附着剑菌对三氯联苯的吸附及降解机制研究

实验研究附着剑菌(Ensifer adhaerens.R2)对持久性有机污染物三氯联苯(2,4,4′-TCB,PCB28)的去除机制,探究菌株对2,4,4′-TCB的生物吸附和生物降解作用,以及其随时间、pH值、温度、菌体密度、金属离子(Ca2+、Mg2+)的变化.灭活菌体对PCBs的去除机制为生物吸附,吸附率在2h基本达到平衡,为85.97%;活体菌株可以通过生物吸附及生物降解作用去除2,4,4′-TCB,在本次实验周期内主要以吸附作用为主,2h吸附率为60.59%,明显高于降解率的12.90%.单因素条件下,pH值为6.0、35℃、OD为0.8、添加1mol/L的Ca2+、Mg2+处理可使活菌对2,4,4′-TCB的吸附达到最优;pH值为7.5,30℃,添加0.05mol/L的Ca2+、Mg2+处理可使活菌对2,4,4′-TCB的降解达到最优.     

多氯联苯污染土壤的植物-微生物联合田间原位修复

选择宿主植物紫花苜蓿(Medicago sativa L. ),同时接种苜蓿根瘤菌(Rhizobium meliloti)或/和地表球囊霉(Glomus versiforme),在田间试验条件下,研究植物-微生物联合作用对多氯联苯(PCBs)污染土壤的修复效应.结果表明,所有种植植物的处理,根际土壤PCBs 的去除率均高于对照,其中紫花苜蓿并接种根瘤菌的处理,土壤PCBs 的去除率最高,达到42.6%,显著高于其他处理.土壤PCBs 同系物分析结果表明,所有种植植物的处理都增加了土壤中低氯代PCBs 的比例,特别是紫花苜蓿并接种根瘤菌的处理.接种根瘤菌明显促进植株的生长以及植株对PCBs 的吸收和转运.     

多氯联苯污染土壤茵根真菌-紫花苜蓿-根瘤菌联合修复效应

选用紫花苜蓿(Medieago sativa L.)作为宿主植物,盆栽试验研究了丛枝菌根真菌(Glomus caledonium)和苜蓿根瘤菌(Rhizobium meliloti)单接种及双接种对PCBs复合污染土壤的联合修复效应.结果表明.在紫花苜蓿.菌根真菌.根瘤菌共生体系中,紫花苜蓿对土壤中PCBs的降低起到明显作用,使轻度污染和重度污染土壤中PCBs浓度分别下降了15.8%、23.5%,紫花苜蓿单接种菌根真菌和苜蓿根瘤菌后轻度污染和重度污染土壤中PCBs浓度分别下降了14.8%、24.1%和20.6%、25.5%,双接种后土壤PCBs分别降低了23.2%、26.9%,而且也改变了紫花苜蓿根际土壤微生物群落的碳源利用程度,改善了微生物群落功能多样性.可见,紫花苜蓿豆科植物.菌根真菌一根瘤菌特殊共生体对PCBs污染土壤显示了较好的修复潜力.     

维生素B12对脱氯功能蓝藻降解2,4,4’-三氯联苯的促进作用研究

多氯联苯(polychlorinated biphenyls,PCBs)是环境中典型的持久性氯代有机污染物.PCBs污染的生物修复问题是当前环境科学领域的热点.以维生素B12(VB12)为实验材料,应用无氯培养体系,研究了VB12对脱氯功能蓝藻Nostoc PD-2脱氯降解2,4,4’-三氯联苯(PCB28)和降解过程基因表达的影响.结果表明,添加不同浓度的VB12能够促进Nostoc PD-2对PCB28的降解,添加浓度分别为10、100和1000μg·L-1的维生素B12时,与未添加VB12组相比,其7 d脱氯百分比分别提高了11.0%、19.7%和21.9%;添加10μg·L-1和100μg·L-1维生素B12条件下,PCB28的降解半衰期从5.53 d缩短至3.08 d.添加维生素B12后,细胞色素b6f复合体铁硫蛋白基因和双加氧酶基因的表达量均与PCB28的降解效果呈现显著相关性,铁硫蛋白基因表达量与PCB28降解效果的相关性更高.上述结果表明添加VB12能够有效促进脱氯功能藻种PD-2对PCB28的降解,并在基因水平上影响功能藻种的降解活性,这能够为开发高效生物降解PCBs的技术和脱氯功能藻种降解PCBs的机制提供科学依据.     

表面活性剂Burkholderia xenovorans LB400体系对低氯代PCBs的好氧强化降解

增强多氯联苯(PCBs)的水溶性是强化PCBs微生物降解的主要控制因素之一,本研究选取了PCB5(2,3-CB)和PCB31(2,4’,5-CB)作为低氯代PCBs的典型代表,以曲拉通100(TX-100)、吐温80(Tween 80)、鼠李糖脂粗提物(RL crude)3种表面活性剂和β-环糊精(HPCD)联合Burkholderia xenovorans LB400构建PCBs好氧降解体系,测试了它们对PCB5和PCB31的溶出率及微生物生长的影响.结果表明,TX-100(CMC=194 mg·L-1)、Tween 80(CMC=13.1 mg·L-1)、RL crude(CMC=50mg·L-1)浓度在1~7 CMC时和HPCD浓度在500~1500 mg·L-1时对PCB5和PCB31溶出率分别达到54.7%~100%、59.8%~100%;10.5%~40.8%、6.8%~31.6%;10.3%~19.9%、3.3%~11.6%和19.5%~34.2%、4.2%~10.7%.TX-100浓度在1~7 CMC时对B.xenovorans LB400生长的抑制率达到30.3%~45.8%,而Tween 80浓度在0.1~1 CMC时对其生长的抑制率为10.0%~15.4%;RL crude本身能作为底物促进LB400的生长,而HPCD对其生长无明显影响.B.xenovorans LB400对PCB31(5 mg·L-1)的降解效率在添加表面活性剂后有不同程度的提高:TX-100,23.7%~65.5%;Tween80,14.6%~44.3%;RL crude,9.6%~27.2%;HPCD,15.3%~20.7%;而表面活性剂对PCB5(10 mg·L-1)的降解效率则无明显影响.表面活性剂主要通过增大溶液中PCBs-表面活性剂的胶束浓度来提高LB400对PCBs的降解效率,在水溶液培养体系中当设置TX-100和Tween 80浓度分别在1和7 CMC时,PCB31的降解效率达到100%和81.7%,而此时B.xenovorans LB400生长的抑制率为30.3%和5.4%.     

多氯联苯污染土壤菌根真菌-紫花苜蓿-根瘤菌联合修复效应

选用紫花苜蓿（Medicago sativa L.）作为宿主植物,盆栽试验研究了丛枝菌根真菌（Glomus caledonium）和苜蓿根瘤菌(Rhizobium meliloti)单接种及双接种对PCBs复合污染土壤的联合修复效应.结果表明,在紫花苜蓿-菌根真菌-根瘤菌共生体系中,紫花苜蓿对土壤中PCBs的降低起到明显作用,使轻度污染和重度污染土壤中PCBs浓度分别下降了15.8%、 23.5%,紫花苜蓿单接种菌根真菌和苜蓿根瘤菌后轻度污染和重度污染土壤中PCBs浓度分别下降了14.8％、 24.1%和20.6%、 25.5%,双接种后土壤PCBs分别降低了23.2％、26.9%,而且也改变了紫花苜蓿根际土壤微生物群落的碳源利用程度,改善了微生物群落功能多样性.可见,紫花苜蓿豆科植物-菌根真菌-根瘤菌特殊共生体对PCBs污染土壤显示了较好的修复潜力.     

好氧生物泥浆法降解土壤中三氯代多氯联苯的影响因素分析

采用好氧生物泥浆法处理多氯联苯（PCBs）污染土壤,基于五因素三水平正交试验探究葡萄糖、联苯、任意甲基化-β-环糊精（RAMEB）、土水比和降解菌剂5个因素对PCBs降解效率的影响.结果表明：在好氧生物泥浆体系中,仅三氯代PCBs含量显著下降（最高降解率为42.1%）,而四氯~七氯代PCBs含量无显著变化.以三氯代PCBs的降解率为试验指标,对正交试验结果进行极差分析,可知影响三氯代PCBs好氧降解率的主次因素依次为：土水比、RAMEB、葡萄糖、降解菌剂、联苯.其中,葡萄糖和联苯对三氯代PCBs的降解有抑制作用,而土水比、RAMEB及降解菌剂对三氯代PCBs的降解有促进作用.因此,通过提升泥浆体系传质水平、提高PCBs生物有效性及增加降解菌数量,有望进一步提高好氧生物泥浆法降解PCBs的效率.     

PCBs降解菌的筛选及其降解特性研究

采用富集培养的方法从多氯联苯(PCBs)污染土壤中筛选到1株高效降解PCBs的细菌,命名为PS-11.经16S rDNA初步鉴定,此菌株属于嗜麦芽寡养单胞菌(Stenotrophomonas maltophilia).结果表明,菌株PS-11能够以PCBs作为唯一碳源生长并且能够降解PCBs,菌株PS-11对2 mg.L-1PCB52 4 d的降解率为31.1%,7 d的降解率可达52.9%;对难降解的高氯代多氯联苯PCB153 7 d的降解率为10.9%.此外,该菌株的环境耐受性比较好,在30℃、pH为7～9、PCB52浓度为2～10 mg.L-1的条件下生长较快、降解效果较好,尤其在pH 7、PCB52浓度为2 mg.L-1时降解率最高;碳源种类不同,菌株PS-11的生长能力也不同,其中在以蔗糖为碳源时PS-11的生长能力最强,以葡萄糖为碳源时PS-11的适应期最短,且蔗糖、葡萄糖和Tween-80均可提高PS-11对PCB52的降解率;同时菌株PS-11还可耐受一定浓度的重金属,其耐受性大小为Pb2+>Cd2+>Zn2+>Cu2+.     

玉米和小麦对城市污泥施用土壤中多氯联苯的吸收和传输特征

城市污泥施用农田能够改善土壤性状及促进作物生长,但也会使农田存在重金属和有机污染物等污染风险. 多氯联苯(polychlorinated biphenyls, PCBs)作为一类持久性有机污染物,被作物吸收、累积后经食物链传递,潜在威胁着人体健康. 为探究城市污泥施用农田后PCBs在土壤和作物(玉米和小麦)中的分布特征,解析玉米和小麦对土壤PCBs的吸收和传输规律与差异,以关中地区城市污泥施用土壤为研究对象,设置不同植物种属、污泥施用量和污泥类型的土壤盆栽培养试验. 结果表明:①城市污泥施用后造成土壤、玉米和小麦的PCBs污染,土壤、植物根和地上部分以低氯代PCBs〔一氯代PCBs(mono-PCBs)~五氯代PCBs(penta-PCBs)〕为主,且百分含量呈依次增加趋势. ②与种植前相比,种植植物后土壤中更低氯代的PCBs占主导;且土壤∑PCBs消减了20.00%~79.30%,各处理对∑PCBs的消减差异表现为玉米高于小麦、单倍污泥施用量高于双倍污泥施用量、有机质含量最高的污泥施用处理∑PCBs的消减率最高. ③植物根可以吸收土壤PCBs并向地上部分传输,且吸收和传输能力与植物种属、污泥施用量和污泥类型有关,小麦对污染土壤∑PCBs及各PCBs同系物的吸收能力均强于玉米,而传输能力较弱;双倍污泥量施用下植物根对∑PCBs、一氯代PCBs(mono-PCBs)~四氯代PCBs(tetra-PCBs)和六氯代PCBs(hexa-PCBs)的吸收减弱;有机质含量最低的污泥施用下植物根对∑PCBs的吸收能力最强. 研究显示,城市污泥施用会引起土壤和作物PCBs污染,种植作物能消减污染土壤PCBs,而小麦和玉米对土壤∑PCBs及各PCBs同系物的消减和吸收传输存在种属差异.      

十氯联苯的超(亚)临界水降解特性

以多氯联苯(Polychlorinated biphenyls,PCBs)中氯代饱和度最高的十氯联苯(Deca-chlorobiphenyl,D10CB)为对象,考察了反应温度、供氧量、停留时间和Na OH对十氯联苯降解效果和PCBs产物分布的影响,并通过产物的GC-MS检测结果,推测了D10CB的降解机理.实验表明,在供氧量50 m L条件下反应10 min,350~450℃时,D10CB去除率均高于96%,总PCBs的去除率为77.2%~81.2%.供氧量的增加有助于提高PCBs去除率,450℃时,供氧量200 m L比无氧条件下提高了10.5%.Na OH的加入不仅明显提高了D10CB和总PCBs的去除率,而且使产物不同氯代水平PCBs含量分布趋于均匀.结合产物中其他小分子有机组分推测,D10CB超(亚)临界水降解首先发生脱氯反应,继而发生苯环开环、小分子基团去除及氧化分解等复杂反应.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

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.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.