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%.     

10种常用农药对赤子爱胜蚓(Eisenia foetida)的急性毒性效应

为了评价农药对土壤无脊椎动物种群的生态风险,采用OECD标准滤纸法和人工土壤法测定了10种常用农药对蚯蚓(Eisenia foetida)的急性毒性效应。采用滤纸法,48h测定结果表明,4种氨基甲酸酯类(异丙威、甲萘威、速灭威和丁硫克百威)和2种有机磷类(毒死蜱和哒嗪硫磷)农药对蚯蚓的急性毒性(其LC50值为3.50(2.77～4.44)～72.42(59.58～88.05)μg·cm-2)明显高于3种昆虫生长调节剂(噻嗪酮、虫酰肼和呋喃虫酰肼)和吡蚜酮对蚯蚓的急性毒性(其LC50值>629.1μg·cm-2)。采用人工土壤法,14d测定结果表明,上述4种氨基甲酸酯类农药对蚯蚓的急性毒性(其LC50值为59.61(55.13～64.44)～134.1(127.0～141.5)mg·kg-1)明显高于上述2种有机磷类农药和其他农药对蚯蚓的急性毒性(其LC50值为193.0(180.1～206.8)～386.4(359.7～414.2)mg·kg-1)。上述结果表明,不同类型的农药对蚯蚓的毒性存在较大差异,且同一类型的不同农药品种对蚯蚓的毒性也存在较大差异。总体来看,氨基甲酸酯类农药比其他类型的农药对蚯蚓具有更高的毒性。根据《化学农药环境安全评价试验准则》,本研究采用人工土壤法测定的所有农药对蚯蚓均为低毒级。     

环境试样中有机磷农残的预处理及检测

环境试样中用胺磷,乐果及甲基对硫磷等有机磷农残用ＦＰＤ,ＮＰＤ及ＥＣＤ检测可准确定性,用甲醇水溶液萃取固体试样及直接进水样技术既简化了预处理步骤,又有足够的精确度,甲醇／水溶液萃取土壤样品的加标回收率在９３％－９８％范围内,３种检测器对水样中乐果的检测限（ｍｇ／Ｌ）分别为０．０５（ＦＰＤ）,０．００１（ＮＰＤ）及０．００２（ＥＣＤ）。     

海螺沟植物和积雪中有机磷酸酯的分布及来源

为研究大气传输以及干湿沉降对偏远地区环境中有机磷酸酯(OPEs)含量及分布的影响,本研究以海螺沟景区为例,采集了海螺沟的植物和积雪样品,用气相色谱-质谱联用仪(GC-MS)定量分析了样品中7种典型有机磷酸酯[磷酸三丁酯(Tn BP)、磷酸三氯乙酯(TCEP)、磷酸三氯丙酯(TCPP)、磷酸三(2,3-二氯丙基)酯(TDCPP)、磷酸三苯酯(TPh P)、磷酸三丁氧乙酯(TBEP)和磷酸三异辛酯(TEHP)]的含量及分布特征.结果表明,海螺沟景区常见的9种植物中7种OPEs(Σ7OPEs)的含量(以DW计)水平在43. 1～1 050. 8 ng·g-1之间,其中TBEP和TPh P含量最高,分别占Σ7OPEs总含量的36%～70%和24%～80%.冰川积雪中主要污染物与植物中一致,TBEP含量最高,占Σ7OPEs总含量的47%,其次为TPh P,占24%.采用Grads、后向轨迹模型及历史风向数据分析得出海螺沟环境显著受到人类活动扰动,其OPEs主要受来自成都方向和云南昭通与宜宾、泸州、西昌交界处方向的大气传输的影响,需要进一步研究其环境行为并加强城市污染控制.     

A screen-printed, amperometric biosensor for the determination of organophosphorus pesticides in water samples

An amperometric biosensor based on screen-printed electrodes (SPEs) was developed for the determination of organophosphorus pesticides in water samples. The extent of acetylcholinesterase (AChE) deactivation was determined and quantified for pesticide concentrations in water samples. An enzyme immobilization adsorption procedure and polyacrylamide gel matrix polymerization were used for fabrication of the biosensor, with minimal losses in enzyme activity. The optimal conditions for enzyme catalytic reaction on the SPEs surfaces were acetylthiocholine chloride (ATChCl) concentration of 5 mmol/L, pH 7 and reaction time of 4 min. The detection limits for three organophosphorus pesticides (dichlorvos, monocrotophs and parathion) were in the range of 4 to 7 g/L when an AChE amount of 0.1 U was used for immobilization.     

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.     

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.     

Rhodococcus sp.BX2菌对乙腈的降解特性及降解途径研究

对Rhodococcus sp.BX2菌降解乙腈的特性及其降解途径进行了研究.结果显示,在底物浓度为800mg·L-1,接种量为1.0%,培养温度为35℃,环境pH为7.5的条件下,16h时Rhodococcus sp.BX2菌对乙腈的降解率为95.98%;添加葡萄糖可在培养初期加快Rhodococcus sp.BX2菌的生长和对乙腈的降解,蔗糖、乙酰胺和尿素对其影响不大.将BX2菌接种到含有高乙腈浓度(25000mg·L-1)的合成废水中,培养180h后,乙腈降解率可达88.59%.在催化反应60min后,Rhodococcus sp.BX2腈水合酶与腈水解酶的总酶活可达到422.81U·mL-1,对其相关基因序列的分析结果表明,Rhodococcus sp.BX2中同时存在腈水解酶基因和腈水合酶基因,因此,确定乙腈的降解主要由腈水合酶途径完成,可能同时存在腈水解酶的降解途径.