多食鞘氨醇杆菌共代谢降解五氯酚

研究了一株从活性污泥中分离得到的多食鞘氨醇杆菌(Sphingobacteriummultivorum)对五氯酚(PCP)的共代谢降解.比较了细菌分别以苯酚和葡萄糖为生长底物时对PCP的降解效果.结果表明,苯酚对细菌的生长有一定的抑制作用;葡萄糖支持细菌共代谢降解PCP,葡萄糖和非生长底物PCP之间不存在底物竞争抑制现象.蛋白质电泳结果表明,葡萄糖为生长底物时,PCP的降解酶是由PCP自身所诱导;GC-MS分析PCP共代谢降解中间产物时检测到苯酚的存在,说明在好氧降解情况下,PCP的共代谢降解可能也存在渐次脱氯生成苯酚并最终被矿化的过程.     

短链脂肪酸对太湖底泥多氯联苯微生物厌氧脱氯的影响

选取二氯联苯PCB5和PCB12、四氯联苯PCB64和PCB71、类二噁英五氯联苯PCB105和PCB114、六氯联苯PCB149和PCB153、七氯联苯PCB170,考察了添加7.5mmol/L乙酸和7.5mmol/L混合酸（乙酸：丙酸：丁酸=1：1：1）条件下,9种典型商业多氯联苯单体在太湖底泥厌氧微环境中24周内的脱氯降解情况.结果表明：乙酸和混合酸的添加均在一定程度上强化了多氯联苯的降解,多氯联苯总浓度降低速率由（0.276±0.023） mg/（kg·week）分别加快至（0.383±0.033）和（0.410±0.036） mg/（kg·week）;提高了部分脱氯路径的相对反应速率,特别是单侧氯取代的对位脱氯,但未改变脱氯微生物对多氯联苯降解底物的选择性及主要脱氯路径;进一步降低了体系类二噁英多氯联苯总毒性当量（TEQ）,24周降幅均在95%以上;乙酸和混合酸所起到的促进效果并无显著性差异.     

Simultaneous anaerobic- aerobic biodegradation of halogenated phenolic compound under oxygen-limited conditions

The successful application of co-immobilized aerobic-anaerobic biomass under limited aeration in wastewater treatment systems would eliminate the problems associated with the intermediates mono-chlorophenol（MCP） and di-chlorophenol（DCP） accumulations. With low initial pentachlorophenol（PCP） concentration, all PCP could be completely removed under oxygen-limited strict anaerobic conditions, and the removal efficiencies with different initial headspace oxygen percentage（IHOP） were not obviously different from each other. While at high initial PCP concentration, under strictly anaerobic conditions PCP and their intermediates were clearly higher than that under other conditions, and produced obvious accumulation, the highest PCP reduction was achieved by the system receiving 30 IHOP, oxygen-limited system also exhibited lower residual TOC concentration and lower concentration of metabolic intermediates MCP and DCP. These results suggested that under strictly anaerobic condition the reductive dechlorination of low chlorinated compounds became rate limiting in the reductive dechlorination pathway, less chlorinated compounds be more amenable to aerobic degradation, and the aerobes of outer layers could function under limited oxygen. The co-immobilized aerobic-anaerobic biomass for methanogenesis under limited-aeration for chlorophenol degradation might be an attractive and efficient alternative for the sequential anaerobic/aerobic system to achieve mineralization of a broad range of recalcitrance highly chlorinated organics and low final TOC concentrations.     

生活垃圾不同填埋阶段的富里酸对五氯苯酚的降解

采用紫外和红外光谱对不同填埋年限生活垃圾的富里酸(fulvic acid,FA)的结构组成和官能团变化进行分析,并对不同填埋阶段富里酸(FA)的电子转移能力和其对五氯苯酚(pentachlorophenol,PCP)的降解能力进行研究.结果表明,以S.oneidensis MR-1作电子供体,同时添加不同阶段填埋富里酸作电子穿梭体可以显著提高PCP的降解率,降解率能达到80%以上.不同填埋阶段富里酸对PCP的降解有不同的还原转化能力的原因是氧化还原性质存在差异.填埋富里酸具有PCP还原转化能力又归因于其具有电子转移能力,这些功能都利于促进PCP还原脱氯.而填埋富里酸电子转移特性主要源于其结构中含有的电子转移功能基团,其中羟基和羧基是填埋过程富里酸分子中重要的活性官能团,其含量高低将影响PCP还原脱氯效率.     

Mineralization of aqueous pentachlorophenolate by anodic contact glow discharge electrolysis

Exhaustive mineralization of pentachlorophenolate ion (PCP) in phosphate buffer was carried out using anodic contact glow discharge electrolysis (CGDE), in which plasma was sustained between the electrolyte and anode. During CGDE, PCP degraded smoothly. The amount of total organic carbon decreased significantly, indicating the eventual conversion of the carbon atoms of benzene nucleus to inorganic carbons. Furthermore, chlorine atoms in PCP were liberated as chloride ions. As a primary intermediate product, 2,3,5,6- tetrachloro-1,4-benzoquinone was detected, and oxalate and formate as byproducts were also found. It was revealed that disappearance of PCP obeyed first-order kinetics. The reaction rate was generally unaffected by both O2 and inert gases in the cell, although it decreased by raising initial pH of solution. In addition, a plausible reaction pathway involving hydroxyl radical was proposed.     

ORC-GAC-Fe0 system for the remediation of trichloroethylene and monochlorobenzene contaminated aquifer: 1. Adsorption and degradation

Activities at a former Chemistry Triangle in Bitterfeld, Germany, resulted in contamination of groundwater with a mixture of tdchloroethylene(TCE) and monochlorobenzene(MCB). The objective of this study was to develop a barrier system,which includes an ORC(oxygen release compounds) and GAC(granular activated carbon) layer for adsorption of MCB and bioregeneration of GAC, a Fe^0 layer for chemical reductive dechlorination of TCE and other chlorinated hydrocarbon in situ. A laboratory-scale column experiment was conducted to evaluate the feasibility of this proposed system. This experiment was performed using a series of continuous flow Teflon columns including an ORC column, a GAC column, and a Fe^0 column. Simulated MCB and TCE contaminated groundwater was pumped upflow into this system at a flow rate of 1.1 ml/min. Results showed that 17%-50% of TCE and 28%-50% of MCB were dissipated in ORC column. Chloride ion, however, was not released, which suggest the dechlorination do not happen in ORC column. In GAC column, the adsorption of contaminants on activated carbon and their induced degradation by adapted microorganisms attached to the carbon surface were observed. Due to competitive exchange processes, TCE can be desorbed by MCB in GAC column and further degraded in iron column. The completely dechlorination rate of TCE was 0.16-0.18 cm^-1, 1-4 magnitudes more than the formation rate of three dichloroethene isomers. Cis-DCE is the main chlorinated product, which can be cumulated in the system, not only depending on the formation rate and its decaying rate, but also the initial concentration of TCE.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

降解多氯联苯的微生物特性研究进展

综述了多氯联苯（ＰＣＢｓ）需氧降解，包括共代谢的需氧微生物，需氧降解途径和微生物降解环境中持久存在的阿罗克尔（Ａｒｏｃｌｏｒ）商业混合物的特性等；厌氧还原脱氯包括淡水和港湾沉积物中厌氧微生物降解ＰＣＢｓ的特性以及一些脱氯方式（过程）和还原脱氯过程的促进发法。     

二氧化锰氧化降解五氯酚的动力学模拟研究

研究了五氯酚(PCP)在二氧化锰(MnO2)氧化作用下的降解反应动力学,并讨论了无机离子和有机组分对PCP降解动力学的影响.采用n级反应速率模型对PCP降解动力学进行非线性拟合,结果显示n＞0.999,这表明一级反应速率模型适用于模拟PCP降解反应.在保证95%置信区间的条件下,采用准一级反应速率模型对0.5 h内的PCP降解动力学进行了非线性拟合,得到的离心法和维生素C破坏法下PcP降解表观速率常数kobs分别是2.86和2.14 h-1.二价金属离子的加入能降低PCP的kobs;当超过MnO2初始浓度2%以上的Mn2 存在时,Mn2 能对PCP的kobs产生显著影响,而其它不同类型和浓度的离子对kobs不产生显著影响.8种酚酸中的咖啡酸、丁香酸和五倍子酸对kobs的抑制作用达到了显著性水平;而肉桂酸、香豆酸、阿魏酸和邻(对)羟基苯甲酸的影响不明显.研究表明,降低PCP降解速率的主要原因是由于导致PCP在MnO2表面的吸附作用减弱或在MnO2表面与PCP发生竞争反应造成的.     

Photocatalytic degradation kinetics and mechanism of pentachlorophenol based on superoxide radicals

Pentachlorophenol could be photocatalytically reduced with superoxide radicals in aqueous solution under simulated sunlight irradiation.     

二氧化锰氧化降解五氯酚

以二氧化锰为氧化剂,研究了pH 4.12的水溶液中五氯酚氧化降解的反应动力学,并讨论了反应溶液的pH对反应动力学的影响.结果表明,五氯酚对二氧化锰的氧化作用具有较强的反应感受性.在pH一定和二氧化锰充分过量的条件下,随着反应的进行,五氯酚的降解速度变慢,遵循的不是简单的准一级反应动力学而是复合的反应动力学.此外,随溶液pH由3.5升高6.6,五氯酚的降解速度发生显著地下降.运用溶剂萃取和气质联用仪的分析方法,检测到2个主产物和1个次产物.其中,次产物是由四氯-1,4-氢醌与四氯儿茶酚组成的混合物;2个主产物是由五氯酚氧自由基偶合而成的二聚体,且是同分异构体.在观测到的表面反应动力学和降解产物的基础上,提出了五氯酚被二氧化锰氧化降解的反应流程图.     

二氧化锰氧化降解五氯酚

以二氧化锰为氧化剂,研究了pH 4.12的水溶液中五氯酚氧化降解的反应动力学,并讨论了反应溶液的pH对反应动力学的影响.结果表明,五氯酚对二氧化锰的氧化作用具有较强的反应感受性.在pH一定和二氧化锰充分过量的条件下,随着反应的进行,五氯酚的降解速度变慢,遵循的不是简单的准一级反应动力学而是复合的反应动力学.此外,随溶液pH由3.5升高6.6,五氯酚的降解速度发生显著地下降.运用溶剂萃取和气质联用仪的分析方法,检测到2个主产物和1个次产物.其中,次产物是由四氯-1,4-氢醌与四氯儿茶酚组成的混合物;2个主产物是由五氯酚氧自由基偶合而成的二聚体,且是同分异构体.在观测到的表面反应动力学和降解产物的基础上,提出了五氯酚被二氧化锰氧化降解的反应流程图.     

Pd-Ni/GC电极电化学还原水中三氯甲烷的研究

通过电沉积法在玻碳板(GC)电极上负载钯镍双金属,并利用正交实验对其进行循环伏安(CV)研究. CV结果表明,钯镍双金属比钯、镍单金属具有更大的氢吸附峰值,可以在- 500 mV(以Hg/Hg2SO4 为参比电极)左右获得- 24.83 mA的氢吸附峰.扫描电镜分析(SEM)表明,镍的加入改变了钯颗粒在GC表面的分布形态,钯镍双金属颗粒形貌明显不同于钯、镍单金属颗粒,钯镍双金属颗粒粒径介于钯、镍单金属颗粒粒径之间.实验考察了脱氯电流、脱氯时间对三氯甲烷去除率的影响.三氯甲烷的去除率随脱氯电流的增大而增大,随脱氯时间的延长而提高.在优化条件下制备的Pd-Ni/GC电极在0.5 mA、180 min的脱氯条件下对三氯甲烷的去除率为42.53%.可以推测,随着脱氯时间的继续延长,三氯甲烷去除率可得到进一步提高.     

氧化铜催化五氯苯生成二英的研究

研究在加热条件下,五氯苯在CuO表面催化生成二英（PCDD/Fs）的过程.结果表明,在200～350℃,PCDD/Fs的生成量随温度的升高而增加;在350～450℃,PCDD/Fs的生成量随温度的升高而减少.温度较低时（200～250℃）,生成的PCDD/Fs以高氯取代同系物为主;温度较高时（400～450℃）,则以低氯取代的同系物为主.但温度的改变并没有引起同一氯取代度PCDD/Fs中的异构体分布模式发生规律性变化.通过比较400℃条件下CuO催化五氯苯生成PCDD/Fs与CuO催化OCDD/F的脱氯降解情况,推测了五氯苯生成PCDD/Fs的途径.低氯取代的PCDDs可能主要来源于五氯苯生成的高氯取代PCDDs的进一步脱氯降解.而PCDFs则主要由五氯苯脱氯降解生成的低氯取代产物直接缩合生成.     

Pentachlorophenol degradation by Pseudomonas stutzeri CL7 in the secondary sludge of pulp and paper mill

A pentachlorophenol (PCP) mineralizing bacterium was isolated from the secondary sludge of pulp and paper mill and identified as Pseudomonas stutzeri strain CL7. This isolate used PCP as its sole source of carbon and energy and was capable of degrading this compound as indicated by stoichiometric release of chloride and biomass formation. P. stutzeri (CL7) was able to mineralize a high concentration of PCP (600 mg/L) than any previously reported Pseudomonad with PCP as sole carbon source. As the concentration of PCP increased from 50 to 600 mg/L, the reduction in the cell growth was observed and the PCP degradation was more than 90% in all studied concentrations. This isolate was able to remove 66.8% of PCP from the secondary sludge of pulp and paper mill when supplemented with 100 mg/L of PCP and grown for two weeks. This study showed that the removal e ciency of PCP by CL7 was found to be very e ective and can be used in PCP remediation of pulp paper mill waste in the environment.     

工业有机废水为共基质培养降解五氯酚厌氧颗粒污泥

研究了工业有机废水和五氯酚(PCP)共存条件下,改良UASB反应器中厌氧污泥的颗粒化过程.实验发现降解PCP厌氧颗粒污泥形成可分成污泥驯化、颗粒污泥出现与成熟3个阶段,污泥颗粒化过程中污泥量、污泥活性和厌氧消化3大类群细菌数量与生态分布发生特征性变化,所培养颗粒污泥具有脱氯降解PCP的活性,产甲烷优势菌为杆状或长丝状产甲烷丝菌,在生物结构上形成互营微菌落,但污泥颗粒无明显层次性微结构.作为共基质的有机废水其种类影响着颗粒化进程、颗粒污泥脱氯活性与产甲烷优势菌.     

Effect of non-solvent additives on the morphology, pore structure, and direct contact membrane distillation performance of PVDF-CTFE hydrophobic membranes

Four common types of additives for polymer membrane preparation including organic macromolecule and micromolecule additives, inorganic salts and acids, and the strong non-solvent H2 O were used to prepare poly(vinylidene fluoride-co-chlorotrifluoroethylene)(PVDF-CTFE) hydrophobic flat-sheet membranes. Membrane properties including morphology, porosity, hydrophobicity, pore size and pore distribution were investigated, and the permeability was evaluated via direct contact membrane distillation(DCMD) of 3.5 g/L Na Cl solution in a DCMD configuration. Both inorganic and organic micromolecule additives were found to slightly influence membrane hydrophobicity. Polyethylene glycol(PEG),organic acids, Li Cl, Mg Cl2, and Li Cl/H2 O mixtures were proved to be effective additives to PVDF-CTFE membranes due to their pore-controlling effects and the capacity to improve the properties and performance of the resultant membranes. The occurrence of a pre-gelation process showed that when organic and inorganic micromolecules were added to PVDF-CTFE solution, the resultant membranes presented a high interconnectivity structure. The membrane prepared with dibutyl phthalate(DBP) showed a nonporous surface and symmetrical cross-section. When H2 O and Li Cl/H2 O mixtures were also used as additives, they were beneficial for solid–liquid demixing, especially when Li Cl/H2 O mixed additives were used. The membrane prepared with 5% Li Cl + 2% H2 O achieved a flux of24.53 kg/(m2·hr) with 99.98% salt rejection. This study is expected to offer a reference not only for PVDF-CTFE membrane preparation but also for other polymer membranes.     

低温碱性熔体脱氯解毒农药废物及氯盐的富集

以二氯苯酚为代表,采用NaOH-KOH混盐熔体对农药废物进行脱氯解毒处理.研究了温度、碱料比、反应时间等参数对脱氯效率的影响.结果表明,当NaOH和KOH摩尔比为1：1时,混盐的熔点较低,脱氯效果最好.提高碱料比和反应时间可以明显提高脱氯效率,当碱料比为20,反应时间为180min,温度为200℃时,二氯苯酚的脱氯效率达到80.1%.采用多种手段对熔渣进行了分析,红外光谱显示二氯苯酚中的苯环和C-Cl键被破坏,形成了多种氧化中间体.X射线衍射图谱显示反应过程中生成的氯化氢有效保留在碱性熔体中形成氯盐并逐渐富集.     

Ag/Fe催化还原体系处理水体中氯代烃的研究

研究了水体中的三氯甲烷(CF)、四氯化碳(CT)、1,1,1-三氯乙烷(1,1,1-TCA)、1,1,2,2-四氯乙烷(1,1,2,2-TeCA)、六氯乙烷(HCA)、三氯乙烯(TCE)、四氯乙烯(PCE)在Ag/Fe以及Fe⁰还原体系中的还原脱氯反应.结果表明,Ag的加入会明显提高氯代烃的还原脱氯速率,铁表面积浓度为150 m²·L^-1时,如果单独使用Fe⁰,CF、CT、1,1,1-TCA、1,1,2,2-TeCA、     

Identification and characterization of integron mediated antibiotic resistance in pentachlorophenol degrading bacterium isolated from the chemostat

A bacterial consortium was developed by continuous enrichment of microbial population isolated from sediment core of pulp and paper mill e uent in mineral salts medium (MSM) supplemented with pentachlorophenol (PCP) as sole source of carbon and energy in the chemostat. The consortia contained three bacterial strains. They were identified as Escherichia coli, Pseudomonas aeruginosa and Acinetobacter sp. by 16S rRNA gene sequence analysis. Acinetobacter sp. readily degraded PCP through the formation of tetrachloro-phydroquinone (TecH), 2-chloro-1,4-benzenediol and products of ortho ring cleavage detected by gas chromatograph/mass spectrometer (GC-MS). Out of the three acclimated PCP degrading bacterial strains only one strain, Acinetobacter sp. showed the presence of integron gene cassette as a marker of its stability and antibiotic resistance. The strain possessed a 4.17 kb amplicon with 22 ORF’s. The plasmid isolated from the Acinetobacter sp. was subjected to shotgun cloning through restriction digestion by BamHI, HindIII and SalI, ligated to pUC19 vector and transformed into E. coli XLBlue1 , and finally selected on MSM containing PCP as sole source of carbon and energy with ampicillin as antibiotic marker. DNA sequence analysis of recombinant clones indicated homology with integron gene cassette and multiple antibiotic resistance genes.