城市污泥中DEHP和DMP的好氧降解特性研究

对城市污泥好氧消化过程中DEHP和DMP的降解进行了研究,并重点研究了难降解有机物DEHP在不同浓度下对易降解有机物DMP的抑制效果.研究表明,好氧消化污泥对DEHP和DMP有较强的降解能力,且对DMP的降解能力明显强于DEHP,好氧消化污泥在500 mg/L难降解有机物DEHP存在的情况下,对50 mg/L有机物DMP的去除率仍高达99.8%;当DEHP的初始浓度在200 mg/L时,对DMP的降解速率影响较大,而在50 mg/L和500 mg/L时,影响较小;但历经10 d以后,不同初始浓度的DEHP对DMP的好氧降解速率几乎没有影响.     

Gas-phase photocatalytic oxidation of motor fuel oxygenated additives.

Methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) were oxidized in the gas phase by photocatalytic oxidation (PCO). Transient PCO was carried out at room temperature on TiO2 (Degussa P25), 0.2% Pt-TiO2, and 2% Pt-TiO2 catalysts. Surface-adsorbed reaction by-products were characterized by temperature-programmed desorption (TPD) and oxidation (TPO). Continuous flow PCO was also carried out at 373 K on TiO2. Acetone, H2O, and CO2 were the gas-phase products for PCO of TBA and MTBE, and formic acid was adsorbed on the TiO2 surface. Temperature-programmed desorption of TBA and MTBE formed 2-methyl-1-propene, water (TBA), and methanol (MTBE). During continuous-flow PCO, acetone desorbed in molar amounts equal to the amount of decomposed TBA and MTBE. The Pt/TiO2 catalysts had higher rates of complete oxidation during PCO and TPO. Injection of water during transient PCO increased the rates of oxidation of adsorbed TBA, formic acid, and acetone. Photocatalytic oxidation of TBA proceeded faster in humid air than dry air, but MTBE oxidation was less sensitive to humidity. The TiO2 catalyst was stable for MTBE, TBA, and acetone PCO at 373 K. The PCO at low conversions followed the Langmuir-Hinshelwood model.     

Photocatalytical polishing of paper-mill effluents.

Photocatalytic oxidation (PCO) is a promising technology for purification of biological pretreated wastewater or destruction of non-biodegradable compounds. For this reason PCO has been investigated as a last step of purification of biologically pre-treated paper-mill effluents. The influence of the parameters pH, TiO2-modification, TiO2-concentration, catalyst re-use, concentration of substances to be oxidised (wastewater quality) has been determined. The TOC of the biologically pretreated wasterwater was up to 55 mg L(-1). This wastewater was treated with a previously presented aerated cascade photoreactor which was modified for batch experiments. A high specific oxidation rate of up to 0.76 g TOC m(-2) h(-1) as well as a complete TOC mineralization has been achieved after the optimisation of the process parameters. The complete destruction of recalcitrant compounds will offer the opportunity to reuse the wastewater in the production process. The increase of the BOD5/TOC ratio after a short irradiation period indicates the transformation of recalcitrant organic compounds to better biodegradable intermediates. The use of PCO as a pre-treatment step for the enhancement of the biodegradability of wastewater, containing recalcitrant or inhibitory compounds is an alternative to a long and energy-intensive total pollutant mineralization.     

再生水厂处理工艺对邻苯二甲酸酯去除效果分析

以北京城区4座不同处理工艺的再生水厂进出水为研究对象,采用固相萃取(SPE)预处理和气相色谱-质谱法(GC-MS)方法对再生水标准中涉及到的邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二(2-乙基己基)酯(DEHP)两类污染物进行了检测,对比分析不同再生水处理工艺的去除效果。结果表明,各水厂进水中DBP和DEHP的浓度范围分别为1.99～5.36μg/L和0.97～6.44μg/L,与上游污水处理厂所采用的处理工艺无明显关联性;出水中DBP浓度为1.74～5.59μg/L,DEHP浓度范围0.42～4.93μg/L,均低于景观环境用水的国家标准限值;常规混凝-过滤-消毒处理工艺的去除效果并不明显,而膜工艺由于膜污染等实际运行问题也没有达到理想去除效果,去除率不足60%。     

杭嘉湖地区饮用水源半挥发性有机物污染现状

采用固相萃取-GC-MS法对杭嘉湖地区16个集中式饮用水源水体中的氯代苯、多环芳烃、硝基苯、多氯联苯、邻苯二甲酸酯等43种半挥发性有机物（SVOCs）进行了分析检测。结果表明,16个集中式饮用水源水共检出10余种有机污染物,浓度范围为0.01~4.26μg/L,检出率为5%~100%;邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、邻苯二甲酸双（2-二乙基己酯）、2,6-二硝基甲苯等化合物的检出率为超过50%;在平水期、丰水期、枯水期,被检出的有机污染物种类分别为12,9,14种,被检出污染物的浓度范围分别为0.05~4.26,0.01~0.20,0.01~1.00μg/L。     

Optimised photocatalytic degradation of a mixture of azo dyes using a TiO(2)/H(2)O(2)/UV process

The aim of the present study was to optimise the photocatalytic degradation of a mixture of six commercial azo dyes, by exposure to UV radiation in an aqueous solution containing TiO(2)-P25. Response surface methodology, based on a 3(2) full factorial experimental design with three replicates was employed for process optimisation with respect to two parameters: TiO(2) (0.1-0.9 g/L) and H(2)O(2) (1-100 mmol/L). The optimum conditions for photocatalytic degradation were achieved at concentrations of 0.5 g TiO(2)/L and 50 mmol H(2)O(2)/L, respectively. Dye mineralisation was confirmed by monitoring TOC, conductivity, sulfate and nitrate ions, with a sulfate ion yield of 96% under optimal reactor conditions. Complete decolorisation was attained after 240 min irradiation time for all tested azo-dyes, in a process which followed a pseudo-first kinetic order model, with a kinetic rate constant of approximately 0.018 min(-1). Based on these results, this photocatalytic process has promise as an alternative for the treatment of textile effluents.     

紫外光照射处理水中邻苯二甲酸二异辛酯的研究

对水体中邻苯二甲酸二异辛酯(DEHP)在紫外光照射下降解情况进行了分析。结果表明, DEHP遵循一级动力学方程进行紫外光解。其紫外光解半衰期在9．63-15．23 min。在不同pH溶液中DEHP紫外光解都生成了邻苯二甲酸单异辛酯和邻苯二甲酸,推测反应机制为:紫外光激发诱导DEHP酯基团断裂,并与H+或OH-进行结合反应。溶液酸、碱性越强,越利于DEHP的水解电离,从而促进此物质紫外光解。此结论可为紫外光照射处理DEHP污染水体提供一定的参考依据。     

UV/H2O2和UV/TiO2/H2O2去除水中微量硝基苯的比较研究

研究比较了UV/H2O2和UV/TiO2/H2O2对水中微量硝基苯的降解效果,并考察了水中常见HCO-3和腐殖酸对硝基苯降解的影响.结果表明,薄膜状TiO2的存在对UV/H2O2降解硝基苯有显著的促进作用,在最佳H2O2投加量2.1 mg/L时,UV/TiO2/H2O2的反应速率常数比UV/H2O2高32.8%;2 min内UV/TiO2/H2O2对硝基苯的去除率达到80%以上.HCO-3和腐殖酸对硝基苯降解有很强的抑制作用,HCO-3和腐殖酸浓度分别为2 mmol/L和3.2 mg/L时,UV/TiO2/H2O2对硝基苯的反应速率常数分别下降84.6%和92.2%.     

Plasticizers and related toxic degradation products in wastewater sludges.

Plasticizers can persist during the treatment of wastewaters in sewage treatment plants (STPs) and can be discharged in effluents and/or accumulated in sewage sludges. For example, di-2-ethylhexyl phthalate (DEHP) is a common plasticizer that is now considered a priority pollutant and is known to accumulate in sludges. This may add constraints to the exploitation of the beneficial uses of sludges that contain significant quantities of plasticizers. Recently, it was demonstrated in studies with pure cultures that the biodegradation of plasticizers including DEHP and di-ethylhexyl adipate (DEHA) generates toxic metabolites including 2-ethylhexanoic acid, 2-ethylhexanol, and 2-ethylhexanal. However, the environmental impacts and fate of the degradation products arising from plasticizers are unknown. Therefore, this work investigated the concentrations of DEHP and DEHA and their metabolites in the sludges from several STPs in Quebec, Canada. DEHP and DEHA were found in concentrations ranging from 15 to 346 mg kg(-1) and 4 to 743 mg kg(-1), respectively, in primary, secondary, digested, dewatered or dried sludges. Metabolites were detected in almost all sludges, except those that had undergone a drying process at high temperature. It is concluded that sludges can represent significant sources of plasticizers and their toxic metabolites in the environment.     

Simultaneous copper, cobalt and phenol removal from aqueous solutions by alternating biosorption and biodegradation

A strategy for removal of heavy metals and phenol from wastewaters is proposed. It involves consecutive cation biosorption by fungi, phenol biodegradation by the yeast association Candida sp. 2326 + Candida sp. 2327 and regeneration. Copper and cobalt removal from aqueous solutions containing 80-120 mg/L phenol by biosorption, using Rhizopus archizus cells immobilized onto poly (vinyl alcohol), was investigated by conducting a series of batch experiments. The removal efficiencies were 81% for Cu and 5% for Co. The residual concentrations of Cu (1.9 mg/L) and of Co (9.5 mg/L) did not change the biodegradation dynamics of phenol. A quantitative biodegradation of 120 mg/L phenol proceeded within 22 h. After biodegradation of phenol, the removal efficiencies achieved by biosorption after regeneration were 90% for Cu and 44% for Co. It was found that copper and cobalt form positively charged complexes with phenol. This complex formation hinders the retention of Cu and Co by the biosorbent and reduces the uptake of their cations.     

Removal of humic acid foulant from ultrafiltration membrane surface using photocatalytic oxidation process.

The experimental results indicated that without the TiO2 particles and PCO treatment, the permeate flux of ultrafiltration (UF) membrane declined to 40% of the initial permeate flux after 8 hours filtration. Feeding the humic acid solution with TiO2 particles dosage of 1 g/L with calcium ions into UF membrane, after the same filtration time and PCO reaction at 120 minutes, the permeate flux was increased to about 90% of the initial permeate flux. At longer PCO reaction times, a better water quality of UF permeate was observed. It has been found that with the coexistence of calcium ions in humic acid solution, the smaller molecular fragments of humic acid (HA) generated by PCO reaction may be transferred to the surface of TiO2 by means of adsorption. The humic acid adsorption by TiO2 in the presence of Ca2+ is also pH dependent. The adsorption rates were 21.0, 14.9 and 10.8 ppmTOC/gTiO2 for pH value of 4, 7 and 10 respectively. The combination of effects of PCO mineralization of humic acid into CO2 and adsorption of humic acid by TiO2 through the forming of HA-Ca(2+)-TiO2 aggregate particles were responsible for the removal of humic acid foulant from UF membrane surface.     

Mobility of 4-nonylphenol and di(2-ethylhexyl) phthalate in three agricultural soils irrigated with untreated wastewater

Agricultural irrigation using raw wastewater is a popular practice in developing countries. However, as endocrine disrupting chemicals have been found in this water, the potential pollution of soil and water sources has become a source of concern. Such pollutants may be removed during the passage of wastewater through the soil by degradation and/or sorption. In this study the sorption and mobility of bis-2-ethyl(hexyl)phthalate (DEHP) and 4-nonylphenol (4-NP) in three different soils (Leptosol, Phaeozem and Vertisol) was compared. The distribution coefficients showed that DEHP is rapidly sorbed onto the three tested soils (K(d) between 1.8 × 10(4) and 4.2 × 0(4) L/kg), while sorption of 4-NP (K(d) between 15 and 80 L/kg) was weaker. In batch experiments the soil sorption capacity observed was as follows: Vertisol > Phaeozem > Leptosol for both compounds. However, in column experiments the retardation factor (R(F)) for 4-NP was higher than for the DEHP in the three soils. This suggests the possible migration of DEHP through the soil via colloids. The column results were found consistent with those observed in the field. It was concluded that the risk of groundwater contamination is higher for Leptosol soil than for Phaeozem and Vertisol soils and that DEHP can reach the aquifer prior to 4-NP.     

Degradation of recalcitrant organic contaminants by solar photocatalysis.

Biological pre-treated landfill leachates of Djebel Chakir contains some macromolecular organic substances that are resistant to biological degradation. The aim of the present work is to assess the feasibility of removing refractory organic pollutants in biological pre-treated landfill leachate by solar photocatalyse process. Leachate pollutant contents are studied to assess their contribution to leachate pollution and their treatability by solar photocatalyse process. Phenol is chosen as model of pollutants, to evaluate its removal and the efficiency of the photocatalytic system. The experiments were carried out in suspended photocatalytic reactor, using TiO2 Degussa P25, under sunlight illumination (UV-A: 15-31 W/cm2). Under optimum operational conditions, applied to single reactant (phenol), the system presents a TOC removal of 90% (the degradation follows a first-order kinetic). Based on the TOC removal, the results shows that the degradation of biological pre-treated leachate follows a zero-order kinetic. After 5 h of sunlight exposure, 74% of COT is removed. The TOC removal is the best without any correction of the pH and at the TiO2 concentration of 2.5 g/L. The photocatalytic degradation of organic contaminants as well as the formation and disappearance of the by-products were followed by GC/MS. The solar photocatalysis processes induce several modifications of the matrix leading to more biodegradable forms: all the remaining and new compounds generated after the biological pre-treatment of leachate are degraded and other types of organics appear, mainly carboxylic acid, aliphatic hydrocarbons and phtalic acids.     

Heterogeneous photocatalytic ozonation of 2,4-D in dilute aqueous solution with TiO2 fiber

Photocatalytic ozonation (O(3)/UV/TiO2) is an emerging oxidation method for recalcitrant organic contaminants in water. However, immobilised TiO2 catalysts suffer from reduced photonic efficiency. Therefore, TiO2 catalysts with excellent mechanical and thermal properties and enhanced photonic efficiencies are sought. This paper aimed to elucidate the mineralisation of low concentration 2,4-D (45.0 microM) by O(3)/UV/TiO2 using the world's first high-strength TiO2 fibre in laboratory batch experiments. 2,4-D degradation and TOC removal followed pseudo first-order reaction kinetic. The removal rates for 2,4-D and TOC in O(3)/UV/TiO2 were 1.5 and 2.4-fold larger than the summation of the values for ozonation (O3)) and photocatalysis (UV/TiO2), respectively. O(3)/UV/TiO2 was characterised by few aromatic intermediates with low abundance, fast degradations of aliphatic intermediates and dechlorination as a major step. The significantly enhanced 2,4-D mineralisation in O(3)/UV/TiO2 was attributed to increased ozone dissolution and decomposition, and reduced electron-hole recombination resulting in large number of hydroxyl radical (*OH) formation from more than one parallel path. The discrepancies in the organic carbon mass budget were attributed to few apparently major unidentified intermediates, while chlorine mass balance was reasonably acceptable. The mineralisation efficiency of O(3)/UV/TiO2 with the TiO2 fibre can further be enhanced by optimisation of experimental design parameters. The new TiO2 fibre is very promising to overcome the problem of reduced efficiency of TiO2 catalyst in an immobilised state.     

一株长江优势菌的降解特性研究

从长江水体中分离到一株最优功能菌株JD1,经初步鉴定该菌株为琼氏不动杆菌属(acinetobacter junii)。该菌株最高可耐受质量浓度600 mg/L的乐果,降解乐果的最适温度为32℃,在30~37℃的广泛温度下仍生长良好,最适pH值为7.2左右,具有广泛的pH值生长范围(pH=5.5~9.0)。研究发现,装液量、接种量对菌株的降解有明显影响。装液量由3/10调整为1/5时,JD1对质量浓度100 mg/L的乐果降解率从21%提高到51.54%。试验表明,该菌株可以在质量浓度高达2 400 mg/L的苯酚中生长良好。     

Biosorption of heavy metals onto nonliving Laminaria japonica

In this paper, study of the biosorption of Cd(2+) and Pb(2+) by nonliving Laminaria japonica in a batch adsorption system is described. The content of acidic sites and the dissociation constant of carboxylic acid functional groups (metal-binding site) of L. japonica were experimentally determined by conductometric and potentiometric titrations and theoretically predicated by using monodentate and bidentate binding models. The models are based on the monodentate or bidentate binding reactions of bivalent metal ions to acidic sites. The acidic site content and carboxylic acid dissociation constants determined are 1.25 and 0.18 mmol L(-1), respectively. The results showed that the bidentate adsorption model fits well the biosorption of bivalent metal ions onto L. japonica with the bidentate binding constants for Cd(2+) and Pb(2+) being 5.72 × 10(3) and 6.24 × 10(4) L mol(-1), respectively. The adsorption process of L. japonica followed the pseudo-second-order kinetics.     

Advanced oxidation of commercial textile biocides in aqueous solution: effects on acute toxicity and biomass inhibition.

In the present study, the decomposition of two biocides used in the textile finishing process with Advanced Oxidation Processes (AOPs) has been studied. Different AOPs, i.e O3/OH-, TiO2/UV-A and Fe2+/H2O2 have been used representing mutually combined components of the chemically and photochemically driven advanced oxidation systems. The course of reaction was examined by changes in chemical oxygen demand (COD), total organic carbon (TOC) and acute toxicity towards the water flea Daphnia magna (assessed in terms of the effective dilution ratio LD50). Particular attention has been paid to determine the inhibitory effect of raw and ozonated biocides on biological activated sludge consortium at concentrations typically encountered in textile finishing effluents. Significant oxidation and mineralization of both biocides could be achieved employing ozonation at pH = 11.5 and heterogeneous photocatalysis (TiO2/UV-A) at pH = 5.0, whereas Fenton's reagent appeared to be less effective in COD and acute toxicity abatement.     

二氧化氯催化氧化降解铬黑T试验研究

在常温常压下,对Fe2O3/γ—A12O3+H2O2和ClO2+TiO2两种催化氧化体系处理铬黑T废水的效果进行了分析。试验结果表明,处理甲基橙废水效果较好的Fe2O3/γ—Al2O3+H2O2组合对铬黑T的降解效果非常有限,而ClO2+TiO2组合的处理效果较好:以500 mg/L的铬黑T溶液为模拟废水,当pH为4,C102投加量为200 mg/L,TiO2投加量为500 mg/L,反应时间为90 min时,脱色率达89.96%,CODCr的去除率可达45.36%。     

Biosorption of As(V) from aqueous solutions by living cells of Bacillus cereus

In this work, the biosorption of As(V) from aqueous solutions by living cells of Bacillus cereus has been reported. The batch biosorption experiments were conducted with respect to biosorbent dosage 0.5 to 15 g/L, pH 2 to 9, contact time 5 to 90 min, initial concentration 1 to 10 mg/L and temperature 10 to 40 °C. The maximum biosorption capacity of B. cereus for As(V) was found to be 30.04 at pH 7.0, at optimum conditions of contact time of 30 min, biomass dosage of 6 g/L, and temperature of 30 ± 2 °C. Biosorption data were fitted to linearly transformed Langmuir isotherms with R(2) (correlation coefficient) >0.99. Bacillus cereus cell surface was characterized using AFM and FTIR. The metal ions were desorbed from B. cereus using both 1 M HCl and 1 M HNO(3). The pseudo-second-order model was successfully applied to predict the rate constant of biosorption.     

Effect of didecyl dimethyl ammonium chloride on nitrate reduction in a mixed methanogenic culture.

The effect of the quaternary ammonium compound, didecyl dimethyl ammonium chloride (DDAC), on nitrate reduction was investigated at concentrations up to 100 mg/L in a batch assay using a mixed, mesophilic (35 degrees C) methanogenic culture. Glucose was used as the carbon and energy source and the initial nitrate concentration was 70 mg N/L. Dissimilatory nitrate reduction to ammonia (DNRA) and to dinitrogen (denitrification) were observed at DDAC concentrations up to 25 mg/L. At and above 50 mg DDAC/L, DNRA was inhibited and denitrification was incomplete resulting in accumulation of nitrous oxide. At DDAC concentrations above 10 mg/L, production of nitrous oxide, even transiently, resulted in complete, long-term inhibition of methanogenesis and accumulation of volatile fatty acids. Fermentation was inhibited at and above 75 mg DDAC/L. DDAC suppressed microbial growth and caused cell lysis at a concentration 50 mg/L or higher. Most of the added DDAC was adsorbed on the biomass. Over 96% of the added DDAC was recovered from all cultures at the end of the 100-days incubation period, indicating that DDAC did not degrade in the mixed methanogenic culture under the conditions of this study.