Effects of different quinoid redox mediators on the removal of sulphide and nitrate via denitrification

The impact of different quinoid redox mediators on the simultaneous conversion of sulphide and nitrate in a denitrifying culture was evaluated. All quinones evaluated, including anthraquinone-2,6-disulphonate (AQDS), 2-hydroxy-1,4-naphthoquinone and 1,2-naphthoquinone-4-sulphonate (NQS) were reduced by sulphide under abiotic conditions. NQS showed the highest reduction rate by sulphide (132 μmol h⁻¹) and promoted the maximum rate of sulphide oxidation (87 μmol h⁻¹) by denitrifying sludge, which represents an increase of 44% compared to the control lacking quinones. The reduced form of AQDS (AH₂QDS) served as an electron donor for the microbial reduction of nitrite and N₂O, which represents the first demonstration of hydroquinones supporting the microbial reduction of denitrifying intermediates. The results taken as a whole suggest that some quinones may significantly increase the rate of removal of S and N under denitrifying conditions.     

Decolorization of direct dyes by salt fractionated turnip proteins enhanced in the presence of hydrogen peroxide and redox mediators

The present paper demonstrates the effect of salt fractionated turnip (Brassica rapa) proteins on the decolorization of direct dyes, used in textile industry, in the presence of various redox mediators. The rate and extent of decolorization of dyes was significantly enhanced by the presence of different types of redox mediators. Six out of 10 investigated compounds have shown their potential in enhancing the decolorization of direct dyes. The performance was evaluated at different concentrations of mediator and enzyme. The efficiency of each natural mediator depends on the type of dye treated. The decolorization of all tested direct dyes was maximum in the presence of 0.6mM redox mediator at pH 5.5 and 30 degrees C. Complex mixtures of dyes were also maximally decolorized in the presence of 0.6mM redox mediator (1-hydroxybenzotriazole/violuric acid). In order to examine the operational stability of the enzyme preparation, the enzyme was exploited for the decolorization of mixtures of dyes for different times in a stirred batch process. There was no further change in decolorization of an individual dye or their mixtures after 60 min; the enzyme caused more than 80% decolorization of all dyes in the presence of 1-hydroxybenzotriazole/violuric acid. However, there was no desirable increase in dye decolorization of the mixtures on overnight stay. Total organic carbon analysis of treated dyes or their mixtures showed that these results were quite comparable to the loss of color from solutions. However, the treatment of such polluted water in the presence of redox mediators caused the formation of insoluble precipitate, which could be removed by the process of centrifugation. The results suggested that catalyzed oxidative coupling reactions might be important for natural transformation pathways for dyes and indicate their potential use as an efficient means for removal of dyes color from waters and wastewaters.     

Effects of different quinoid redox mediators on the removal of sulphide and nitrate via denitrification

The impact of different quinoid redox mediators on the simultaneous conversion of sulphide and nitrate in a denitrifying culture was evaluated. All quinones evaluated, including anthraquinone-2,6-disulphonate (AQDS), 2-hydroxy-1,4-naphthoquinone and 1,2-naphthoquinone-4-sulphonate (NQS) were reduced by sulphide under abiotic conditions. NQS showed the highest reduction rate by sulphide (132 μmol h⁻¹) and promoted the maximum rate of sulphide oxidation (87 μmol h⁻¹) by denitrifying sludge, which represents an increase of 44% compared to the control lacking quinones. The reduced form of AQDS (AH₂QDS) served as an electron donor for the microbial reduction of nitrite and N₂O, which represents the first demonstration of hydroquinones supporting the microbial reduction of denitrifying intermediates. The results taken as a whole suggest that some quinones may significantly increase the rate of removal of S and N under denitrifying conditions.     

Biological decolourisation of simulated azo dye in aqueous phase by algae Spirogyra species

Biological decolourisation of two azo dye effluents (direct and reactive dye) were investigated using a commonly available green algae Spirogyra sp. in viable form. Batch studies revealed the potential of algal species in removing the dye colour and dye removal was dependant on initial algal inoculum, concentration and application class of the dye. Maximum dye uptake was noticed on the third day for both the dyes. Higher dye uptake was observed in the case of direct red 28 compared to reactive red 2. Dye colour removal by the algal species may be attributed to biosorption of the dye molecules onto the surface of algal cell and subsequent diffusion and participation in metabolism (bioconversion). The remaining dye molecules could be further removed from the aqueous phase by adsorption and/or chelation reaction of the exopolymers released by the algae (biocoagulation). The results of the present study reveal the potential nature of algae in treating azo dyes which in turn can be extended to oxidation pond system of wastewater treatment.     

Biodecolorization of the azo dye Reactive Red 2 by a halotolerant enrichment culture.

The decolorization of the azo dye Reactive Red 2 (RR2) under anoxic conditions was investigated using a mesophilic (35 degrees C) halotolerant enrichment culture capable of growth at 100 g/L sodium chloride (NaCl). Batch decolorization assays were conducted with the unacclimated halotolerant culture, and dye decolorization kinetics were determined as a function of the initial dye, biomass, carbon source, and an externally added oxidation-reduction mediator (anthraquinone-2,6-disulphonic acid) concentrations. The maximum biomass-normalized RR2 decolorization rate by the halotolerant enrichment culture under batch, anoxic incubation conditions was 26.8 mg dye/mg VSSxd. Although RR2 decolorization was inhibited at RR2 concentrations equal to and higher than 300 mg/L, the halotolerant culture achieved a 156-fold higher RR2 decolorization rate compared with a previously reported, biomass-normalized RR2 decolorization rate by a mixed mesophilic (35 degrees C) methanogenic culture in the absence of NaCl. Decolorization kinetics at inhibitory RR2 levels were described based on the Haldane model (Haldane, 1965). Five repetitive dyeing/decolorization cycles performed using the halotolerant culture and the same RR2 dyebath solution demonstrated the feasibility of biological renovation and reuse of commercial-strength spent reactive azo dyebaths.     

Ozonation of hydrolyzed azo dye reactive yellow 84 (CI).

The combination of chemical and biological water treatment processes is a promising technique to reduce recalcitrant wastewater loads. The key to the efficiency of such a system is a better understanding of the mechanisms involved during the degradation processes. Ozonation has been applied to many fields in water and wastewater treatment. Especially for textile mill effluents ozonation can achieve high color removal, enhance biodegradability, destroy phenols and reduce the chemical oxygen demand (COD). However, little is known about the reaction intermediates and products formed during ozonation. This work deals with the degradation of hydrolyzed Reactive Yellow 84 (Color Index), a widely used azo dye in textile finishing processes with two monochlorotriazine anchor groups. Ozonation of the hydrolyzed dye in ultra pure water was performed in a laboratory scale cylindric batch reactor. Decolorization, determined by measuring the light absorbance at the maximum wavelength in the visible range (400 nm), was almost complete after 60 and 90 min with an ozone concentration of 18.5 and 9.1 mg/l, respectively. The TOC/TOC0 ratio after ozonation was about 30%, the COD was diminished to 50% of the initial value. The BOD5/COD ratio increased from 0.01 to about 0.8. Oxidation and cleavage of the azo group yield nitrate. Cleavage of the sulfonic acid groups of aromatic rings caused increases in the amount of sulfate. Formic acid and oxalic acid were identified as main oxidation products by high performance ion chromatography (HPIC). The concentrations of these major products were monitored at defined time intervals during ozonation.     

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.     

A kinetic study of anaerobic digestion of olive mill wastewater at mesophilic and thermophilic temperatures

The kinetics of the anaerobic digestion of olive mill wastewater (OMW) was studied in the mesophilic and thermophilic ranges of temperature. Two completely mixed continuous flow bioreactors operating at 35 degrees C and 55 degrees C and with an average biomass concentration of 5.45 g VSS litre(-1) were used. The thermophilic reactor worked satisfactorily between hydraulic retention times (HRT) of 10 to 40 days, removing between 94.6 and 84.4% of the initial chemical oxygen demand (COD). In contrast, the mesophilic reactor showed a marked decrease in substrate utilization and methane production at a HRT of 10 days. TVFA levels and the TVFA/alkalinity ratio were higher and close to the suggested limits for digester failure. The yield coefficient for methane production (1 CH(4) STP g(-1) COD(added)) was 28% higher in the thermophilic process than in the mesophilic one. Macroenergetic parameters, calculated using Guiot's kinetic model, gave yield coefficients for the biomass (Y) of 0.18 (mesophilic) and 0.06 g VSS g(-1) COD (thermophilic) and specific rates of substrate uptake for cell maintenance (m) of 0.12 (mesophilic) and 0.27 g COD g(-1) VSS.day(-1) (thermophilic). The experimental results showed the rate of substrate uptake (R(s); g COD g(-1) VSS.day(-1)), correlated with the concentration of biodegradable substrate (S(b); g COD litre(-1)), through an equation of the Michaelis-Menten type for the two temperatures used.     

Removal of nitric oxide in a biotrickling filter under thermophilic condition using Chelatococcus daeguensis

The development of a thermophilic biotrickling filter (BTF) system to inoculate a newly isolated strain of Chelatococcus daeguensis TAD1 for the effective treatment of nitric oxide (NO) is described. A bench-scale BTF was run under high concentrations of NO and 8% O2 in thermophilic aerobic environment. A novel aerobic denitrifier Chelatococcus daeguensis TAD1 was isolated from the biofilm of an on-site biotrickling filter and it showed a denitrifying capability of 96.1% nitrate removal rate in a 24 h period in aerobic environment at 50 degrees C, with no nitrite accumulation. The inlet NO concentration fluctuated between approximately 133.9 and 669.6 mg m-3 and kept on a steady NOx removal rate above 80% in an oxygen stream of 8%. The BTF system was able to consistently remove 80-93.7% NO when the inlet NO was 535.7 mg m-3 in an oxygen stream of 2-20%. The biological removal efficiency of NO at 50 degrees C is higher than that at 25 degrees C, suggesting that the aerobic denitrifier TAD1 display well denitrification performance under thermophilic condition. Starvation for 2, 4 and 8 days resulted in the re-acclimation times of Chelatococcus daeguensis TAD1 ranging between 4 and 16 hours. A longer recovery time than that for weekend shutdown will be required when a longer starvation occurs. The results presented here demonstrate the feasibility of biotrickling filter for the thermophilic removal of NOx from gas streams. Implications: A novel denitrifier Chelatococcus daeguensis TAD1 was isolated from an on-site biotrickling filter in aerobic environment at 50 degrees C. To date, C. daeguensis has not been previously reported to be an aerobic denitrifier. In this study, a thermophilic biotrickling filter system inoculated with Chelatococcus daeguensis TADI for treatment of nitric oxide is developed. In coal-fired power plants, influent flue gas stream for nitrogen oxides (NOx) removal typically exhibit temperatures between 50 and 60 degrees C. Traditionally, cooling gases to below 40 degrees C prior to biological treatment is inevitable, which is costly. Therefore, the application ofthermophilic microorganisms for the removal of nitric oxide (NO) at this temperature range would offer great savings and would greatly extend the applicability ofbiofilters and biotrickling filters. Until now there has not been any study published about thermophilic biological treatment of NO under aerobic condition.     

Photocatalytic and combined anaerobic-photocatalytic treatment of textile dyes

A photocatalytic process based on immobilized titanium dioxide was used to treat crude solutions of azo, anthraquinone and phthalocyanine textile dyes. In addition, the process was applied to the treat autoxidized chemically reduced azo dyes, i.e. representatives of recalcitrant dye residues after biological sequential anaerobic-aerobic treatment. Photocatalysis was able to remove more than 90% color from crude as well as autoxidized chemically reduced dye solutions. UV-absorbance and COD were also removed but to a lower extent (50% in average). The end products of photocatalytic treatment were not toxic toward methanogenic bacteria. The results demonstrate that photocatalysis can be used as a pre- or post-treatment method to biological anaerobic treatment of dye-containing textile wastewater.     

Biogenic sulphide plays a major role on the riboflavin-mediated decolourisation of azo dyes under sulphate-reducing conditions

The effect of high concentrations of sulphate on the reductive decolourisation of different azo dyes by anaerobic sludge was studied in batch cultures. Sludge cultures were pre-incubated under sulphate-reducing conditions prior addition of dyes. Little or no effects of sulphate (5-10 g sulphate l(-1)) on the rate of decolourisation of Reactive Orange 14 (RO14), Direct Blue 53 (DB53) and Direct Blue 71 (DB71) were observed when no external redox mediator was provided. However, an increase in sulphate concentration, in the presence of riboflavin (20 microM), enhanced the decolourisation of all dyes. The first-rate constant of decolourisation (k) was increased up to 2-, 3.6- and 2-fold for RO14, DB53 and DB71, respectively, by supplying high sulphate concentrations, compared to the controls lacking sulphate, in the presence of the redox mediator. Sulphate reduction did not take place during the course of azo reductions, but was only evident before dye addition and after complete decolourisation, suggesting azo dyes reduction out-competed sulphate reduction for the available reducing equivalents. The experimental data suggest that reduction of azo dyes by riboflavin, which had been reduced by biogenic sulphide, was the major mechanism implicated during decolourisations, which was corroborated by abiotic incubations. Riboflavin greatly accelerated the abiotic reduction of RO14, so that the k value was increased up to 44-fold compared to the control lacking riboflavin.     

Comparative mesophilic and thermophilic anaerobic digestion of palm oil mill effluent using upflow anaerobic sludge blanket

The effects of organic loading rate and operating temperature on the microbial diversity and performances of upflow anaerobic sludge blanket (UASB) reactors treating palm oil mill effluent (POME) were investigated. The following two UASB reactors were run in parallel for comparison: (1) under a mesophilic condition (37 degrees C) and (2) under a mesophilic condition in transition to a thermophilic condition (57 degrees C). A polymerase chain reaction (PCR)-based denaturing gradient gel electrophoresis (DGGE) analysis showed that the microbial population profiles significantly changed with the organic loading rate (OLR) and the temperature transition from the mesophilic to the thermophilic condition. Significant biomass washout was observed for the mesophilic UASB when operating at a high organic loading rate (OLR) of 9.5 g chemical oxygen demand (COD)/L.d. In contrast, the thermophilic UASB can be operated at this OLR and at a temperature of 57 degrees C with satisfactory COD removal and biogas production. The PCR-based DGGE analysis suggested that the thermophilic temperature of 57 degrees C was suitable for a number of hydrolytic, acidogenic, and acetogenic bacteria.     

Treatment of textile dyeing wastewater by biomass of Lactobacillus: Lactobacillus 12 and Lactobacillus rhamnosus

The main purpose of this study was to investigate the effectiveness of Lactobacillus 12 and Lactobacillus rhamnosus as both cells and biomasses for the removal of dye from real textile dyeing wastewater. The removal experiments were conducted according to the Box–Behnken experimental design, and the regression equations for the removal of dye were determined by the Minitab 14 program. The optimum variables were found to be 10 g/?L biomass concentration for biomasses, 3 for initial pH of the solution, and 20 °C for temperature with an observed dye removal efficiency of about 60 and 80 % with L. 12 and L. rhamnosus biomasses, respectively. Scanning electron microscopy and Fourier transform infrared spectroscopy images also showed that the biomass characteristics studied were favored by the sorption of the dye from the textile industry wastewater. Consequently, these biomasses may be considered as good biosorbents due to their effective yields and the lower cost of the removal of dyes from the effluents of the textile dyeing house.     

Decolorization of mono-azo dyes in wastewater by advanced oxidation process: A case study of acid red 1 and acid yellow 23

Advanced Oxidation Processes (AOPs) have been used as emerging wastewater treatment technologies which can effectively handle various hazardous organics in wastewater and groundwater. The photooxidation of two non-biodegradable azo dyes, acid red 1 and acid yellow 23, were studied in an UV/hydrogen peroxide photochemical reactor with a 5 kW low pressure mercury lamp. It was observed that the decomposition of both azo dyes were pseudo-first order reactions with respect to the azo dye concentrations. Simultaneously, the effects of hydrogen peroxide dosage, pH, initial concentration of the azo dyes and intensity of UV light were also studied. Moreover, the time required for the 50% removal of azo dyes and observed pseudo-first order rate constants were used as parameters to show the efficiency of azo dye treatment.     

Decolorization and biodegradability of photocatalytic treated azo dyes and wool textile wastewater

The photodegradation and biodegradability have been investigated for four non-biodegradable commercial azo dyes, Reactive YellowKD-3G, Reactive Red 15, Reactive Red 24, Cationic Blue X-GRL, an indicator. Methyl Orange, and one industrial wool textile wastewater, using TiO2 suspensions irradiated with a medium pressure mercury lamp. The color removal of dyes solution and dyeing wastewater reached to above 90% within 20-30 min. of photocatalytic treatment. Biochemical oxygen demand (BOD) was found to increase, while chemical oxygen demand (COD), total organic carbon (TOC) decreased, so that the ratio of BOD5/COD of the wastewater increased from original zero up to 0.75. The result implies that photocatalytic oxidation enhanced the biodegradability of the dye-containing wastewater and therefore relationship between decolorization and biodegradability exists. When the color disappeared completely, the wastewater biodegraded normally and could be discharged for further treatment. The experimental results demonstrate that it is possible to combine photocatalysis with conventional biological treatment for the remedy of wastewater containing generally non-biodegradable azo dyes.     

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。     

Influence of redox mediators and metal ions on synthetic acid dye decolourization by crude laccase from Trametes hirsuta

In this paper, the effect of redox mediators on synthetic acid dye decolourization (Sella Solid Red and Luganil Green) by laccase from Trametes hirsuta cultures has been investigated. All the redox mediators tested, 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), 1-hydroxybenzotriazole (HBT) and Remazol Brilliant Blue R (RBBR), led to higher activities than those obtained without mediators addition showing the suitability of the laccase/mediator system (LMS) in the decolourization of acid dyes. HBT was by far the most effective mediator, showing a decolourization percentage of 88% in 10 min for Sella Solid Red and of 49% in 20 min for Luganil Green. On the other hand, the stability of laccase against several metal ions, normally found in textile wastewater, was assessed. Laccase was stable at a concentration of 1mM for 7d against all the metal ions tested except for Zn+2, CrO4(-2), Cd+2, Cr2O7(-2), Fe+2, Cu+2 and especially Hg+2. When the concentration was increased to 10mM laccase stability decreased against all the metals assayed, in particular against Fe+2. In addition, the effect of metal ions on the decolourization process was also studied. It was found that Hg+2 inhibited the dye decolourization process, being the presence of HBT absolutely required for dye decolourization.     

硫酸盐在偶氮染料厌氧生物脱色中的作用

以沼泽红假单胞菌W1为研究对象,考察了厌氧条件下硫酸盐还原对活性黑5(Reactive Black 5,RB5)和直接黄11(Direct Yellow 11,DY11)生物脱色的影响。结果表明,硫酸盐本身对2种染料脱色无明显影响,而硫酸盐的还原产物———硫化物能通过氧化还原介体使2种染料化学脱色,其脱色过程能在3 min内迅速完成。在无介体加入的情况下,硫化物能够通过RB5自身产生的介体加速RB5的脱色;而对于不能产生氧化还原介体的DY11,硫化物对其脱色无明显影响。硫化物经染料氧化后形成的硫单质能够被菌株W1重新转化为硫化物,继续还原染料。     

活性污泥缺氧转化1-2-7-三氨基-8-羟基-3-6-萘二磺酸简

1-2-7-三氨基-8-羟基-3-6-萘二磺酸（TAHNDS）作为偶氮染料的脱色产物很难被常规的厌氧-好氧染料废水处理工艺所去除。研究了未经驯化的活性污泥对TAHNDS的缺氧转化效果。结果表明,只有在特定的缺氧条件下（ORP在-50~-150 mV之间）,TAHNDS才能被活性污泥所降解转化。当浓度在10~80 mg/L范围内,TAHNDS可在72 h内转化93%以上。加入100 mg/L的硝酸盐和0.64 mmol/L的氧化还原介体蒽醌-2-磺酸钠（AQS）可将40 mg/L的TAHNDS的转化时间从84 h缩短到36 h。光谱及HPLC-MS分析表明,TAHNDS在缺氧条件下主要是通过脱氨基和脱磺酸作用生成已知可好氧生物降解的3,5-二氨基-4-羟基萘-2-磺酸。因此,缺氧处理有望作为预处理工艺促进废水中TAHNDS的完全降解。     

Performance of oxalic acid-chitosan/alumina ceramic biocomposite for the adsorption of a reactive anionic azo dye

Environmental Science and Pollution Research - A biocomposite system was developed and tested for the removal of the azo dye Reactive Red (RR195) from wastewater. The biocomposite was synthesized...