Reductive dehalogenation of chlorinated dioxins by an anaerobic bacterium

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs and PCDFs) are among the most notorious environmental pollutants. Some congeners, particularly those with lateral chlorine substitutions at positions 2, 3, 7 and 8, are extremely toxic and carcinogenic to humans. One particularly promising mechanism for the detoxification of PCDDs and PCDFs is microbial reductive dechlorination. So far only a limited number of phylogenetically diverse anaerobic bacteria have been found that couple the reductive dehalogenation of chlorinated compounds--the substitution of a chlorine for a hydrogen atom--to energy conservation and growth in a process called dehalorespiration. Microbial dechlorination of PCDDs occurs in sediments and anaerobic mixed cultures from sediments, but the responsible organisms have not yet been identified or isolated. Here we show the presence of a Dehalococcoides species in four dioxin-dechlorinating enrichment cultures from a freshwater sediment highly contaminated with PCDDs and PCDFs. We also show that the previously described chlorobenzene-dehalorespiring bacterium Dehalococcoides sp. strain CBDB1 (ref. 3) is able to reductively dechlorinate selected dioxin congeners. Reductive dechlorination of 1,2,3,7,8-pentachlorodibenzo-p-dioxin (PeCDD) demonstrates that environmentally significant dioxins are attacked by this bacterium.     

零价金属脱氯降解有机氯化污染物研究进展

综述了国内外在零价金属还原脱氯降解有机氯化物领域的研究情况,讨论了零价铁还原脱氯作用机理,展望了零价金属还原脱氯降解有机氯化物研究领域的发展前景。     

地下水高浓度三氯乙烯厌氧生物降解的进展

 三氯乙烯是工业中普遍使用的有机溶剂,是土壤和地下水中普遍存在的污染物,而高浓度三氯乙烯污染更具有持久性。本文从高浓度三氯乙烯脱氯降解的可行性入手,分析其厌氧还原脱氯的降解途径和降解机制的重要要素：电子供体和微生物。同时,讨论了pH值及各种抑制因素对脱氯程度和速率的影响,着重综合比较了常用的还原降解动力学模型,并对今后的研究发展趋势进行了展望。在试验方面,耐高浓度氯代乙烯的脱氯菌株的筛选和培养,以及电子供体基质的效果需要进一步研究;在数值模拟方面,生物反应、水文地球化学反应和地下水物理流动、多组分溶质运移相耦合的模型仍较缺乏,此外模型中的诸多反应类参数仍缺少系统的实验验证,这些都需要进一步研究。     

1，1-二氯乙烷微生物降解菌群的生理学鉴定

从纽约哈得逊河河底淤泥样品中富集分离得到的微生物菌群,在厌氧条件下,可将1,1-二氯乙烷通过还原脱氯的呼吸代谢方式降解生成一氯乙烷.这个微生物菌群可以利用氢气、甲酸、乙酸、苯甲酸和延胡索酸作为电子供体进行还原脱氯生长,并能以丙酮酸发酵的呼吸方式生长,但丙酮酸不能用来作为电子供体进行还原脱氯.通过对其他氯代化合物是否能作为电子受体的实验,发现只有1,1-二氯乙烷能被脱氯.在培养基中加入亚硫酸盐可完全抑制二氯乙烷的还原脱氯,但硫酸盐、硝酸盐和延胡索酸盐的加入却不影响还原脱氯.在以氢气作为电子供体进行还原脱氯时,每摩尔氯原子的还原相应地使细胞干重增加(4.402±1.241)g.同时对富集分离的菌群进行16S rRNA基因序列分析发现,在脱氯生长方式下,该微生物菌群中Dehalobacter细菌占主导地位.     

Interactively interfacial reaction of iron-reducing bacterium and goethite for reductive dechlorination of chlorinated organic compounds

The interactively interfacial reactions between the iron-reducing bacterium （Shewanella decolorationis, S12） and iron oxide （α-FeOOH） were investigated to determine reductive dechlorination transformation of chlorinated organic compounds （chloroform and pentachlorophenol）. The results showed that the interactive system of S12＋ α-FeOOH exhibited relatively high dechlorination rate. By comparison, the S12 biotic system alone had no obvious dechlorination, and the α-FeOOH abiotic system showed low dechlorination rate. The enhanced dechlorination of chloroform and pentachlorophenol in the interactive system of S12＋α-FeOOH was derived from the promoted generation of adsorbed Fe（Ⅱ） by S12. A decrease in redox potential of the Fe （Ⅲ）/Fe （Ⅱ） couple in the interactive reaction system was determined by cyclic voltammetry. Our results will give new insight into interactively interfacial reaction between iron-reducing bacterium and iron oxides for degradation of chlorinated organic compounds under anaerobic condition.     

Reduction of cytochrome c oxidase by a second electron leads to proton translocation

Cytochrome c oxidase, the terminal enzyme of cellular respiration in mitochondria and many bacteria, reduces O(2) to water. This four-electron reduction process is coupled to translocation (pumping) of four protons across the mitochondrial or bacterial membrane; however, proton pumping is poorly understood. Proton pumping was thought to be linked exclusively to the oxidative phase, that is, to the transfer of the third and fourth electron. Upon re-evaluation of these data, however, this proposal has been questioned, and a transport mechanism including proton pumping in the reductive phase--that is, during the transfer of the first two electrons--was suggested. Subsequently, additional studies reported that proton pumping during the reductive phase can occur, but only when it is immediately preceded by an oxidative phase. To help clarify the issue we have measured the generation of the electric potential across the membrane, starting from a defined one-electron reduced state. Here we show that a second electron transfer into the enzyme leads to charge translocation corresponding to pumping of one proton without necessity for a preceding turnover.     

氯代芳烃脱氯速率常数的QSPR研究

测定钯／铁催化还原水中８种氯代烃的反应速率常数,以ＰＭ３算法计算了表征氯代芳烃分子结构的量子化学参数,并用一元回归分析对氯代芳烃的分子结构与与其催化还原脱氯速率进行了定理结构－性能相关研究。     

拉恩氏菌LRP3诱导形成碱式磷酸锌沉淀及其在Zn污染土壤修复中的作用

采用批式和土壤培养实验考察拉恩氏菌LRP3对Zn的磷酸盐矿物诱导及其在Zn污染土壤修复中的作用, 并进行X射线衍射、 扫描电子显微镜、 能谱及Fourier变换红外光谱分析. 结果表明, 菌株LRP3对Zn²⁺的最大耐受质量浓度为120 mg/L; 对溶液中Zn²⁺的去除率为菌体细胞（97.4%）>发酵液（88.2%）>无菌发酵液（81.6%）; 菌株LRP3的发酵液可通过生物矿化作用诱导形成结晶良好的立方体状Zn₂(OH)PO₃矿物晶体; 菌株LRP3的发酵液加入土壤后可快速降低DTPA-Zn的质量比, 培养5 d后DTPA-Zn的质量比平均下降784%, 培养6 d后土壤中Zn的弱酸提取态和可氧化态的质量比分别下降72.5%和562%, 可还原态和残渣态的质量比分别增加85.1%和14.8%. 因此, 菌株LRP3对Zn²⁺具有较强的抗性和吸附能力, 可通过降解植酸释放磷酸根, 进一步诱导形成碱式磷酸锌矿物晶体, 从而降低土壤中Zn的生物有效性, 可用于Zn污染土壤的绿色可持续修复.     

海星内生细菌的分离与初步鉴定

从罗氏海盘车（Aster rollestoni Bell）的胃、幽门盲囊和生殖腺内共分离到20株菌株．其中从其胃中分离到14株,幽门盲囊中分离到5株,生殖腺中分离到1株．根据菌落及菌体形态特征和生理生化实验结果初步认定海星胃中的W1^#、幽门盲囊中的Y1^#以及生殖腺中的S1^#为同一菌株,另外海星胃中的两株菌株（W13^#、W2^#）分别与幽门盲囊中的两株菌株（Y3^#、Y4^#）相同．所得菌株中只有一株为革兰氏阳性球菌,其余为革兰氏阴性杆菌．实验表明海星内生细菌中有62．5％的菌株分属于假单胞菌属（Pseudomonas）和弧菌属（Vibrio）．     

氯酚前驱物气相中形成二噁英类物质（ PCDD/Fs）的研究进展

评述了氯酚前驱物在气相中形成二噁英类物质（PCDD/Fs）的机制,总结了理论上形成PCDD/Fs的主要步骤,包括：氯苯氧基活性基的生成、苯氧基的自缩合作用、产生的初步的中间体经环化作用和脱氯反应形成PCDDs和PCDFs.     

硫化纳米零价铁对五氯苯酚的脱氯及其增强反应

硫化作用可以提高纳米零价铁(nZVI)的催化活性.利用硼氢化物还原法合成了硫化钠米零价铁(S-nZVI),采用比表面积(BET)、X射线衍射(XRD)、扫描电镜(TEM)、傅立叶变换-红外光谱(FT-IR)和X射线光电子能谱(XPS)等方法对材料进行了物理化学性质的表征,应用高效液相色谱仪和离子色谱仪研究了S-nZVI对五氯苯酚(PCP)的脱氯性能.结果表明:与nZVI相比,S-nZVI在聚集体形态和孔隙率上发生明显改变;不同n(Fe2+)/n(S2-)、溶液pH、S-nZVI的老化以及S-nZVI的重新硫化活化对S-nZVI催化PCP的脱氯均有重要的影响;PCP脱氯效率在n(Fe2+)/n(S2-)=60时达到最大;S-nZVI对PCP的还原转化率随溶液pH(5~8)的升高而显著增加;老化的S-nZVI对PCP的降解性能降低,归因于该老化材料的结构发生了变化;而重新硫化活化产生的FeS层可以减小S-nZVI表面的钝化,从而延长S-nZVI的寿命.文中研究对拓展纳米零价铁的应用和环境污染物治理方面具有一定的参考价值.     

MWNTs/TiO2对1,2,3-三氯苯的吸附与光降解协同作用研究

以典型氯苯类有机化合物1,2,3-三氯苯(1,2,3-TCB)为目标去除物,研究复合光催化剂MWNTs/TiO2(多壁碳纳米管负载二氧化钛)对其吸附与光催化降解协同作用.结果表明,在不同温度、pH值、复合光催化剂投加量、紫外光光强等影响因素作用条件下,MWNTs对1,2,3-TCB的吸附去除率与纳米TiO2对1,2,3-TCB的光催化降解去除率的叠加理论计算值曲线均在MWNTs/TiO2对1,2,3-TCB吸附与光催化降解共同作用曲线的下方,充分体现了MWNTs/TiO2对1,2,3-TCB的吸附与光降解初始阶段的协同作用.溶液中温度或pH值降低,有利于复合光催化剂对1,2,3-TCB的去除;复合光催化剂投加量增多或紫外光光强增大将提高复合光催化剂对1,2,3-TCB的去除率.     

混凝-水解-接触氧化处理造纸漂白废水的研究

本文研究了混凝,厌氧酸化,生物接触氧化一体化反应器处理造纸制浆含氯漂白废水,在水力停留时间为15h时,整个系数CODcr总去除率达88．1％,BOD5去除率达81％,AOX去除率达98．4％,毒性值去除了92％,絮凝单元去除的主要是大分子氯代有机物,厌氧单元通过还原脱氯及酸性水解,氯代有机物得到了基本的去除;好氧单元对COD有较高的去除率,红外光谱的分析结果表明：废水中既有木素又有纤维素和半纤维素,虽然漂白废水厌氧处理效果不如好氧处理,但厌氧,好氧联合处理可有效地提高其处理效果。     

A candidate NAD+ transporter in an intracellular bacterial symbiont related to Chlamydiae

Bacteria living within eukaryotic cells can be essential for the survival or reproduction of the host but in other cases are among the most successful pathogens. Environmental Chlamydiae, including strain UWE25, thrive as obligate intracellular symbionts within protozoa; are recently discovered relatives of major bacterial pathogens of humans; and also infect human cells. Genome analysis of UWE25 predicted that this symbiont is unable to synthesize the universal electron carrier nicotinamide adenine dinucleotide (NAD+). Compensation of limited biosynthetic capacity in intracellular bacteria is usually achieved by import of primary metabolites. Here, we report the identification of a candidate transporter protein from UWE25 that is highly specific for import of NAD+ when synthesized heterologously in Escherichia coli. The discovery of this candidate NAD+/ADP exchanger demonstrates that intact NAD+ molecules can be transported through cytoplasmic membranes. This protein acts together with a newly discovered nucleotide transporter and an ATP/ADP translocase, and allows UWE25 to exploit its host cell by means of a sophisticated metabolic parasitism.     

松苗根际生防菌的研究

采用平皿稀释分离法,通过对320株湿地松根际细菌分离物的筛选,获得1株拮抗性强的细菌菌株;运用16S rDNA序列分析方法,对菌株进行了分子鉴定,结果为洋葱伯克霍尔德菌(Burkholderia cepacia)。以镰刀菌属(Fusarium)、丝核菌属(Rhizoctonia)、链格孢菌属(Alternaria)的真菌为病原菌,该菌株和生防菌株Pseudomonas fluorescens Q287、279、1M196、Pf5、HT51、Q3787、MVP14、FFL1R8共同对病原菌的平皿对峙试验,该菌株对立枯丝核菌、链格孢菌都有较强的拮抗作用,120 d盆栽测试得知,菌株P.fluorescens Q287最高保存率为77%,该菌株的最高保存率为62%,其拮抗效果和菌株Q287一样,均高于其他7个生防菌株,试验证明该菌株具有防治松苗猝倒病的潜力。     

三株染料脱色优势菌的分离与鉴定

从温州印染厂废水池污泥中分离出三株染料脱色优势菌,其中Ａ１对活性桃红ＫＤ－８Ｂ脱色率为８７．５％,Ａ２对活性桃红ＫＤ－８Ｂ脱色率为９０．２％,Ａ３对弱酸猩红ＦＧ的脱色率为８６．４％,并根据各菌株的个体、群体形态和生理化实验对细菌进行鉴定,三株细菌分别定名为：Ａ１为睾丸酮假单胞菌,Ａ２为嗜麦芽黄单胞菌,Ａ３为恶臭假单胞菌。     

气固法合成氯磺化聚乙烯I.气-固相反应机理

以氯化聚乙烯为原料,氯气和二氧化硫为反应气体,紫外光引发,气固法合成了氯磺化聚乙烯。通过元素分析得出,氯磺化反应中不存在氯化和脱氯的副反应。在釜式反应器内研究了氯磺化反应的气固相反应机理,发现气体的内扩散和本征化学反应是氯磺化反应的控制步骤,升高温度（在30－50℃范围内）使氯磺化反应后期的速率显著提高,这是由氯化聚乙烯的共结晶的熔融引起的。还讨论了氯化聚乙烯的链结构和固态结构对氯磺化反应的影响。     

SUBSTITUENT EFFECTS IN THE BIRCH REDUCTION REACTION OF SUBSTITUTED BENZENES

The substituent effects in the Birch reduction reaction of substituted benzenes are discussed. A nonplanar^boat-form conformation is suggested for the benzene radical union formed by the transfer of an electron to a substituted benzene-molecule. In this conformation the 1,4 -dienyl radical union has two double bonds isolated,the negative charge is localized on po-sion 6 and the. single electron is on position 3.the farthest position from the negative charge, when the substituent is electron-withdrawing. Both alkyl and alkoxy groups are considered to be electron-withdrawing. These sub-stituents should be activating groups for their inductive effect. The reaction rate decreasing of alkyl benzenes may be caused by reasons other than electronic effect. The reduction of benzole acid and. benzamide, in which 1,4-dihydro benzenes are obtained,is considered to be an exceptional example,in which an extra stabilized Y-aromatic radical union may be involved.     

一株融合菌的构建及其调剖特征研究

利用原生质体融合的方法构建了微生物采油菌株,并通过其耐温、产糖量等指标筛选了一株优秀的融合子RH18.适应性实验表明,RH18在40℃下能代谢不溶于水的生物多糖,在有杂菌的地层水中也能生长代谢;岩心驱替实验表明,RH18在多孔介质中流动会优先进入大孔道,发酵产糖后能较好地封堵大孔道、调整吸水剖面和提高非均质油层的采收率;从岩心剖面电镜照片上观察到了生物多糖的形状及其分布,分析了融合菌调剖堵水的微观机理.     

Dechlorination of 2,4-dichlorophenol by nickel nanoparticles under the acidic conditions

Metal nanoparticles are effective for remediation of contamination with a range of compounds including chlorinated organics.However,the sorption process of the passivation oxide layers on the metal nanoparticle surfaces may result in incomplete degradation of contaminants.This phenomenon can be prevented by an acidic washing procedure or reaction in an acidic medium.In this paper,nickel nanoparticles manufactured via the carbonyl powder process were analyzed using scanning electron microscopy,transmission electron microscopy,X-ray diffraction and energy-dispersive X-ray spectroscopy.The sorption and degradation of 2,4-dichlorophenol (2,4-DCP) by nickel nanoparticles under acidic conditions was then investigated.Transmission electron microscopy and XRD results showed that the nickel nanoparticles range in size from 10 to 20 nm,and a thin passivation layer of NiO is present on the surface.This oxide layer can be removed by pretreatment washing with acidic solutions.It was indicated that dechlorination was the key reaction pathway for degradation of 2,4-DCP by nickel nanoparticles under acidic conditions.The main degradation products were 4-Chlorophenol,2-Chlorophenol,and Phenol,and among these,Phenol was dominant.The acidic medium promoted degradation by providing an appropriate pH,and H+ may be involved in the reaction.Dechlorination of 2,4-DCP by nickel nanoparticles under the acidic condition follows the second order kinetic model,and the rate constants at 298,306,316 K are 0.02,0.2 and 0.3 (g L h)-1,respectively.