QuEChERS-GC/ECD法分析土壤和沉积物中残留有机氯农药和多氯联苯

建立了用快速、简单、廉价、有效、可靠及安全(Qu ECh ERS)的方法净化、GC/ECD法测定沉积物中有机氯农药和多氯联苯的分析方法。目标化合物质量浓度在1.0~100μg/L范围内线性良好,相关系数均0.999,检出限为0.08~0.17μg/L。以沉积物标准样品SRM1944为研究对象,用Qu ECh ERS方法和传统方法进行提取比较,并用沉积物样品进行验证,回收率为87.8%~100.3%。方法快速、简单、可靠、安全。     

Novel pipette-tip graphene/poly (vinyl alcohol) cryogel composite extractor for the analysis of carbofuran and carbaryl in water

A novel pipette-tip extractor of a graphene/poly (vinyl alcohol) cryogel (graphene/PVA) composite sorbent was prepared to preconcentrate carbamate pesticides in environmental water samples before analysis with a gas chromatograph-flame ionization detector (GC-FID). This novel pipette-tip extractor with the graphene/PVA sorbent exhibited a high porosity when observed through a scanning electron micrograph (SEM). Under optimal conditions, using only 1.0 mL of sample and 0.75 mL of eluting solvent, the developed method provided a wide linear range of 10–700 ng mL^?1 and 10–500 ng mL^?1 with limit of detection (LOD) of 6.40 ± 0.18 and 9.17 ± 0.34 ng mL^?1 for carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) and carbaryl (1-naphthyl methylcarbamate), respectively. The pipette-tip extractor provided high extraction efficiency with high accuracy indicated, by good recoveries in the range of 74.5 ± 4.8% to 119.7 ± 1.6% and 76 ± 15% to 114 ± 19% for carbofuran and carbaryl, respectively. In addition, the fabrication procedure showed a good pipette-tip extractor-to-pipette-tip extractor reproducibility with a relative standard deviation of 1.3–9.8% (n = 5). When the developed pipette-tip extractor was applied for the extraction of carbofuran and carbaryl in surface water samples near vegetable plantation areas, 25.9 ± 8.2 ng mL^?1 of carbofuran was found, and carbaryl was also detected in concentrations that ranged from 45.0 ± 4.0 to 191 ± 13 ng mL^?1.     

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.     

Assessment of daily intake of organochlorine pesticides from milk in different regions of Poland

The common occurrence of organochlorine compounds in the environment, food and human tissues may constitute a serious threat to human health. The method of gas chromatography-mass spectroscopy was used to determine the content of pesticides in 15 samples of raw cow's milk from different regions of Poland. The results revealed high levels of p,p′-DDE, p,p′-DDT, heptachlor and aldrin. The studied milk contained lindane in average concentrations within the maximum limits. Although in 20% of all samples tested, the concentration of lindane exceeded permissible limits, while in 15% of samples the content of Σ DDT was too high. But the average daily consumption of milk containing organochlorine pesticides poses no direct threat to human health, because daily intake (DI) for all compounds were below the acceptable daily intake (ADI). Attention should be paid to the exposure of consumers to pesticide residues from other dairy foods.     

Validation of a multiclass multiresidue method and monitoring results for 210 pesticides in fruits and vegetables by gas chromatography-triple quadrupole mass spectrometry

A rapid, sensitive, accurate and reliable multiresidue method for the identification and quantification of 210 relevant pesticides in four representative fruit and vegetable commodities (tomato, potato, spring onion and orange) has been developed and validated by gas chromatography in tandem with triple quadrupole mass spectrometry. The method has been fully validated and applied to 292 samples from different countries. Prior to instrumental analysis, an extraction procedure based on a sample extraction of multiclass analytes, using the ethyl acetate method was employed. Mass spectrometric conditions were individually optimized for each compound in the selected reaction monitoring (SRM) mode to achieve maximum sensitivity. The pesticides were separated in less than 25 min. This was followed by an exhaustive control of the retention times. The Retention Time Locking Method was applied, working at a constant pressure throughout the analysis. System maintenance was reduced by using a purged capillary flow device that provided backflush capabilities by reversing column flow immediately after elution of the last compound of interest. Istotopically labelled internal standards were employed to improve the quality of the analytical results.     

Impact of biofumigation with solarization on degradation of pesticides and heavy metal accumulation

A greenhouse study was conducted to evaluate the effect of biofumigation (with sheep and chicken manure) combined with solarization on the dissipation of pesticides (pyrifenox, DDT and dieldrin), and on soil metals accumulation. The treatments consisted of a control, and soil disinfestations by biofumigation combined with solarization (B+S) for two, four, five, six consecutive years. B+S enhanced the dissipation of pyrifenox with regard to control treatment. Significant differences were not detected among plots disinfected with B+S for consecutive years. On the other hand, B+S had no effect on the dissipation of DDT and dieldrin, probably due to the resistance of these pesticides to microbial degradation and/or high temperatures. Biofumigation is considered to be an environmentally safe practice, since no accumulation of heavy metals such as Cd, Co, Cu, Cr, Pb, Ni, or Zn was observed after the subsequent application of organic matter through the treatments.     

苏南地区香樟树皮中有机氯农药(OCPs)的污染水平及来源解析

利用树皮作为被动采样介质,2012年8月于苏南地区采集了33个香樟树皮进行有机氯农药(OCPs)的分析.结果表明,苏南地区香樟树皮中六氯苯(HCB)、滴滴涕(DDTs)和氯丹(Chlordanes)的含量范围(以干重计)分别为0.31~1.81、0.40~17.3和n.d.~1.03 ng·g-1.由于六氯苯挥发性较强,其含量的空间差异性不明显.同其它研究结果相比,苏南地区树皮中六氯苯含量相对较低.苏南地区DDT主要来源于工业DDT的历史残留和三氯杀螨醇的使用.根据反式氯丹(TC)/顺式氯丹(CC)的比值判定,苏南地区城区中氯丹可能来源于近期的直接使用,而乡村地区则来源于历史残留.     

珠江河口水域有机磷农药水生生态系统风险评价

通过风险商法和概率风险法评价了珠江河口水域中甲拌磷、敌敌畏及乙拌磷等9种有机磷农药对硅藻、水蚤及糠虾等8种水生生物的生态风险.风险商法评价结果表明,9种有机磷农药混合物总风险商为:糠虾处于高风险中水平,水蚤和摇蚊在中等风险水平,硅藻、牡蛎、鲤鱼、鲶鱼和鳗鱼均处于低风险水平;甲拌磷对风险值的贡献最大,且对每种生物都有影响.概率风险法结果表明,以HC5为参考值评估总风险商时,95%置信水平下的HC5比50%置信水平的HC5保守,50%置信水平的HC5中乐果的HC5最大,毒死蜱的最小;丰水期9种有机磷农药混合物总风险比枯水期农药混合物总风险大,甲拌磷对总风险贡献最大.单一污染物的概率风险表明,甲拌磷和乙拌磷对珠江河口水域中10%以上的生物都有危害;而9种有机磷农药混合物的概率风险表现为:丰水期大于枯水期,均大于5%,说明超过了保护95%生物的安全阈值.     

北京官厅水库中农药类内分泌干扰物分布和来源

研究了北京官厅水库中农药类内分泌干扰物污染水平、分布特点和来源.结果表明,官厅水库及其支流水体受到农药类内分泌干扰物轻度污染.从农药在官厅水库中的分布推断,官厅水库以及各支流周边地区及农田排水渠是水库中农药的重要来源.底泥中农药通过底泥孔隙向表面水扩散,是表面水农药的1个污染源.由于水库周边较多的农业活动,可能导致水中农药浓度提高.为了减少污染和水生生物对内分泌干扰物的暴露,需要进行定期监测,减少农药的使用和农事操作.     

OCCURRENCE OF PESTICIDES IN GROUND WATER OF THE OZARK PLATEAUS PROVINCE1

ABSTRACT: Pesticides were detected in ground-water samples collected from 20 springs and nine wells in the Ozark Plateaus Province of Arkansas, Kansas, Missouri, and Oklahoma. From April through September 1993, water samples were collected from 50 shallow domestic wells and 50 springs in the Springfield Plateau and Ozark aquifers and analyzed for 47 pesticides and metabolites. Pesticides were detected in 17 water samples from the Springfield Plateau aquifer and 12 water samples from the Ozark aquifer. Fourteen pesticides were detected, with a maximum of four pesticides detected in any one sample. The most commonly detected pesticides were atrazine (14 detections), prometon (11 detections), and tebuthiuron (seven detections). P, P' DDE, a metabolite of DDT, was detected in water samples from three wells and one spring. The remaining pesticides were detected in three or less samples. The occurrence and distribution of pesticides probably are related to the local land use near a sampling site. Pesticide detections were significantly related to aquifer, site type, and discharge of springs.