珠江口典型河段内分泌干扰物的空间分布及风险评价

选择珠江口典型河段为研究对象,调查上覆水和沉积物中5种典型内分泌干扰物(EDCs)4-辛基酚(4-t-OP)、4-壬基酚(4-NP)、双酚A(BPA)、三氯生(TCS)和三氯卡班(TCC)的空间分布特征,并利用风险商值法(RQ)对其上覆水及沉积物进行风险评价.结果表明,5种EDCs在珠江河流上覆水和沉积物样品中均有检出,水体中4-t-OP、4-NP、BPA、TCC、TCS的水体质量浓度分别为:49.19~512.82、112.66~717.31、23.54~2189.88、1.90~120.99、1.51~54.75 ng·L~(-1).沉积物中4-t-OP、4-NP、BPA、TCC、TCS的沉积物质量分数分别为:56.60~1606.56、69.52~6524.35、18.55~522.45、1.54~179.66、0.71~130.92 ng·g-1.5种EDCs在沉积物和上覆水中的空间分布基本遵循上游到下游逐渐减少的趋势.4-t-OP、4-NP、BPA、TCC和TCS的风险商(RQ)在上覆水和沉积物中的范围分别为0.03~4.20和0.026~149.28.对生态健康产生极大压力.沉积物来源、粒度分布和有机质含量均对EDCs在沉积物中的富集有影响,且主要影响因素为沉积物有机质含量.     

太湖流域宜溧河酚类内分泌干扰物的空间分布及风险评价

以NP(nonylphenol,壬基酚)、4-t-OP(4-t-octylphenol,辛基酚)和BPA(bisphenol A,双酚A)为目标物质,研究酚类EDCs(内分泌干扰物)在太湖流域宜溧河地表水体和悬浮物中的空间分布特征及风险评价. 结果表明,太湖流域宜溧河地表水体中ρ(NP)、ρ(4-t-OP)和ρ(BPA)分别为156.2～434.0、11.8～19.4和89.8～353.8 ng/L,悬浮物中w(NP)、w(4-t-OP)和w(BPA)分别为520.0～9 818.2、52.0～454.5和39.0～2 454.5 ng/g. 流域内生活及工业污水排放可能是宜溧河流域水体中酚类EDCs的主要来源,ρ(NP)与ρ(NO₃-)呈显著正相关(R=0.860,P<0.01). 宜溧河水系中酚类EDCs在水相-悬浮物相的有机碳标准分配系数为4.14～6.41,表明悬浮颗粒物的吸附是水体中EDCs迁移的一个重要途径. 研究区域中NP、4-t-OP和BPA的入湖量分别为506、57.9和297 kg/a. 风险评价结果表明,该地区部分河段ρ(EDCs)具有潜在的生态风险.      

低密度聚乙烯(LDPE)膜对内分泌干扰物的动态富集研究

低密度聚乙烯膜(Low-Density Polyethylene,LDPE)在有机物原位被动采样中具有使用简便、耗用量少、成本低廉的优点,但在内分泌干扰物(Endocrine Disrupting Chemicals,EDCs)被动采集方面鲜见应用,有关其平衡分配系数(KLDPE)也不十分清楚.基于此,本文选取7种EDCs,包括双酚A(BPA)、壬基酚(4-NP)、辛基酚(4-t-OP)、雌酮(E1)、β17-雌二醇(E2)、三氯生(TCS)和三氯卡班(TCC),室内模拟LDPE原位动态富集过程,探究了环境因素(温度、pH)对LDPE富集效果的影响,并确定了不同EDCs在LDPE上的富集参数(KLDPE).研究发现,溶液温度升高可以加速LDPE膜对EDCs的吸附,在过低温度条件下(实验设置为4℃),EDCs较难达到膜-水分配平衡;溶液pH对于不同EDCs的影响不尽相同,这可能是因为不同pH条件下EDCs在溶液中形态差异明显,进而影响其在LDPE膜-水之间的分配平衡;7种EDCs的KLDPE实测值均低于各自的经验理论值,这主要由于经验理论值计算过程中未考虑达到分配平衡时有机物从LDPE膜上的解吸附过程,且只考虑了EDCs在膜-水两相之间的平衡.上述结果表明,为提高被动采样测定环境样品中EDCs的准确性,在尽量与实际条件相似的室内条件下获取KLDPE实测值是非常必要的.     

Assessment of source water contamination by estrogenic disrupting compounds in China

Detection of estrogenic disrupting compounds (EDCs) in drinking waters around China has led to rising concerns about health risks associated with these compounds. There is, however, a paucity of studies on the occurrence and identification of the main compounds responsible for this pollution in the source waters. To fill this void, we screened estrogenic activities of 23 source water samples from six main river systems in China, using a recombinant two-hybrid yeast assay. All sample extracts induced significant estrogenic activity, with E2 equivalents (EEQ) of raw water ranging from 0.08 to 2.40 ng/L. Additionally, 16 samples were selected for chemical analysis by gas chromatography-mass spectrometry. The EDCs of most concern, including estrone (E1), 17βup-estradiol (E2), 17αup-ethinylestradiol (EE2), estriol (E3), diethylstilbestrol (DES), estradiol valerate (EV), 4-t-octylphenol (4-t-OP), 4-nonylphenols (4-NP) and bisphenol A (BPA), were determined at concentrations of up to 2.98, 1.07, 2.67, 4.37, 2.52, 1.96, 89.52, 280.19 and 710.65 ng/L, respectively. Causality analysis, involving comparison of EEQ values from yeast assay and chemical analysis identified E2, EE2 and 4-NP as the main responsible compounds, accounting for the whole estrogenic activities (39.74% to 96.68%). The proposed approach using both chemical analysis and yeast assay could be used for the identification and evaluation of EDCs in source waters of China.     

梁子湖水体中环境激素的分布及生态风险评价

该文对枯水期、平水期和丰水期梁子湖水体中2种双酚类和9种类固醇类(5种雌激素、3种雄激素和1种孕激素)环境激素(EH)的浓度水平及分布特征进行了研究,并进行生态风险评价和内分泌干扰效应分析。结果表明,梁子湖水体中有双酚S(BPS)、双酚A(BPA)、雌三醇(E₃)、17α-乙炔雌二醇(17α-EE₂)、雌酮(E₁)、康力龙(SZ)和孕酮(PG)7种环境激素检出。从检出浓度和检出率来看,BPA和PG是梁子湖水体主要的环境激素污染物。枯水期、平水期和丰水期的环境激素总浓度(∑EH)分别为ND～18.17 ng/L、ND～4.21 ng/L和ND～3.50 ng/L,且枯水期和丰水期∑EH最大值均出现在梁子湖入湖口处。与国内外其他湖泊相比,梁子湖水体中双酚类和雌激素的浓度处于中等偏下水平,雄激素和孕激素的污染处于比较低的水平。生态风险评价结果表明,枯水期和平水期分别有50%和63%点位的环境激素总风险商RQs大于1,对水生生物存在高风险,主要是17α-EE₂的贡献,其余处于低风险或无风险;丰水期整体处于低...     

罗时江中5种环境内分泌干扰物的分布特征

以典型的农业面源污染河流——大理洱海罗时江作为研究对象,采用固相萃取、超声萃取和气相色谱质谱联用技术,对河流水体和表层沉积物样品中5种EDCs〔环境内分泌干扰物,包括BPA(双酚A)、E1(雌酮)、E2(17β-雌二醇)、EE2(乙炔基雌二醇)和E3(雌三醇)〕进行分析测定.结果表明,罗时江水体中普遍存在EDCs,其中ρ(BPA)为1.01～43.64 ng/L,ρ(E1)为2.54～20.53 ng/L,ρ(E2)为nd～23.18 ng/L,ρ(EE2)为1.16～13.74 ng/L,ρ(E3)为nd～26.55 ng/L.各采样点EDCs污染通量结果显示,右所、邓川2个乡镇对EDCs污染贡献量最为显著,之后由于湿地截留以及河流的自净作用EDCs污染通量有所削减.罗时江对洱海的入湖EDCs贡献量为1.35～3.70μg/s.在城镇下游处沉积物中E1和E3的富集倍数均为各采样点中最高,这与河流水体中的污染通量变化趋势一致,进一步说明该处污染负荷的加剧,并且说明EDCs会在污染发生时于下游就近沉积.沉积物中w(E3)最高(1.48～28.44μg/kg),其次为w(E1)(0.36～2.95μg/kg),E2因迅速降解不易富集.      

湘江源头某河段水体重金属污染特征与健康风险评价

为探究湘江源头某河段水体重金属分布特征并探讨其对沿岸居民健康的影响,在丰水期、枯水期以及平水期对该河段13个地表水样品中的5种重金属(As、Cu、Pb、Zn、和Cd)进行监测,通过内梅罗综合污染指数法、健康风险评价模型评价了该河段水体中5种重金属的污染现状、分布特征和可能产生的健康风险.结果表明,该河段水体中重金属浓度...     

城市污水处理厂内分泌干扰物浓度分布和去除规律

采集南方某城市3个污水处理厂进出水及各工艺单元的水样,通过固相萃取-衍生化过程对水样进行预处理,并用气相色谱-质谱联用仪定量检测水样中的17α-雌二醇(17α-E2)、雌酮(E1)、雌二醇(E2)、雌炔醇(EE2)、雌三醇(E3)、辛基酚(OP)、正壬基酚(NP)和双酚A(BPA)等8种内分泌干扰物(EDCs).连续4个季度的分析结果显示,3个污水厂进出水及各工艺单元中均有EDCs检出,EE2和BPA是含量最高的两种EDCs,出水中最高浓度分别达到498.9ng.L-1和2652.5ng.L-1,其他6种EDCs浓度均不超过100ng.L-1;生物处理工艺对EE2、E3、NP、OP和BPA有较高的去除率,平均去除率约为57%～85%,但对于E1、E2和17α-E2的去除率较低且不稳定;一级处理工艺对EDCs仅有低于18%的去除率;紫外辐照消毒工艺对EDCs的去除没有明显效果;EDCs浓度季节差异显著,由于雨水的稀释作用,旱季浓度约为雨季的2.5～7.8倍.本文对于了解我国南方地区污水处理工艺中EDCs类物质的分布和转化特点有一定的参考意义.     

湄洲湾海域环境雌激素的污染特征及生态风险评估

2011年8月,对湄洲湾海域表层水体中雌激素类化合物(EDCs)进行了调查。在湄洲湾表层水体中,仅检出雌三醇(E3)、双酚A(BPA)和4-壬基酚(NP)三种EDCs,其总浓度范围为:(15.47~1997.74)ng/L,平均值为274.64±545.91 ng/L。以BPA和NP为主雌激素污染处于中等的水平,湄洲湾中部密集工业污水排放是其主要来源。BPA的浓度从湾内向湾外有逐渐递减的趋势,NP的浓度在大多数站位水平相当,湄洲湾的水动力条件及沿岸的化工企业污水排放影响其的分布。利用商值法得出湄洲湾BPA的残留水平存在生态风险,联合雌激素效应作用可能对该区域的生态环境造成危害。     

松花江水中13种内分泌干扰物的初步调查

用固相萃取(SPE)/高效液相色谱法(HPLC)同时测定了松花江水中的13种典型内分泌干扰物(EDCs).结果表明,哈尔滨段江水中雌三醇(E3)、雌二醇(E2)、雌酮(E1)、乙炔雌醇(EE2)及乙烯雌酚(DES)5种雌激素物质的浓度普遍较高.最高可达66 ng·L-1;酞酸二甲酯(DMP)、酞酸二乙酯(DEP)、酞酸二正丁酯(DnBP)及酞酸二(2-乙基己基)酯(DEHP)4种酞酸酯丰度最大,其中DnBP浓度最高可达330μg·L-1;4-正壬基酚(4-n-NP),带支链的对壬基酚(NP)及4-叔-辛基酚(4-t-OP)3种烷基酚的浓度范围为25-1261 ng·L-1;双酚A(BPA)浓度变化较小,保持在20-50 ng·L-1之间.经与相关报道比较,初步认为松花江水中雌激素类物质及酞酸酯污染较为严重,应当引起有关部门的警惕.     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

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.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

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.