Validation of a QuEChERS-based gas chromatographic method for analysis of pesticide residues in Cassia angustifolia (senna)

A simple multi-residue method based on modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach was established for the determination of 17 organochlorine (OC), 15 organophosphorous (OP) and 7 synthetic pyrethroid (SP) pesticides in an economically important medicinal plant of India, Senna (Cassia angustifolia), by gas chromatography coupled to electron capture and flame thermionic detectors (GC/ECD/FTD) and confirmation of residues was done on gas chromatograph coupled with mass spectrometry (GC-MS). The developed method was validated by testing the following parameters: linearity, limit of detection (LOD), limit of quantification (LOQ), matrix effect, accuracy–precision and measurement uncertainty; the validation study clearly demonstrated the suitability of the method for its intended application. All pesticides showed good linearity in the range 0.01–1.0 μg mL^?1 for OCs and OPs and 0.05–2.5 μg mL^?1 for SPs with correlation coefficients higher than 0.98. The method gave good recoveries for most of the pesticides (70–120%) with intra-day and inter-day precision < 20% in most of the cases. The limits of detection varied from 0.003 to 0.03 mg kg^?1, and the LOQs were determined as 0.01-0.049 mg kg^?1. The expanded uncertainties were <30%, which was distinctively less than a maximum default value of ±50%. The proposed method was successfully applied to determine pesticide residues in 12 commercial market samples obtained from different locations in India.     

Hydrolysis and soil sorption of insecticide pyraclofos

The hydrolysis of the insecticide pyraclofos in buffered solutions at pH 5.0, 7.0 and 9.0, and its sorption on four soils of different physicochemical properties were investigated. The results showed that the degradation of pyraclofos in buffered solutions followed pseudo-first-order kinetics. At 40°C, the rate constants for the hydrolysis of pyraclofos at pH 5.0, 7.0 and 9.0 were 0.0214, 0.1293, and 2.1656 d^?1, respectively. Pyraclofos was relatively stable under both acidic and neutral conditions, while it was readily hydrolyzed under basic conditions. The sorption of pyraclofos on four soils was well described by the Freundlich equation. The sorption constant, K _f, increased with an increase in soil organic carbon content, suggesting that organic carbon content was an important factor affecting sorption. The K _oc values for Xiaoshan clay loam soil, Hangzhou I clay loam soil, Hangzhou II soil, and Fuyang silt loam soil were 30.4, 6.7, 5.3, and 7.1, respectively. These results suggest that the sorption of pyraclofos on the tested soils was relatively weak.     

Pesticides residues in the Prochilodus costatus (Valenciennes, 1850) fish caught in the São Francisco River,Brazil

The objective of this study was to determine the levels of pesticides in the fish Prochilodus costatus caught in São Francisco River, one of most important rivers in Brazil. Thirty-six fish were captured in three different areas, and samples of the dorsal muscle and pooled viscera were collected for toxicological analysis. We evaluated the presence of 150 different classes of insecticides, fungicides, herbicides and acaricides by multiresidue analysis technique using liquid chromatography-tandem mass spectrometry (LC-MS/MS), with the limit of detection of 5 ppb. In this study, organophosphorus and carbamate pesticides were detected at the highest levels in the caught fish. Among the 41 organophosphorus pesticides surveyed, nine types were detected (chlorpyrifos, diazinon, dichlorvos, disulfoton, ethion, etrimfos, phosalone, phosmet and pyrazophos) in the muscle, viscera pool, or both in 22 (61.1%) fish. Sampled tissues of 20 (55.6%) fish exhibited at least one of the eight evaluated carbamate pesticides and their metabolites: aldicarb, aldicarb sulfoxide, carbaryl, carbofuran, carbosulfan, furathiocarb, methomyl and propoxur. Fungicides (carbendazim, benalaxyl, kresoxim-methyl, trifloxystrobin, pyraclostrobin and its metabolite BF 500 pyraclostrobin), herbicides (pyridate and fluasifop p-butyl), acaricide (propargite) and pyrethroid (flumethrin) were also detected. In conclusion, P. costatus fish caught in the São Francisco River contained residues of 17 different pesticides, in both muscles and the viscera pool, indicating heavy environmental contamination by pesticides in the study area.     

A multi-residue method for the analysis of organophosphorus residues in cooked and polished rice using accelerated solvent extraction and dispersive-solid phase extraction (D-SPE) technique and uncertainty measurement

Quick, simple and efficient multi-residue analytical methods were developed and validated for the determination of organophosphorous insecticides from polished and cooked rice. Polished rice was extracted using a simple, automated technique namely accelerated solvent extraction (ASE) using dichloromethane as the extraction solvent. Cooked rice was extracted with acetone and cleaned up using dispersive-solid phase extraction (D-SPE) technique. The single step extraction method adopted for polished rice using accelerated solvent extractor provided satisfactory recovery for eight organophosphorus pesticides (OPPs) which ranged from 85.5–116.7%; 90.0–110.3% and 93.5–118.8% at 1, 5 and 10 limit of quantification (LOQ) levels, respectively. The recovery of cooked rice was in the range of 74–124%; from 75–100% and from 73–87% for 1, 5 and 10 level of fortification, respectively. The total uncertainty was evaluated, taking four main independent sources viz., weighing, purity of the standard, GC calibration curve and repeatability under consideration. The expanded uncertainty was found to be in the range of 5–20%.     

闽江上游溪流沉积物有机磷空间分布及其环境意义分析

为探究闽江上游土地利用方式对溪流沉积物磷的分布及潜在释放能力的影响,利用IVANOFF法,重点研究闽江上游不同流域沉积物有机磷形态及其空间分布特征,探讨沉积物的理化性质对有机磷(OP)形态含量分布的影响.结果表明:①建溪和沙溪流域的沉积物总氮(TN)和总磷(TP)含量要高于富屯溪流域,这应与建溪和沙溪流域附近农田和居民区较多、富屯溪流域周围多以林地为主有关;②3个流域沉积物中TN含量及建溪和富屯溪流域沉积物中的TP含量均有上游中游下游的规律,显然是溪流上游多山地、林地,而中下游人类活动多造成的;③3个流域沉积物有机磷形态都以非活性有机磷(NLOP)为主,表明闽江上游总体受外源污染影响较小,其形态相对比例在不同流域的沉积物中的变化较大,而在同一河流的不同地段中变化则较小;④沉积物的理化性质对有机磷形态与分布有明显影响,其中有机质(OM)、TP和TN的影响最为明显,但对不同流域沉积物的影响程度存在差异.因此,为保障闽江上游水质,应加强对流域附近的生活污染源及农业污染源的控制.     

喀斯特山区植被恢复过程中土壤水解酶和氧化酶活性的响应

土地利用方式的改变,如农田退耕是影响土壤有机碳固持的重要因素.喀斯特地区正开展大规模的生态系统恢复工程,然而生态系统恢复过程中土壤有机碳的固持机制依然不甚清楚.土壤有机碳的分解是土壤碳循环的一个关键过程.不同组分有机碳的分解受不同酶的活性控制,因此,在西南喀斯特山区不同植被恢复阶段下开展土壤酶活性特征研究,有助于了解该地区土壤有机碳固持机制并为该地区的生态恢复实践提供理论支撑.本研究在广西河池市环江县典型喀斯特区域的农田、草地、灌丛、次生林4种不同植被恢复阶段下采集0~10 cm深度的土壤样品,采用荧光光度法和紫外分光光度法测定3种土壤水解酶(即β-葡糖苷酶、α-纤维素酶和β-木糖苷酶)和1种氧化酶(过氧化物酶)的活性及相关土壤理化属性指标,研究植被恢复过程中土壤水解酶(参与活性碳库的分解)和氧化酶活性(参与惰性碳库的分解)的响应.结果显示,随着植被恢复土壤水解酶活性不断增加(次生林灌丛草地农田),而土壤氧化酶无明显变化.导致该结果的原因可能是由于喀斯特地区土壤有机碳极高的稳定性导致微生物趋向于利用活性有机碳库,而对于惰性有机碳库的分解并无显著差别.本研究间接说明喀斯特地区农田退耕后将有利于土壤惰性有机碳的累积.     

Exposure of organophosphorus pesticides to turbulent diffusion flames

The development of effective fire-fighting strategies for warehouses storing large quantities of toxic chemicals depends on an understanding of the uncontrolled combustion of such toxics. This paper describes an experimental system for studying fires of this kind. Results are presented from a test programme involving fires with rates of convective heat release in the range 3–30 kW and four organophosphorus pesticides. This work on the combustion chemistry of toxic materials is part of a wider study, involving a number of laboratories, into other inter-related aspects of warehouse fires. The significance of the results for hazard assessment and emergency planning is considered.     

生物电化学传感器测定农药残留的研究进展

生物传感器在环境监测方面具有灵敏及便于携带等优点.以胆碱酯酶的催化活性为基础的抑制型酶电极和以有机磷水解酶(OPH)为基础的直接测定型酶电极近来研究广泛、发展迅速.本文通过对传感器原理以及近10年酶固定技术的发展的叙述,总结了各种电化学传感器的优缺点,提供了酶生物传感器在测定有机磷农药残留的最新研究进展.     

分散固相萃取法对果蔬中农药残留前处理的优化

以分散固相萃取法为前处理技术,乙腈为提取溶剂,建立了气相色谱-硫磷检测器（GC-FPD）分析苹果中10种有机磷农药残留的方法。实验表明,该方法可获得较高的回收率和精密度。分散固相萃取法较传统前处理方法更加简便,快速,是一种更有效的前处理技术。     

我国有机磷农药废水的生化法处理研究进展

农药废水的污染已受到国内外环保工作者的重视 ,我国也不例外。各种处理方法层出不穷 ,而生化法是各处理方法中的重要方法 ,本文仅就我国生化法处理有机磷农药废水的研究进展作一概述