Study of the degradation of dyes by MnP of Phanerochaete chrysosporium produced in a fixed-bed bioreactor

The production of ligninolytic enzymes by the fungus Phanerochaete chrysosporium in a fixed-bed tubular bioreactor, filled with cubes of nylon sponge, operating in semi-solid-state conditions, was studied. Maximum individual manganese-dependent peroxidase (MnP) and lignin peroxidase (LiP) activities of 1293 and 225 U/l were detected.The in vitro decolourisation of two structurally different dyes (Poly R-478, crystal violet) by the extracellular liquid obtained in the above-mentioned bioreactor was monitored in order to determine its degrading capability. The concentration of some compounds (sodium malonate, manganese sulphate) from the reaction mixture was optimised in order to maximise the decolourisation levels. A percentage of Poly R-478 decolourisation of 24% after 15 min of dye incubation was achieved.On the other hand, a methodology for a long treatment of these dyes based on the continuous addition of MnP enzyme and H(2)O(2) was developed. Moreover, this enzymatic treatment was compared with a photochemical decolourisation process. The former allowed to maintain the degradation rate almost constant for a long time, resulting in a decolourisation percentage of 70% and 30% for crystal violet and Poly R-478, respectively, after 2 h of treatment. As for the latter, it was not able to degrade Poly R-478, whereas crystal violet reached a degradation of 40% in 2 h.     

Fe(3+)- and Cu(2+)-reduction by phenol derivatives associated with Azure B degradation in Fenton-like reactions

Several phenol derivatives were evaluated regarding their capacities for Fe(3+) and Cu(2+) reduction. Selected compounds were assayed in Fenton-like reactions to degrade Azure B. 3,4-Dihydroxyphenylacetic, 2,5-dihydroxyterephtalic, gallic, chromotropic and 3-hydroxyanthranilic acids were the most efficient reducers of both metallic ions. The reaction system composed of 3-hydroxyanthranilic acid/Fe(3+)/H(2)O(2) was able to degrade Azure B at higher levels than the conventional Fenton reaction (87% and 75% of decolorization after 20min reaction, respectively). Gallic and syringic acids, catechol and vanillin induced Azure B degradations at lower levels as compared with conventional Fenton reaction. Azure B was not degraded in the presence of 10% (v/v) methanol or ethanol, which are OH radical scavengers, confirming the participation of this radical in the degradation reactions. Iron-containing reactions consumed substantially more H(2)O(2) than reactions containing copper. In iron-containing reactions, even the systems that caused a limited degradation of the dye consumed high concentrations of H(2)O(2). On the other hand, the reactions containing Fe(3+), H(2)O(2) and 3-hydroxyanthranilic acid or 3,4-dihydroxyphenylacetic acid were the most efficient on degradation of Azure B and also presented the highest H(2)O(2) consumption. These results indicate that H(2)O(2) consumption occurs even when the dye is not extensively degraded, suggesting that part of the generated OH radicals reacts with the own phenol derivative instead of Azure B.     

Decolorization and degradation of H-acid and other dyes using ferrous-hydrogen peroxide system

In this study, advanced oxidation process utilizing Fenton's reaction was investigated for the decolorization and degradation of two commercial dyes viz., Red M5B, Blue MR and H-acid, a dye intermediate used in chemical industries for the synthesis of direct, reactive and azo dyes. Effect of Fe2 +, H2O2, pH, and contact time on the degradation of the dyes was studied. Maximum color and COD removal was obtained for Red MSB, H-acid and Blue MR at 10-25 mg/l of Fe2+ dose and 400-500 mg/l of H2O2 dose at pH 3.0. The initial oxidation reaction was found to fit into first order rate kinetics and the rate of oxidation of H-acid was higher than the other dyes. Release of chloride and sulfate from the Fenton's treated Red M5B dye and sulfate from H-acid and Blue MR indicates that the dye degradation proceeds through cleavage of the substituent group.     

Degradation of azo dyes using low iron concentration of Fenton and Fenton-like system

This study investigated Fenton and Fenton-like reactions at low iron concentration (相似文献   

缺氧-好氧生物滤池中高效菌对活性红KN-3B的降解特性

为了研究高效脱色菌在缺氧好氧生物滤池（A/O biofilter）中对偶氮染料的降解特性，以活性红KN-3B（C.I. reactive red 180）为降解对象，缺氧生物滤池以火山碎石为填料，接种高效脱色菌CK3柯氏柠檬酸杆菌启动，好氧生物滤池以牡蛎壳为填料，接种污水处理厂活性污泥启动。试验考察了不同工况下缺氧-好氧生物滤池对色度和COD的去除效果，结果表明：生物滤池中微生物对偶氮染料活性红KN-3B的脱色和对COD降解的最适pH条件为弱酸性；缺氧滤池中高效菌对色度的去除需要外加碳源，且增加外加碳源有助于脱色率的提高；该高效菌为耐盐菌，当进水NaCl浓度达30 g/L时，色度去除率仍可达93%以上；当染料负荷达500 mg/L时，脱色率仍可达95%。通过紫外-可见扫描图谱分析初步推断CK-3柯氏柠檬酸杆菌对偶氮染料活性红KN-3B的脱色主要是生物降解作用。     

Decolorization of synthetic dyes using a copper complex with glucaric acid

Selected azo, acridine, triphenyl methane, anthraquinone and thiazine-based dyes were decolorized using a catalytic system consisting of Cu(II)/glucaric acid/H(2)O(2). More than 90% decolorization was obtained with 100 ppm Acridine Orange, Azure B, Chicago Sky Blue, Crystal Violet, Methyl Orange, Poly B-411, Reactive Black 5, Reactive Blue 2, and Remazol Brilliant Blue R within 24 h. Seventy to eighty percent decolorization was achieved within the first 6 h. The decolorizaton was not affected by pH. The involvement of hydroxyl radicals produced in the system in the decolorization of the dye molecules was confirmed by electron spin resonance study.     

高铁酸盐对活性及分散染料的脱色研究

采用湿法制备了高铁酸钾(K₂FeO₄)氧化剂，研究了其对染料活性艳红X-3B(X-3B) 和分散蓝2BLN(2BLN)在不同pH条件下的脱色效果，并对Al₂ (SO₄)₃、K₂FeO₄及O₃对活性及分散染料的脱色效果进行了比较。结果表明：高铁酸钾对活性及分散染料的脱色效果明显， X-3B脱色率随pH的增加不断提高，2BLN脱色率在pH 6～10范围内无明显变化，在pH＝5时达到最大值。在X-3B及2BLN浓度同为100 mg／L，pH分别为10、5， K₂FeO₄浓度分别为100 mg／L和200 mg／L时，BLN及X-3B的脱色率分别达到92.3％和87.3％。在相同条件下，K₂FeO₄对活性艳红X-3B的脱色效果好于Al₂(SO₄)₃和O₃； 而K₂FeO₄对分散蓝2BLN的脱色效果虽比Al₂ (SO₄)₃稍差，但比臭氧的脱色效果要好。同时还研究了K₂FeO₄对活性及分散染料的脱色机理，结果表明： 高铁酸钾对X-3B的脱色依赖于K₂FeO₄的氧化作用，而对的2BLN的脱色则以絮凝为主。     

Decolourization of synthetic dyes by Trametes hirsuta in expanded-bed reactors

The present paper studies the decolourization of different synthetic dyes (Indigo Carmine, Bromophenol Blue, Methyl Orange and Poly R-478) by the white-rot fungus Trametes hirsuta at bioreactor scale under solid-state conditions, operating with ground orange peelings as a support-substrate. Dye decolourization was performed in both batch and continuous mode. Batch cultivation led to high decolourization percentages in a short time (100% for Indigo Carmine in 3h and 85% for Bromophenol Blue in 7 h). As for continuous cultivation, different hydraulic retention times (HRT) were studied (0.8, 1, 1.5 and 3d). The highest decolourization percentages were obtained operating at a HRT of 3d, especially for the dyes Methyl Orange and Poly R-478 (81.4% and 46.9%, respectively). This is a very interesting result, since there are few studies dealing with the continuous decolourization of dyes at bioreactor scale by fungal laccases.     

Electrochemical decolourisation of structurally different dyes

The electrochemical decolourisation of structurally different dyes (bromophenol blue, indigo, poly R-478, phenol red, methyl orange, fuchsin, methyl green and crystal violet) by means of the application of DC electric current was assessed. It was found that the electrochemical process allowed a colour removal of all dyes studied, although the decolourisation rate largely depended on the chemical structure of the different dyes. Nearly complete decolourisation was achieved for bromophenol blue followed by methyl orange and methyl green, whereas phenol red was hardly decolourised (30% in 60 min). In mixtures of two dyes, the decolourisation rate became similar for both dyes. However, the addition of a redox mediator, (Co(2+/3+)) clearly enhanced the degradation rate of all tested dyes, but the simplest dye molecules were attacked firstly, followed by dyes with more complex chemical structures. The results revealed the suitability of the process to effectively decolourise wastewaters from dyeing process.     

Degradation of reactive dyes I. A comparative study of ozonation, enzymatic and photochemical processes

The environmental problems associated with textile activities are represented mainly by the extensive use of organic dyes. A great number of these compounds are recalcitrant and shown carcinogenic or mutagenic character. In this work three processes were studied for degradation of an anthraquinone dye (C.I. reactive blue-19). The ozonation process leads to complete decolorization with a very short reaction time; however, effective mineralization of the dye was not observed. The enzymatic process promotes quick decolorization of the dye; nevertheless, maximum decolorization degrees of about 30% are insignificant in relation to the decolorization degree achieved by the other processes. The best results were found for the photocatalytical process. The use of ZnO or TiO2 as photocatalysts, permits total decolorization and mineralization of the dye with reaction times of about 60 min.     

Mechanism of decolorization and degradation of CI Direct Red 23 by ozonation combined with sonolysis

The decolorization and degradation of CI Direct Red 23, which is suspected to be carcinogenic, were investigated using ozonation combined with sonolysis. The results showed that the combination of ozonation and sonolysis was a highly effective way to remove color from waste water. The operational parameters, namely concentration of the dye, pH, ozone dose and ultrasonic density, were investigated during the process. The decolorization of the dye followed pseudo-first-order kinetics. Increasing the initial concentration of Direct Red 23 led to a decreasing rate constant. The optimum pH for the reaction was 8.0, and both lower and higher pH decreased the removal rate. The effect of the ozone dose on the dye decolorization was much greater than that of the sonolysis density. Intermediates such as naphthalene-2-sulfonic acid, 1-naphthol, urea and acetamide were detected by gas chromatography coupled with mass spectrometry in the absence of pH buffer, while nitrate and sulfate ions and formic, acetic and oxalic acids were detected by ion chromatography. A tentative degradation pathway was proposed without any further quantitative analyses. During the degradation, all nitrogen atoms and phenyl groups of Direct Red 23 were degraded into urea, nitrate ion, nitrogen and formic, acetic and oxalic acids, etc.     

Kinetics of oxidative decolorization and mineralization of Acid Orange 7 by dark and photoassisted Co2+-catalyzed peroxymonosulfate system

A kinetic model was proposed and used to interpret the experimental data for degradation of Acid Orange 7 (AO7) in aqueous solution induced by Co(2+)/peroxymonosulfate (Co/PMS) reagent in terms of both decolorization and mineralization. The pseudo first-order decolorization rate constants are related to [Co(2+)], [PMS], reciprocal of [H(+)] and [AO7](0). Activation energy of the AO7 decolorization process was determined to be 75.7 kJ mol(-1). UV and visible light can accelerate the decolorization and mineralization process due to different mechanisms. In the combined UV/Co/PMS system, UV light can decompose PMS to generate hydroxyl ((*)OH) and sulfate radicals (SO(4)(*-)), while in the Vis/Co/PMS system, excited AO7 molecules can transfer electrons to PMS or Co(3+) and thus accelerate the decomposition of PMS and catalytic cycle of Co(3+)/Co(2+).     

Involvement of siderophores in the reduction of metal-induced inhibition of auxin synthesis in Streptomyces spp

Unlike synthetic metal chelators, microbe-assisted phytoremediation provides plants with natural metal-solubilizing chelators which do not constitute a potential source of environmental pollution. Concurrently with microbial chelators, plant growth promotion can be enhanced through bacterially-produced phytohormones. In this work, the simultaneous production of siderophores and auxins by Streptomyces was studied to gain insight for future application in plant growth and phytoremediation in a metal-contaminated soil. Standard auxin and siderophore detection assays indicated that all of the investigated Streptomyces strains can produce these metabolites simultaneously. However, Al(3+), Cd(2+), Cu(2+), Fe(3+) and Ni(2+), or a combination of Fe(3+) and Cd(2+), and Fe(3+) and Ni(2+) affected auxin production negatively, as revealed by spectrophotometry and gas chromatography-mass spectrometry. This effect was more dramatic in a siderophore-deficient mutant. In contrast, except for Fe, all the metals stimulated siderophore production. Mass spectrometry showed that siderophore and auxin-containing supernatants from a representative Streptomyces species contain three different hydroxamate siderophores, revealing the individual binding responses of these siderophores to Cd(2+) and Ni(2+), and thus, showing their auxin-stimulating effects. We conclude that siderophores promote auxin synthesis in the presence of Al(3+), Cd(2+), Cu(2+) and Ni(2+) by chelating these metals. Chelation makes the metals less able to inhibit the synthesis of auxins, and potentially increases the plant growth-promoting effects of auxins, which in turn enhances the phytoremediation potential of plants.     

类Fenton反应对偶氮染料橙黄II的脱色研究

以橙黄II染料溶液为研究对象,通过正交实验确定了Fe-NTA/H2O2构成的类Fenton反应中各影响因子的最佳操作条件为:[H2O2]=20 mmol/L,[Fe-NTA]=2.5 mmol/L,pH=3。同时考察了反应时间、溶液pH值、H2O2浓度、Fe-NTA浓度对脱色效率的影响。实验表明脱色反应在30 m in内基本完成,类Fenton试剂能在较宽的pH范围内保持较好的脱色效果,而且在pH=6时,类Fenton试剂比传统Fenton试剂的脱色效率提高约75%。增加双氧水浓度可以提高橙黄II溶液脱色率,但超过20 mmol/L后效果提高不明显。在0.5~2.5 mmol/L的范围内,Fe-NTA浓度对脱色效果的影响不显著。     

Optimization of photo-Fenton process parameters on carbofuran degradation using central composite design

Carbofuran, one of the most toxic and biorefractory carbamate compounds, is widely used in insecticides in Taiwan (9-18% of total insecticides production per year). In the present study, a central composite design experiment was used to study the effect of photo-Fenton treatment on carbofuran solution and to optimize the process variables such as carbofuran concentration (1-100 mg L(-1)), H(2)O(2) dosage rate (0.25-6 mg L(-1) min(-1)) and Fe(3+) dosage (1-50 mg L(-1)), which influenced the efficiency of carbofuran degradation and mineralization. The results indicated that all the variables investigated in this study had significant roles in the degradation and mineralization of carbofuran in solution. The carbofuran degradation and mineralization efficiencies were increased with increase in H(2)O(2) dosage rate and Fe(3+) dosage, and with decrease in carbofuran concentration. Furthermore, optimum values of both H(2)O(2) dosage rate and Fe(3+) dosage were found to shift to higher values as carbofuran concentration increased. Based on the model obtained in this study, optimum H(2)O(2) dosage rate and Fe(3+) dosage were found to be 4 mg L(-1) min(-1) and 20 mg L(-1), respectively, for 51 mg L(-1) of carbofuran concentration. Under these conditions, carbofuran was completely removed within 30 min and coupled with 78% mineralization at the end of experiment.     

真菌和细菌对染料吸附脱色的高效共培养体系研究

在含有真菌G 1培养液中加入染料厂污水排放口的污泥样品 ,从发生快速脱色降解染料的混合培养液中分离出 2株染料脱色细菌L_1和L_2 ,经API鉴定系统鉴定 ,确定菌株L_1为Enterobactersp .,菌株L_2为Peudomonassp .。研究比较了单一和不同组合混合的真菌G_1菌株 (Penicilliumsp .)、细菌L_1菌株 (Enterobactersp .)和L_2菌株 (Pseu domonassp .)对偶氮染料红M - 3BE(C .I .ReactiveRed 2 41)和蒽醌染料艳蓝KN -R(C .1.ReactiveBlue 19)的去除情况 ,发现G - 1真菌和 2种细菌组合的共培养体系对 5 0mg/L红M - 3BE和艳蓝KN -R处理 5h去除率达 10 0 %和 97.9% ,并且是以脱色降解作用为主 ,建立了染料脱色降解菌的最佳组合 ;进一步测定了此最佳共培养体系对另外 13种不同结构染料的脱色降解 ,结果表明 ,除对蒽醌染料R - 478脱色降解较差外 ,对其他染料均可在lh— 3d被完全脱色降解 ,表现出脱色降解染料的广谱性 ;向培养 4d的共培养体系中依次加入 8种染料 ,菌体可对染料连续脱色 ,维持脱色能力达 8d左右     

亚铁催化声化学降解罗丹明B

比较了不同金属离子对罗丹明B的声化学降解作用,发现超声时加入Fe2 反应速率常数为单独超声波降解时的1.6倍,反应在前5 h内符合假一级动力学.研究了亚铁离子强化声化学对罗丹明B的降解作用,考察了Fe2 用量,溶液初始pH值,曝气,反应温度和超声功率等因素对脱色速率的影响.研究表明,酸性条件有利于染料的脱色;有曝气时的声化学脱色速率常数是单独超声时的6倍;声化学反应的活化能较低,反应在低温就可以进行;超声功率的改变对脱色速率的影响不大.UV-VIS扫描图谱显示,染料在225 nm和256 nm处的紫外吸收明显降低,初步探讨了罗丹明B的降解机理.     

高压电弧放电处理偶氮染料废水

用高压电弧放电产生的低温等离子体对含偶氮染料的废水进行了处理，以甲基橙为例研究了电压幅值、处理时间、溶液初始浓度、溶液初始pH值、投加Fe^2＋和Fe^3＋对染料脱色的影响。实验结果表明，甲基橙浓度为50mg／L时其降解率随时间和电压幅值的增加而增加。溶液初始浓度对染料去除效果影响较为明显，同等条件下初始浓度越低降解率越高。酸性条件下有利于低温等离子体处理甲基橙。Fe^2＋和Fe^3＋对低温等离子体降解甲基橙有一定的催化作用。电压8kV处理3min，Fe^2＋为20mg／L时去除率由89．64％增至99．72％。Fe2（SO4），的最佳投加量为5mg／L（以Fe^3＋计），而FeCl，的最佳投加量为80mg／L（以Fe^3＋计）。     

Evaluation of different electrochemical methods on the oxidation and degradation of Reactive Blue 4 in aqueous solution

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.     

Kinetics of chemical decolorization of the azo dye C.I. Reactive Orange 96 by sulfide

The mechanism of decolorization of azo dyes based on the extracellular chemical reduction with sulfide (H2S, HS-, S2-) was postulated for sulfate reducing environments. To design technical decolorization processes of textile wastewater treatment with sulfide produced by sulfate reducing bacteria (SRB), kinetics is of great significance. Batch experiments were made in order to investigate the kinetics of abiotic decolorization of the reactive mono-azo dye C.I. Reactive Orange 96 (RO 96) with sulfide, with varying pH. The decolorization of RO 96 by sulfide under the exclusion of O2 corresponded to first-order kinetics with respect to both dye and sulfide concentration. The decolorization of RO 96 with sulfide at neutral pH (7.1) was advantageous compared with that at pH for 4.1, 6.3, and 6.5. This is attributed to an increase in the fraction of HS- of total sulfide species at neutral pH. The rate constants k for the decolorization at 37 degrees C were obtained as 0.01 for pH = 4.1, 0.06 for pH = 6.3, 0.08 for pH = 6.5, and 0.09 for pH = 7.1 in mM(-1) min(-1). The high rate constants for sulfide at pH 6.5-7.1 support that the decolorization through SRB (i.e. by bio-sulfide) can be effective in anaerobic bacterial systems with sulfate.