广东省典型区域农业土壤中六六六(HCHs)和滴滴涕(DDTs)的残留及其分布特征

2002年10月—2005年11月采集广东省典型区域(汕头市、湛江市、东莞市、惠州市、中山市、珠海市和佛山市顺德区)的农业土壤表层(0～20 cm)样品444个,采用气相色谱方法对土壤中六六六(HCHs)和滴滴涕(DDTs)进行分析,初步揭示广东省农业土壤中有机氯农药的分布及残留情况. 结果表明:HCHs的检出率为95.9%,w(HCHs)为未检出～104.38 ng/g,平均值5.90 ng/g;DDTs的检出率为95.7%,w(DDTs)为未检出～157.75 ng/g,平均值为10.18ng/g. HCHs的4种异构体中,w(β-HCH)最高,平均值为2.96 ng/g,而p,p′-DDE是3种DDTs异构体中含量最高的,平均值为5.09 ng/g. 不同土壤利用类型中,有机氯农药残留总量为水稻田>菜地>香蕉地>旱坡果园地>甘蔗地,汕头市土壤中有机氯农药残留总量明显高于该研究区的其他地方. 与国内外其他地区农业土壤中的DDTs和HCHs含量和我国土壤环境质量标准(GB15618-1995)相比,广东省典型区域污染程度较低.      

Organochlorine pesticides and polychlorinated biphenyl congeners in wild terrestrial mammals and birds from Chubu region, Japan: Interspecies comparison of the residue levels and compositions

In order to understand the residue levels of organochlorine compounds (OCs) and their accumulation patterns in wildlife inhabiting Chubu region, Japan, the concentrations of polychlorinated biphenyls (PCBs), hexachlorocyclohexane isomers (HCHs), DDT compounds (DDTs) and hexachlorobenzene (HCB) were measured in 8 species of terrestrial mammals and 10 species of birds. In view of feeding habits, the contamination levels of OCs were found to be higher in omnivorous mammals than in herbivorous ones, and in fish-eating ones and raptores than in omnivorous birds. In fox and dog, PCB-180 (2, 2′, 3, 4, 4′, 5, 5′-heptachlorobiphenyl) was the most dominant PCB congener, while in the other species PCB-153 (2, 2′, 4, 4′, 5, 5′-hexachlorobiphenyl) was the most persistent. The ratios of lower chlorinated PCB congeners (tri- to tetra-) to total PCBs were larger in fish-eating birds than in the other birds. The results indicate that the compositions of PCB congeners would reflect the differences of feeding habits and xenobiotic metabolizing systems among each species.     

贵州遵义地区土壤中有机氯农药残留调查

于2008年3月-5月对遵义地区土壤中有机氯农药残留进行了调查。结果表明,15种有机氯农药在所有样品中都有不同程度的检出。HCHs、DDTs类物质的检出率分别为90．7％、45．7％。∑HCH残留量为未检出～12．7μg／kg,平均值为1．6μg／kg;2DDT残留量为未检出-239．7μg／kg,平均值为2．8μg／kg;总有机氯杀虫剂平均残留量为4．51μg／kg,同国内其他地区相比,其残留水平偏低。     

几种低分子量有机酸对红壤中DDTs类物质释放动力学的影响

采用自行设计的动力学试验装置,系统研究了3种低分子量有机酸(草酸、酒石酸和柠檬酸)和水对红壤中滴滴涕(DDTs)类物质的释放动力学行为.结果表明:10 mmol/L的低分子量有机酸可使DDTs类物质的释放百分率相对于水提高15～18个百分点,特别在淋洗液的前250mL更为明显.水对DDTs类物质的释放动力学数据可用表观一级动力学方程很好拟合(R²>0.99,p<0.000 1),说明DDTs的释放可能以土壤矿物表面扩散为主,而有机酸存在体系中的该类物质的释放却更好符合抛物线方程、双常数方程,说明低分子量有机酸的存在使DDTs的释放机理复杂化,这可能与有机酸对矿物的溶解、对矿物表面固有有机质结构的干扰有关.     

Tissue distribution of organochlorine pesticides in fish collected from the Pearl River Delta, China: implications for fishery input source and bioaccumulation

Fish tissues from different fishery types (freshwater farmed, seawater farmed and seawater wild) were analyzed for organochlorine pesticides (OCPs), with the aim to further our understanding of bioaccumulation, and reflect the state of different fishery environments. Significantly higher SigmaOCP levels were found in seawater farmed fish than others, and among three freshwater farmed species, the lowest levels occurred in filter-feeding fish (bighead carp). Liver contained the highest SigmaOCP levels, while no significant differences were found among other tissues. Among DDT components, p,p'-DDT was abundant in seawater fish, while for freshwater fish, p,p'-DDE was the predominant congeners, except for northern snakehead (34% for p,p'-DDE and 30% for p,p'-DDT). The new source of DDTs to freshwater fish ponds was partly attributed to dicofol, whereas sewage discharged from the Pearl River Delta and anti-fouling paint were likely the DDTs sources to seawater farmed fish.     

Levels and regional trends of persistent organochlorines and polybrominated diphenyl ethers in Asian breast milk demonstrate POPs signatures unique to individual countries

Human breast milk samples collected in 2007–2008 from four countries, Vietnam (Hanoi), China (Beijing), Korea (Seoul) and Japan (Sendai, Kyoto and Takayama), were analyzed for persistent organic pollutants (POPs) such as dichlorodiphenyltrichloroethane and its metabolites (DDTs), chlordane-related compounds (CHLs), hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Comparing with previous surveys, the present study indicates that the DDTs in breast milk from China and Vietnam had gradually decreased during the last decade, but were still 5–10 times higher than those in other nations. The ratios of p,p′-DDE/p,p′-DDT and o,p′-DDT/p,p′-DDT were higher in Beijing than in the other countries, suggesting that there is less fresh intake of commercial DDT products and a possible exposure to dicofol in China. CHL and PCB levels were relatively higher in mothers from Japan, whereas β-HCH and HCB were more common in Chinese women. In Japan, it is suspected that mothers in the urban/coastal area (Sendai) were more continuously exposed to organochlorine pesticides (OCPs) than mothers in the rural/inland area (Takayama). In addition, OCP levels in primiparae were significantly higher than those in multiparae from Japan and Korea. These indicate that both parity and regional factors are major determinants of the levels of OCPs and PCBs in human milk. On the other hand, higher concentrations of PBDEs were observed in mothers' milk from Korea. The congener was dominated by BDE-47 (43–54%), followed by BDE-153 (23–33%) in all regions except for Beijing where BDE-28 (23%) was relatively abundant. In Japanese breast milk, regional and parity-dependent distributions were not observed for PBDEs. Among PBDE congeners, age-dependency was observed for BDE-153, which was negatively correlated (p < 0.05) to the age of mothers in Kyoto (17 participants were housewives), while it increased with age in Sendai (10 participants were clerks). No such correlation was seen for BDE-47, indicating that BDE-47 was ingested and assimilated via different kinetics or routes from BDE-153 in Japan.     

某典型农业活动区土壤与地下水有机氯农药污染健康风险评价

以长江三角洲某农业活动区为目标研究区域,分别采集研究区O～20 cm、20～40 cm、40～60 cm深度土壤样与浅层地下水样,分析该区有机氯农药六六六(HCHs)与滴滴涕(DDTs)在不同深度土壤至潜水含水层中的残留分布特征,并应用美国RBCA模型对研究区HCHs和DDTs进行健康风险评价.结果表明:在表层、第二层、第三层3个土层中β-HCH与DDE最大检出水平分别为50.28 μg· kg-1与60.35μg·kg-1、30.25μg·kg-1与30.29μg·kg-1、3.54 μg· kg-1与7.63 μg· kg-1,检出率分别为76.5％与69.8％、75.2％与65.2％、40.3％与30.5％,而该区浅层地下水中农药残留未检出.基于RBCA健康风险评价模型计算该农业活动区中HCHs和DDTs累加致癌风险值为4.7×10-5,致癌风险较小;HCHs和DDTs的平均浓度值和最大浓度值对应的非致癌健康风险均未超出US EPA安全阈值1.0,风险较低.     

Study of DDT and its derivatives DDD, DDE adsorption and degradation over Fe-SBA-15 at low temperature

Mesoporous SBA-15 with different Fe₂O₃ loading were synthesized by an in-situ coating progress for removals of dichlorodiphenyltrichloroethane (DDT) and its derivatives, i.e., 1,1-dichloro-2,2-bis-(p-chlorophenyl)ethane (DDD) and 1,1-dichloro-2,2-bis-(4-chloro -phenyl) ethane (DDE). The results from XRD (X-ray diffractometer), TEM (transmission electron microscopy) indicated that the iron could be well dispersed on SBA-15 within 6 wt.% Fe₂O₃ loading. Nitrogen adsorption-desorption tests indicated that the synthesized materials were characterized by ordered meso-structure, high surface area and large pore volume. DDTs were removed from aqueous media in 12-hr treatment and high removal efficiency of DDTs was achieved at over 94%. DDTs could be completely degraded at 350℃ under the existence of SBA-15 with 4 wt.% Fe₂O₃ loading. The final degradation products of DDT were dichlorobenzophenone (DCB) and bis-(4-chloro-phenyl) methane (DDM), suggesting a complete dechlorination from trichloromethyl.     

中国沉积物中有机氯农药滴滴涕和六六六的分布特征

通过研究过去国内常用的两种有机氯农药滴滴涕（DDTs）和六六六（HCHs）在沉积物岩芯中的相关文献，总结和分析其在中国各地的历史沉积情况.结果表明：（1）∑₄DDTs（p，p'-DDT， o，p'-DDT， p，p'-DDD， p，p'-DDE）浓度在安徽巢湖北岸六岔河流域最高，在1965年达到最大值（457ng/g dw），∑₆DDTs（p，p'-DDT， o，p'-DDT， p，p'-DDD， o，p'-DDD， p，p'-DDE， o，p'-DDE）浓度在广东省海陵湾最高，在2008~2010年达到最大值（3480ng/g dw），∑₄HCHs（α-HCH，β-HCH，γ-HCH，δ-HCH）浓度在澳门河口最高，在1993年达到最大值（82.3ng/g dw）；（2）∑₄DDTs和∑₄HCHs沉降通量在珠江三角洲最高，二十世纪七八十年代达到最大值，分别为115ng/（cm²×a）和32.5ng/（cm²×a），总体来说，DDTs和HCHs在中国沉积物岩芯中的浓度和沉降通量在南部地区要高于北部地区，平原地区和低纬度地区高于高寒地区（青藏高原）和高纬度地区（东北地区），水产养殖区或种植区高于非养殖区和非种植区；（3）从全国范围看，∑₄DDTs和∑₆DDTs浓度和沉降通量主要在20世纪70年代和21世纪中期出现峰值，少数研究区域峰值年份早在20世纪60年代，∑₄HCHs浓度和沉降通量峰值主要出现在20世纪70年代和21世纪初，少数研究区域峰值年份早在20世纪60年代；（4）从全国范围看，（DDD+DDE）/DDT比值没有可循的变化规律，DDTs可能来源于历史沉积、成岩作用以及外源土壤、三氯杀螨醇的使用等新输入，而很多地区在20世纪后期到21世纪中期均出现α-HCH/γ-HCH降低到小于3，表明这段时期HCHs主要来源于林丹的使用.     

珠江澳门河口沉积物柱样中有机氯农药的垂直分布特征

以GC/ECD内标法定量测定了沉积物柱样品中有机氯农药含量 ,以便探讨柱样中有机氯农药的垂直变化特征及可能的来源 .样品采自珠江澳门河口 ,柱样以2 10 Pb同位素法定年 .定量测定结果表明以BHCs、DDTs总量计算时 ,样品中含量分别为 0 4 8～ 2 6 2 8ng/ g、1 92～ 39 1 3ng/ g .柱样中农药含量随深度变化和珠江口区的水域水流量随年份的变化有着很好的对应性 .有机氯农药主要是来源于施用农药长期风化后的土壤 .样品中DDTs的浓度超过了河口沉积物化学品风险评价最低值标准 .