固相萃取-GC/MS法测定水中16种有机氯农药

采用HLB固相萃取柱富集水样,乙酸乙酯溶剂洗脱,加入氘代菲作为内标,利用气相色谱/质谱联用法选择离子模式测定水中16种有机氯农药,优化了固相萃取条件。16种有机氯农药在5.00μg/L~250μg/L范围内线性良好,按1 L水样计算,方法最低检出限为1.4 ng/L~19.4 ng/L,相对标准偏差为3.5%~20.0%,平均加标回收率为44.7%~119%。     

Background biomonitoring of residue levels of 137 pesticides in the blood plasma of the general population in Beijing

Due to the widespread use of pesticides, human exposure to pesticides is possible and can potentially cause adverse impacts on public health. We measured 137 pesticides including organophosphorus, organochlorine, pyrethroid and carbamate pesticides together with various herbicides in 100 human blood samples collected from the general population in Beijing. The samples were analysed by triple quadrupole tandem gas chromatography-mass spectrometry. In total, 24 organochlorine pesticides, 5 pyrethroid pesticides and 6 organophosphorus pesticides were detected. The detection rates of HCB, α-HCH, β-HCH, γ-HCH, p,p′-DDE and quintozene were 99, 96, 74, 72, 96 and 95%, respectively. No statistically significant gender difference in the blood concentrations of the pesticides was found. Consistent with the trend of the increasing β-HCH, p,p′-DDE and quintozene concentrations with age, a strong positive correlation between the age and concentrations of β-BHC, p,p′-DDE and quintozene was observed.     

Pesticide Residues in Bovine Milk from a Predominantly Agricultural State of Haryana, India

One hundred forty seven samples of bovine milk were collected from 14 districts of Haryana, India during December 1998–February 1999 and analysed for the presence of organochlorine pesticide (OCPs) residues. ∑HCH, ∑DDT, ∑endosulfan and aldrin were detected in 100%, 97%, 43% and 12% samples and with mean values of 0.0292, 0.0367, 0.0022 and 0.0036 μg/ml, respectively. Eight percent samples exceeded the maximum residue limit (MRL) of 0.10 mg/kg as recommended by WHO for ∑HCH, 4% samples of 0.05 mg/kg for α-HCH, 5% samples of 0.01 mg/kg for γ-HCH, 26% samples of 0.02 mg/kg for β-HCH as recommended by PFAA and 24% samples of 0.05 mg/kg as recommended by FAO for ∑DDT. Concentrations of β-HCH and p,p′-DDE were more as compared to other isomers and metabolites of HCH and DDT.     

Persistent organic pollutants in sediment from the southern Baltic: risk assessment

The concentrations of organochlorine pesticides, PCBs, and PCDD/Fs were measured in sediment samples collected from the Gulf of Gdańsk, the Gdańsk Deep, the Vistula Lagoon and the off-shore waters in the southern Baltic Sea. The determinations were conducted in the fraction <63 μm. The highest levels of pollutants were found in sediments from the Gulf of Gdańsk and the Gdańsk Deep. In these sediments, concentrations of pp'-DDT and its metabolites (pp'-DDE and pp'-DDD) ranged from 2 to 11 μg kg(-1) dw. Concentrations of HCB were between 0.1 and 1.0 μg kg(-1) dw. Concentrations of the sum of α-, β-, γ-HCH were between 0.3 and 2.58 μg kg(-1) dw. Concentrations of marker PCBs ranged from about 2 to 11 μg kg(-1) dry weight. Total TEQ PCDD/F/dl-PCB values in the studied samples varied between 1 and 18 ng kg(-1) dw. The data were evaluated in terms of ecotoxicological criteria based on the environmental impact of the pollutant effects. Our research indicated that in the sediment from the southern Baltic Sea, the PCDD/F and PCBs occurred at concentrations which could be dangerous to marine organisms.     

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％。     

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。     

Assessment of pesticide residues in vegetables from the Western Usambara and Uruguru Mountains in Tanzania

Assessment of levels of pesticide residues in vegetables was carried out in some villages in the Western Usambara and Uluguru Mountains of Tanzania where varieties of vegetables are grown. Tomatoes and cabbages were the most popular enterprise grown all year round and therefore were selected as the model crops for this study. Analysis of the cleaned sample extracts on a gas chromatography with electron capture detector (GC-ECD) and confirmation on the Gas chromatography–mass spectrometry (GC-MS) revealed dominance of organochlorine pesticides. Organophosphorous pesticides (parathion and marathion) were only detected in some samples, however, in most cases with higher concentrations compared to organochlorine pesticides. Levels of pesticide residues detected in vegetables were up to: parathion 5.07 μg/Kg, marathion 3.73 μg/Kg, α-endosulfan 0.32 μg/Kg, β-endosulfan 0.53 μg/Kg, dieldrin 1.36 μg/Kg, γ-HCH 0.25 μg/Kg, α-HCH 0.09 μg/Kg, and p, p′-DDT 0.64 μg/Kg. These results clearly show that vegetables are contaminated with different pesticide residues. However, the total levels of pesticide residues in both tomatoes and cabbages are lower than their respective codex alimentarius maximum residue levels (MRLs). This means that the vegetables produced in the area are suitable for human consumption.     

Distribution and sources of organochlorine pesticides in sediments of the Xiangjiang River, south-central China

The Xiangjiang River (XR), the second largest tributary of the Yangtze River, is mainly located in Hunan province in south-central China. Nineteen surface sediment samples (the top 3-cm layer) collected from XR were analyzed to determine the concentrations, distribution, sources, and ecological risk of organochlorine pesticides (OCPs). The concentrations of OCPs were 3.0–29.8 ng/g (dry weight) with a mean of 12.6?±?7.7 ng/g. The widely detected compounds included HCHs, DDTs, HCB, and dieldrin. Overall, the dominant OCPs in the sediments were mainly composed of residual and degradation products, e.g., β-HCH with a mean of 42.2 % in HCHs and p,p′-DDE with a mean of 43.5 % in DDTs, implying that OCPs in the sediments had suffered from long-term aging without fresh inputs in XR. However, there was a high proportion of p,p′-DDT to DDTs in three sites, suggesting that there was use of technical DDT from their surrounding areas at present. The ratios of α-HCH/γ-HCH and p,p′-DDD?+?p,p′-DDE/DDTs increase from the upper reaches to the lower reaches of XR, suggesting sediments enriched with α-HCH and metabolites DDD and DDE during sediment transport process and could be attributed to the transformation of γ-HCH to α-HCH and DDT to DDE or DDD. The assessment of the ecological risk indicates that the OCPs in the sediments of XR have a moderate adverse biological effect on organisms.     

Assessment of dietary intakes of nineteen pesticide residues among five socioeconomic sections of Hyderabad—a total diet study approach

Total diet study approach was used to assess the dietary intakes of pesticide residues among the select population in Hyderabad. When assessed by a food frequency questionnaire, it was found that the food intakes varied among five socioeconomic sections (SES). Therefore, we intended to compare the intakes of pesticide residues through these foods among the five SES. A total of 195 foods from different markets were collected and analyzed for 19 pesticides. The residues were analyzed with a gas chromatograph and were confirmed with mass spectrometry. About 51 % of the samples were detected with one or more residues. Thirteen out of the 19 residues were present in levels above detection limits in various concentrations. The median concentrations of the residues in all the samples tested, ranged from 0.00010 to 0.33 mg/kg. Highest median concentration was for β-HCH in water samples. Exposures to all the residues were below the respective ADIs at both mean and 95th percentile levels of food intakes with highest estimated dietary intakes (EDIs) of β-HCH in both the cases. The EDIs of β-HCH were the highest among all the residues at both the intake levels among all the SES. The EDIs of β-HCH were significantly higher in lower SES than higher SES possibly due to the consumption of rice cooked in water contaminated with β-HCH. EDIs for other residues did not differ significantly among the five SES.     

Assessment of organochlorine pesticide residues in Indian flue-cured tobacco with gas chromatography-single quadrupole mass spectrometer

Presence of pesticide residues in tobacco increases health risk of both active and passive smokers, apart from the imminent potential health problems associated with it. Thus, monitoring of pesticide residue is an important issue in terms of formulating stringent policies, enabling global trade and safeguarding the consumer’s safety. In this study, a gas chromatography-single quadrupole mass spectrometry (GC-MS) method based upon quantifier-qualifier ions (m/z) ratio was employed for detecting and assessing ten organochlorine pesticide residues (α-HCH, β-HCH, γ-HCH, δ-HCH, 2,4-DDT, 4,4-DDT, endrin, α-endosulfan, β-endosulfan and endosulfan sulphate) in 152 flue-cured (FC) tobacco leave samples from two major tobacco growing states, Karnataka and Andhra Pradesh, of India. In the majority of samples, pesticide residue levels were below the limit of quantification (LOQ). In few samples, pesticide residues were detected and they found to comply with the guidance residue levels (GRL) specifications of the Cooperation Center for Scientific Research Relative to Tobacco (CORESTA). Detection of the phase out pesticides like DDT/HCH might be due to transfer of persistent residues from the environmental components to the plant. This is the first report on these ten organochlorine pesticide residues in Indian FC tobacco.     

Occurrence and distribution of organochlorine pesticides (DDT and HCH) in sediments from the middle and lower reaches of the Yellow River, China

Sediments used in this study were selected from 23 stations in the middle and lower reaches of the Yellow River and its tributaries in November 2005. The levels and distribution patterns of selected organochlorine pesticides (OCPs = p,p ^′-DDT, o,p ^′-DDT, p,p ^′-DDE, p,p ^′-DDD, α-, β-, γ-, and δ-HCH) in samples were investigated by analysis of gas chromatography coupled with micro-electronic capture detector. Concentration of OCPs in the sediments from the Yellow River ranged from 0.05 to 5.03 ng g^???1 (mean, 1.02 ng g^???1) for ∑DDT, 0.09–12.89 ng g^???1 (mean, 1.08 ng g^???1) for ∑HCH. The concentration distribution of ∑DDT and ∑HCH varied significantly with different sampling station, indicating their different contamination sources. Composition analyses demonstrated that residues of DDTs in sediments came from the previous inputs of organochlorine pesticides, while β-HCH and γ-HCH significantly dominated in the sediments for HCHs.     

Organochlorine compounds in red deer (Cervus elaphus L.) and fallow deer (Dama dama L.) from inland and coastal Croatia

Polychlorinated biphenyl (PCB) and organochlorine pesticide (OCP) levels in fat tissue of red and fallow deer (Cervus elaphus L. and Dama dama L.) from two inland and an Adriatic area were established. Of 17 analysed PCBs, PCB-28, PCB-138, PCB-153, PCB-180 and PCB-118 were found in all samples, whilst PCB-101 and PCB-170 were found in more than 50% of samples. They ranged between 0.03 and 5.98 ng g(-1) fat weight. Of seven analysed OCPs, HCB, γ-HCH and 1,1-dichloro-2,2-di(4-chlorophenyl)ethylene (DDE) were found in all samples, whilst β-HCH was found in more than 50% of samples. They ranged between 0.17 and 22.14 ng g(-1) fat weight. The dominating compounds were DDE, PCB-138, PCB153, PCB-118 and PCB-180. According to the Duncan multistage test, the levels of PCB-138, PCB-153, PCB 170 and PCB-180 were significantly higher in perirenal fat samples of specimens taken from the Adriatic area. DDE was significantly higher in the inland deer samples. Some species differences were determined and were mostly related to higher PCB and β-HCH levels in fallow deer samples and higher DDE levels in red deer samples. No sex difference was established. As for age, significantly higher levels of PCB-118 and PCB-52 were found in fawns.     

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.     

Residue levels of hexachlorocyclohexane and dichlorodiphenyltrichloroethane in human milk collected from Beijing

Forty-eight human breast milk samples were collected from mothers in Beijing. The hexachlorocyclohexane (HCH) and dichlorodiphenyltrichloroethane (DDT) (including α-HCH, β-HCH, γ-HCH, δ-HCH, p,p′-DDE, p,p′-DDD, o,p′-DDT, and p,p′-DDT) contents of the samples were determined by gas chromatography/electron capture detection and gas chromatography/mass spectrometry. α-HCH, β-HCH, γ-HCH, p,p′-DDE, p,p′-DDD, and p,p′-DDT were detected at rates of 20, 100, 10, 100, 10, and 22 %, respectively. The average residue levels in the samples were 174.6 ng/g fat for β-HCH, 333.8 ng/g fat for p,p′-DDE, 6.57 ng/g fat for α-HCH, 7.67 ng/g fat for γ-HCH, 4.18 ng/g fat for p,p′-DDD, and 11.4 ng/g fat for p,p′-DDT. The results showed that the infants’ daily intake levels of HCH and DDT were 0.95 and 1.76 μg/kg body weight/day, respectively. Our result suggested that the total residue level of these organochlorine pesticides in breast milk from Beijing decreased and was lower than that from other coastal and heavy industrial cities in China. On the other hand, the levels of HCH and DDT were higher than those from some developed countries, but lower than those from other developing countries such as India.     

固相萃取-高效液相色谱法测定饮用水中酚类化合物

采用固相萃取-高效液相色谱法测定饮用水中酚类化合物,优化了试验条件。方法在0 mg/L~40.0 mg/L范围内线性良好,14种酚类化合物的检出限为0.6μg/L~2.6μg/L,水样平行测定的RSD为0.2%~2.7%,加标回收率为96.3%~99.9%。     

Spatial and seasonal variations of pesticide contamination in agricultural soils and crops sample from an intensive horticulture area of Hohhot, North-West China

The spatial variability and temporal trend in concentrations of the organochlorine pesticides (OCPs), hexachlorocyclohexane (HCH) and dichlorodiphenyltrichloroethane (DDT), in soils and agricultural corps were investigated on an intensive horticulture area in Hohhot, North-West China, from 2008 to 2011. The most frequently found and abundant pesticides were the metabolites of DDT (p,p′-DDE, p,p′-DDT, o,p′-DDT and p,p′-DDD). Total DDT concentrations ranged from ND (not detectable) to 507.41 ng/g and were higher than the concentration of total HCHs measured for the range of 4.84–281.44 ng/g. There were significantly positive correlations between the ∑DDT and ∑HCH concentrations (r ²>0.74) in soils, but no significant correlation was found between the concentrations of OCPs in soils and clay content while a relatively strong correlation was found between total OCP concentrations and total organic carbon (TOC). β-HCH was the main isomer of HCHs, and was detected in all samples; the maximum proportion of β-HCH compared to ∑HCHs (mean value 54%) was found, suggesting its persistence. The α/γ-HCH ratio was between 0.89 and 5.39, which signified the combined influence of technical HCHs and lindane. Low p,p′-DDE/p,p′-DDT in N1, N3 and N9 were found, reflecting the fresh input of DDTs, while the relatively high o,p′-DDT/p,p′-DDT ratios indicated the agricultural application of dicofol. Ratios of DDT/(DDE+DDD) in soils do not indicate recent inputs of DDT into Hohhot farmland soil environment. Seasonal variations of OCPs featured higher concentrations in autumn and lower concentrations in spring. This was likely associated with their temperature-driven re-volatilization and application of dicofol in late spring.     

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.     

小体积液液萃取-GC/MS法测定地表水中有机磷农药

采用小体积液液萃取-气相色谱/质谱联用法测定地表水中有机磷农药,以1.2 mL正己烷为萃取剂,磷酸三苯酯为内标,对8种目标化合物的富集倍数达156～436.方法在1.00 μg/L～20.0 μg/L范围内线性良好,8种有机磷农药的检出限均为0.2 μg/L,实际水样平行测定的RSD为2.1%～9.7%,平均加标回收率...     

Distribution of persistent organochlorine chemical residues in blood plasma of three species of vultures from India

The presence of persistent organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) were determined in blood plasma of white-backed vulture Gyps bengalensis, Egyptian vulture Neophron percnopterus, and griffon vulture Gyps fulvus collected from Ahmedabad, India. All the samples had varying levels of organochlorine pesticides and PCBs. Statistically significant (P?<?0.05) differences among species were detected for beta-hexachlorocyclohexane (??-HCH), ??HCH, and dichloro-diphenyl-trichloroethane (DDT). The mean concentration of ??HCH, ??DDT, and ??PCBs among plasma ranged from 43.7 to 136, 8.8 to 64.8, and 226 to 585 ng/ml, respectively. Among the various OCPs analyzed, 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (p,p ^??-DDE) was detected most frequently. The concentrations of cyclodiene insecticides detected were lower than the other organochlorine residues. The levels of pesticides measured in plasma samples of three species of vulture were comparable to the results documented for a number of avian species and were lower than those reported to have deleterious effects on survival or reproduction of birds. Although no threat is posed by any of the organochlorine pesticides detected, continuous monitoring of breeding colonies is recommended. This study is also the first account of a comprehensive analysis of toxicants present in blood plasma of vulture species in India. The values reported in this study can serve as guidelines for future research in general as well as control values during the analysis of samples obtained from birds in the event of suspected organochlorine poisoning.     

QuEChERS-气相色谱法快速测定土壤中8种有机氯农药

建立QuEChERS-气相色谱法同时检测土壤中8种有机氯农药的方法,优化分散固相萃取剂用量。土壤样品通过分散固相萃取净化技术,氮吹浓缩后用正己烷定容,最后通过气相色谱测定。结果表明,在2.0~100μg/L质量浓度范围内呈线性,相关系数r为0.9895~0.9991。空白样品在0.5,5和20μg/kg加标浓度下的回收率为75.3%~92.3%,相对标准偏差为3.2%~5.6%(n=5),方法检出限为0.053~0.064μg/kg,测定下限为0.21~0.26μg/kg。该方法操作简单、结果准确、有机试剂用量少、分析成本低,适用于土壤中有机氯农药的残留检测与分析。