大亚湾海域多氯联苯及有机氯农药研究

1999年 8月 4日采集了大亚湾次表层水、悬浮颗粒物和表层沉积物并用气相色谱 (电子捕集检测器 )分析了其中 12个多氯联苯 (PCBs)和 18个有机氯农药样品。总PCBs含量 ,水体中介于 91.1～ 135 5 .3ng/L ,沉积物中为 (0 .85～ 2 7.37)× 10 -9;总HCHs含量水体中介于 35 .5～ 12 2 8.6ng/L ,沉积物中则为 (0 .32～ 4 .16 )×10 -9;总DDTs含量在水体中介于 2 6 .8～ 975 .9ng/L ,沉积物中为 (0 .14～ 2 0 .2 7)× 10 -9;而在悬浮颗粒物中均未检出。水体和沉积物中DDT/(DDE DDD)比值较大 ,表明近期仍有此类化学物质输入大亚湾海域。本研究为大亚湾养殖海区提供难降解有机污染物的现状资料。     

武汉典型饮用水水源中典型POPs污染特征与健康风险评估

为了揭示武汉典型饮用水水源中典型持久性有机污染物(POPs)的污染特征与风险水平,采用固相萃取-气相色谱-质谱定性定量分析法,对武汉长江及其支流上18个典型集中式饮用水水源地,共26个采样点水体中多环芳烃(PAHs)、有机氯农药(OCPs)和多氯联苯(PCBs)浓度进行了检测,分析了 POPs的污染水平,并开展健康风险评估.结果表明,26个采样点均有PAHs检出,除苯并[k]荧蒽检出率为88.46％外,其他15种单体检出率均为100.00％,多环芳烃累积ρ(∑PAHs)检出范围为57.04～475.79 ng·L-1,平均值为173.86 ng·L-1.PAHs污染程度总体较低,PAHs主要以中低环芳烃为主,来源于以石油源为主的混合源.共有8种OCPs被检出,(∑OCPs)范围为ND-4.57 ng.L-1,平均值为0.78 ng·L-1,OCPs浓度水平相对较低.共有24种PCBs被检出,ρ(∑PCBs)范围为ND-77.49 ng·L-1,平均值为9.88 ng·L-1,PCBs主要以不易降解的高氯联苯为主,部分点位PCBs浓度超过我国地表水环境质量标准限值,HeptaCBs-180物质需要引起持续关注.健康风险评估结果显示,研究区域内PAHs和PCBs的致癌风险指数均处于10-6～10-4,对人体可能产生潜在的致癌风险;OCPs和PCBs的非致癌风险指数均小于1,不会对人体产生非致癌风险.     

海河河口表层沉积物中PCBs和OCPs的源解析

采集海河河口表层沉积物样品,测定了其中12种多氯联苯(PCBs)和20种有机氯农药(OCPs)的浓度,运用主成分分析-多元线性回归法(PCA-MLR)解析该区域沉积物中PCBs和OCPs的来源,并定量计算了各污染源的贡献量.结果表明,海河沉积物中PCBs的特征源为非故意产生和大气输送2类,基于多元线性回归法的贡献率分别为55%和45%,对PCBs总量的贡献量均值为6.94,9.42ng/g;OCPs的特征源为历史残留和新的输入2类,贡献率分别为13%和87%,对OCPs总量的贡献量均值为21.18,171.97ng/g.海河河口沉积物中POPs的源贡献与该区域的工业生产有关,改善工业结构和妥善处理历史遗留的生产废物是控制海河河口沉积物中POPs的有效途径.     

南四湖沉积物中有机氯农药和多氯联苯垂直分布特征

通过对采集于南四湖湖区的沉积物柱状样品中有机氯农药（OCPs）和多氯联苯（PCBs）同系物的GC-ECD定量分析测定,并结合²¹⁰Pb同位素定年分析,重建了南四湖湖区有机污染物的污染史.结果表明,样品中OCPs、HCHs、DDTs和PCBs的含量范围分别为1.64～17.9、0.66～12.5、0.24～2.99和7.84～42.8 ng·g^-1.柱状沉积物的沉积速率为0.330 cm·a^-1,平均沉积通量为0.237 g·(cm²·a)^-1,所采集的样品沉积时间为1899～2000年.OCPs和PCBs分别在1960和1970年左右出现浓度峰值,随后含量逐渐下降.污染物来源分析表明,HCHs来源于新的工业HCH和林丹2种工业品,HCH和DDT污染主要源于历史上的使用;PCBs主要来自于造纸漂白过程和焚烧炉排放.生态风险评价结果表明,除β-HCH、γ-HCH和艾氏剂3种污染物在14～16　cm附近、对应沉积时间为1960年左右测试数据略高于风险水平低值,其余污染物的所有数据均低于风险水平低值.整体而言,南四湖柱状沉积物中的OCPs和PCBs含量属于低生态风险水平.     

长江口潮滩表层沉积物中PCBs和OCPs的分布

对长江口潮滩表层沉积物中的多氯联苯(PCBs)和有机氯农药(OCPs)进行GC-ECD测试,结果表明PCBs含量分布在0.19～18.95ng/g,平均值为2.70ng/g,其分布随采样点的位置变化显著:排污口附近出现最大值,离排污口越远,即受排污影响的程度越小,其含量越低.OCPs含量在1.25～36.01ng/g,平均值为8.50ng/g,分布特征与PCBs相似,表明了它们来源的相似性.研究区内PCBs和OCPs的含量低于ER-L值,尚未对生物造成显著的负面影响.     

天津滨海地区表层沉积物中持久性有机污染物的含量特征与生态风险

从天津滨海地区不同地表水表层沉积物取样,测定4类持久性有机污染物即多环芳烃(PAHs)、有机氯农药(OCPs)、多氯联苯(PCBs)和多溴联苯醚(PBDEs)的含量,目的是了解该区4类持久性有机污染物的含量特征并对其生态风险进行评估.结果表明,天津滨海地区10个沉积物采样点中16种优先控制的PAHs均有检出,PAHs总含量范围为274.06～2 656.65μg.kg-1、平均为1 198.51μg.kg-1.化石燃料(例如煤和汽油)的燃烧是该区表层沉积物中PAHs的主要来源,个别地方混有石油类产品的输入.在大沽排污河采样点,22种OCPs总含量为3 103.36μg.kg-1,35种PCBs和14种PBDEs的总含量分别为87.31μg.kg-1和13.88μg.kg-1.其它采样点OCPs、PCBs和PBDEs的含量均较低.该区表层沉积物中总有机碳含量与PAHs的相关性很好,但与OCPs、PCBs和PBDEs的相关性较差,这可能与PAHs主要来自面源污染而其它污染物主要来自点源污染有关.沉积物中PAHs(尤其是低分子量PAHs)的风险较大,在多个采样点中,萘和/或苊的含量超过可能效应浓度,极有可能对底栖生物产生不良影响.在大沽排污河,七氯环氧化物和林丹(gamma-BHC)超过可能效应浓度,极有可能对底栖生物产生不良影响;其它采样点OCPs的生态风险较小.整体上,PCBs和PBDEs的生态风险较小.     

家庭室内PM2.5中POPs污染状况及其与儿童哮喘的关系

为了探讨家庭室内PM_(2.5)中POPs的污染状况及其与儿童哮喘的关系.于2014年12月—2015年3月对上海市29个哮喘患儿童及31个健康儿童的家庭室内PM_(2.5)进行采样.采用GC-MS测定了样本中13种PBDEs、17种PAHs及27种PCBs的质量浓度,用GC-μECD测定了9种OCPs的质量浓度,并用SPSS19.0进行数据的统计学分析.家庭室内PM_(2.5)中持久性有机污染物污染状况的结果表明,所有样本∑PBDEs的浓度平均值为32.2 pg·m~(-3),其中,BDE-209占比最大(61.7%);∑PAHs浓度平均值为52.3 ng·m~(-3),7种致癌多环芳烃占比51.8%;∑OCPs浓度平均值为1016.4 pg·m~(-3),HCHs占比最大(43.7%),其次为DDTs,占比29.1%;∑PCBs浓度平均值为72.7 pg·m~(-3),以PCB-82、PCB-99、PCB-8及PCB-49为主.分析污染状况与哮喘的关系发现,病例组样本的∑PBDEs浓度和∑PAHs浓度高于对照组,两者间的差异具有统计学意义(p0.05);病例组样本的∑OCPs浓度和∑PCBs浓度低于对照组,仅∑OCPs浓度在两组间的差异具有统计学意义(p0.05).研究表明,家庭室内PM_(2.5)中POPs污染普遍存在,且哮喘儿童患者家庭室内PM_(2.5)中部分PBDEs、PAHs、OCPs浓度与对照组之间存在显著差异.     

活性炭柱分离有机氯农药和多氯联苯

建立了活性炭层析柱分离16种OCPs和10种PCBs的技术方法。通过比较活性炭的活化温度、活化时间、粒径以及淋洗剂的类型对16种有机氯农药(OCPs)和10种多氯联苯(PCBs)分离效果的影响,结果表明,当活性炭为80目～200目,温度为350℃活化1 h,流动相为20 mL CH3COCH3和10 mL5%的C2H2Cl2-CH3COCH3混合溶液依次洗脱活性炭层析柱时,16种OCPs和10种PCBs的分离效果较好;海水提取液中OCPs和PCBs,经活性炭层析柱洗脱的馏分,用毛细管气相色谱-电子捕获检测器(GC-ECD)测定,其结果证实,该方法可以分离海水样品中的OCPs和PCBs。     

灌河口海域沉积物中有机氯农药的空间分布、来源解析与风险评估

2011年4月通过GC定量检测和210Pb测年对灌河口海域表层和柱状沉积物中OCPs (Organochlorine Pesticides)的空间分布、来源解析进行了研究。结果表明:灌河口海域表层沉积物中OCPs的浓度在nd~58.310-9 (干重)之间,河口海域O,P'-DDT浓度明显高于潮间带和入海河段,3个区域浓度排序为:潮间带河口海域入海河段。DDTs和HCHs浓度均处于国内中等水平。柱状沉积物中OCPs浓度在(2.0~850.0)10-9之间、平均值210.010-9,90年代初期OCPs浓度有所下降,2000年后又在波动中升高。来源解析及柱状样中OCPs浓度变化、转化情况均表明该海域沉积物有新的DDTs源输入。参照加拿大颁布的沉积物质量标准对灌河口沉积物进行风险评估,结果表明灌河口海域以DDT和DDD为主的毒性已处于频繁效应,需深入开展沉积物的环境风险评估研究,确认开展OCPs底质修复方案及区域。     

快速、同时测定海洋沉积物中21种有机氯农药和7种多氯联苯

建立了一种ASE同时提取,SPE净化,气相色谱法(GC-ECD)同时测定海洋沉积物中21种OCPs和7种PCBs的快速分析方法.结果表明:利用SPE Florisil小柱可快速从提取液中分离28种OCPs和PCBs.对含杂质较少的沉积物样品仅需4 mL C6H14和7 mL C6H14/CH2Cl2(V/V 1:1)淋...     

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.     

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.     

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.     

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.     

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.     

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

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Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.