffs Basic Blue 41 and Reactive Black 5 were immobilized onto corn cobs by adsorption, and the adsorption process was characterized by a pseudo-second-order kinetic equation. Klebsiella sp. UAP-b5 was previously isolated from the corn waste and shown to decolorize these dyes in liquid systems. Here, we demonstrate anaerobic decolorization and reductive biodegradation of these dyes by means of spectrophotometry, HPLC, and IR spectroscopy of the solid waste and desorption solutions. We also demonstrate adsorption of compounds that resemble known degradation products.     

Bioaugmentation on decolorization of C.I. Direct Blue 71 by using genetically engineered strain Escherichia coli JM109 (pGEX-AZR)

The study showed that Escherichia coli JM109 (pGEX-AZR), the genetically engineered microorganism (GEM) with higher ability to decolorize azo dyes, bioaugmented successfully the dye wastewater bio-treatment systems to enhance C.I. Direct Blue 71 (DB 71) decolorization. The control and bioaugmented reactors failed at a around pH 5.0. However, the bioaugmented one succeeded at around pH 9.0, the influent DB 71 concentration was 150 mg/L, DB 71 concentration was decreased to 27.4 mg/L in 12h. The 1-3% NaCl concentration of bioaugmented reactors had no definite influence on decolorization, DB 71 concentration was decreased to 12.6 mg/L in 12h. GEM was added into anaerobic sequencing batch reactors (AnSBRs) to enhance DB 71 decolorization. Continuous operations of the control and bioaugmented AnSBRs showed that E. coli JM109 (pGEX-AZR) could bioaugment decolorization. The concentrations of activated sludge and GEM were still more than 2.80 g/L and 1.5 x 10(6)cells/mL, respectively, in the bioaugmented AnSBR. All the microbial communities changed indistinctively with time. The microbial community structures of the control AnSBR were similar to those of the bioaugmented one.     

Optimization of Fenton-biological treatment scheme for the treatment of aqueous dye solutions

Degradation of dyes especially, azo dyes are difficult due to their complex structure and synthetic nature. The main objective of this study was to evaluate the Fenton-biological (aerobic) treatment train for decolorization and mineralization of azo dyes viz. Reactive Black 5 (RB5), Reactive Blue 13 (RB13) and Acid Orange 7 (AO7). The objective of Fenton treatment was only to decolorize the dyes (breakage of -NN-), as it was considered that after breakage of -NN-, the dyes will become amenable to biodegradation and can be further treated in aerobic biological system. Hence studies were carried out to optimize the lower Fenton's doses for decolorization of dyes. The optimum doses for decolorization (>95%) of all the three dyes were found out to be 15 mgL(-1) of Fe(2+) (0.27 mM) and 50 mgL(-1) (1.47 mM) of H(2)O(2) dose at optimum pH 3. Further it was also investigated that at lower doses, the main problem of Fenton process (sludge generation) can also be minimized. Later the mineralization of the dye (removal of aromatic amines) was achieved in the aerobic biological treatment system. Overall reduction of 64, 89 and 75% in the aromatic amines (at 254 nm), 88, 95 and 78% in naphthalene ring associated compounds (near 310 nm) and 49, 89 and 91% reduction in benzene ring associated compounds (near 226 nm) were observed for RB5, RB13 and AO7, respectively. Thus this treatment system seems to be quite effective and economical option for the treatment of recalcitrant compounds like dyes, as the cost in the chemical treatment is considered mainly due to chemicals thus at lower doses the operational cost is saved. Further, as the sludge generation was almost negligible at lower doses, thus the savings in cost of handling and disposal of hazardous sludge also adds to economy of treatment.     

Exploring effects of chemical structure on azo dye decolorization characteristics by Pseudomonas luteola

This follow-up study tended to provide a systematic comparison for how the variation of functional groups and molecular structures present in model azo dyes affects color removal capability of Pseudomonas luteola. As sulfo group at methyl orange (p-MO) or carboxyl group at 4-(4'-dimethylaminophenylazobenzoic acid) sodium salt (denoted p-MR) were both para to azo bond, the ranking of decolorization rate was p-MO>p-MR due to the stronger electron-withdrawing effect of the sulfo group. For isomers, when the functional groups (sulfo group at 2-(4'-dimethylamino-phenylazo) benzenesulfonic acid sodium salt (o-MO) or carboxyl group at methyl red (o-MR)) were ortho to azo bond, the decolorization rate significantly decreased (e.g., p-MO>o-MO or p-MR>o-MR) likely due to steric hindrance near azo linkage(s). Similarly, for phenolic azo dyes the series of decolorization rate was 3-(4'-dimethylaminophenylazo) phenol (m-OH)>2-(4'-dimethylaminophenylazo) phenol (o-OH). Apparently, azo dyes with different properties of substituent on aromatic ring could affect the efficiency of biodecolorization of P. luteola. Moreover, the relative position (e.g., ortho, meta, para) of the substituent to azo bond could also influence the capability of biodecolorization of P. luteola. Regarding the electronic effect, azo dyes with stronger electron-withdrawing group (e.g., sulfo group) at specific positions (e.g., at para) could be more easily biodecolored than those with a carboxyl group.     

Decolorization of sulfonated azo dye Metanil Yellow by newly isolated bacterial strains: Bacillus sp. strain AK1 and Lysinibacillus sp. strain AK2

Two different bacterial strains capable of decolorizing a highly water soluble azo dye Metanil Yellow were isolated from dye contaminated soil sample collected from Atul Dyeing Industry, Bellary, India. The individual bacterial strains Bacillus sp. AK1 and Lysinibacillus sp. AK2 decolorized Metanil Yellow (200 mg L(-1)) completely within 27 and 12h respectively. Various parameters like pH, temperature, NaCl and initial dye concentrations were optimized to develop an economically feasible decolorization process. The maximum concentration of Metanil Yellow (1000 mg L(-1)) was decolorized by strains AK2 and AK1 within 78 and 84 h respectively. These strains could decolorize Metanil Yellow over a broad pH range 5.5-9.0; the optimum pH was 7.2. The decolorization of Metanil Yellow was most efficient at 40°C and confirmed by UV-visible spectroscopy, TLC, HPLC and GC/MS analysis. Further, both the strains showed the involvement of azoreductase in the decolorization process. Phytotoxicity studies of catabolic products of Metanil Yellow on the seeds of chick pea and pigeon pea revealed much reduction in the toxicity of metabolites as compared to the parent dye. These results indicating the effectiveness of strains AK1 and AK2 for the treatment of textile effluents containing azo dyes.     

Optimization of process variables for decolorization of Disperse Yellow 211 by Bacillus subtilis using Box-Behnken design

Decolorization of textile azo dye Disperse Yellow 211 (DY 211) was carried out from simulated aqueous solution by bacterial strain Bacillus subtilis. Response surface methodology (RSM), involving Box-Behnken design matrix in three most important operating variables; temperature, pH and initial dye concentration was successfully employed for the study and optimization of decolorization process. The total 17 experiments were conducted in the study towards the construction of a quadratic model. According to analysis of variance (ANOVA) results, the proposed model can be used to navigate the design space. Under optimized conditions the bacterial strain was able to decolorize DY 211 up to 80%. Model indicated that initial dye concentration of 100 mgl(-1), pH 7 and a temperature of 32.5 degrees C were found optimum for maximum % decolorization. Very high regression coefficient between the variables and the response (R(2)=0.9930) indicated excellent evaluation of experimental data by polynomial regression model. The combination of the three variables predicted through RSM was confirmed through confirmatory experiments, hence the bacterial strain holds a great potential for the treatment of colored textile effluents.     

Kinetic study approach of remazol black-B use for the development of two-stage anoxic-oxic reactor for decolorization/biodegradation of azo dyes by activated bacterial consortium

The laboratory-isolated strains Pseudomonas aeruginosa, Rhodobacter sphaeroides, Proteus mirabilis, Bacillus circulance, NAD 1 and NAD 6 were observed to be predominant in the bacterial consortium responsible for effective decolorization of the azo dyes. The kinetic characteristics of azo dye decolorization by bacterial consortium were determined quantitatively using reactive vinyl sulfonated diazo dye, remazol black-B (RB-B) as a model substrate. Effects of substrate (RB-B) concentration as well as different substrates (azo dyes), environmental parameters (temperature and pH), glucose and other electron donor/co-substrate on the rate of decolorization were investigated to reveal the key factor that determines the performance of dye decolorization. The activation energy (E(a)) and frequency factor (K(0)) based on the Arrhenius equation was calculated as 11.67 kcal mol(-1) and 1.57 x 10(7)mg lg MLSS(-1)h(-1), respectively. The Double-reciprocal or Lineweaver-Burk plot was used to evaluate V(max), 15.97 h(-1) and K(m), 85.66 mg l(-1). The two-stage anoxic-oxic reactor system has proved to be successful in achieving significant decolorization and degradation of azo dyes by specific developed bacterial consortium with a removal of 84% color and 80% COD for real textile effluents vis-à-vis >or=90% color and COD removal for synthetic dye solution.     

Toxicity of textile dyes and their degradation by the enzyme horseradish peroxidase (HRP)

The enzyme peroxidase is known for its capacity to remove phenolic compounds and aromatic amines from aqueous solutions and also to decolorize textile effluents. This study evaluates the potential of the enzyme horseradish peroxidase (HRP) in the decolorization of textile dyes and effluents. Some factors such as pH and the amount of H(2)O(2) and the enzyme were evaluated in order to determine the optimum conditions for the enzyme performance. For the dyes tested, the results indicated that the decolorization of the dye Remazol Turquoise Blue G 133% was approximately 59%, and 94% for the Lanaset Blue 2R; for the textile effluent, the decolorization was 52%. The tests for toxicity towards Daphnia magna showed that there was a reduction in toxicity after the enzymatic treatment. However, the toxicity of the textile effluent showed no change towards Artemia salina after the enzyme treatment. This study verifies the viability of the use of the enzyme horseradish peroxidase in the biodegradation of textile dyes.     

Controllable synthesis of self-assembled Cu2S nanostructures through a template-free polyol process for the degradation of organic pollutant under visible light

Cu₂S nanostructures were fabricated by polyol method and then characterized by X-ray diffractometer, scanning electron microscopy, transmission electron microscopy (TEM) and high resolution TEM. The morphologically different Cu₂S nanostructures such as vertically nanorod arrays, nanoflowers assembled by nanorod arrays, nanoparticles and nanowires, can be successfully synthesized under different experimental conditions. The growth mechanism for the different nanostructures is proposed. The photocatalytic activity of the prepared samples was evaluated based on the degradation of organic pollutant, active brilliant red X-3B (X-3B), under visible light. Among the Cu₂S nanostructures, self-assembled nanoflowers have the highest photocatalytic activity. In addition, the prepared Cu₂S nanostructures are found to be able to decolorize X-3B with iron ions for the formation of Fenton reagent. This study provides a more choice to prepare self-assembled nanostructures for the application of environmental pollution control.     

Degradation of azo dye active brilliant red X-3B by composite ferrate solution

Composite ferrate(VI) solution (CFS) with improved stability was successfully prepared in this study. The stability of Fe(VI) increased from hours for potassium ferrate at pH 9-10 to 16d for 1 mmol L(-1) Fe(VI) in CFS at 25 degrees C, decomposing 24%. The Fe(VI) was more stable at low concentration (1 mmol L(-1)) than that at high concentration (10 mmol L(-1)). The degradation of the azo dye reactive brilliant red X-3B (X-3B) by CFS was investigated. The results showed that pH, initial dye concentration and CFS dosage affected the degradation efficiency. For 0.08 mmol L(-1) X-3B simulate wastewater, the optimal pH and CFS dosage were 8.4 and 25 mg L(-1) (as K(2)FeO(4)), and about 99% X-3B was decolorized after 20 min under this conditions. The color decay was considerably faster than the decrease in COD and TOC, which was attributed to the ease of chromophore destruction. Compared with the decolorization, the removal percentage of COD and TOC were 42% and 9% after 60 min, respectively. The Fe(VI) and ClO(-) were contained in CFS, which have synergetic effect for the degradation of X-3B. Additionally, phthalic acid and muconic acid were identified as intermediates by GC/MS, which was in accordance with the lowered pH with the reaction time. The complete mineralization of X-3B cannot be achieved under the oxidation by CFS. And a tentative pathway for the oxidative degradation of X-3B was postulated.     

Media effects on the optical properties of proton donor group containing azobenzene derivatives

A series of hydroxy and carboxy group containing azobenzene compounds were synthesized and investigated by UV–vis and fluorescence spectroscopy. It could be shown that the ambient medium exerted a strong influence on the absorption behavior and the trans–cis isomerization behavior of the azo compounds. Especially in the case of hydroxy group functionalized azobenzenes, deprotonation with NaOH or a polymeric base changed the spectral behavior of the compounds remarkably. A strong bathochromic shift of the dyes’ longest wavelength absorption band was observed. Furthermore, the influence of different solvents and different polymeric matrices on the trans–cis isomerization behavior of the azobenzenes was investigated. The results are discussed in terms of utilization of the azo dyes as probe molecules for interactions in polymer blends.     

Effects of gap size and UV dosage on decolorization of C.I. Acid Orange 7 by UV/H2O2 process

Wastewater from textile processing plants can be highly colored and difficult to decolorize. During the past few years attention has been drawn to chemical techniques that could be used to textile wastewater decolorization. A crucial feature in designing such systems is the optimization of operating conditions. In the present study, advanced oxidation treatment, the UV/H(2)O(2) process has been applied to decolorization of the azo dye C.I. Acid Orange 7 (AO7) in aqueous solution in a batch photo reactor. The effects of the reactor gap size and UV dosage on decolorization of dye have been investigated. The method of study involved monitoring the rate of dye solution decolorization during irradiation by a low-pressure mercury lamp and varying gap size and volume of the reactor. The rate of color removal was studied by measuring of the absorbance at characteristic wavelength. The gap size of the reactor was adjusted by different depths of the reactor. The results of this study showed that the removal efficiency of AO7 is optimal with 0.3 cm gap size and 83.33 Wl(-1) of UV dosage.     

疏水性阳离子淀粉的制备与应用

采用环氧氯丙烷、乙二胺对可溶性淀粉进行交联改性,制备了疏水性阳离子淀粉(HCS)。通过红外光谱(IR)、X射线衍射(XRD)、扫描电镜(SEM)及紫外-可见光谱(UV)等测试手段对材料的微观相态结构和性能进行了表征。同时,比较了HCS与亲水性聚合氯化铝以及物理吸附剂活性炭的脱色率,考察了投料量、絮体沉降时间以及搅拌速度对脱色率的影响。结果表明,HCS为非定型态,且表面粗糙多孔的物质;投加量为2 g/L,沉降时间仅为20 min时,脱色率即可达到91%,其性能远优于聚合氯化铝和活性炭。     

Photocatalytic degradation of three azo dyes using immobilized TiO2 nanoparticles on glass plates activated by UV light irradiation: Influence of dye molecular structure

In order to discuss the effect of chemical structure on photocatalysis efficiency, the photocatalytic degradation of three commercial textile dyes (C.I. Acid Orange 10 (AO10), C.I. Acid Orange 12 (AO12) and C.I. Acid Orange 8 (AO8)) with different structure and different substitute groups has been investigated using supported TiO₂ photocatalyst under UV light irradiation. All the experiments were performed in a circulation photochemical reactor equipped with a 15-W UV lamp emitted around 365 nm. The investigated photocatalyst was industrial Millennium PC-500 (crystallites mean size 5–10 nm) immobilized on glass plates by a heat attachment method. SEM images of the immobilized TiO₂ nanoparticles showed the good coating on the plates, after repeating the deposition procedure three times. Our results indicated that the photocatalytic decolorization kinetics of the dyes were in the order of AO10 > AO12 > AO8. Photocatalytic mineralization of the dyes was monitored by total organic carbon (TOC) decrease, changes in UV–vis spectra and ammonium ion formation. The dye solutions could be completely decolorized and effectively mineralized, with an average overall TOC removal larger than 94% for a photocatalytic reaction time of 6 h. The nitrogen-to-nitrogen double bond of the azo dyes was transformed predominantly into NH₄⁺ ion. The kinetic of photocatalytic decolorization of the dyes was found to follow a first-order rate law. The photocatalysis efficiency was evaluated by figure-of-merit electrical energy per order (E_EO).     

Inorganic polyphosphate accumulation by Cunninghamella elegans (UCP 542) and its influence in the decolorization of textile azo dye Orange II

The inappropriate disposal of dyes in wastewater constitutes an environmental problem and can cause damage to the ecosystem. Alternative treatments have been reported that employ fungi that are particularly effective in the decolorization of textile effluents. In these methods, the biomass can be used for industrial removal of dyes by biosorption. The current study has investigated the accumulation of polyphosphate (poly P) in the fungus Cunninghamella elegans UCP 542 and evaluated the capacity of the inactivated biomass, obtained from 144 h of incubation, to decolorize the dye Orange II. The results suggest the transport of the inorganic phosphorus, as demonstrated through the cellular bioaccumulation. The biochemical and physiological aspects of bioaccumulation in the poly P form were related to the process of removal of the color of Orange II, with the reduction of 60 % of the dye solution.     

Comparative study on reaction selectivity of azo dye decolorization by Pseudomonas luteola

This study is to inspect how the variation of molecular structures and functional groups present in our model azo dyes (i.e., Congo red, Eriochrome black T (EBT), methyl orange, and methyl red) affects biodecolorization capability of Pseudomonas luteola. The most viable decolorization was found at pH 7-9 and the optimal cellular age for the most effective decolorization was 7 days after static incubation in dye-free cultures. In decolorization, the maximal absorption wavelength in UV-vis spectra for the different dye-containing cultures shifted from visible light range towards the ultraviolet visible range. Methyl red was not decolorized in contrast to methyl orange, Congo red, and Eriochrome black T. The sulfonic group para to azo bond (-N=N-) in methyl orange was a strong electron-withdrawing group through resonance to cause an enhancement of color removal to be easily biodecolorized. As a charged carboxyl group on methyl red is at ortho position (i.e., in the proximity) to azo bond, this led to a complete inhibition to decolorization. However, decolorization of Congo red and EBT in the absence of charged group (e.g., hydroxy or amino group) near azo bond was not completely repressed like methyl red. Thus, the presence of electron-withdrawing groups as the substituents on azo dyes enhanced decolorization capability for biodegradability. In addition, Monod kinetic model provided better predictions to all dye decolorization at initial short periods of time due to negligible intermediate formed at initial short time duration, but significant intermediate accumulation took place at longer period of time. In contrast, the decolorization performances of methyl orange at 400ppm and EBT at 230ppm were significantly less than those predicted from the Monod kinetic model likely due to accumulated intermediates exceeding the threshold levels for feedback inhibition.     

Degradation of azo dyes by sequential Fenton's oxidation and aerobic biological treatment

A two stage sequential Fenton's oxidation followed by aerobic biological treatment train was used to achieve decolorization and to enhance mineralization of azo dyes, viz. Reactive Black 5 (RB5), Reactive Blue 13 (RB13), and Acid Orange 7 (AO7). In the first stage, Fenton's oxidation process was used while in the second stage aerobic sequential batch reactors (SBRs) were used as biological process. Study was done to evaluate effect of pH on Fenton's oxidation process. Results reveal that pH 3 was optimum pH for achieving decolorization and dearomatization of dyes by Fenton's process. Degradation of dye was assessed by COD reduction and reduction in aromatic amines (naphthalene chromophores) which was measured by reduction in absorbance at 200 nm. More than 95% of color was removed with Fenton's oxidation process in all dyes. In overall treatment train 81.95, 85.57, and 77.83% of COD reduction was achieved in RB5, RB13, and AO7 dyes, respectively. In the Fenton's oxidation process 56, 24.5, and 80% reduction in naphthalene group was observed in RB5, RB13, and AO7, respectively, which further increased to 81.34, 68.73, and 92% after aerobic treatment. Fenton's oxidation process followed by aerobic SBRs treatment sequence seems to be viable method for achieving significant degradation of azo dye.