Activated sludge-mediated biodegradation of dimethyl phthalate under fermentative conditions

The biodegradation of dimethyl phthalate(DMP)was investigated under fermentative conditions in this study.The nature of the intermediate compounds and the extent of mineralization were probed using high-pressure liquid chromatography(HPLC)and liquid chromatography-mass spectrometry(LC-MS)methods.The fermentative bacteria were able to biodegrade the DMP under anaerobic conditions,with the biodegradation rate of 0.36 mg DMP/(L·h).The results demonstrated that the DMP degradation under fermentative conditio...     

Dimethyl phthalate biodegradation by Dunaliella tertiolecta

Dunaliella tertiolecta has an ability to biodegrade dimethyl phthalate(DMP) was found in this study, and the average of the biodegradation rates were 11.3 mg/(L·d) and 30.5 mg/(L·d), and the average of the phthalic acid (PA) production rates were 1.5 mg/(L·d) and 3.6 mg/(L·d), for initial 100 mg/L and 300 mg/L DMP, respectively. The larger amount of accumulation by D. tertiolecta under higher DMP concentration may be responsible for the increase of biodegradation rate, and one of products of DMP biodegradation by D. tertiolecta may be PA. By fitting the process of DMP biodegradation by D. tertiolecta with a kinetic equation newly suggested, the standard deviations between calculated and observed values were 2.5 mg/L and 5.7 mg/L, respectively.     

Electrochemical incineration of dimethyl phthalate by anodic oxidation with boron-doped diamond electrode

The anodic oxidation of aqueous solutions containing dimethyl phthalate (DMP) up to 125 mg/L with sodium sulfate (Na2SO4) as supporting electrolyte within the pH range 2.0–10.0 was studied using a one-compartment batch reactor employing a boron-doped diamond (BDD) as anode. Electrolyses were carried out at constant current density (1.5–4.5 mA/cm2). Complete mineralization was always achieved owing to the great concentration of hydroxyl radical (.OH) generated at the BDD surface. The e ects of pH, apparent current density and initial DMP concentration on the degradation rate of DMP, the specific charge required for its total mineralization and mineralization current e ciency were investigated systematically. The mineralization rate of DMP was found to be pH-independent and to increase with increasing applied current density. Results indicated that this electrochemical process was subjected, at least partially, to the mass transfer of organics onto the BDD surface. Kinetic analysis of the temporal change of DMP concentration during electrolysis determined by High Performance Liquid Chromatography (HPLC) revealed that DMP decay under all tested conditions followed a pseudo first-order reaction. Aromatic intermediates and generated carboxylic acids were identified by Gas Chromatography- Mass Spectrometry (GC-MS) and a general pathway for the electrochemical incineration of DMP on BDD was proposed.     

Biodegradability of terephthalic acid in terylene artificial silk printing and dyeing wastewater

As the characteristic pollutant,terephthalic acid(TA)was in charge of 40%-78% of the total COD of terylene artificial silk printing and dyeing wastewater(TPW-water).The studies on biodegradability of TA were conducted in a serial of activated sludge reactors with TPW-water.TA appeared to be readily biodegradable with removal efficiency over 96.5% under aerobic conditions,hardly biodegradable with removal efficiency below 10% under anoxic conditions and slowly biodegradable with a turnover between 31.4% and 56.0% under anaerobic conditions. TA also accounted for the majority of BOD in TPW-water.The process combined by anoxic,anaerobic and aerobic activated sludge reactor was suitable for TA degradation and TPW-water treatment.Further, the aerobic process was essentially much more effective than the anaerobic or anoxic one to degrade TA in TPW-water.     

Anoxic degradation of nitrogenous heterocyclic compounds by activated sludge and their active sites

The potential for degradation of five nitrogenous heterocyclic compounds(NHCs), i.e.,imidazole, pyridine, indole, quinoline, and carbazole, was investigated under anoxic conditions with acclimated activated sludge. Results showed that NHCs with initial concentration of 50 mg/L could be completely degraded within 60 hr. The degradation of five NHCs was dependent upon the chemical structures with the following sequence:imidazole pyridine indole quinoline carbazole in terms of their degradation rates.Quantitative structure–biodegradability relationship studies of the five NHCs showed that the anoxic degradation rates were correlated well with highest occupied molecular orbital.Additionally, the active sites of NHCs identified by calculation were confirmed by analysis of intermediates using gas chromatography and mass spectrometry.     

Fate and degradation of nonylphenolic compounds during wastewater treatment process

In order to explore the biodegradation behavior of nonylphenolic compounds during wastewater treatment processing, two full-scale wastewater treatment plants were investigated and batch biodegradation experiments were conducted. The biodegradation pathways under the various operational conditions were identified from batch experiments: shortening of ethoxy-chains dominated under the anaerobic condition, whereas oxidizing of the terminal alcoholic group prevailed over the other routes under the aerobic condition. Results showed that the anoxic condition could accelerate the biodegradation rates of nonylphenolic compounds, but had no influence on the biodegradation pathway. The biodegradation rates of nonylphenol (NP) and short-chain nonylphenol polyethoxylates (NPnEOs, n: number of ethoxy units) increased from the anaerobic condition, then the anoxic, finally to the aerobic condition, while those of long-chain NPnEOs and nonylphenoxy carboxylates (NPECs) seemed similar under the various conditions. Under every operational condition, long-chain NPnEOs showed the highest biodegradation activity, followed by NPECs and short-chain NPnEOs, whereas NP showed relatively recalcitrant characteristics especially under the anaerobic condition. In addition, introducing sulfate and nitrate to the anaerobic condition could enhance the biodegradation of NP and short-chain NPnEOs by supplying more positive redox potentials.     

Products of methotrexate during chlorination

Methotrexate(MTX)is a cytotoxic drug widely used in the treatment of tumors,autoimmune diseases and severe asthma. jen00883 This drug has been frequently detected in the aquatic environment with concentrations up to μg/L levels. The MTX present in environmental water might be transformed and removed during chlorination disinfection treatment. In this work,the fate of MTX during aqueous chlorination was investigated in laboratory batch experiments,and the transformation products of MTX were identified. Aqueous solutions of MTX(1 mg/L)were chlorinated by sodium hypochlorite solution at room temperature under neutral p H conditions. Chlorinated products were pre-concentrated with solid-phase extraction(SPE)cartridges and determined by liquid chromatography electrospray ionization tandem mass spectrometry(LC–ESI–MS/MS). The reaction of MTX chlorination exhibited pseudo-first-order kinetics and the half-life time of MTX degradation was calculated to be 1.65 min,when the initial chlorine concentration was 2 mg/L. Two chlorinated MTX congeners,4-amino-3-chlorinated-N10-methylpteroylglutamic(monochloro-MTX)and 4-amino-3,5-dichloro-N10-methylpteroylglutamic(dichloro-MTX)were found in the chlorinated solution. Monochloro-MTX was successfully fractionated by high performance liquid chromatography(HPLC)and its structure was further identified using ~1H nuclear magnetic resonance(NMR)analysis. The presence of the two products in real hospital wastewater was then examined and both compounds were detected. Finally,the effects of MTX and monochloro-MTX on the cell cycle progression in vitro were evaluated using zebrafish liver cell line. It was found that both compounds could inhibit the proliferation of zebrafish liver cells through S phase arrest and their effects on the cell cycle profile had no significant difference.     

Abiotic degradation of four phthalic acid esters in aqueous phase under natural sunlight irradiation

Abiotic degradability of four phthalic acid esters (PAEs) in the aquatic phase was evaluated over a wide pH range 5–9. The PAE solutions in glass test tubes were placed either in the dark and under the natural sunlight irradiation for evaluating the degradation rate via hydrolysis or photolysis plus hydrolysis, respectively, at ambient temperature for 140 d from autumn to winter in Osaka, Japan. The e ciency of abiotic degradation of the PAEs with relatively short alkyl chains, such as butylbenzyl phthalate (BBP) and di-nbutyl phthalate (DBP), at neutral pH was significantly lower than that in the acidic or alkaline condition. Photolysis was considered to contribute mainly to the total abiotic degradation at all pH. Neither hydrolysis nor photolysis of di-ethylhexyl phthalate (DEHP) proceeded significantly at any pH, especially hydrolysis at neutral pH was negligible. On the other hand, the degradation rate of diisononyl phthalate (DINP) catalyzed mainly by photolysis was much higher than those of the other PAEs, and was almost completely removed during the experimental period at pH 5 and 9. As a whole, according to the half-life (t1=2) obtained in the experiments, the abiotic degradability of the PAEs was in the sequence: DINP (32–140 d) > DBP (50–360 d), BBP (58–480 d) > DEHP (390–1600 d) under sunlight irradiation (via photolysis plus hydrolysis). Although the abiotic degradation rates for BBP, DBP, and DEHP are much lower than the biodegradation rates reported, the photolysis rate for DINP is comparable to its biodegradation rate in the acidic or alkaline condition.     

Anoxic gas recirculation system for fouling control in anoxic membrane reactor

Anoxic gas recirculation system was applied to control the membrane fouling in pilot-scale 4-stage anoxic membrane bioreactor(MBR). In the anaerobic-anoxic-anoxic-aerobic flow scheme,hydrophilic polytetrafluoroethylene(PTFE) membrane(0.2 μm, 7.2 m2/module) was submerged in the second anoxic zone. During 8 months operation, the average flux of the membrane was 21.3L/(m2·hr). Chemical cleaning of the membrane was conducted only once with sodium hydroxide and sodium hypochlorite. Dissolved oxygen(DO) concentration in the second anoxic zone was maintained with an average of 0.19 ± 0.05 mg/L. Gas chromatography analysis showed that the headspace gas in the second anoxic reactor was mainly consisted of N2(93.0% ± 2.5%), O2(3.8% ± 0.6%), and CO2(3.0% ± 0.5%), where the saturation DO concentration in liquid phase was 1.57 mg/L. Atmospheric O2 content(20.5% ± 0.8%) was significantly reduced in the anoxic gas. The average pH in the reactor was 7.2 ± 0.4. As a result, the recirculation of the anoxic gas was successfully applied to control the membrane fouling in the anoxic MBR.     

Degradation of indomethacin in river water under stress and non-stress laboratory conditions: degradation products, long-term evolution and adsorption to sediment

The pharmaceutical compound indomethacin is not totally removed in wastewater treatment plants,whose effluents flow into aquatic environments;concentrations in the 0.1-100 ng/L range are commonly found in surface waters,and its fate is unknown.Here,biological,photochemical and thermal degradation assays were conducted under stress and non-stress conditions to estimate its degradation rate in river water and establish its degradation products over time.The results revealed that direct sunlight irradiation promoted the complete degradation of indomethacin(2 μg/L) in less than 6 hr,but indomethacin was detected over a period of 4 months when water was kept under the natural day-night cycle and the exposure to sunlight was partially limited,as occurs inside a body of water.The biological degradation in water was negligible,while the hydrolysis at pH 7.8 was slow.Residues were monitored by ultra-pressure liquid chromatography/quadrupole time-of-flight/mass spectrometry after solid-phase extraction,and six degradation products were found;their structures were proposed based on the molecular formulae and fragmentation observed in high-resolution tandem mass spectra.4-Chlorobenzoic and 2-acetamido-5-methoxybenzoic acids were the long-term transformation products,persisting for at least 30 weeks in water kept under non-stress conditions.Furthermore,the degradation in the presence of sediment was also monitored over time,with some differences being noted.The adsorption coefficients of indomethacin and degradation products on river sediment were calculated;long-term degradation products did not have significant adsorption to sediment.     

Dimethyl phthalate biodegradation by Dunaliella tertiolecta

Dunaliella tertiolecta has an ability to biodegrade dimethyl phthalate(DMP) was found in this study, and the average of the biodegradation rates were 11.3mg/L and 30.5mg/L per day, and the average of the phthalic acid (PA) production rates were 1.5 mg/L and 3.6 mg/L per day, for initial 100mg/L and 300 mg/L DMP,respectively. The larger amount of accumulation by D. tertiolecta under higher DMP concentration may be responsible for the increase of biodegradation rate, and one of products of DMP biodegradation by D. Tertiolecta may be PA. By fitting the process of DMP biodegradation by D. Tertiolecta with a kinetic equation newly suggested, the standard deviations between calculated and observedvalues were 2.5 mg/L and 5.7 mg/L, respectively.     

斜生栅藻降解邻苯二甲酸二甲酯和苯胺的动力学研究

斜生栅藻降解邻苯二甲酸二甲酯和苯胺的动力学研究阎海雷志芳叶常明（中国科学院生态环境研究中心，北京１０００８５）关键词斜生栅藻；邻苯二甲酸二甲酯；苯胺；降解动力学邻苯二甲酸酯类是广泛使用的人工合成有机物，主要作为塑料和橡胶等化工产品的增塑剂，我国和...     

DMP和DEP在氧化铁多相体系中的光催化降解

应用水热合成法制备了4种自然界常见的氧化铁:纤铁矿、赤铁矿、针铁矿和磁赤铁矿,选取邻苯二甲酸二甲酯(DMP)和邻苯二甲酸二乙酯(DEP)作为目标物,研究了它们在氧化铁体系中,紫外光和可见光下的降解过程。重点探讨草酸、光源和氧化铁对其光解效率的影响机制,并与其它文献报道的光解体系进行比较。结果显示,如没有草酸的协同作用,目标物很难发生光解;草酸能够显著促进目标物的光解效率,当目标物初始浓度为20 mg/L,紫外光条件下,DMP和DEP反应60 min后的最高降解率可达到98%以上,可见光条件下,反应180min后可达到96%以上。研究体系与其它光解体系比较,绿色、经济的特点显著。     

Fe(VI)/CaO2双氧化体系降解水环境中的DMP

研究了高铁酸盐（Fe（VI））/过氧化钙（CaO₂）联合处理对邻苯二甲酸二甲酯（DMP）的降解性能及机理,分析了共存离子的影响.基于响应面方法中的Box-Behnken实验设计进行了多因素实验,采用二次多项式和逐步回归法拟合了DMP去除率与Fe（VI）投加量、CaO₂投加量和反应时间之间的关系,对实验条件进行了优化分析.结果表明,在初始pH值为中性条件下,Fe（VI）/CaO₂可以有效去除DMP,降解过程符合准一级动力学模型.当Fe（VI）/CaO₂/DMP物质的量比为1.1/4.4/1时,模型预测DMP最大降解率为95.57%,和验证实验得出的降解率90.14%相近,表明该响应面模型具有较好的模拟和预测能力.HCO₃^-和Mg²⁺对DMP的降解有一定抑制作用.自由基清除实验结果显示,羟基自由基（HO·）和超氧自由基（O₂^-·）对DMP的降解具有重要贡献,表明Fe（VI）和CaO₂可形成类芬顿试剂协同降解污染物.DMP的主要降解途径包括酯基水解、侧链氧化和苯环的羟基化;主要降解产物为邻苯二甲酸单甲酯,2,5-二羟基苯甲酸,间苯二甲酸,草酸等.     

邻苯二甲酸二甲酯的好氧生物降解及生化途径

从红树林底泥中驯化富集培养分离得到的苯二甲酸酯类化合物的降解菌。对此菌株进行了16S rDNA分子生物学的鉴定,并研究了该菌对邻苯二甲酸二甲酯的生物降解特性以及生物降解途径。实验得出该菌能够在邻苯二甲酸甲酯作为唯一碳源和能源的培养基中生长。邻苯二甲酸二甲酯能够在好氧条件下被快速降解,浓度为50 mg/L的邻苯二甲酸二甲酯在5d内可以完全被降解。用高效液相色谱检测降解过程,主要的中间产物为邻苯二甲酸一甲酯(MMP)和邻苯二甲酸(PA)。试验结果表明,邻苯二甲酸二甲酯能够被红树林环境中的微生物降解,而且分离得到的菌株Rhodococcus rubber1k对邻苯二甲酸二甲酯具有高效的降解作用。     

邻苯二甲酸二甲酯在颗粒活性炭中的穿透特性

在25℃条件下,研究了颗粒活性炭(GAC)对水中邻苯二甲酸二甲酯（DMP）的动态吸附特性及其影响因素.在不同进水流量（0.65～4 mL·min^-1）、GAC粒径（550～1　250　μm）、DMP初始浓度（50～400　mg·L^-1）和GAC炭量（0.75～1.4 g）条件下,考察了DMP在GAC柱中的穿透特性.研究表明,GAC对DMP的吸附容量较大,Yoon-Nelson模型能够很好地拟合各种工况下的动态穿透曲线;动态吸附容量随着进水流量和GAC粒径的增大而减小,相反,随着DMP初始浓度和GAC炭量的增大而增大.根据试验数据和Yoon-Nelson模型计算出穿透参数K′、T和穿透点t₁以及平衡点t₂.在建立了各影响因素与Yoon-Nelson穿透模型参数之间的关系基础上,得到了活性炭柱出水浓度与穿透时间和各影响因素之间的动态关系模型.     

邻苯二甲酸酯在黄河沉积物上的吸附特性

文章利用反相高效液相色谱技术研究了黄河兰州段沉积物对水中邻苯二甲酸二甲酯(DMP)的吸附动力学,以及DMP、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸正二丙酯(DnPrP)和邻苯二甲酸二丁酯(DBP)在沉积物上共存的等温吸附行为,探讨了助溶剂甲醇、离子强度等对吸附的影响。结果表明,在一定的浓度范围内,DMP在沉积物上的吸附速率先快后慢;DMP、DEP在沉积物上的等温吸附行为符合线性方程,而DnPrP、DBP的吸附等温线以Freundlich方程拟合最佳;沉积物对DMP的吸附容量还随着离子强度和溶液中甲醇百分比含量的增大而降低。     

邻苯二甲酸酯类化合物生物降解动力学

用改进的鼓泡衰变实验装置,对五种邻苯二甲酸酯进行生物降解反应动力学研究。发现氮单胞菌属(Azomonas)是降解这类化合物的有效菌种,除邻苯二甲酸二辛酯外,其它四种在经过28天反应之后,降解率在98%以上。生物降解反应速率符合一级反应动力学方程。