长江江苏段饮用水源地3种雌激素污染特征

分析了丰、平、枯不同水情下长江江苏段28个集中式饮用水源地中雌激素的污染水平和时空分布特征,评价了水源地雌激素活性.研究结果表明,长江江苏段水源地雌酮(E1)、雌二醇(E2)、双酚A(BPA)的浓度处于ng·L~(-1)水平,各雌激素总浓度的均值分别为(1.00±1.72)、(0.65±1.49)、(4.41±5.29)ng·L~(-1),BPA的检出率和平均浓度水平均高于E1和E2,不同水情下浓度差异表现为丰水期枯水期平水期.水源地E1、E2、BPA的活性分别为(0.25±0.43)、(0.65±1.49)、(0.00062±0.00074)ng·L~(-1)(以雌二醇当量计,下同).考虑到雌激素对水生生物的内分泌干扰作用,需在今后的水源地水质安全评价指标体系中加强雌激素监测.     

深圳大鹏湾海域表层沉积物和生物体中多环芳烃残留及其风险评价

为了研究深圳大鹏湾海域沉积物和生物体中多环芳烃的污染状况,2011年10月在大鹏湾采集表层沉积物及鱼类、虾类和贝类等生物样品,采用气相色谱-质谱法(GC-MS)分析了16种优先控制多环芳烃(PAHs)的含量.结果表明,大鹏湾海域表层沉积物和生物样品中PAHs总量范围分别为216.56~1 314.92 ng·g-1(干重,下同)和70.88~251.90 ng·g-1(湿重,下同);生物样品按平均含量计,鱼类最高(171.52 ng·g-1),贝类次之(134.75 ng·g-1),虾类最低(123.35 ng·g-1).与全球其他海域相比,大鹏湾海域表层沉积物和生物体PAHs污染处于中等水平.沉积物中PAHs的组成以4环为主,来源分析表明该海域PAHs污染主要来源于化石燃料燃烧源和石油污染源的共同输入.生物体中PAHs主要为2~3环PAHs,这与其生活习性和污染物的生物可利用性等因素有关.风险评价表明,大鹏湾表层沉积物中的PAHs在一定程度上可能会对该海域生物产生不利影响;生物样品PAHs的苯并(a)芘等效浓度值相对较高,长期食用这些水产品可能会有潜在的健康风险.     

珠江口水体、沉积物及水生动物中HCHs和DDTs的含量与生态风险评价

利用气相色谱(GC-ECD)方法对珠江口水、沉积物及水生动物体内六六六(HCHs)和滴滴涕(DDTs)的污染现状进行了调查,并对该类污染物在水体多介质中的转移分配规律及对水生态环境安全的影响作了初步研究.结果表明,珠江口表层水中HCHs总量检出范围为1.12～8·91ng·L-1,平均值为4.25ng·L-1;;DDTs总量检出范围为2.61～16.86ng·L-1,平均值为7.66ng·L-1.表层沉积物(以干重计)中HCHs总量检出范围2.51～4.75ng·g-1,平均值为3.61ng·g-1;;DDTs总量检出范围为3.01～6.24ng·g-1平均值为4.33ng·g-1.水生动物中河蚬体内的HCHs和DDTs含量最高,分别为44.49和122.62ng·g-1;;虾类次之,为41.04和82.27ng·g-1;;鱼类最低,平均值分别为27.95和65.43ng·g-1.同国内外其他地区河流比较,珠江口水体和底泥中的HCHs和DDTs污染程度较低,但仍具有一定的潜在生态风险.林丹、三氯杀螨醇取代工业生产HCHs、DDTs,成为该水域有机氯污染的重要来源.     

广东典型海水养殖区沉积物及鱼体中磺胺类药物的残留及其对人体的健康风险评价

采用高效液相色谱-紫外检测器(HPLC-UV)分析了广东沿海大亚湾和阳江两个典型海水养殖区中沉积物以及7种养殖鱼类肌肉和肝脏组织中磺胺嘧啶(SDZ)、磺胺二甲嘧啶(SM2)和磺胺甲基异噁唑(SMX)的残留量,并依据药品最高残留量(MRL)值和每日允许摄入量(ADI)值对海水养殖鱼类中磺胺类抗生素污染进行人体健康风险评价.结果表明,在所有沉积物样品中都能检出磺胺类抗生素.含量(干重)范围为:2.1~35.2 ng·g-1,检出率大小顺序为SDZ(85.7%)>SM2(71.4%)>SMX(28.6%).大亚湾养殖区磺胺药物在沉积物和鱼类样品中的检出频率大于阳江养殖区.3种磺胺类药物在鱼肝脏组织中的含量显著高于在肌肉组织中的含量(P<0.05).SDZ、SM2和SMX在鱼体肌肉组织中的含量(湿重)范围分别为11.6~37.9、16.3~27.8和4.9~20.0 ng·g-1.3种磺胺类药物的平均日摄入量范围为3.37~36.72 ng·kg-1,仅占食用肉类ADI的最高限值(50μg·kg-1)的0.007%~0.073%(<1%ADI),健康风险为可以忽略,膳食安全性高.     

血吸虫病疫区水生生物体内氯苯化合物的污染特征与潜在风险

采用GC/MS技术对典型血吸虫病疫区不同水期采集的1种软体生物和5种鱼体肌肉进行分析.实验发现3类二氯苯和六氯苯(HCB)为优势污染物.ΣCBs在软体生物肌肉中几何均值(以脂肪质量计,下同)为11 947 ng·g-1;在鱼体肌肉中范围为1 851~8 159 ng·g-1,鱼体ΣCBs最高浓度出现在鲶鱼体内,最低浓度出现在鲫鱼体内;实验结果与国内外相关文献报道值比较,显示该区域软体生物体内HCB含量与其他区域相当;鱼体肌肉中HCB含量则处于较高污染水平.癌症风险评价结果表明因软体生物和鱼类摄入HCB而带来的风险分别为1.49×10-7和3.73~21.1×10-7,说明研究区域水生生物中因HCB污染引起的癌症风险处于可接受水平.     

青藏高原湖泊流域土壤与牧草中多环芳烃和有机氯农药的污染特征与来源解析

2007年8月采集了青藏高原中部与北部6个典型湖泊流域的土壤与牧草样品,分析了样品中多环芳烃和有机氯农药(包括六六六和滴滴涕)的污染水平.土壤样品中Σ16PAHs、ΣHCHs和ΣDDTs的浓度范围分别为60.6~614 ng·g-1(平均194 ng·g-1)、0.06~0.74 ng·g-1(平均0.31 ng·g-1)和N.D.~0.17 ng·g-1(平均0.07 ng·g-1).牧草样品中Σ15PAHs(不包括萘)、ΣHCHs和ΣDDTs的浓度分别为262~519 ng·g-1(平均327 ng·g-1),0.55~3.92 ng·g-1(平均2.17ng·g-1)和0.20~2.19 ng·g-1(平均0.92 ng·g-1),均远低于欧洲高山中相应介质中POPs的浓度.牧草的生物浓缩效应显著,其生物浓缩因子达到4.2~19.3.POPs的浓度分布与有机质/脂肪含量、海拔均无显著相关关系.PAHs的组成以较轻组分(2、3环PAHs)为主,占总浓度的80%以上.PAHs的特征单体比值表明生物质和化石燃料的低温燃烧是青藏高原PAHs的主要来源,同时较低的α/γ-HCH比率和较高的o,p’-DDT/p,p’-DDT比率表明,林丹以及三氯杀螨醇的使用对高原介质中有机氯农药的污染有一定的贡献.根据反向气团轨迹模型,推断冬季青藏高原中部与北部的污染主要受西风带影响,夏季高原中部位点的污染物主要源自印度次大陆,而北部位点还受到中国内陆省份的影响.     

典型生活污水处理工艺对雌激素效应的去除

针对水环境中内分泌干扰物低浓度、高风险的特点,采用酵母菌法和酶联免疫法对3个污水处理工艺流程中污水的雌激素活性和雌二醇(E2)水平进行评价.结果表明,污水厂进水的雌二醇当量(EEQ)和E2的水平分别为4.35~7.58 ng·L~(-1)和36.95~83.43 ng·L~(-1).雌激素活性和E2的去除主要发生在生物处理阶段,如氧化沟、A~2/O和A~2/O+MBR工艺,且经以上工艺处理之后,雌激素活性和E2分别降低71.10%~75.54%和75.88%~80.72%.污泥对雌激素效应具有一定的去除作用,通过吸附作用污泥的EEQ和E2的含量分别为1.84~2.43 ng·g~(-1)和8.45~12.84 ng·g~(-1).但污水厂出水仍具有较高的雌激素活性,其EEQ为1.06~2.19 ng·L~(-1),对受纳水体的水生生物具有潜在的危害.酶联免疫法与酵母菌法具有很好的一致性,并为水环境雌激素的快速筛选和评价提供了一个新方法.     

珠江口水、沉积物及水生动物中氯苯类有机物的含量及分布

对珠江口水、沉积物及水生动物体内氯苯类有机物(CBs)的污染现状进行了调查,并对该类污染物在水体多介质体系中的转移分配规律进行了初步研究1.结果表明,珠江口表层水中CBs的总浓度为16.44～963.20ng·L-,DCBs(二氯苯)对污染的贡献较为突出,占74.4%;表层沉积物(干重)中CBs总含量为7.83～40.09 ng·g-1,DCBs、TCBs(三氯苯)、TeCBs(四氯苯)、PeCB(五氯苯)和HCB(六氯苯)分别占总量的71.4%、11.1%、13.0%、1.2%、3.6%;水生动物中贝类的CBs平均含量是38873.0ng·g-1、鱼类为2360.3ng·g-1、虾类则为565.0ng·g-1,DCBs和TeCBs是水生动物体内的主要污染物.CBs在水、沉积物及生物体之间存在明显的富集和放大作用.     

珠江河流胶体中的典型内分泌干扰物

采用切向流超滤、固相萃取、气相色谱-质谱联用等分离和分析方法,研究了珠江2条河流中典型内分泌干扰物(EDCs)在胶体相中的含量分布、胶体/水相间的分配作用.结果发现:胶体中4-壬基酚(NP)、双酚A(BPA)、雌酮(E1) 的含量范围分别为23.2~108ng/L、2.3~97.6ng/L、n.d.(未检出)~0.32ng/L,平均值分别为70,31.4,0.3ng/L;17β-雌二醇(E2)、己烯雌酚(DES)、17α-乙炔雌二醇(EE2)、雌三醇(E3)则未在胶体样品中检出.除石龙外,其余各采样点表、底水层间的胶体EDCs浓度水平无显著差异.NP和BPA含量与胶体有机碳(COC)含量、紫外吸收强度(UV254)均呈正相关,说明COC是控制酚类雌激素在胶体相中分布的一个重要因素,NP、BPA和COC之间的相互作用与胶体有机碳的芳香性有关.计算发现,珠江河水中约21%~67% 的 NP、4%~74% 的BPA、24%~26% 的E1存在于胶体相,NP和BPA在胶体/水相间的有机碳归一化分配系数(Kcoc)分别为10 (5.69±0.50)、10 (5.51±0.77),高出各自的悬浮颗粒物/水分配系数(Koc)1个数量级,表明胶体的强吸附能力对EDCs在水环境介质间分配、迁移、转化发挥了重要作用.     

安徽省部分城市土壤中全氟化合物空间分布及来源解析

为探究安徽省城市土壤中全氟化合物(perfluorinated compounds,PFCs)的污染特征、空间分布及潜在的来源.2013年采集安徽省7个城市共11个土壤样品,利用超高效液相色谱-串联质谱联用分析了15种PFCs的含量,并运用主成分分析-线性回归法解析其可能来源.结果表明,被调查的11个城市土壤样品中的ΣPFCs的含量(以干重计,下同)范围为1.15~5.89 ng·g-1,平均含量2.69 ng·g-1.含量最高的单体PFCs是全氟辛烷磺酸(perfluorooctane sulfonate,PFOS),含量范围为n.d.~3.56 ng·g-1,均值含量为0.96 ng·g-1,其次是全氟辛烷羧酸(perfluorooctane acid,PFOA),含量范围为n.d.~2.89ng·g-1,均值含量为0.64 ng·g-1;ΣPFCs含量最高地区是滁州地区(5.89 ng·g-1),以PFOS和PFOA为主,其次为宣城市泾县(4.04 ng·g-1),而其中PFOS含量高达3.56 ng·g-1,占ΣPFCs的88.1%,这可能与该地发达的造纸行业有关;与我国其他地区土壤中PFCs含量相比,安徽省被调查地区的城市土壤中PFCs的含量居于中等水平;安徽省部分城市土壤中60%的PFCs可以有4个因子进行解释,代表性PFCs有PFOA、全氟丁烷磺酸(perfluorobutane sulfonate,PFBS)、全氟十二烷羧酸(perfluorododecanoic acid,PFDo A)、全氟丁烷羧酸(perfluorobutane acid,PFBA)和PFOS.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

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.     

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.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

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.     

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.     

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.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

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 heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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