Potentials of high-temperature anaerobic treatment and redox mediators for the reductive decolorization of azo dyes from textile wastewaters.

The discharge of dye-colored wastewaters in surface water represents a serious environmental problem because it may decrease the water transparency, therefore having an effect on photosynthesis, and a public health concern because dyes and their reducing products are carcinogenic. In recent years, big achievements have been made in the use of anaerobic granular sludge not only on colored wastewaters but also on the detoxification of other xenobiotics compounds. This paper compiles some important findings related to the potentials of high-temperature anaerobic treatment and redox mediators on the reductive decolorization of azo dyes from textile wastewaters.     

Kinetics of anaerobic biodecolourisation of azo dyes.

Kinetics of anaerobic biodecolourisation (methanogenic environment) of four azo dyes (Acid Orange 6, Acid Orange 7, Methyl Orange and Methyl Red) was investigated with regard to their electrochemical properties as well as under variation of dye and sludge concentrations, pH and temperature. Cyclic voltammetry revealed a correlation between the potential of irreversible reduction peak of the dye and its first-order decolorisation constant. For each dye tested, this decolourisation constant was adversely proportional to dye concentration (0.086-1.7 mM) and had a saturation (hyperbolic) dependency on sludge concentration (0.04-1.1 g VSS/l), a bell-shape dependency on pH (4.0-9.0) and Arrhenius dependency on temperature (24-40 degrees C). Transfer from methanogenic to sulphate reducing environment led to an increase of decolorisation constant for all the dyes investigated due to the abundant presence of sulphide as a reducing agent in the reaction medium. Similar transfer to a denitrifying environment resulted in an almost complete decease of decolourisation because nitrate easily outcompetes azo dyes as an electron acceptor.     

Application of a sequential batch reactor system for textile dyes degradation: comparison between azo and phthalocyanine dyes.

Photocatalysis on supported TiO2 was combined with aerobic biological treatment in a sequential batch reactor to compare the degradation of two textile dyes: a blue azo dye (DR KBL CDG) and a green phthalocyanine dye (DR K4GN). Three reactors were run in parallel. SBR1 was used as a reference and was fed with urban wastewater only. SBR2 and SBR3 were fed with the same urban wastewater combined with pretreated (for SBR2) and non-pretreated (for SBR3) dye solution. For an azo dye concentration of 12 mg/L decolouration yields of 78 and 27% were achieved, respectively, in SBR2 and SBR3. For the phthalocyanine dye, the decolouration yields decreased to 24 and 15%, respectively. Concerning COD removal it decreases for both dyes with and without pretreatment, when the dye concentration increases. Although a detrimental effect on biomass could be observed, bacteria were able to cope with the inhibitory effect of the dyes.     

卢沟桥污水处理厂生化系统自控运行的探索与研究

对北京卢沟桥污水处理厂生化系统三年多的自控运行中出现的问题进行探索和研究,并提出可行的解决措施.同时,对生化系统手动运行和自控运行的效果和成本进行了对比统计和分析,结果表明,生化系统自控运行模式下出水水质稳定达标,运行成本经济.     

Iron and manganese removal from textile effluents in anaerobic attached-growth bioreactor filled with coirfibres.

A laboratory scale study on Fe and Mn removal in upflow anaerobic bioreactor of a working volume of 20 L with coir fibre as the filter medium was investigated for a period of 312 days. The maximum Fe and Mn levels considered were 10 and 5 mg/L respectively, which are the typical average values of textile effluents subsequent to the primary and secondary treatments. Ten sub-experimental runs were conducted with varying HRTs (5 days to 1 day), ratios of COD:SO42- (20 to 3.5), Fe levels (0.005 to 10 mg/L) and Mn levels (0 to 5 mg/L). COD:SO2 of 3.5 was identified as the optimum point at which sulphate reducing bacteria (SRBs) out competed methane producing bacteria (MPBs) and further reduction of this ratio caused total and/or significant inhibition of MPBs, thus building sulphate reducing conditions. The effluent contained Fe and Mn below the permissible levels (1.6 and 1.1 mg/L for Fe and Mn, respectively) stipulated by US National Pollution Discharge Elimination System (NPDES) for inland surface waters at HRTs higher than 3 days. Results of the mass balance showed more Fe accumulation (60%) in sediments whereas 27% in the filter media. An opposite observation was noticed for Mn.     

Syntrophic acetate oxidation in two-phase (acid-methane) anaerobic digesters

The microbial processes involved in two-phase anaerobic digestion were investigated by operating a laboratory-scale acid-phase (AP) reactor and analyzing two full-scale, two-phase anaerobic digesters operated under mesophilic (35 °C) conditions. The digesters received a blend of primary sludge and waste activated sludge (WAS). Methane levels of 20% in the laboratory-scale reactor indicated the presence of methanogenic activity in the AP. A phylogenetic analysis of an archaeal 16S rRNA gene clone library of one of the full-scale AP digesters showed that 82% and 5% of the clones were affiliated with the orders Methanobacteriales and Methanosarcinales, respectively. These results indicate that substantial levels of aceticlastic methanogens (order Methanosarcinales) were not maintained at the low solids retention times and acidic conditions (pH 5.2-5.5) of the AP, and that methanogenesis was carried out by hydrogen-utilizing methanogens of the order Methanobacteriales. Approximately 43, 31, and 9% of the archaeal clones from the methanogenic phase (MP) digester were affiliated with the orders Methanosarcinales, Methanomicrobiales, and Methanobacteriales, respectively. A phylogenetic analysis of a bacterial 16S rRNA gene clone library suggested the presence of acetate-oxidizing bacteria (close relatives of Thermacetogenium phaeum, 'Syntrophaceticus schinkii,' and Clostridium ultunense). The high abundance of hydrogen consuming methanogens and the presence of known acetate-oxidizing bacteria suggest that acetate utilization by acetate oxidizing bacteria in syntrophic interaction with hydrogen-utilizing methanogens was an important pathway in the second-stage of the two-phase digestion, which was operated at high ammonium-N concentrations (1.0 and 1.4 g/L). A modified version of the IWA Anaerobic Digestion Model No. 1 (ADM1) with extensions for syntrophic acetate oxidation and weak-acid inhibition adequately described the dynamic profiles of volatile acid production/degradation and methane generation observed in the laboratory-scale AP reactor. The model was validated with historical data from the full-scale digesters.     

Treatment of chemical-pharmaceutical wastewater in packed bed anaerobic reactors.

Biological degradation in packed bed anaerobic mesophilic reactors with five different support materials was studied for the treatment of chemical-pharmaceutical wastewater with high COD (23-31 g/L), which contains toxic organic compounds. Experimental up-flow bio-filters were operated at different organic loads for a two-year period. Removals of 80-98% were obtained in the reactors with sand, anthracite and black tezontle, but at relatively low organic loads, less than 3.6 kg m(-3)d(-1). The reactor with granular activated carbon (GAC) had a better performance; efficiencies higher than 95% were obtained at loads up to 17 kg m(-3)d(-1) and higher than 80% with loads up to 26 kg m(-3)d(-1). Second in performance was the reactor with red tezontle which allows COD removals higher than 80% with loads up to 6 kg m(-3)d(-1). The use of GAC as support material allows greater biodegradation rates than the rest of the materials and it makes the process more resistant to organic load increases, inhibition effects and toxicity. Methanogenic activity was inhibited at loads higher than 21.9 kg m(-3)d(-1) in the GAC-reactor and at loads higher than 3.6 kg m(-3)d(-1) in the rest of the reactors. At loads lower than the previously mentioned, high methane production yield was obtained, 0.32-0.35 m3CH4/kg CODremoved.     

Bioremoval of textile dyes with different chemical structures by Aspergillus versicolor in molasses medium

Bioremoval of 17 dyes with different chemical structures by Aspergillus versicolor was detected in this study. Maxilon Red GRL (MR-GRL), Everdirect Fast Black VSF (EFB-VSF) and Brillant Blue R (BB-R) were removed better by fungal mycelia. Optimum pH values were found as 6 for all three dyes. In further experiments in the highest dye concentrations tested in this study, 58.3, 100 and 49% removal yields and 14.8, 12.6, 9.0 q(m) values were found for MR-GRL, EFB-VSF and BB-R, respectively. Chemical oxygen demand (COD) reduction after seven days of incubation period and role of laccase activity of Aspergillus sp. were also investigated. COD reduction and laccase activities were 55.6% and 2.93 U/mL for MR-GRL, 90.7% and 3.0 U/mL for EFB-VSF and 69.0% and 1.79 U/mL for BB-R, respectively. According to these results A. versicolor deserves notable attention for removal of these dyes in wastewater effluents.     

Bioremediation of direct dyes in simulated textile effluents by a paramorphogenic form of Aspergillus oryzae

Azo dyes are extensively used for coloring textiles, paper, food, leather, drinks, pharmaceutical products, cosmetics and inks. The textile industry consumes the largest amount of azo dyes, and it is estimated that approximately 10-15% of dyes used for coloring textiles may be lost in waste streams. Almost all azo dyes are synthetic and resist biodegradation, however, they can readily be reduced by a number of chemical and biological reducing systems. Biological treatment has advantages over physical and chemical methods due to lower costs and minimal environmental effect. This research focuses on the utilization of Aspergillus oryzae to remove some types of azo dyes from aqueous solutions. The fungus, physically induced in its paramorphogenic form (called 'pellets'), was used in the dye biosorption studies with both non-autoclaved and autoclaved hyphae, at different pH values. The goals were the removal of dyes by biosorption and the decrease of their toxicity. The dyes used were Direct Red 23 and Direct Violet 51. Their spectral stability (325-700 nm) was analyzed at different pH values (2.50, 4.50 and 6.50). The best biosorptive pH value and the toxicity limit, (which is given by the lethal concentration (LC(100)), were then determined. Each dye showed the same spectrum at different pH values. The best biosorptive pH was 2.50, for both non- autoclaved and autoclaved hyphae of A. oryzae. The toxicity level of the dyes was determined using the Trimmed Spearman-Karber Method, with Daphnia similis in all bioassays. The Direct Violet 51 (LC(100) 400 mg · mL(-1)) was found to be the most toxic dye, followed by the Direct Red 23 (LC(100) 900 mg · mL(-1)). The toxicity bioassays for each dye have shown that it is possible to decrease the toxicity level to zero by adding a small quantity of biomass from A. oryzae in its paramorphogenic form. The autoclaved biomass had a higher biosorptive capacity for the dye than the non-autoclaved biomass. The results show that bioremediation occurs with A. oryzae in its paramorphogenic form, and it can be used as a biosorptive substrate for treatment of industrial waste water containing azo dyes.     

Treatment of wine distillery wastewater by high rate anaerobic digestion.

Wine distillery wastewaters (WDW) are acidic and have a high content of potential organic pollutants. This causes high chemical oxygen demand (COD) values. Polyphenols constitute a significant portion of this COD, and limit the efficiency of biological treatment of WDWs. WDW starting parameters were as follows: pH 3.83, 4,185 mg/l soluble COD (COD(s)) and 674.6 mg/l of phenols. During operation, amendments of CaCO3 and K2HPO4, individually or in combination, were required for buffering the digester. Volatile fatty acid concentrations were < 300 mg/l throughout the study, indicating degradation of organic acids present. Mean COD(s) removal efficiency for the 130 day study was 87%, while the mean polyphenol, removal efficiency was 63%. Addition of 50 mg/l Fe(3+) between days 86 and 92 increased the removal efficiencies of COD(s) to 97% and of polyphenols to 65%. Addition of Co(3+) improved removal efficiencies to 97% for COD(s) and 92% for polyphenols. Optimization of anaerobic treatment was achieved at 30% WDW feed strength. Removal efficiencies of 92% and 84% were recorded at increased feed strength from days 108 to 130. High removal efficiencies of COD(s) and polyphenols after day 82 were attributed to the addition of macronutrients and micronutrients that caused pH stability and thus stimulated microbial activity.     

Thermophilic anaerobic digestion in compact systems: investigations by modern microbiological techniques and mathematical simulation.

Thermophilic anaerobic digestion in compact systems can be an economical and ecological reasonable decentralised process technique, especially for rural areas. Thermophilic process conditions are important for a sufficient removal of pathogens. The high energy demand, however, can make such systems unfavourable in terms of energy costs. This is the case when low concentrated wastewater is treated or the system is operated at low ambient temperatures. In this paper we present experimental results of a compact thermophilic anaerobic system obtained with fluorescent in situ hybridisation (FISH) analysis and mathematical simulation. The system was operated with faecal sludge for a period of 135 days and with a model substrate consisting of forage and cellulose for a period of 60 days. The change in the microbial community due to the two different substrates treated could be well observed by the FISH analysis. The Anaerobic Digestion Model no. 1 (ADM1) was used to evaluate system performance at different temperature conditions. The model was extended to contribute to decreased methanogenic activity at lower temperatures and was used to calculate energy production. A model was developed to calculate the major parts of energy consumed by the digester itself at different temperature conditions. It was demonstrated by the simulation study that a reduction of the process temperature can lead to higher net energy yield. The simulation study additionally showed that the effect of temperature on the energy yield is higher when a substrate is treated with high protein content.     

两相厌氧处理湿式氧化后剩余污泥的研究

针对工业废水剩余污泥可生化性差、处理费用高等问题,以石油化工废水剩余污泥为研究对象,进行了湿式氧化后两相厌氧处理的研究。即剩余污泥经温和的湿式氧化预处理后,有机物从微生物体内释放出来并转移到液相,上清液采用两相厌氧处理。系统研究了两相厌氧中 COD_(Cr)、产气量、BOD_5、N、SO_4~(2-)的变化,以及水力停留时间对处理效率的影响,对影响两相厌氧的主要因素讲行了分析。     

垃圾渗滤液曝气生物处理中好氧氧反硝化现象探讨

通过试验,对垃圾渗滤液间歇曝气(曝气时D0为5.5～7 mg/L;停止时DO为1.1～5.5 mg/L),在仅有有机碳、无机氮的条件下进行好氧反硝化脱氮研究.试验结果表明:间歇曝气条件下,渗滤液中存在的好氧反硝化土著微生物茵落会成为优势菌种,在溶解氧充足的条件下,能够发生好氧反硝化反应,使得硝化和反硝化可以真正同步进行;外加碳源不仅是厌氧反硝化所必须的,同样也是好氧反硝化的必要条件;好氧反硝化的最佳曝气方式为间歇曝气.     

Treatment of organic synthesis wastewater using anaerobic packed bed and aerobic suspended growth bioreactors.

The performance of an anaerobic mesophilic packed bed reactor, with a mixture of GAC and tezontle, followed by an aerobic suspended growth system was studied for the treatment of organic chemical wastewater with a high COD concentration (22-29 g/L). The testing of the anaerobic-aerobic system was conducted in an experimental set-up for almost 2.5 years. Different operational conditions were evaluated. The anaerobic reactor showed performance stability and COD removals higher than 80% were obtained with loads up to 16.6 kg x m(-3) x d(-1). The acclimation of the aerobic biomass to the substrate in the anaerobic effluent was very quick and COD removals higher than 94% were obtained even at high organic loads. The combined anaerobic-aerobic system allowed total COD removals higher than 99.5% and the accomplishment of the discharge requirements of 200 mgCOD/L when the anaerobic reactor was operated with loads of 8-11 kg x m(-3)x d(-1) and the aerobic reactor with 0.33 kg x kg(-1) x d(-1), being the total HRT of 4.4. The average TKN removal in the anaerobic-aerobic system was 97%, the average for the anaerobic reactor being 52% and that one for the aerobic system being 94%.     

Instrumentation in anaerobic treatment--research and practice.

High rate anaerobic treatment reactors are able to uncouple solids and liquid retention time, resulting in high biomass concentrations. Principal advantages of anaerobic treatment include: energy efficiency, low biomass yield, low nutrient requirement and high volumetric organic loadings. In order to facilitate small reactors operation with stable and good performance automatic process control systems in combination with on-line instrumentation are proposed. The paper reviews the development and availability of the principal instrumentation for anaerobic treatment processes. First, the most important measuring principles are discussed, followed by a review of the most important process variables with emphasis on the development of their instrumental measurement techniques and application in research. Finally, a summary of actual application of instrumentation in full-scale anaerobic treatment plants is presented.     

Modelling biological processes under anaerobic conditions through integrating titrimetric and off-gas measurements-applied to EBPR systems.

An innovative method for modelling biological processes under anaerobic conditions is presented and discussed. The method is based on titrimetric and off-gas measurements. Titrimetric data is recorded as the addition rate of hydroxyl ions or protons that is required to maintain pH in a bioreactor at a constant level. An off-gas analysis arrangement measures, among other things, the transfer rate of carbon dioxide. The integration of these signals results in a continuous signal which is solely related to the biological reactions. When coupled with a mathematical model of the biological reactions, the signal allows a detailed characterisation of these reactions, which would otherwise be difficult to achieve. Two applications of the method to the enhanced biological phosphorus removal processes are presented and discussed to demonstrate the principle and effectiveness of the method.     

Control of C/N ratio for butyric acid production from textile wastewater sludge by anaerobic digestion

Increasing textile wastewaters and their biotreatment byproduct-waste activated sludge are serious pollution problems. Butyric acid production from textile wastewater sludge by anaerobic digestion at different C/N ratios was investigated. Adding starch to textile wastewater sludge with a C/N ratio of 30 increased the butyric acid concentration and percentage accounting for total volatile fatty acids (TVFAs) to 21.42 g/L and 81.5%, respectively, as compared with 21.42 g/L and 10.6% of textile wastewater sludge alone. The maximum butyric acid yield (0.45 g/g VS), conversion rate (0.74 g/g VS(digest)) and production rate (2.25 g/L d) was achieved at a C/N ratio of 30. The biological toxicity of textile wastewater sludge also significantly decreased after the anaerobic digestion. The study indicated that the anaerobic co-digestion of textile wastewater sludge and carbohydrate-rich waste with appropriate C/N ratio is possible for butyric acid production.     

Treatment of distillery vinasse in a high rate anaerobic reactor using low density polyethylene supports.

An anaerobic fixed bed reactor, filled with small floating supports of polyethylene material (Bioflow 30) as inert media, was operated for 6 months to treat vinasse (wine residue after distillation). Bioflow 30 has a density of 0.93 and a specific area of 320 m2/m3. The experimental results showed that the efficiency of the reactor in removal of soluble COD was very good with a maximum organic loading rate of more than 30 g of COD/L x d and a COD removal efficiency of more than 80%. Bioflow 30 showed a high capability of biomass retention with 4-6 g of dried solids per support. Thus, at the end of the experiment, the fixed biomass represented 57 g of solids/L of reactor. The visual observation of the supports and the specific activity (0.54 g COD/g solids x d) of the fixed solids, which remained close to the values obtained with suspended biomass, showed that entrapment was playing an important role in the retention of the biomass inside the reactor. It was then possible to operate the reactor with a very high loading rate as the result of the increase of the solids in the reactor and the maintaining of the specific activity. Bioflow 30 is then an excellent support for use in a high rate anaerobic fixed bed.     

Thermophilic treatment by anaerobic granular sludge as an effective approach to accelerate the electron transfer and improve the reductive decolorization of azo dyes in bioreactors.

The effects of temperature, hydraulic retention time (HRT), and the redox mediator, anthraquinone-2,6-disulfonate (AQDS), on electron transfer and subsequent reductive decolorization of dyes from textile wastewater was assessed in mesophilic and thermophilic anaerobic bioreactors. The results clearly show that compared to mesophilic anaerobic treatment, thermophilic treatment at 55 degrees C is an effective approach for increasing the electron transfer capacity in bioreactors, and thus improving the decolorization rates. At an HRT of 2.5 h and in the absence of AQDS, the color removal was 5.3-fold higher at 55 degrees C compared to 30 degrees C. Furthermore, similar decolorizations were found at 55 degrees C between the AQDS-free and AQDS-supplemented reactors, whereas a significant difference (up to 3.6-fold) on dye reduction occurred at 30 degrees C.     

Application of enzymes in anaerobic digestion.

Owing to the very low economic value of brewer's spent grains, its utilisation for biogas production is very promising. The hydrolysis of ligno-cellulose is the rate limiting step in anaerobic digestion. Enzymatic pre-treatment promotes the hydrolysis of ligno-cellulose, breaking it down to lower molecular weight substances which are ready to be utilised by the bacteria. A cheap raw multi-enzyme produced by a solid state fermentation (SSF) process is a good substitute for expensive conventional enzyme. The SSF enzyme application to spent grain has been investigated by carrying out enzymatic solubility tests, hydrolytic experiments and two-step anaerobic fermentation of spent grain. Gas chromatograph analysis was conducted to quantify fatty acids concentrations, while CH(4), CO(2), O(2), H(2) and H(2)S were measured to determine biogas quality by means of a gas analyser. DS, oDS, pH were also measured to analyse the anaerobic digestion. The result shows that enzyme application promotes the hydrolysis of ligno-cellulose, indicated by higher enzymatic solubility and fatty acid concentration in a hydrolytic bioreactor. Moreover, biogas production is also increased. The quality of the gases produced is also enhanced. Since the anaerobic digestion can be operated in a stable performance, it can also be concluded that SSF enzyme is compatible with anaerobic digestion.