冀中典型农业区农作物中有机氯农药的生物富集特征与健康风险评价

分析了冀中典型农业区土壤-农作物体系中有机氯农药(OCPs)残留与生物富集特征,探讨了该地区所产农作物的可食部分对人体健康产生的潜在风险。结果表明:11种OCPs以滴滴涕(DDTs)和六六六(HCHs)为主要残留物。土壤中DDTs和HCHs残留量总计达36.52~73.45ng/g,在各自的异构体中p,p’-DDT和γ-HCH所占比例最高,表明OCPs污染主要为近期输入所致。玉米和小麦各器官中,OCPs均在籽粒中最高,分别残留20.66~33.33、19.14~34.57ng/g。小麦和玉米对HCHs的富集能力均强于DDTs。研究显示,该地区玉米与小麦籽粒中OCPs含量虽未超过《农产品安全质量无公害蔬菜安全要求》(GB 18406.1—2001)和《食品安全国家标准食品中农药最大残留限量》(GB 2763—2012),但OCPs致癌总风险相对较高,玉米和小麦中均超过了1×10-6,小麦中OCPs的非致癌总风险和致癌总风险均大于玉米,因此该地区应该优先关注OCPs对小麦所造成的粮食安全问题。     

采用气相色谱法测定土壤中有机磷农药

建立了一种用GC-FPD测定土壤中的5种有机磷农药的测定方法,经索氏提取,GPC净化浓缩后直接进样分析。用保留时间定性,外标法定量。5种有机磷农药的回收率为86.5%～103.2%,精密度(以相对标准偏差表示)为2.47%～5.70%;检测限为0.000 1～0.000 2 mg/kg。该方法准确度和灵敏度高,前处理简单,可同时测定土壤中的5种有机磷农药。     

舟山近岸海域贝类中有机氯农药残留水平及人体健康风险评估

于2012年的7月在舟山群岛新区的海域采集贝类样本,测定了其中的有机氯农药残留量,并进行了人体健康风险评估和安全食用量推算。结果表明,采集的5种贝类样本中,六六六(BHCs)的各组分均未被检出,而滴滴涕(DDTs)在各种样本中均有检出,其中僧帽牡蛎和部分縊蛏样本中DDTs总量超过《海洋生物质量标准》(GB 18421—2001)一类标准(10μg/kg);健康风险评估结果显示,贝类样本中α-BHC、β-BHC、γ-BHC、p,p’-滴滴伊(p,p’-DDE)、p,p’-滴滴滴(p,p’-DDD)、p,p’-DDT的总致癌风险指数均低于10-4,致癌风险均在可接受的安全范围,α-BHC、β-BHC、γ-BHC、p,p’-DDE的总接触风险指数均小于1,接触风险指数未超过危害剂量参考值,人体食用舟山近岸海域的贝类是安全的;按可接受的致癌风险指数进行评估,人体的贝类安全消费量为9.8~138.0g/(kg·d)(按体重计,下同),而按可接受的接触风险指数进行评估,人体的贝类安全消费量在24.6~235.0g/(kg·d)。     

碳纳米管顶空固相微萃取-气相色谱法测定土壤中有机氯农药

采用碳纳米管顶空固相微萃取-气相色谱法测定了土壤中有机氯农药,探讨了萃取时间、萃取温度、搅拌速度、离子强度、有机溶剂和土壤加水量对萃取效率的影响.该方法的线性范围为0.5～50.0 ng/g,r0.991 5,检出限为0.03～0.33 ng/g.样品的加标回收率为91.4%～120.0%,相对标准偏差不大于12.7%.     

典型区域农业土壤中多环芳烃相关性分析研究

对某大型钢铁集团周边农业土壤中15种多环芳烃(PAHs)各组分间及其与总量间的相关性、与有机氯农药(OCPs)的相关性进行统计分析.结果表明,除萘(Nap)外,其他14种组分间及其与总量间的相关性极显著;δ-六六六(δ-HCH)与除Nap和二苯并[a,h]蒽(Daa)外的大部分PAHs组分呈极显著相关关系;p,p'-滴滴滴(p,p'-DDD)与大多数PAHs组分相关性极显著.     

土壤中六六六和滴滴涕的堆肥生物修复研究

采用堆肥生物修复法对土壤中六六六(HCH)和滴滴涕(DDT)的降解效果进行了研究.试验结果表明,六六六和滴滴涕的降解先后经历了快速降解阶段和缓慢降解阶段;堆肥第21天后,六六六和滴滴涕降解率均达60%以上;γ-HCH降解效果最好,其次为β-HCH,α-HCH和δ-HCH的降解效果差别较大;p,p'-DDE的降解效果要好于p,p'-DDD,初始质量浓度为0.03 mg/kg的p,p'-DDT未得到降解;微生物对六六六和滴滴涕的降解作用均较明显.     

城市污水处理厂不同工艺段中有机氯农药残留

建立了基于HLB固相萃取柱和气相色谱 /电子捕获 (GC/ECD)分析城市污水中有机氯农药的分析方法 ,同时分析了北京市高碑店和北小河两个污水处理厂中 4个不同工艺段水体中有机氯农药的浓度。在两个污水处理厂的水体中共检出了 6种有机氯类农药 ,分别是α 六六六、β 六六六、γ 六六六、δ 六六六、艾氏剂和 4 ,4’ 滴滴滴 ,浓度在 1 89—6 9 6ng/L之间。结果表明 ,曝气活性污泥法对六六六类有机氯农药的去除效果较好。     

气氛含氧量对DDT热处理特性的影响

滴滴涕属于有机氯农药,其所含成分DDTs在环境中难以降解,并具有生物毒性。利用高温管式炉研究气氛中含氧量对滴滴涕热处理特性的影响,为研发废弃滴滴涕高温热处理技术提供理论依据。实验结果表明,在600℃时,滴滴涕去除率最高为含氧量21%时的70.48%;在900℃条件下,当含氧量为21%时DDT去除率≥99%;在1 200℃条件下,当含氧量≥12%时DDT去除率≥99.9%。在滴滴涕热处理残渣中,o,p’-DDT占DDTs总量的比例在3个温度段中都随含氧量的增加而增长,DDT则都随含氧量增加而减少,且上述变化随温度升高而幅度加大。在尾气中,p,p’-DDE占DDTs总量的比例在3个温度段中都随含氧量增加而递增,在1 200℃条件下尤为明显。     

不同洗脱剂对有机氯农药污染场地土壤修复效果比较

为了筛选出能有效修复有机氯农药污染土壤的洗脱剂,选取了16种洗脱剂对2种复合有机氯农药(六六六(HCHs)和滴滴涕(DDTs)、氯丹和灭蚁灵)污染场地土壤进行超声洗脱修复。结果表明,对于HCHs和DDTs复合污染土壤,乙酸乙酯和丙酮对HCHs的洗脱率最高,分别为87.6%和87%,其余有机溶剂对其洗脱率也在70%以上。乙酸乙酯和丙酮对于DDT仍为最优,分别为86.9%与78.4%,其余有机试剂对DDT的洗脱率在60%以上。相对于有机溶剂,表面活性剂对HCHs和DDTs复合污染土壤的洗脱效果不好,总洗脱率均低于4%。同样,对于氯丹和灭蚁灵复合污染土壤,有机溶剂的洗脱效果也明显优于表面活性剂。有机溶剂对灭蚁灵的洗脱率,除了正丙醇较低(63.5%)外,其余均在80%左右。对氯丹的洗脱率,除石油醚(59.6%)、正己烷(49.3%)和正丙醇(42%),其余均在70%以上。相同摩尔浓度的表面活性剂中,吐温80对氯丹的洗脱率为54%,环糊精为20%,鼠李糖脂和曲拉通100为13%左右,其余则小于5%,吐温80对灭蚁灵的洗脱率为29.6%,曲拉通100的为12.4%,鼠李糖脂为5.7%,其余则更低。因此,高效低毒的有机试剂,如乙酸乙酯、丙酮和乙醇等可作为有机氯农药污染土壤修复的首选。     

太湖流域水源地有机氯农药分布特征与生态风险评价

为系统了解太湖流域主要水源地有机氯农药(OCPs)污染情况,于2012年3月和6月采集太湖流域主要水源地水相、悬浮颗粒物和沉积物样品,并利用气相色谱(GC)—质谱(MS)联用仪对水源地OCPs的浓度水平进行监测分析。结果表明,3月水相和悬浮颗粒物中OCPs的质量浓度分别为4.03~18.70ng/L、ND(未检出)~27.60ng/g,高于6月的0.23~1.57ng/L、1.06~5.05ng/g。3月沉积物中仅有Y3采样点检出OCPs,而6月各采样点均有检出。6月水相中Y5、Y7和Y10采样点以α-六六六(α-HCH)为主,Y3和Y8采样点以γ-六六六(γ-HCH)为主,其余采样点均为β-六六六(β-HCH)占绝对优势;悬浮颗粒物中γ-HCH、α-HCH构成六六六(HCHs)的主要物质,而稳定性较高的β-HCH浓度却很低。与国内外研究比较,太湖流域水源地OCPs污染水平较低。大部分悬浮颗粒物中OCPs污染低于风险评价高值(ER-M),部分采样点高于风险评价低值(ER-L),表明存在一定的生态风险,需加强相关方面的防治工作。沉积物中污染物的浓度均低于ER-L,表明太湖流域沉积物的污染程度较低,在安全生态风险范围内。     

Residues of organochlorine and organophosphorus pesticides in sugarcane crop soils and river water

The presence of residual organochlorine and organophosphorus pesticides was evaluated at different periods of sugarcane cultivation in agricultural soil and water samples from the town of Tlaltizapan, which is located in the state of Morelos in Mexico, to determine the presence and persistence of these compounds and their possible effects on the region. The compounds p,p′-DDE, p,p′-DDD (metabolites of p,p′-DDT), γ-HCH and heptachlor were found in more of 95% of the sampling zones in the three monitoring periods performed along 2 years. The highest concentration detected (129.6 μg/kg _{dry soil}) was for α-HCH, but its frequency of detection was ～5%. The low detection frequency of α-HCH and the high concentration values of γ-HCH indicate the repeated use of technical-grade HCH and Lindane (γ-HCH) in the region. Among the organophosphorus pesticides, ethyl parathion was the compound with the highest soil concentration, at ～2000 μg/kg_{dry soil}, during the initial monitoring. However, this compound was detected in the second monitoring with a concentration of ～4 μg/kg_{dry soil}, but it was not detected in the third, indicating that is was not accumulated in the environment. The heptachlor was the compound most commonly found in all water samples, within a range of 0.45–1.25 ng/L. The presence of this organochlorine compound in the water samples indicated a possible migration from the soil to water bodies due to soil erosion. The presence of organophosphorus compounds was not detected in the water samples, which could be attributed to the moderate persistence of these compounds and their consequent degradation before arriving at the water bodies.     

Comparison of two sample preparation methods for analysis of organochlorine pesticides residues in fish muscle

The aim of this study was to compare recoveries of organochlorine pesticides (heptachlor, α-HCH, β-HCH, γ-HCH, op′-DDD, pp′-DDD, pp′-DDE, op′-DDT, pp′-DDT) from fish muscle dried by two alternative methods: (i) grinding with anhydrous sodium sulphate and (ii) freeze drying. Pesticide residues content was determined by gas chromatography-mass spectrometry (GS-MS) method. For four pesticides (γ-HCH, α-HCH, heptachlor and pp;-DDD) in four of five fish species, higher recoveries were obtained from the freeze-dried samples. For five remaining pesticides, correlations between fish species and drying method were not found. The results of this study do not clearly indicate which drying method caused lower losses of analytes. Recoveries from the freeze-dried samples ranged from 69.9 to 117.6 %, while recoveries from the samples ground with sodium sulphate varied from 64.4 to 126.7 %. Either of the methods gave satisfactory recoveries and they both can be used interchangeably.     

Method for the determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum based on a gel permeation chromatographic clean-up

A gel permeation chromatographic (GPC) clean-up based method was developed for determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum. The method permits automation of the sample extract clean-up stage and is designed to work with small amounts of sample. Different working variables were studied in its development, including injection volume, flow rate, and fat amount as the most representative coextract. The method provides solvent and time savings. Initial extraction was performed using 96-well solid-phase disk extraction plates, and quantification was performed by gas chromatography with electron capture detection and mass spectrometry. Recoveries of PCB congeners 28, 52, 101, 118, 138, 153, and 180 and organochlorine pesticides HCB, β-HCH, γ-HCH, heptachlor epoxide, p,p′-DDE, and p,p′-DDT at two spiking levels ranged from 55% to 115% with relative standard deviations ranging from 2.0% to 14.6%. Limits of quantification ranged from 0.06 to 0.16 ng mL⁻¹ for PCBs and from 0.12 to 0.36 ng mL⁻¹ for organochlorine pesticides. Finally, the method was applied to the analysis of 38 serum samples and the results were compared with those of another procedure validated at the laboratory.     

Dietary habits associated with the presence of organochlorine pesticides in human milk

Abstract

This study aims to establish the relationship between the consumption of certain foods and the presence of organochlorine pesticides in human milk. A total of 167 samples of breastmilk were collected. Sample analysis was carried out by gas chromatography with electron capture detector. Pesticide concentrations (op’DDT, pp’DDT, pp’DDE, Σ-DDT, HCB, β-HCH) were grouped by consumption level of fish, dairy products, meat, eggs, and seafood and then were compared to each other. The odds ratio (OR) was calculated between the concentration of pesticides (higher and/or lower than median) and the exposure variable (high consumption). The results indicated low median concentrations of HCB, β???HCH, op’DDT and pp’DDT, whose fluctuations and trends between different frequencies of food consumption were not significant. pp’DDE and Σ???DDT values according to the increase in consumption of fish were significantly increased. Women with high fish consumption have a higher risk of high concentrations of pp’DDE and Σ-DDT (OR: high consumption: 5.6 (1.3–23.6). A protective effect was observed in the consumption of dairy products (β-HCH and op’DDT), meat (HCB), and seafood (pp’DDT). These results suggest that it is possible that the consumption of fish, dairy products, meat, and seafood influences the presence of organochlorine pesticides in the studied population.     

Residue levels of organochlorine pesticides in cattle meat and organs slaughtered in selected towns in West Shoa Zone,Ethiopia

Residue levels of organochlorine pesticides (OCP) in a total of 90 cattle samples comprising meat, liver and kidney collected from carcasses slaughtered in six towns in West Shoa Zone, Ethiopia, (Ambo, Guder, Ginchi, Gedo, Holeta and Tikur Inchini), have been determined. The pesticides were extracted by solid phase extraction (SPE) and quantification was carried out using gas chromatography-mass spectrometry (GC-MS). A good linearity (r² > 0.998) was found in the range 0.001–7.00 mg/kg for the samples studied. Most of the pesticides had recoveries in the range 81–99% and values of relative standard deviation (RSD) <7.2% for repeatability and reproducibility, showing good accuracy and precision of the method. The concentration level of the studied organochlorines followed the order: p, p’ dichloro-diphenyl-trichloroethane (DDT) > endosulfan>o,p′-DDT >lindane>dieldrin>endrin>aldrin>chlorothanolin while the order of contamination in the analyzed organs was liver > kidney > meat. Heat treatment of the meat, kidney and liver samples (boiling for 90 min.) produced an overall reduction of 62.2%, 44.5%, 37.7%, 29%, 31%, 34.3% and 30.8% in lindane, o, p′-DDT, endosulfan, p, p′-DDT, chlorothanolin, aldrin, dieldrin, and endrin, respectively. Although the residual contents of the organochlorines detected in all the contaminated samples analyzed from the six cities were below the respective maximal permissible levels set by international organizations, samples from Holeta town were more contaminated and may necessitate effective monitoring as bioaccumulation of these residues may pose health problems in human beings.     

A novel pretreatment approach for fast determination of organochlorine pesticides in biotic samples

Recent studies have focused on enantiomeric behaviors of chiral organochlorine pesticides (OCPs) in biotic matrix because they provide insights into the biotransformation processes of chiral OCPs. In the present paper, a double in-line column chromatographic method was developed to effectively remove the lipid impurity in different biotic samples for clean-up of OCPs. After an initial Soxhlet extraction of OCPs from the biotic samples by a mixture of acetone and dichloromethane (DCM), dimethyl sulfoxide (DMSO) was directly added to the extract, and low boiling point solvents (acetone and DCM) were then evaporated. OCPs remained in DMSO were eluted via column 1 filled with silicon gel, and subsequently passed through column 2 packed with 15% deactivated florisil. This novel method was characterized by significant time and solvent savings. The recovery rates of α -HCH (hexachlorocyclohexane), β -HCH, γ -HCH and δ -HCH were 78.5 ± 3.1%, 72.4 ± 7.7%, 72 ± 4.0% and 70.0 ± 8.7%, respectively, and 92.5 ± 3.8%, 79.7 ± 6.7% and 83.4 ± 6.5% for 1,1-dichloro-2-(2-chlorophenyl)-2-(4- chlorophenyl) ethylene (o,p′-DDE), 1,1-dichloro-2-(2-chlorophenyl)-2-(4-chloro phenyl)ethane (o,p′-DDD) and 1,1,1-trichloro-2-(2-chlorophenyl)-2-(4-chlorophenyl) ethane (o,p′-DDT), separately. In addition, the separation efficiencies of the target compounds by both achiral and chiral gas chromatographic columns were satisfactory using the established method. Therefore, the double in-line column chromatography was a useful alternative method for pretreatment of OCPs in different biotic samples.     

Determination of organochlorine and organophosphate pesticide residues in fruits,vegetables and sediments

Abstract

A method is described for the determination of organochlorine and organophosphate pesticide residues in fruits, vegetables and sediments. The concentrated solvent extract was sealed in a polymeric membrane tube, dialysed in cyclohexane and the solvent replaced with hexane. The organophosphates were analysed on a specific thermionic detector without further clean‐up. For the organochlorine pesticides the extract was eluted through 3 g of alumina and analysed on GC/ECD. The clean‐up for sediment extract was carried out on a10 g alumina column with 100 mL hexane containing 5% acetone and the eluate was concentrated to 5 mL.

The detection limit for organophosphates on a 40 g sample and a final volume of 10 mL was on the average 0.01 mg/kg. The detection limit for organochlorine pesticides, with the final volume of 25 mL, was 0.005 mg/kg for all pesticides except for p,p'‐DDT and endosulfan sulphate, which was 0.01 mg/kg.

The detection limit for oganochlorine pesticides in sediment, with the final volume of 2 mL, was less than 1 μg/kg and for organophosphate pesticides less than 10 μg/kg when the final volume was made to 0.5 mL. At the detection limits the method produced a very high coefficient of variation for both organochlorine and organophosphate pesticides.     

Residues of organochlorine pesticides and PCBs in some Brazilian municipal solid waste compost

Persistent organic pollutants (POPs), organochlorine pesticides and polychlorinated biphenyls (PCBs), listed as per the Stockholm Convention (α -HCH, β -HCH, γ -HCH, p,p′-DDT, o,p′-DDT, p,p′-DDD, p,p′-DDE, aldrin, endrin, dieldrin, PCBs 28, 52, 118, 138, 153, and 180), were analyzed in municipal solid waste (MSW) compost samples from three different Brazilian composting plants located in three São Paulo State cities: Araras, Araraquara and São Paulo (Vila Leopoldinha). Quantitative and qualitative analyses were carried out using gas chromatography electron capture detection (GC-ECD) and gas chromatography mass spectrometry (GC-MS) (Ion Trap, electron impact ionization), respectively. The samples were analyzed in triplicate and the target POPs were not detected by GC-ECD. Twelve pollutants were identified in two samples when qualitative analysis (GC-MS) was used (β -HCH, γ -HCH, p,p′-DDT, o,p′-DDT, p,p′-DDD, and p,p′-DDE, PCBs 28, 118, 138, 153 and 180). The composting process has advantages such as urban solid waste reduction and landfill life-span increase, however the MSW compost quality, which can be utilized for agricultural purposes, should be evaluated and be controlled. This kind of study is the first step in making available information to answer questions regarding MSW compost for sustainable agricultural use, such as the pollutants accumulation in soil and in groundwater, and plants uptake.     

Organochlorine pollutants in human blood and their relation with age, gender and habitat from North-east India

Organochlorine pesticides (OCPs) have been beneficial to man and environment but their inadvertent use has caused considerable harm to human health. Despite the proliferation of different types of pesticides, organochlorines such as HCH and DDT still account for two third of the total consumption in India because of their low cost and versatility in action again various pests. Since, Assam, a state in North-eastern part of India is an endemic area with perennial transmission where mosquito borne diseases are serious health problems; these pesticides are still being used in huge quantities in vector control as well as in agriculture. A total of 331 human blood samples were collected from district Nagaon and Dibrugarh of Assam to determine the residue levels of DDT and HCH in human blood. The concentrations of selected persistent organochlorine pollutants were measured with gas chromatography-electron capture detector. The results demonstrated that the mean levels of total DDT and HCH were 743 μg L(-1) and 627 μg L(-1) for district Nagaon while 417 μg L(-1) and 348 μg L(-1) for district Dibrugarh. The difference of total HCH and total DDT between these two districts was found to be highly significant (P<0.0001). Among DDT metabolites, the same trend was observed for both the districts as p,p-DDT was the principal component contributed 41% for Nagaon and 58% for Dibrugarh. In case of HCH residues, for Nagaon, β-HCH was the predominant contaminant comprised more than 34% while for Dibrugarh, it was α-HCH that was contributing 43% of total HCH concentration.     

The health risk assessment of organochlorine pesticides in smoked fish products available in Szczecin,Poland

The aim of this study was to determine the concentration of organochlorine pesticides [HCH and isomers (α, β, γ), aldrin, dieldrin, endrin, heptachlor and heptachlor epoxide and DDT and its metabolites (op’-DDD, pp’-DDD, op’-DDT, pp’-DDE, pp’-DDT] in smoked fish. Analysis was made of 12 typical smoked fish products that are the most popular among customers from the city of Szczecin, Poland. Pesticide residues were found in all samples of smoked fish. The smoked sprat and cold-smoked Baltic salmon were the most contaminated smoked fish products in terms of chlorine pesticides. The sum of DDT metabolites ranged from 1.48 (smoked mackerel) to 35.53 ng/g wet weight (smoked sprat), with the lowest concentrations found for op’-DDT and the highest for pp’-DDE. The level of heptachlor epoxide isomer B was low and ranged from 0.06 ± 0.01 (smoked eel) to 0.27 ± 0.07 ng/g w.w. (smoked sprat). The content of heptachlor was 0.48–1.99 ng/g w.w. Concentration of endrin was higher compared to other pesticides, ranged from 1.50 (cold-smoked salmon fillet) to 16.84 ng/g w.w (hot-smoked warehou). The contamination of smoked products was significantly low and poses no risk to the health of consumers provided that they eat a diverse diet. The concentration of organochlorine pesticides in the analysed products was below the standards accepted in European countries.