SPE-GC-MS法测定地下水中26种有机氯农药

采用固相萃取(SPE)技术,结合气相色谱/质谱(GC-MS)选择离子检测法(SIM)对水样中26种有机氯农药(OCPs)进行提取、净化、浓缩前处理,优选了固相萃取小柱填料及萃取、净化条件,优化了GC-MS的工作参数,建立了地下水中26种有机氯农药的SPE-GC-MS分析方法。针对不同的组分,本法加标回收率为76.422%~112.512%,相对标准偏差为4.905%~15.524%,检出限为0.014~0.089μg/L。该方法操作简单,消耗费用低,分析速度快,具有较高的灵敏度和回收率。     

基于权重敏感度分布研究太湖有机磷农药单一和复合风险

基于实验室能得到的有限毒性数据的物种敏感度分布法(species sensitivity distribution, SSD)很难充分代表特定区域生态系统的物种分布,需要采用考虑生物区系特征进行赋予权重的物种敏感度分布法(weighted species sensitivity distribution,WSSD)。基于太湖物种组成构建WSSD,使用最大累积率(maximum cumulative ratio, MCR)(含风险商法(hazard quotient, HQ))和概率风险评价法(probabilistic risk assessment, PRA)对太湖地区单一和混合有机磷农药的风险进行研究。结果表明,相对于传统SSD方法,加权SSD方法计算的风险商大,且5%生物受影响的概率更大。单一风险评价中,敌敌畏和乐果5%生物受影响的概率超过40%,需要优先控制;最大累积率表明,敌敌畏是复合风险的主要贡献者,单一风险评价中风险较小的马拉硫磷和对硫磷也对复合风险贡献较大,复合暴露风险评价是必要的,混合物的风险商>1,5%生物受复合暴露影响的概率高达90%,有机磷农药复合生态风险不容忽视。     

Assessment of GC–MS response of selected pesticides in apple matrices related to matrix concentration

A uniform analyte response is required for GC–MS analysis in order to obtain acceptable quantitative results. The response of pesticides in complex matrices is susceptible to variation due to the interactions of co-extractives, both with pesticides or with GC–MS system. This study was conducted to determine the magnitude of the interactions, called matrix effect, and their behavior with the matrix dilution. The response of pyrimethanil (4,6-dimethyl-N-phenylpyrimidin-2-amine), cyprodinil (4-cyclopropyl-6-methyl-N-phenylpyrimidin-2-amine), trifloxystrobin (methyl-(2Z)-2-methoxyimino-2-[2-[[(E)-1-[3(trifluoromethyl)phenyl]ethylidene amino]oxymethyl]phenyl]acetate) and bifenthrin(2-methyl-3-phenylphenyl)methyl-3-[(Z)-2-chloro-3,3,3-trifluoroprop-1-enyl]-2,2-dimethylcyclopropane-1-carboxylate), used in apple crops protection, was evaluated in different concentrations of peel and flesh extracts of Granny Smith, Golden Delicious and Demi Rouge, selected as representatives of different matrix types. The matrix effect ranged from ?0.05 to 146.14%, depending on matrix type and pesticide. The highest response variation was observed in extracts of Granny Smith—an enhancement in flesh and suppression in peel extract. With the dilution, the matrix effect decreased with different magnitudes, but for Granny Smith peel extract an inverted effect was observed. The presence of the matrix effect in GC–MS pesticides analysis was obvious, requiring the application of matrix-matched calibration in quantification procedures for each variety, with calibration standards matched by the matrix concentration.     

N-methylcarbamate pesticides and their phenolic degradation products: hydrolytic decay,sequestration and metal complexation studies

We report on the rates of decomposition of a group of N-methylcarbamate (NMC) pesticides (carbaryl, carbofuran and propoxur) under pre-determined tropical field conditions. Rates of decomposition for three NMCs were determined at pH 7.08 and T?=?20?°C and pH 7.70 and T = 33?°C respectively, as follows: carbaryl (78?days and 69?days); carbofuran (143?days and 83?days) and propoxur (116?days and 79?days). Investigation on methods for removal of NMCs and their phenolic decomposition products shows that activated charcoal outperforms zeolite, alumina, diatomaceous earth, cellulose and montmorillonite clay in the removal of both NMCs and phenols from aqueous solution. Furthermore, metal complexation studies on the NMCs and phenols showed that Fe (III) forms a complex with isopropoxyphenol (IPP) within which the Fe:IPP ratio is 1:3, indicative of the formation of a metal chelate complex with the formula Fe(IPP)₃.     

泉州湾沉积物中有机氯农药含量及风险评估

参照美国EPA 8000系列方法及质量保证/质量控制(QA/QC),将泉州湾表层沉积物分为上(0～2 cm)、下(2～10 cm)2层,分析沉积物中有机氯农药(OCPs)含量特征.结果表明,OCPs含量由高至低依次为内湾、秀涂-石湖一线和外湾,吸附性强的硫丹硫酸盐、七氯环氧化合物倾向于在上层富集.残留有机氯农药的降解主要发生在厌氧环境下,上层降解程度大于下层.西南偏南向潮流造成来自江河的污染物长期滞留,降低了内湾自净化能力.对照Ingersoll风险评估标准,认为泉州湾上、下层沉积物中有机残留具有较高的生态风险性,会对该海域深水养殖和底栖食泥生物产生较大影响.      

凝胶渗透色谱净化在土样有机氯测定中的应用

建立凝胶渗透色谱自动净化土壤萃取样品的方法,去除萃取样品中的干扰组分,提高气相色谱检测有机氯农药残留的效率。将该净化方法应用于实际土样的净化,并和佛罗里硅土净化方法相比较,经凝胶渗透色谱净化的20种有机氯农药空白加标的平均回收率为79.0%,比佛罗里硅土净化的空白加标平均回收率高14.9%,且凝胶渗透色谱的净化效率较好。     

对有机磷农药敏感的海鱼脑AChE筛选研究

以10种海洋鱼类:鲅鱼、黄花鱼、鲈鱼、黄鱼、美国红鱼、真鲷、黑鲷、面包鱼、黑头鱼和鳗鲡为实验材料,采用半抑制浓度(IC₅₀)和双分子速率常数(K_i)为指标,通过体外抑制作用比较了这10种海鱼脑AChE对马拉硫磷和甲基对硫磷的敏感性,并分析了海鱼脑AChE作为监测海水中有机磷农药指示酶的可行性,由此筛选出适于制备海水有机磷农药酶传感器的指示酶.实验表明:10种海鱼脑AChE的基础活性在4.62～35.65μmol/(min·g)之间,面包鱼的酶活性最高,黄花鱼的酶活性最低.对马拉硫磷,由IC₅₀所得到的AChE敏感性为:鲅鱼、黄鱼、鲈鱼、真鲷>黑鲷>黑头鱼、鳗鲡>美国红鱼、黄花鱼>面包鱼;由Ki所得到的AChE敏感性为:鲅鱼>黄鱼、鲈鱼、真鲷>黑鲷、黑头鱼、鳗鲡>美国红鱼、黄花鱼>面包鱼.对甲基对硫磷,由IC50所得到的AChE敏感性为:鲅鱼>鲈鱼>黄鱼、黄花鱼、真鲷、黑鲷、黑头鱼、鳗鲡>美国红鱼>面包鱼;由Ki所得到的AChE敏感性为:鲅鱼>鲈鱼、黄鱼、黄花鱼、黑鲷、黑头鱼、鳗鲡>真鲷>美国红鱼>面包鱼.鲅鱼脑AChE对2种有机磷农药都较为敏感.影响鱼脑AChE对有机磷农药敏感性的主要因素为生物来源、农药种类和抑制方式,而与酶的基础活性无关.海鱼脑AChE活力抑制作用与水体中的有机磷农药具有良好的剂量-效应关系,在1～50mg/L浓度范围内,两者间呈现较好的线性相关性(r²≥0.93).根据AChE的敏感性及其对有机磷农药的线性响应程度,鲅鱼脑AChE适于作为监测马拉硫磷和甲基对硫磷酶传感器的指示酶.     

Gridded inventories of historical usage for selected organochlorine pesticides in Heilongjiang River Basin, China

Introduction O rganochlorine pesticides (O C Ps) is a com m on nam e of a group of pesticides consisting of benzene and chlorine. Som e of O C Ps belong to persistent organic pollutants (PO Ps) that are sem i-volatile, bioaccum ulative, persistent and toxic (V allack et al., 1998; Jones and de V oogt, 1999). O CPs are ubiquitous pollutants due to their long-range transport potential. These chem icals have even been found in rem ote areas like the A rctic (M acdonald etal., 2000; A M A …     

土壤中残留的三种有机磷农药快速分析方法的研究

本文介绍一种简便，快速的前处理和气相色谱法测定土壤中甲胺磷．乐果及甲基—１６０５残留量。选择甲醇—丙酮混合溶剂为萃取剂，振荡后取未经净化及浓缩的上清液直接进样。样品加标回收率分别为８５．７％，９３．４％，９２．０％；最低检出浓度分别为０．１ｍｇ／ｋｇ，０．００５ｍｇ／ｋｇ，０．００５ｍｇ／ｋｇ。     

光催化降解有机磷农药的研究

研究以ＴｉＯ２粉末作为光催化剂,光降解３种不同结构的有机磷农药的可行性。结果表明,有机磷农药结构不同其光降解率不同;浓度１．０×１０－４ｍｏｌ／Ｌ的４种有机磷农药,３７５Ｗ中压汞灯照射４０ｍｉｎ有机磷将完全转变为无机磷,并检测出人效磷农药催化降解的部分中间产物。研究光催化剂ＴｉＯ２的用量、空气流量、外加Ｆｅ３＋浓度对光催化降解的影响,并初步探讨了机理。