海南岛沿岸牡蛎体内DDTs的时空分布特征及评价

于2006年~2012年在海南岛东寨港、马袅港、八所港和榆林港4个典型港湾采集近江牡蛎（Crassostrea rivularis ）样品,用气相色谱法测定其滴滴涕（DDTs）的质量分数。结果显示,DDTs残留范围为未检出-4.51 ng·g-1（湿质量）,平均为1.45 ng·g-1,4个采样点w（DDTs）的区域差异不显著（P〉0.05）。与国内外其他海域相比,海南岛沿岸贝类体内DDTs残留水平较低。在2006年~2012年间,DDTs于2007年出现了一个相对高值,之后5年呈先下降后趋于平稳的趋势。此研究结果与1985年海南岛近海贝类体内的DDTs残留量均处于100 ng·g-1水平级范围。通过对牡蛎样品DDTs的组分特征分析,认为目前检测到的DDTs主要来源于历史使用残留,但推断2006年~2007年可能有三氯杀螨醇来源的DDTs输入。结果表明,海南岛沿岸牡蛎体内DDTs符合中国《海洋生物质量》一类质量标准,也未超出中国相关残留限量标准,其食品安全风险在可接受范围内。     

滇池周边大棚土壤中六六六和滴滴涕残留特征

采用气相色谱(ECD)对滇池周边不同年限大棚土壤中六六六(HCHs)和滴滴涕(DDTs)残留量进行了测定, 探讨其残留分布特征。结果表明: (1)大棚种植年限对土壤中残留量影响显著, 种植年限长于10 年的大棚土壤中HCHs 和DDTs 的残留量显著高于年限短于10 年的大棚, DDTs 是有机氯农药(OCPs)的主要组成成分;短于10 年的大棚间, 土壤中HCHs 和DDTs 残留量差异不显著。(2)不同土层中, HCHs 残留量在土壤剖面上的变化趋势不明显, 而DDTs 在表层土壤(0~20 cm)中残留量显著高于下层。(3)从HCHs 和DDTs 的同系物组成来看, HCHs 以β-HCH 残留量最高, 部分样点中p,p′-DDT/(DDD+DDE)比值大于1。可判断HCHs 残留主要是过去施用的残留物, 而DDTs 仍有新的污染输入, 有待进一步调查研究。     

福建省海水贝类养殖区表层沉积物及贝类滴滴涕的残留与风险评价

为了评估福建省海水贝类养殖区滴滴涕(DDTs)的残留水平和风险,于2005年8月和2006年8月,采集养殖区20个站位的表层沉积物样品20个、养殖贝类样品46个,用气相色谱法测定其中DDTs的残留量,并对其残留水平、分布趋势和组成特征进行分析,以期对该地区污染状况、生态风险及贝类食用安全进行探讨与评价。结果表明,福建省贝类养殖区表层沉积物DDTs含量范围为1.93～56.6μg/kg(干重),平均值15.8μg/kg;40%的样品DDTs的污染指数在0.697～2.83之间,不同程度受到DDTs的污染,提示存在一定的潜在生态风险。养殖贝类DDTs含量范围为2.04～107μg/kg(湿重),平均21.7μg/kg;贝体DDT残留量符合中国无公害水产品质量安全标准,低于欧盟、美国、日本的食品安全限量;以每人50 g/d的摄食量估算,沿海居民食用养殖贝类的DDTs暴露量远低于WHO暂定的TDI值、美国EPA推荐的RfD值,由此引起的健康风险小。与国内邻近海域相比较,福建省贝类养殖区表层沉积物和养殖贝类体中DDTs残留量处于中等水平,与亚太等国外海域相比较,处于较高水平;从DDTs的组成特征推测,调查区部分海域有新的DDTs污染源输入。     

紫菜中六六六、滴滴涕和扑草净的检测

利用气相色谱-质谱联用技术测定紫菜中六六六、滴滴涕和扑草净的残留量。试样用乙腈提取,经石墨化炭黑/氨基复合柱净化,采用气相色谱-电子轰击源质谱测定,检测模式采用选择离子监测(SIM),外标法定量。研究结果显示,六六六方法定量限为5.0μg/kg,滴滴涕为2.5–5.0μg/kg,扑草净为2.5μg/kg。各组分加标回收率在78.5%–112.0%之间,相对标准偏差在3.6%–10.3%之间。结果表明,该方法简便、快速,其准确度和精密度能够满足紫菜中六六六、滴滴涕和扑草净同时检测的要求。     

福建漳江口水产品中六六六和滴滴涕的残留及其人体健康风险

采用气相色谱(GC-ECD)方法分析了漳江口水产品中六六六(HCHs)、滴滴涕(DDTs)的残留量,并对其残留水平、组成特征和人体健康风险进行了探讨与评价。结果表明:鱼类、虾类和贝类中HCHs残留量(以湿重计)分别为0.842 ng·g-1(未检出~1.42ng·g-1)、0.374 ng·g-1(未检出~0.762 ng·g-1)、1.04 ng·g-1(未检出~1.59 ng·g-1);DDTs残留量分别为96.3 ng·g-1(3.40~432 ng·g-1)、6.79 ng·g-1(1.53~12.1ng·g-1)、37.0 ng·g-1(9.02~78.0 ng·g-1)。水产品中DDTs残留量鱼类贝类虾类,且其残留量均高于HCHs的残留量。与其它地区相比,漳江口水产品中HCHs、DDTs含量属于中等水平。组成特征显示研究区域近期无HCHs污染源输入,但局部区域近期有新DDT的输入,可能与三氯杀螨醇的使用有关。所采集的水产品中HCHs、DDTs残留量尚低于我国食品安全国家标准—食品中农药再残留限量(GB2763-2014),亦低于日本、欧盟等发达国家和地区相关的最大残留限量,HCHs、DDTs通过膳食的暴露暂时不会对该地区的人体健康产生危害。     

Fate and plant uptake of persistent organic pollutants in soil

Many persistent organic pollutants (POPs), notably hexachlorocyclohexanes (HCHs), chlorinated cyclodienes, and dichlorodiphenyltrichloroethanes (DDTs), remain in Japanese farming soils, more than 40 years after their use as insecticides was prohibited. In recent years, residues of chlorinated cyclodienes in cucurbit fruits have become a problem. But, though HCHs and DDTs have been staying in the soil, residues of these chemicals in crops have not been a problem. So we compared the fates of HCHs (α-, β-, γ-HCHs), chlorinated cyclodienes (dieldrin, endrin, heptachlor exo-epoxide), and DDTs (DDE, dichlorodiphenyldichloroethylene; DDD, dichlorodiphenyldichloroethane) in soil and investigated their uptake by several non-cucurbits and cucurbits. As for the fate of POPs in soil, not only the total concentrations but also the concentrations in soil solution as bioavailable POPs were determined. The half-lives of total β-HCH and DDTs in soil were the longest, and α- and γ-HCHs the shortest. On the other hand, the half-lives of bioavailable POPs ranged from 1/3 to 1/20 of those of total POPs. The ratio of the half-lives of bioavailable POPs to those of total POPs decreased in the order of HCHs > chlorinated cyclodienes > DDTs. Because hydrophobic chemicals were adsorbed strongly to the soil, the bioavailable POPs in soil are controlled by their hydrophobicity, indicated by the values of log K _OW (K _OW: n-octanol-water partition coefficient). The shoot concentrations of chlorinated cyclodienes and DDTs were higher in cucurbits than in non-cucurbits. However, among POP insecticides, HCHs did not show clear differences. As for the root concentrations, all tested POPs were higher in cucurbits than in non-cucurbits. Through the determination of POPs in soil solution, we could compare the abilities of plants to take up the chemicals using soil solution bioconcentration factors (BCF_SS). The values of BCF_SS increased with the magnitude of log K _OW, in the order of HCHs < chlorinated cyclodienes < DDTs. In addition, BCF_SS did not show marked differences among isomers or chemicals with similar structure. Therefore, plant uptake ability was influenced mainly by log K _OW. After being applied to agricultural land, α- and γ-HCHs seemed to disappear quickly, β-HCH persisted longer but the uptake in roots was low because of the low log K _OW, and DDTs also persisted longer but the bioavailability decreased rapidly in the soil because of their high log K _OW. Chlorinated cyclodienes have remained in the soil and have remained available, because they are less likely than HCHs (except β-HCH) to disappear and less likely than DDTs to become adsorbed to the soil. In addition, their higher log K _OW than that of HCHs makes them more easily taken up by roots. However, shoot concentrations were high only in cucurbits, for which they remain a problem in Japan.     

蔬菜不同部位对DDTs的富集与分配作用

在可控条件下研究了人为污染土壤中DDT类污染物在蔬菜(菠菜和胡萝卜)不同部位的富集与分配规律.结果表明,DDT类污染物在菠菜和胡萝卜叶部和根部均有一定富集,其中菠菜叶面富集量占富集总量的68.6%～92.2%之间;而胡萝卜叶部富集占富集总量的34.9%～41.6%之间.不同DDTs在菠菜和胡萝卜体内的生物富集量呈:P,p'-DDE>p,p'-DDT>p,P'-DDD>o,p'-DDE>o,P'-DDT的规律.DDTs通过不同途径在菠菜和胡萝卜内的生物富集系数表现如下规律:BCF大气-菠菜>BCF大气-胡萝卜>BCF土壤-胡萝卜>BCF土壤-菠菜.不同DDTs在蔬菜体内的生物富集系数表现为:BCFp,p-DDE>BCFo,p'-DDE>BCFp,p'-DDD>BCFp,p'-DDT>BCFo,p'-DDT.由于DDTs在蔬菜体内富集后,可沿食物链传递和放大,对农产品质量和人体健康构成直接威胁.     

Bioaccumulation of hexachlorocyclohexane,dichlorodiphenyltrichloroethane, and estradiol-17β in catfish and carp during the pre-monsoon season in India

This investigation was performed to monitor hexachlorocyclohexane isomers (HCHs), dichlorodiphenyltrichloroethane (DDT, and its metabolites, refered to as DDTs), plasma levels of estradiol-17β (E2), and the gonadosomatic index (GSI) between sampling sites of unpolluted ponds of Gujartal, Jaunpur (control site) and the polluted rivers Gomti (Jaunpur) and Ganga (Varanasi), which affect the reproductive physiology of some edible catfish and carp during the pre-monsoon season. HCHs and DDTs were measured by gas liquid chromatography (GLC) and hormones by radioimmunoassay (RIA). The results indicated that the level of HCHs and DDTs was very high in both the catfish and the carp captured from the polluted rivers compared with the fish captured from the control site. The GSI and E2 values were lower in both groups of fish when compared to the fish from the control site. The results also indicate that catfish showed greater bioaccumulation of HCHs and DDTs than carp, above the permissible limit, as compared to the fish from the control site. In conclusion, fish from the Gomti and Ganga rivers were highly polluted when compared with fish from the control site, as was evident from high levels of tissue bioaccumulation of HCHs and DDTs and decreased levels of plasma E2, inhibiting the reproductive physiology of these species at the receptor level. The levels exceeded the maximum residue limits (MRL) as recommended by Codex, hence it is suggested that the fish should be avoided for food purposes.     

珠海养殖池塘沉积物中BHC和DDT残留与风险分析

测定了珠海水产养殖池塘沉积物中六六六(BHC)和滴滴涕(DDT)残留量。结果显示,ΣBHC、ΣDDT残留量(湿重)分别为0.36～1.67、0.95～2.59μg·kg~(-1),平均分别为0.91、1.81μg·kg~(-1),明显低于一些江河、湖泊、海湾沉积物中的含量,符合我国无公害水产品产地沉积环境质量标准。γ-BHC/ΣBHC 比值为0～21.6%,(DDE DDD)/ΣDDT 比值为61.1%～76.7%,表明珠海池塘养殖环境中的 BHC 日趋减少,推测残留的DDT 大部分已降解为 DDE 和 DDD,近年没有 BHC 和 DDT 输入。BHC 和 DDT 含量低于 ERL 值,表明 BHC 和DDT 残留对珠海池塘养殖基地造成的生态风险极低。     

福建沿海中北部主要贝类养殖区沉积物、贝类质量的初步分析和评价

2009年8至9月对福建沿海中北部主要贝类养殖区沉积物及贝类质量状况进行了全面的调查。结果表明,沉积物中有机碳、石油类、Hg、Cd、Pb、As、HCHs、PCBs含量均符合海洋沉积物质量第一类标准,部分海域硫化物、DDTs含量超标,整体上贝类养殖环境质量良好。贝类体内Hg、As、Pb、HCHs、PCBs、DDTs含量均符合无公害水产品质量安全要求,仅有小部分站点贝类体内镉含量超标,但贝类受石油烃污染较严重。