不同进样溶剂对有机氯农药测定的影响研究

在实际操作中,水、土壤及沉积物中有机氯农药的测定需要进行前处理,二氯甲烷、正己烷是普遍使用的溶剂,而标准物质考核样品溶剂为甲醇。采用了气相色谱-质谱的方法研究了不同溶剂对有机氯农药(α-HCH、β-HCH、γ-HCH、δ-HCH、p,p′-DDE、p,p′-DDD、o,p′-DDT、p,p′-DDT)测定的影响。结果表明,不同溶剂对待测物质的响应值是有差异的,但保留时间不变,且随着待测物浓度的增加,这种溶剂效应对大部分待测物的作用减少;溶剂的极性对有机氯农药的响应值有显著的影响,甲醇溶剂中待测物的响应值低于其他两种溶剂相;甲醇标准物质可用二氯甲烷配制,测定值满足在推荐值之内。     

基于污染指数与ArcGIS的聊城市耕地OCPs污染研究

按8 km×8 km网格将聊城市耕地划分为136个采样点,调查六六六(BHCs)、滴滴涕(DDTs)、艾氏剂、狄氏剂、异狄氏剂、六氯苯和七氯等7种有机氯农药(OCPs)的残留状况。采用单因子污染指数和综合污染指数法进行污染评价,以此判断OCPs的污染程度。对7种OCPs在各样点中的含量进行差异分析,并应用ArcGIS8.3,以污染评价结果为数据支持,进行OCPs污染空间分布研究。结果表明,聊城市OCPs污染程度依次为DDTs>狄氏剂>七氯>艾氏剂>BHCs>异狄氏剂>六氯苯,总体变异程度依次为DDTs>狄氏剂>异狄氏剂>BHCs>七氯>六氯苯>艾氏剂。各OCPs空间分布没有固定的变化趋势;各采样点综合污染水平存在地域差异,以临清市污染最为严重,其他各县市污染较轻。     

POPs监测技术在环境样品中应用

利用超声提取、固相萃取(SPE)净化和GC-MS技术对某市四个区的的果蔬基地7个土壤样品进行了土壤中持久性有机氯污染物分析.结果显示,土壤样品中主要有机污染物为γ-HCH、异狄氏剂和α-HCH,其中γ-HCH的检出率为100%,不同样品中γ-HCH和异狄氏剂差异明显,异狄氏剂和α-HCH检出率分别为86%和71.4%.     

G C/MS法测定环境空气中痕量POPs类有机氯农药及降解产物

采用快速溶剂萃取-氟罗里硅土柱净化-气相色谱/质谱联用法测定环境空气中POPs类有机氯农药及其降解产物.艾氏剂、狄氏剂、异狄氏剂、六六六、滴滴涕,七氯、氯丹、灭蚁灵及其降解产物的检出限为2.0 ng～4.6 ng,空白加标回收率为62.1%～118%,RSD为6.8%～15.2%.     

超声波萃取-气相色谱/质谱法测定土壤中15种Pops类有机氯农药

用探头式超声波萃取仪、己烷/丙酮混合溶剂提取土壤中的15种Pops类有机氯农药(包括六氯苯、七氯、六六六、氯丹、艾氏剂、狄氏剂、异狄氏剂、灭蚁灵、滴滴涕),萃取溶液经氟罗里硅土柱净化、氮吹浓缩,用气相色谱/质谱仪(GC-MS)进行测定。方法检出限0.4～1.4μg/kg,空白样品有机氯农药加标回收率为52.8%～118%、有机氯标记替代物回收率为71.0%～122%,RSD为6.8%～16.5%。     

洞庭湖流域土壤中有机氯杀虫剂的残留规律研究

2004年5月采集了洞庭湖流域45个土壤样品,用AES萃取技术,使用GC/MS方法测定了样品中的六氯笨、滴滴涕(DDTs)、氯丹、艾氏剂、狄氏剂、异狄氏剂、七氟和灭蚁灵.结果表明,六氯苯、滴滴涕的检出率为100%,氯丹和灭蚁灵的检出率很低,艾氏剂、狄氏剂、异狄氏剂和七氯未检出.总有机氯杀虫剂残留量平均值216.24μg/k,其中滴滴涕214.7μg/kg,占总OCPs的99.3%,且有些土壤样品中w(DDT)/w(DDE DDD)值较大,说明DDTs曾作为湘江流域的主要杀虫剂在洞庭湖流域土壤中广泛施用过,并且近期内仍然有输入.六氯苯的残留量虽然较低,但其施用范围广泛.总OCPs在棉田中的残留量很高,在茶场土壤中最低,表明棉田土壤曾因为各种原因施用过大量的有机氯杀虫剂,茶场土壤中有机氯农药的残存量处于安全范围.     

固相萃取-气相色谱法测定水中多种农药类内分泌干扰物

建立了水样中用固相萃取小柱提取和净化、GC-ECD检测、GC-MSD定性证实的农药类内分泌干扰物检测方法,该方法样品提取、浓缩、净化步骤简便,能实现31种目标物同时检测。方法检测限0.05~0.50μg/L。添加回收率69%~101%,相对标准偏差低于10%。选择农药包括有机氯类(如滴滴涕、六六六、三氯杀螨醇、艾氏剂、异狄氏剂、狄氏剂、七氯、硫丹、氯丹等),氨基甲酸酯类(如甲草胺、乙草胺等),除虫菊酯类(如氯氰菊酯、速灭菊酯等)及其它农药(如氟乐灵、除草醚、毒死蜱)。该方法应用到测定某水库的水样,水库中31种农药类内分泌干扰物总浓度为48.8~890 ng/L,平均浓度295 ng/L。     

贵州农作物土壤中OCPs残留现状与差异性分析

通过在贵州主要农作物种植区域采集5 cm、10 cm、15 cm深度的土壤样品，检测其中22种OCPs的残留量。结果表明：在所有水稻土壤样品中除了环氧七氯-A、反式九氯和狄氏剂未检出外，其余19种OCPs均有不同程度检出；OCPs在上述3种深度土壤中总残留量分别为0.526 ng/g、0.497 ng/g、1.605 ng/g。DDTs在3种深度水稻土壤中的总残留量(0.359 ng/g)低于HCHs总残留量(1.135 ng/g)。水稻土壤中γ-HCH、δ-HCH残留量显著高于玉米土壤。水稻土壤中HCHs和硫丹残留主要源自历史上工业制剂的使用，DDTs在水稻土壤中的降解方式主要为厌氧。农作物种植区域土壤中OCPs残留量均符合国家农用地土壤污染风险管控标准。     

无锡某地区土壤中有机氯农药污染状况调查

调查分析了无锡市某地区土壤有机氯农药污染状况。数据表明，该地区土壤有机氯农药主要残留组分为p，p＇-DDE和p，p’-DDT，其浓度处于较低水平，对生态环境和人类健康无显著危害。     

ASE萃取-SPE净化-气相色谱法测定土壤中有机氯农药

建立了加速溶剂萃取-固相萃取净化-气相色谱测定土壤中α-六六六、β-六六六、γ-六六六、δ-六六六、P，P′-DDE、P，P′-DDD、O，P′-DDT、P，P′-DDT等8种有机氯农药的方法。在0μg／L～500μg／L范围内方法线性良好，8种有机氯农药的检出限在0．06μg／kg～0．21μg／kg之间，基质加标试验的相对标准偏差为2．2％～5．8％，回收率为81．5％～113％。     

固相萃取- GC/MS法测定水中有机氯农药

建立了固相萃取-气相色谱／质谱联用测定水中痕量六六六、滴滴涕和环氧七氯的方法。采用C18固相萃取柱富集水样，二氯甲烷／丙酮混合溶剂洗脱，加入菲-d10作为内标，利用气相色谱／质谱联用仪选择离子监测模式检测，内标法定量，定性、定量准确，线性响应良好，干扰小，按采样1 L计算，方法检出限为4．26ng／L～19、2ng／L，RSD在0、4％-6、3％之间，平均加标回收率在77．7％～118％之间，实际样品测定结果表明方法能满足环境水体中痕量有机氯农药的监测要求。     

Changing patterns of organochlorine pesticide residues in raw bovine milk from Haryana, India

Bovine milk samples were collected and analyzed during 1992 and 1998 from rural areas of 14 different districts of Haryana state for the presence of HCH and DDT residues. The study revealed that the mean residues of ΣHCH in raw bovine milk have declined by 67.5% while mean levels of ΣDDT have decreased by 92.8% during six years gap. The obtained results reveal that during 1992 p,p'-DDT was the main component followed by p,p'-DDD, α-HCH and β-HCH while in 1998, p,p'-DDE and β-HCH followed by p,p'-DDT were relatively more as compared to other isomers and metabolites of these pesticides.     

Organochlorine insecticide residues in Ganga river water near Farrukhabad,India

Multiple residues of organochlorine insecticides were monitored in Ganga river water in the district of Farrukhabad in northern Indian for one year (1991–1992). Almost all the samples were found to be contaminated with residues of HCH and DDT. Residues of aldrin, endosulfan and heptachlor were also detected in a larger number of samples. Alpha-HCH, pp-DDT and alpha-endosulfan were found to dominate over the other isomers of HCH, DDT and endosulfan, respectively. Enhanced percentage of beta-HCH suggests accumulation of this isomer in the aquatic environment. The average concentration of aldrin was more than that of dieldrin. Aldrin residues often exceeded the WHO guideline value for drinking water and the concentration of heptachlor occasionally exceeded the specified limits.     

Organochlorine Pesticide Residues in Wheat and Drinking Water Samples from Jaipur, Rajasthan, India

The organochlorine pesticide contamination in dietary sources has caused serious threat to the human progeny. The present study was therefore conducted to evaluate the pesticide contamination in wheat flour and drinking water from Jaipur City, Rajasthan, India using Gas Chromatograph. All the wheat and water samples were found to be contaminated with various organochlorine pesticide residues of DDT and its metabolites, HCH and its isomers, heptachlor and its expoxide and aldrin. The amount of pesticide detected in wheat flour was higher than the permissible limits prescribed by WHO/FAO. In drinking water only a few pesticides exceeded the permissible limits. Seasonal variations of pesticides residues were also observed during the study period.     

Determination and Assessment of HCHs and DDTs Residues in Sediments from Lake Dongting, China

The contamination of organochlorine pesticides hexachlorocyclohexane (HCH) and Dichlorodiphenyltrichloroethane (DDT) and their eco-environmental assessment in surface sediments from Lake Dongting, the second-largest freshwater lake in China, were studied. Concentrations of ∑HCH (=α-HCH + β-HCH + γ-HCH +δ-HCH) were 0.21--9.59 ng/g dry weight and those of ∑ DDT = p,p'-DDD+p,p'-DDE+o,p'-DDT+p,p'-DDT) ranged from under detectable limit to 10.15 ng/g dry weight. The ratios of α-HCH to γ-HCH were above 7 at most sampling sites while no or a small amount of β-HCH were found at all sites, suggesting the degradation of HCH used in the history and possibly current use of HCH in the region. The low ratios (below 2.0 in most cases) of (p,p'-DDE+p,p'-DDD) to p,p'-DDT and high levels of individual isomers of DDT at some sites also suggested that there have still been fresh inputs of DDT into Lake Dongting. Through the comparison between concentrations of HCH and DDT residues in sediments of Lake Dongting and those from other places in China and also from the results of our eco-environmental assessment, it can be concluded that Lake Dongting is the water body with high contamination of both HCH and DDT in its sediments in comparison with other water bodies in China.     

Monitoring of organochlorine pesticides in and around Keoladeo National Park, Bharatpur, Rajasthan, India

Keoladeo National Park (KNP) is an important wintering ground for thousands of birds that undertake a perilous journey over the Himalaya to make a seasonal home in a wetland ecosystem. However, this wetland is now getting polluted by various types of contaminants such as pesticides because of the agricultural practices in the catchment area from where the park receives water. Keeping this in mind, the present study has been undertaken to assess the organochlorine pesticide (OCP) residues in the sediments inside and around KNP. Samples were collected from the different blocks of the park. The concentrations of α-HCH, β-HCH, γ-HCH, δ-HCH, S-HCH, aldrin, dieldrin, heptachlor, hept.epoxide, endosulfan-I, endosulfan-II, endo.sulfate, S-endosulfan, endrin, 4,4'-DDE, 4,4'-DDD, and DDT were quantified using gas chromatography with electron capture detection. Analysis showed that the samples were contaminated with the above mentioned pesticides and that the concentration of total OCPs in the sediments varied from 0.1173 (dieldrin) to 5.558 ppm (γ HCH) in the samples collected from inside the park, whereas a range of pesticides varying in concentration from 0.1245 (4,4'-DDD) to 7.54 ppm (γ HCH) was found in samples from outside the park. Residues of S-HCH and S-endosulfan were not detected in any of the sediment samples. The occurrence of pesticides inside the park is a major threat to the park's biodiversity. Eco-friendly agriculture practices with minimal use of inorganic chemicals are suggested to minimize the pesticide residue levels in the park.     

Persistent Organochlorine Pesticide Residues in Soil and Surface Water of Northern Indo-Gangetic Alluvial Plains

This study reports the concentration levels and distribution pattern of the organochlorine pesticide (OCPs) residues in the soil and surface water samples collected from the northern Indo-Gangetic alluvial plains. A total of 31 soil and 23 surface water samples were collected from the study region in Unnao district covering an area of 2150 km² and analyzed for aldrin, dieldrin, endrin, HCB, HCH isomers, DDT isomers/metabolites, endosulfan isomers (α and β), endosulfan sulfate, heptachlor and its metabolites, α-chlordane, γ-chlordane and methoxychlor. In both the soil and surface water samples β- and δ-isomers of HCH were detected most frequently, whereas, methoxychlor was the least detected pesticide. The results showed contamination of soil and surface water of the region with several persistent organic pesticides. The total OCPs level ranged from 0.36–104.50 ng g^–1 and 2.63–3.72 μg L^–1 in soil and surface water samples, respectively.     

Ground water contamination by organochlorine insecticide residues in a rural area in the indo-gangetic plain

Residues of several organochlorine insecticides were monitored in the ground water from a rural area near Farrukhabad in the vicinity of the Ganga River in northern India for one year (1991–1992). Almost all the samples were found to be contaminated with residues of Hexachlorocyclohexane (HCH) and Dichloro-diphenyl-trichloroethane (DDT). Residues of Aldrin, endosulfan and heptachlor were also detected in a large number of samples. The concentrations of aldrin residues greatly exceeded the WHO guideline value for drinking water, concentrations of heptachlor and DDT residues also occasionally exceeded the specified limits. Migration of pollutants through ground water recharge with polluted Ganga River water and monsoon rains carrying undergraded residues downwards from the soil surface are throught to be important sources of insecticide contamination of ground water in the region.     

Organochlorine pesticides in the soil of a karst cave in Guilin, China

Organochlorine pesticides (OCPs) including HCH, DDT, chlordane, endosulfan, and endosulfan sulfate were analyzed in surface soil of the Dayan Cave to investigate their source and concentration levels in September 2006. Generally, the data showed that outside soil of the cave had much higher concentrations than inside soil for the most detected OCPs in the cave and both inside soil and outside soil showed much lower concentration levels (basically, the levels of OCPs were less than 0.7 ng/g) than those observed in other regions within and outside China other than TC (ranging from 3.22 to 5.00 ng/g) and CC (ranging from 3.89 to 5.08 ng/g) in the soil outside. The ratios of α-/γ-HCH ranged from 0.88 to 1.20 in the soil of the cave, together with the averaged percentages of β-HCH and δ-HCH among the total HCH isomers (accounting for 39.0% and 14.2%, respectively), implied that a historical residue of local technical HCH contamination was likely to be dominant in the soil of the cave. Based on (1) the accordance of TC/CC ratios (ranging from 0.83 to 0.98) between the values observed in the outside soil and the potentially available chlordane products in the markets, and (2) the high concentrations of TC and CC observed in the outside soil, it appeared that the illegal usage of technical chlordane was done in Guilin. The low concentrations of TC (0.02 to 0.56 ng/g) and CC (0.10 to 1.71 ng/g) in the inside soil, together with the significant distinctions of TC/CC ratios between the inside soil (ranging from 0.03 to 0.33) and the outside soil, implied that the chlordane in the inside soil of the cave was a historical residue of local technical chlordane contamination. The similar ratios of DDT isomers (o,?p (')-DDT/p,?p (')-DDT and p,?p (')-DDE+DDD/DDT) between the outside soil and the inside soil of the cave suggested that they may have the similar DDT source. The ratios of p,?p (')-DDE+DDD/DDT (ranging from 3 to 8) indicated that DDT was relatively aged. The values of o,?p (')-DDT/p,?p (')-DDT ratios (ranging from 3 to 7.5 with a mean value of 5.45) were found to be much higher than that of technical DDT, and very similar to that of dicofol products, implied that the primary source of DDT in the soil of the cave was most probably from dicofol-type DDT products. The low concentration levels of endosulfan and the higher levels of metabolite endosulfan sulfate indicated that the residue from historical usage of technical endosulfan was likely to be dominant in the soil of the cave.     

Levels and distribution of persistent organochlorine pesticide residues in water and sediments of Gomti River (India)—a tributary of the Ganges River

This study reports the concentration levels and distribution pattern of the persistent organochlorine pesticide (OCPs) residues in the water and bed-sediments of the Gomti River collected seasonally over a period of 2 years. The water and bed-sediment samples were collected from eight different sites and analyzed for aldrin, dieldrin, endrin, HCB, HCH isomers, DDT isomers/metabolites, endosulfan isomers (alpha and beta), endosulfan sulfate, heptachlor and its metabolites, alpha-chlordane, gamma-chlordane and methoxychlor. In the river water and sediments SigmaOCPs residues ranged between 2.16 and 567.49 ng l(-1) and 0.92 and 813.59 ng g(-1), respectively. The results, further, suggested that source of DDT contamination is from the aged and weathered agricultural soils with signature of recently used DDT in the river catchments. To assess any adverse effect of OCPs contamination on river's biological component, the threshold effect level (TEL) was used. The results revealed that bed-sediments of the Gomti River are contaminated with lindane, endrin, heptachlor epoxides and DDT, particularly at site-4 and may contribute to sediment toxicity in the freshwater ecosystem of the river.