太湖流域双酚AF和双酚S人体健康水质基准的研究

作为双酚A(Bisphenol A, BPA)的替代物,双酚AF(Bisphenol AF, BPAF)和双酚S(Bisphenol S, BPS)在工业中被广泛使用.近年来,BPAF和BPS在水环境中不断被检出,由于其难降解特性和较高的毒性效应,可能会对水生态系统和人体健康造成不利影响.基于此,本文以太湖流域为研究对象,开展太湖的人体健康基准研究,依据本土化人体暴露参数、水质参数、BPAF和BPS的生物累积系数等相关数据,推导出太湖流域BPAF和BPS基于人体健康风险的水环境质量基准值(Ambient Water Quality Criteria, AWQC)分别为0.4455μg·L~(-1)和10.02μg·L~(-1).此外,通过对特殊人群和普通人群的人体健康基准值进行比较,发现特殊人群的基准值均低于普通人群的基准值.该研究推导的BPAF和BPS基于人体健康风险的水环境质量基准值,可为我国双酚替代物的环境风险管理、人体健康基准研究和水环境质量标准的修订工作提供技术支持.     

人体健康水质基准特征参数研究及应用

人体健康水质基准是指在摄入饮用水和水产品时,保护人群健康不受危害的相对应水体中污染物的浓度.我国近年来系统开展了水质基准的研究,但在人体健康水质基准方面的报道相对较少.为保护我国人群健康免受水体中污染物的危害,依据人体健康水质基准制定方法,对基准制定过程中涉及的我国人群暴露参数〔体重（BW）、饮水量（DI）和水产品摄入量（FI）〕和水环境参数〔溶解性有机碳（DOC）、颗粒态有机碳（POC）浓度以及水生生物脂质分数〕进行研究与总结,建议在制定我国人体健康水质基准时,普通人群暴露参数BW、DI和FI分别采用61.9 kg、2.785 L/d和0.030 1 kg/d,水环境参数DOC和POC浓度分别采用2.68和0.73 mg/L,第2、3、4营养级淡水水生生物的脂质分数分别采用2.47%、3.08%、3.16%.基于我国人群暴露参数和水环境参数,推导了12种多环芳烃（PAHs）的人体健康水质基准,其中苯并[a]芘的基准值（4.53×10-4 μg/L）最小,蒽的基准值（173 μg/L）最大.此外,在人体健康水质基准的制定过程中,除饮水途径外,建议充分考虑食用水产品对人体健康产生的危害效应;针对关注区域、年龄组与致癌风险水平不同造成的基准值的较大差异,建议在人体健康水质基准制定过程中对其予以充分考虑.      

不同形态的砷水生生物基准探讨及在辽河流域的初步应用

有毒元素砷在我国各流域分布广泛,主要包括三价和五价两种价态,其毒性差别很大,目前我国缺乏本土的砷水质基准研究,而国外的砷水质基准多以总砷表示,科学性有待商榷.因此,本文分别搜集了三价砷、五价砷和总砷对我国本土水生生物的毒性数据,共获得三价砷12属12种,五价砷18种23属,以及总砷25属29种的合格数据.利用美国环保局推荐的物种敏感度排序法,通过数据分析得出,三价砷的急性和慢性基准阈值分别为84.26μg·L-1和56.55μg·L-1,五价砷的急性和慢性基准阈值分别为1171μg·L-1和633.3μg·L-1,总砷的急性和慢性基准阈值分别为264.4μg·L-1和150.7μg·L-1;总砷的基准阈值与美国现行砷基准值相当,而五价砷基准阈值与三价砷基准阈值体现出数量级的差异,因此,需要分价态考虑砷基准的制定.基于推算的砷基准阈值,用商值法评价了辽河流域枯水期总砷暴露的生态风险.检测结果表明,辽河的总砷暴露浓度范围在2.6~82.4μg·L-1之间,全部位点均无风险,但西辽河段上游支流两点位的砷浓度分别超出三价砷慢性基准阈值的1.20和1.45倍,表明可能存在潜在的砷暴露风险.     

实测/预测辽河铬(Ⅵ)水生生物基准与风险评估

该研究对辽河流域重金属铬(Ⅵ)的水生生物毒性数据进行搜集与筛选,推导辽河流域铬(Ⅵ)的水生生物基准值,并对辽河流域25个采样点位采集水样,测定铬(Ⅵ)的环境暴露浓度,最后对辽河流域水生生物铬(Ⅵ)暴露的潜在风险进行评估.此外,采用美国环境保护署(US EPA)物种种间关系估算模型(ICE)对辽河流域物种毒性值进行预测,并对基于预测毒性值的水生生物基准进行推导.结果表明,辽河流域基于实测毒性数据的水生生物急性基准值(CMC)为17.73μg·L-1,慢性基准值(CCC)为12.15μg·L-1;ICE模型预测的辽河流域生物毒性值推导的CMC值为13.97μg·L-1,实测CMC值与预测值比较接近,表明ICE模型可应用于水生生物基准值的预测.铬(Ⅵ)的水质分析结果表明25个采样点位水体铬(Ⅵ)浓度较低,均达到GB 3838-2002地表水质标准中铬(Ⅵ)的Ⅰ类或Ⅱ类标准,水质状况良好;然而,在对水生生物的潜在风险方面,通过生态风险评估得出7月辽河流域25个点位中环境暴露值超过慢性基准CCC值的有7个,12月超过慢性基准CCC值的有6个,表明辽河流域个别点位铬(Ⅵ)暴露可能会对水生生物产生不可接受的风险.     

铅水生生物基准研究与初步应用

文章搜集筛选了重金属铅对我国淡水生物的25种急性毒性数据,采用美国水生生物基准技术对铅水生生物基准进行推算,得出保护我国淡水生物的铅急性基准值为0.131 mg/L,慢性基准为0.005 1 mg/L。以荷兰和澳大利亚-新西兰的基准计算技术对基准计算结果进行了比对,结果表明美国基准技术方法相对可行。应用获得的铅基准值对辽河流域区域进行铅暴露生态风险评价,结果表明大部分区域点位都存在一定的铅暴露生态风险,风险位点主要集中在城市区域以及河流下游,研究结论可为铅水质标准制定和流域水环境管理提供技术支持。     

基于人体血铅指标的区域土壤环境铅基准值

由于铅对儿童的强烈神经毒性且土壤铅已经成为儿童铅暴露的主要来源,土壤环境铅基准一般基于儿童血铅含量的方法制定.收集国内现有资料,总结并确定出符合我国实际的关键参数取值范围,其中空气、饮水中铅含量分别在0.12~1.0μg.m-3、2~10μg.L-1之间;0~6岁儿童饮食暴露途径铅摄入量约10~25μg.d-1;育龄妇女血铅几何均值4.79μg.dL-1,标准差1.48.采用国际上认可度较高的综合暴露吸收生物动力学模型(IEUBK)和成人血铅模型(ALM),计算我国居住用地和工业/商业用地土壤环境铅基准值分别为282 mg.kg-1和627 mg.kg-1,略低于英美等国.参数敏感性分析表明,我国儿童平均铅暴露量明显高于发达国家且暴露场景与欧美发达国家有明显不同.我国亟需开展环境铅暴露与儿童血铅含量相互关系研究,制定基于血铅指标的铅污染土壤风险评估方法导则.     

陆浑水库饮用水源地水体中金属元素分布特征及健康风险评价

在2016年对陆浑水库饮用水源地46个水样中12种金属元素(包括重金属As、Cd、Cr、Cu、Fe、Hg、Mn、Mo、Ni、Pb、Zn和轻金属Al)进行测定,探讨了水体中金属元素的分布特征,并借助健康风险评价模型评价了水体中金属人体健康风险.结果表明,陆浑水库饮用水源地水体中Al最大浓度(200.27μg·L~(-1))和Mo所有浓度(151.42~170.69μg·L~(-1))均超过《地表水环境质量标准》(GB 3838-2002)和《生活饮用水卫生标准》(GB 5749-2006)规定的标准限值,超标率依次为4.35%和100%.陆浑水库饮用水源地水体中金属浓度分布具有较明显的空间差异性,高值区域集中在库区西南部(上游)、东北部(下游).健康风险评价结果表明,儿童暴露剂量明显高于成人暴露剂量,金属元素经饮用水途径引起的健康风险均高于皮肤接触途径.金属致癌风险中,Cr和As致癌风险超过最大可接受风险水平(5.0×10~(-5)a~(-1)),超标率分别为100%和3.80%,Cr对总致癌风险的贡献率平均达到85%;非致癌性金属元素健康风险(10~(-12)~10~(-7)a~(-1))呈现出AlMoCuPbNiHgFeZnMn,比最大可接受风险水平低2~7个数量级.     

磺胺甲噁唑淡水水生生物水质基准与生态风险评估

磺胺甲噁唑是一种被广泛使用的磺胺类抗生素.它在江河湖泊等地表水中广泛存在,且对生物具有一定毒性,被认为是淡水环境中重要的污染物之一.为得到磺胺甲噁唑的水生生物保护浓度,本研究基于搜集筛选的磺胺甲噁唑对中国淡水水生生物的17个物种的急性毒性数据,10个物种的慢性毒性数据,采用物种敏感度分布法推导了磺胺甲噁唑对中国淡水水生生物的水质基准,得出磺胺甲噁唑的短期水质基准值为34.87μg·L^-1,长期水质基准值为21.73μg·L^-1.此外,为探究磺胺甲噁唑在我国淡水环境中的风险水平,本研究结合推导出的磺胺甲噁唑水质基准以及急性毒性数据,分别使用熵值法和安全阈值法对我国部分流域进行生态风险评估.结果表明两种方法得出的结果并无较大差异,磺胺甲噁唑在我国淡水流域中几乎没有生态风险.     

七大流域氨氮水生生物水质基准与生态风险评估初探

氨氮是我国流域水环境管理的国控指标之一,为评估不同流域的氨氮基准差异性,以七大流域(松花江流域、辽河流域、海河流域、黄河流域、淮河流域、长江流域和珠江流域)为研究对象,基于水质参数对氨氮毒性的影响,借鉴US EPA(美国国家环境保护局)水环境基准技术方法,分夏季和非夏季2种情况推算了各流域氨氮水生生物基准值. 结果显示:①流域和季节的不同导致氨氮基准值的差异均很明显,不同流域的氨氮基准值差异可超过6倍,同一流域不同季节的氨氮基准值差异可超过2倍. ②淮河流域夏季和非夏季氨氮基准值均为最低,夏季氨氮急、慢性基准值分别为0.37和0.06 mg/L,非夏季分别为0.81和0.15 mg/L. ③氨氮暴露生态风险初步评估结果表明,珠江流域风险较小;松花江流域、辽河流域、长江流域次之;黄河流域风险较大;海河流域和淮河流域风险最大,海河7个断面中有2个存在高风险,淮河27个断面中16个存在高风险. 根据各流域不同季节氨氮基准值及氨氮暴露生态风险的差异,建议对不同流域、不同季节实行差异化管理.      

基于人体健康模型（IEUBK、ALM）的温岭地区土壤环境铅基准值研究

以浙江温岭市人群(孕妇、儿童)为研究对象,借鉴国际上认可度较高的由美国国家环境保护署开发的综合暴露吸收生物动力学模型(IEUBK)及成人血铅模型(ALM),采用实验室检测、问卷调查、文献查询等多种方式优化模型参数,推导出该区域基于人群健康风险的土壤环境铅基准值分别为180 mg·kg-1(IEUBK)、555.6 mg·kg-1(ALM),低于英美等发达国家不同场地铅土壤环境基准值.同时,对2种模型参数进行蒙特卡罗分析,探讨模型单因子变化对预测结果造成的影响.结果发现,IEUBK模型参数中空气、饮用水2种介质的铅暴露浓度敏感性均为50.8%,ALM模型中育龄妇女血铅含量几何标准差GSD、根据设定目标血铅浓度时保护人群的概率水平取值n等参数均呈负敏感性,且敏感性最高分别为-39.6%、-19.5%.由敏感性分析结果可知,呼吸暴露途径对模型结果的影响较为显著且普遍高于经口暴露,但由于经口暴露累加的消化吸收量较高,对模型的预测结果也造成一定程度的影响.本研究中优化模型参数提高推导结果的灵敏度可使预测结果更为科学、准确,降低其不确定性,可为后期我国污染土壤铅基准值的制定提供理论依据.此外,需要说明的是,模型涉及的人群铅暴露途径受体为美国人群,是否完全适合中国人群尚需要进一步研究.     

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.     

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.     

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.     

Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.     

Sorption of 1-naphthol by plant cuticular fractions

The contribution of aliphatic-rich plant biopolymer to sorption of hydrophobic organic compounds is significantly important because of their preservation and accumulation in the soil environment,but sorption mechanism is still not fully understood.In this study, sorption of 1-naphthol by plant cuticular fractions was examined to better understand the contributions of respective fraction.Toward this end,cuticular materials were isolated from the fruits of tomato by chemical method.The tomato cuticle sheet consisted of waxes (6.5 wt%),cuticular monomer (69.5 wt%),and polysaccharide (24.0 wt%).Isotherms of l-naphthol to the cuticular fractions were nonlinear (N value (0.82-0.90)) at the whole tested concentration ranges.The KodKow ratios for bulk cuticle (TC1),dewaxed cuticle (TC2),cutin (TC4),and desugared cuticle (TC5) were larger than unity,suggested that tomato bulk cuticle and cutin are much powerful solption medium.Sorption capability of cutin (TC4) was 2.4 times higher than the nonsaponifiable fraction (TC3).The 1-naphthol interactions with tomato cuticular materials were governed by both hydrophobic-type interactions and polar (H-bonding) interactions. Removal of the wax and polysaccharide materials from the bulk tomato cuticle caused a significant increase in the sorption ability of the cuticular material.There was a linear negative trend between K_(oc) values and the amount of polysaccharides or fraction's polarities ((N O)/C);while a linear positive relationship between K_(oc) values and the content of cutin monomer (linear R~2=0.993) was observed for present in the cuticular fractions.Predominant sorbent of the hydrophobic organic compounds (HOCs) in the plant cuticular fraction was the cutin monomer,contributing to 91.7% of the total sorption of tomato bulk cuticle.     

Seed selections for crystallization of calcium phosphate for phosphorus recovery

Seed induces and promotes the crystallization of calcium phosphate, and acts as carrier of the recovered phosphorus （P）. In order to select suitable seed for P recovery from wastewater, three seeds including Apatite （AP）, Juraperle （JP） and phosphate-modified Juraperle （M-JP） were tested and compared. Batch and fixed-bed column experiments of seeded crystallization of calcium phosphate were undertaken by using synthetic wastewater with 10 mg/L P phosphate. It shows that AP has bad enduring property in the crystallization process, while JP has better performance for multiple uses, and M-JP is a hopeful seed for P recovery by crystallization of calcium phosphate.