Heterogeneous reactions of suspended parathion, malathion, and fenthion particles with NO(3) radicals

Organophosphorus pesticides (OPPs) emit into the atmosphere in both gas and particulate phases via spray drift from treatments and post-application emission, but most of their degradations in the atmosphere are not well known. In this study, the heterogeneous reactions of nitrate (NO₃) radicals with three typical OPPs (parathion, malathion, and fenthion) absorbed on azelaic acid particles are investigated using an online vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). The reaction products observed with the VUV-ATOFMS are identified on the basis of GC/MS analysis of the products in the reaction between NO₃ radicals and the coating of the pesticide. Paraoxon is identified as the only product of parathion; malaoxon and bis(1,2-bis-ethoxycarbonylethyl)disulfide as the products of malathion; fenoxon, fenoxon sulfoxide, fenthion sulfoxide, fenoxon sulfone, and fenthion sulfone as the products of fenthion. The degradation rates of parathion, malathion, and fenthion under the experimental conditions are 5.5 × 10⁻³, 5.6 × 10⁻², and 3.3 × 10⁻² s⁻¹, respectively. The pathways of the heterogeneous reactions between the three OPPs and NO₃ radicals are proposed. The experimental results reveal the possible transformations of these OPPs through the oxidation of NO₃ radicals in the atmosphere.     

Distribution of PAEs in the middle and lower reaches of the Yellow River, China

Samples of water, sediment and suspended particulates were collected from 13 sites in the middle and lower reaches of the Yellow River in China. Phthalic acid esters (PAEs) concentrations in different phases of each sample were determined by Gas Chromatogram GC-FID. The results are shown as follows: (1) In the Xiao Langdi–Dongming Bridge section, PAEs concentrations in water phase from the main river ranged from 3.99 × 10⁻³ to 45.45 × 10⁻³ mg/L, which were similar to those from other rivers in the world. The PAEs levels in the tributaries of the Yellow River were much higher than those of the main river. (2) In the studied branches, the concentration of PAEs in sediment for Luoyang Petrochemical Channel (331.70 mg/Kg) was the highest. The concentrations of PAEs in sediment phase of the main river were 30.52 to 85.16 mg/Kg, which were much higher than those from other rivers in the world. In the main river, the concentration level of PAEs on suspended solid phases reached 94.22 mg/Kg, and it reached 691.23 mg/Kg in the Yiluo River – one tributary of the Yellow River. (3) Whether in the sediment or on the suspended solid phases, there was no significant correlation between the contents of PAEs and TOC or particle size of the solid phase; and the calculated Koc of Di (2-Ethylhexyl) Phthalate (DEHP) in the river were much less than the theoretical value, which inferred that PAEs were not on the equilibrium between water and suspended solid phases/sediment. (4) Among the measured PAEs compounds, the proportions of DEHP and di-n-butyl phthalate (DBP) were much higher than the others. The concentrations of DEHP exceeded the Quality Standard in all the main river and tributary stations except those in the Mengjin and Jiaogong Bridge of the main river. This indicates that more attention should be paid to pollution control and further assessment in understanding risks associated with human health.     

加压流体萃取-气相色谱法测定土壤中酞酸酯类化合物

建立了土壤中15种酞酸酯的加压流体萃取-弗罗里硅土柱净化-气相色谱测定方法。就萃取条件探讨了溶剂、温度、时间和循环次数对萃取效率的影响,就净化条件探讨了净化柱和洗脱溶剂对萃取效率的影响。根据研究结果,确定萃取条件以二氯甲烷为萃取溶剂,在萃取温度120℃、压强1 500 psi时,预热5 min,静态提取5 min,循环萃取2次,用体积为60%萃取池体积的萃取溶剂冲洗萃取池,之后用氮气吹扫萃取池90 s;净化条件为萃取溶液过弗罗里硅土固相萃取柱净化后,以正己烷∶丙酮(体积比为5∶1)洗脱。15种酞酸酯类化合物加标回收率为67.1%~124%,方法检出限为0.017~0.048 mg/kg。     

气相色谱法测定工作场所空气中多苯类、多环芳烃类、不饱和脂肪族酯类化合物

建立了同时测定工作场所空气中多苯类、多环芳烃类、不饱和脂肪族酯类化合物的检测方法,该方法操作简便,重复性好,在目标化合物质量浓度2~100 mg/L范围内线性良好,回收率90%,RSD5%,检出限为0.4~0.6 mg/L。结果表明,方法适用于工作场所空气中多苯类、多环芳烃类、不饱和脂肪族酯类化合物的检测要求。     

土壤介质中酞酸酯类污染物分析方法研究

介绍了加压流体提取(PFL、ASE)提取-GPC净化-GC/MS分析土壤中酞酸酯类污染物方法的程序和质控要求,研究了每个步骤对分析六种目标物准确度和精密度的影响以及测定实际土壤样品的情况.结果显示,加压流体提取(PFL)、浓缩和GPC净化各步骤全程序空白加标回收率分别在86.3%～108%、78.5%～117%和87.4%～103%范围,精密度均在15%以内.在实际土壤样品中加入六种酞酸酯标准的加标回收率在45.2%～103.4%范围内,其相对标准偏差8%～23%.     

土壤中15种酞酸酯类化合物测定

采用气相色谱-质谱联用仪(GC-MS)分析了东北某钢铁厂土壤中15种酞酸酯类化舍物(PAEs).结果表明,该方法对15种酞酸酯分离好,平均加标回收率为74.8%～121%,精密度RSD(n=5)在8.3%～13.9%之间,方法检出限为0.01～0.09mg/kg.方法操作简便、准确,具有较好的实用性.     

固相微萃取-车载气相色谱测定污染事故现场有机磷农药分析方法的探讨

探讨了在污染事故现场采用固相微萃取-车载气相色谱联用测定有机磷农药的分析方法,寻找出较适宜灵敏度与较短分析时间的最佳结合点,以适应污染事故应急现场测定有机磷农药的需求。该法完成一个样品的全部分析时问为30min,简便、高效,适用于应急现场5种有机磷农药的测定。     

农药厂周边有机磷农药在生物体中残留的检测方法研究

测定南京某农药厂附近大米、蔬菜及肉类中11种有机磷农药含量,通过使用气相色谱/质谱联用的方法,建立GC／MS定性定量分析方法,检出限达到0．05μg／kg（肉类）和0．1μg／kg（大米和蔬菜）,回收率均符合测定要求。环境样品监测结果显示,大米和蔬菜中有机磷农药的含量高于肉类中的含量,说明在大米和蔬菜表面残留的农药量要高于进入生物体体内的含量。南京蔬菜样品中有机磷农药高于常州蔬菜样品,说明农药厂对蔬菜表面残留农药量有影响。不同的有机磷农药在不同的介质中,检出情况不一样,说明不同的环境介质对有机磷农药的保留水平不一样。     

气相色谱法测定有机磷农药残留的常见问题探讨

针对气相色谱法测定有机磷农药残留过程中常见的基线噪声大、活性位点吸附、热分解和基质效应等4个问题,从气相色谱仪的结构和有机磷农药的性质出发,探讨了解决办法。提出从气路故障、检测器、外部干扰等3个方面排查,降低基线噪声;正确使用玻璃衬管和色谱柱,消除活性位点;合理设置进样口和检测器温度,防止发生热分解现象;采用基质净化、基质匹配校准及加入分析保护剂的方法,避免基质效应。     

气相色谱-火焰光度法测定土壤中有机磷农药残留

土壤样品用正己烷-丙酮(体积比为1∶1)混合溶液提取,配合硅胶小柱净化,用乙酸乙酯洗脱,再用气相色谱-火焰光度法测定待测液中14种有机磷农药残留,方法在0.100 mg/L~1.00 mg/L范围内线性良好,当取样量为10 g时,方法检出限为1.3μg/kg~2.3μg/kg。用该方法测定有机磷的有证标准溶液,结果均在保证值范围内,RSD为2.2%~6.7%。实际土壤样品的13种有机磷农药加标回收率为59.2%~125%(敌百虫除外),敌百虫回收率为0,说明目标物在测定过程中被降解,该方法不适用于敌百虫的测定。