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。     

DDTs污染农田土壤的强化微生物修复研究

为了提高微生物对DDTs污染土壤的修复效率,利用混合菌[球形节杆菌(Arthrobacter globiformis)和甲基营养型芽孢杆菌(Bacillus methylotrophicus)]对沈阳市沈北新区设施农业DDTs污染土壤进行现场修复实验,研究定期添加血粉(3X)和阴-非离子混合表面活性剂SDBS-Tween 80(3H)对混合菌修复DDTs污染土壤的强化效果,分析修复过程对DDT同分异构体及初级代谢产物的影响。结果表明:接种混合菌可有效降低土壤中DDTs的残留,连续3次接种的修复效果(3PN-1)比1次(PN-1)好,90 d后DDTs降解率可达50.5%,比对照组提高了45.9%。在此基础上,添加血粉和SDBS-Tween 80均可显著降低土壤中DDTs的残留,其中SDBS-Tween 80的处理效果较好,DDTs降解率最高达到63.2%,比单独接种混合菌处理提高了12.8%。DDT同分异构体及初级代谢产物分析表明,SDBS-Tween 80强化修复对生态毒性较强的p,p′-DDE降解率达到了62.4%,有效降低了修复后的生态风险。因此,SDBS-Tween 80强化混合菌处理可以作为DDTs污染土壤微生物修复的适宜措施。     

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。     

广东红海湾海域银杏齿喙鲸体组织中DDT含量的分布特征与污染评价

采用Agilent 6890 N型气相色谱仪,DB-1701型毛细管气相色谱柱(30 m×0.32 mm×0.25 μm)和63Ni放射源-μECD检测器,测定了搁浅于广东红海湾的银杏齿喙鲸(Mesoplodon ginkgodens)的8种组织中∑DDT(pp′-DDT、pp′-DDE、pp′-DDD和op-DDT)含量.结果表明,该鲸不同组织中的∑DDT含量范围为15.2～177.1 μg ·kg-1(湿重),其高低顺序为鲸脂>肝脏>胃>心脏>肾脏>肌肉>胰>肺,不同组织中的∑DDT含量与其组织中的脂肪含量呈显著正相关(R=0.9968,P<0.01).与国外文献报道的数据比较,所分析的鲸脂中∑DDT含量相对较低,尚未达到造成生理危害的水平.DDE/∑DDT和pp′-DDT/op-DDT的平均比值分别为0.27和5.7,据此推测可能有新的DDT输入此鲸栖息海域,主要来源可能是含DDT化学品的使用和环境中残留DDT的重新释放.     

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。     

滇池外海沉积物中滴滴涕类农药的残留特征

滴滴涕类农药(DDTs)既是环境内分泌干扰物,也是持久性有机污染物,为了解滇池沉积物中DDTs的残留水平,本文采集滇池外海的18个表层沉积物样品,分析其DDTs农药的残留量,结果表明:1滇池沉积物中∑DDTs农药的含量为0.2~4.9 ng/g(干重),p,p′-DDE和p,p′-DDD是目前滇池外海表层沉积物中DDTs农药最主要的赋存组分,含量检测平均值为1.14 ng/g(干重)和0.78 ng/g(干重);2沉积物中的DDTs主要来源于历史残留,未发现新的污染源输入;3多数点位的WDDD/WDDE1,表明DDTs的降解环境以好氧条件为主;4滇池外海沉积物中DDTs的残留水平低于已有报道的国内其他水体,空间分布呈现北部湖区高于中部和南部湖区的特征。     

贵州草海耕地土壤与农作物中DDTs和HCHs残留及污染特征

采集草海流域周边成熟期整株农作物及土壤样品,分析测试其中DDTs和HCHs的含量,对比研究了土壤和作物中DDTs和HCHs污染水平及其在作物中富集能力。结果表明:研究区域土壤中HCHs和DDTs残留检出率均为100%,残留范围分别为0.06~16.66μg·kg-1和0.08~39.77μg·kg-1,土壤中HCHs和DDTs的残留量均小于国家土壤环境质量一级标准;三种农作物中DDTs、HCHs及Σ(DDTs,HCHs)残留量差异显著,HCHs含量最高的是玉米,DDTs和Σ(DDTs,HCHs)最高的是马铃薯;三种农作物中HCHs和DDTs残留的风险系数均为1.1,属于低度风险,农作物中DDTs、HCHs及Σ(DDTs,HCHs)的安全指数IFSC均小于1,DDTs和HCHs残留量对三种农作物安全影响的风险是可以接受的。     

花生对DDT的吸收积累

采用盆栽试验,通过向土壤中添加DDT设置3个浓度处理(T1,295 ng g-1;T2,3723 ng g-1;T3,6109 ng g-1)和1个对照(CK,31 ng g-1),研究花生(Arachis hypogaea)对DDT的吸收积累。花生果实成熟后将植株分成根、茎、果壳和果仁四部分,GC-ECD测定各部位中的DDT浓度。结果表明,在T2和T3处理中,花生果仁中的DDT含量高达200 ng g-1左右,超过100 ng g-1的WHO/FAO最大残留限量标准。虽然在CK和T1中,花生的果仁没有超标,但是,果壳和茎中,特别是根中DDT的高浓度值得关注。根部的总量最大,果仁中的总量最小,根部是DDT吸收积累的最主要部位。花生根部和茎部较高的生物蓄积系数暗示着花生对DDT具有较强的吸收积累能力。此外,研究显示花生果仁中高的含油量可能有助于亲脂性DDT的吸收积累。     

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.     

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。