中国典型流域有机磷酸酯的污染特征与风险评估

有机磷酸酯（OPEs）作为溴代阻燃剂的替代品,在生产生活中被广泛使用,其环境污染和毒性效应受到广泛关注.梳理中国七大典型流域水体中OPEs的含量水平和分布特征,计算中国成人、青少年和儿童的OPEs日均饮水暴露量,对其健康风险进行评估,并通过蒙特卡洛模拟方法评价了结果的可靠性.检索整理了12种OPEs对水生生物的毒性效应浓度,构建物种敏感度分布（SSD）曲线,对生态风险进行评估.结果表明,低等暴露水平下,七大流域ΣOPEs的第5百分位浓度为52.61 ng·L^-1;中等暴露水平下,七大流域ΣOPEs的中位浓度为499.74 ng·L^-1,磷酸三氯乙酯（TCEP）、磷酸三乙酯（TEP）和磷酸三（1,3-二氯-2-丙基）酯（TDCP）为主要污染物;高等暴露水平下,七大流域ΣOPEs的第95百分位浓度为1904.4 ng·L^-1,是其中等暴露水平的3.8倍,长江流域的ΣOPEs浓度最高.健康风险评估表明,不同人群通过饮用水暴露于OPEs的非致癌风险均在可接受范围内.磷酸三甲酯（TMP）、磷酸三异丁酯（TiBP）和TCEP是致癌风险的主要贡献者.生态风险评估结果表明,TCEP在高等暴露水平下存在中等生态风险;磷酸三正丁酯（TnBP）在中等暴露水平下存在中等生态风险,在高等暴露水平下,有较高生态风险;磷酸三苯酯（TPhP）在低中高3种暴露水平下的风险商均大于1,有较高生态风险,需要重点关注.     

气相色谱法测定蔬菜中多种有机磷农药

探讨同时测定蔬菜中多种有机磷农药残留量的方法.蔬菜样品经前处理后用气相色谱仪测定甲胺磷、敌敌畏、乙酸甲胺磷、氧化乐果、甲拌磷、乐果、马拉硫磷和对硫磷等8 种有机磷农药残留量,测定了方法的回收率和精密度,分析了干扰情况.上述8 种农药的平均回收率分别为99.0%,96.0%,130.4%,101.3%,95.9%,99.4%,92.4%,91.0%,变异系数分别为6.91%,6.09%,9.23%,9.63%,9.18%,7.01%,6.82%,7.50%.该方法操作简便,回收率和精密度较好,干扰少.     

Adult respiratory distress syndrome in human organophosphate poisoning cases

Adult respiratory distress syndrome (ARDS) is a clinical syndrome which occurs due to various direct or indirect noxious agents and pyhsical mechanisms. One of the etiological factors is ingested chemicals (e.g. paraquat, ethylene glycol). The organophosphorous (OP) insecticides are the most toxic and frequently encountered chemicals that produce poisoning in humans. Studies were undertaken to investigate whether OP insecticides may produce ARDS. Fifteen autopsy cases due to suicidal OP insecticide poisoning were investigated. Toxicological analyses were performed with a gas chromatography-nitrogen phosphorous detector (GC-NPD). Methamidophos, dimefox and dichlorvos were the detected OP. Lungs were examined macroscopically. Two cases showed features compatible with ARDS in which the only cause of death was OP poisoning. Due to the severity of ARDS it is important to assess insecticidal exposure in an attempt to enhance survival patterns following OP poisoning in patients in order to initiate therapy.     

Monitoring of Seasonal Vegetables for Pesticide Residues

Market samples (60) of six seasonal vegetables were monitoredduring 1996–1997 to determine the magnitude of pesticidalcontamination. The estimation of insecticide residuesrepresenting four major chemical groups i.e. organochlorine,organophosphorous, synthetic pyrethroid and carbamate, was doneby adopting a multiresidue analytical technique employingGC-ECD and GC-NPD systems with capillary columns. The testedsamples showed 100% contamination with low but measurableamounts of residues. Among the four chemical groups, theorganophosphates were dominant followed by organochlorines,synthetic pyrethroids and carbamates. About 23% of the samplesshowed contamination with organophosphorous compounds abovetheir respective MRL values. More extensive studies coveringdifferent regions of Haryana state are suggested to get a clearidea of the magnitude of vegetable contamination with pesticideresidues.     

有机磷农药二元混合物联合效应评价新方法的研究

以敌敌畏、乐果联合作用于线虫的毒理学实验为基础,基于FH插值法理论,通过较少的实验数据建立有机磷农药二元混合物联合效应模型,求解作用效应表达式并绘制联合效应三维曲面图;基于合并用药分析公式,计算联合作用评价q值并绘制农药浓度与q值的联合作用评价三维曲面图,结果表明敌敌畏与乐果混合物联合作用不仅表现为相加作用,而且还在局部低浓度表现为拮抗作用,与多元统计分析结果一致。上述研究表明FH插值法理论可作为二元有机磷农药联合效应分析及评价的一种新方法。     

The rise of glyphosate and new opportunities for biosentinel early‐warning studies

Glyphosate has become the most commonly used herbicide worldwide and is reputedly environmentally benign, nontoxic, and safe for use near wildlife and humans. However, studies indicate its toxicity is underestimated and its persistence in the environment is greater than once thought. Its actions as a neurotoxin and endocrine disruptor indicate its potential to act in similar ways to persistent organic pollutants such as the organochlorines dichlorodiphenyltrichloroethane (DDT) and dioxin. Exposure to glyphosate and glyphosate‐based herbicides for both wildlife and people is likely to be chronic and at sublethal levels, with multiple and ongoing exposure events occurring in urban and agricultural landscapes. Despite this, there has been little research on the impact of glyphosate on wildlife populations, and existing studies appear in the agricultural, toxicology, and water‐chemistry literature that may have limited visibility among wildlife biologists. These studies clearly demonstrate a link between chronic exposure and neurotoxicity, endocrine disruption, cell damage, and immune suppression. There is a strong case for the recognition of glyphosate as an emerging organic contaminant and substantial potential exists for collaborative research among ecologists, toxicologists, and chemists to quantify the impact of glyphosate on wildlife and to evaluate the role of biosentinel species in a preemptive move to mitigate downstream impacts on people. There is scope to develop a decision framework to aid the choice of species to biomonitor and analysis methods based on the target contaminant, spatial and temporal extent of contamination, and perceived risk. Birds in particular offer considerable potential in this role because they span agricultural and urban environments, coastal, inland, and wetland ecosystems where glyphosate residues are known to be present.     

超高效液相色谱-串联质谱法测定污水中14种有机磷酸酯阻燃剂

建立了超高效液相色谱-串联质谱(UPLC-MS/MS)联用法同时测定污水中14种有机磷酸酯阻燃剂(OPEs)的分析方法.样品采集后,经GF/C膜过滤,HLB固相萃取小柱净化后进样分析.以BEH C18色谱柱为分离柱,乙腈和水混合液为流动相(0.2 mL min-1)梯度洗脱,15 min内可完成14种OPEs的分离.在电喷雾正离子模式下,采用多反应监测模式(MRM)进行质谱测定.在加标浓度为1.0μg·L-1时,14种OPEs在污水处理厂进水和出水中的回收率分别为52.1%—119%、43.6%—114%,相对标准偏差(RSD)分别为1.2%—16.2%、0.4%—9.2%,方法的检出限(LOD)在0.3—6.0 ng·L-1间.方法精密度好,准确度高,可满足同时对污水样品中的14种OPEs进行定性及定量分析的要求.     

Use of cholinesterase activity in monitoring chlorpyrifos exposure of steer cattle after topical administration

The aim of this work was to study the pharmacokinetic behavior and the inhibitory effect of acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) activities of chlorpyrifos (CPF) in steer cattle after pour-on administration. Determination of cholinesterase activity in plasma and erythrocyte was carried out according to Ellman kinetic method. CPF was analyzed by gas chromatography. AChE was the predominant form of cholinesterase analyzed, with low levels of BChE in plasma. Following the treatment with CPF, the maximum inhibitory effect on AChE or BChE were 50.88 ± 11.57 and 42.66 ± 12.01%, respectively. The chlorpyrifos plasma concentrations observed were low and they presented a high variability. Chlorpyrifos peak plasma concentration (10.42 ± 4.76 μ g/L) was reached at 8.42 ± 13.97 h. The pesticide was not detected in plasma after 48 h post treatment. The values of area under the curve (AUC) were 118.48 ± 87.46 μ g· h/L and mean resistance time (MRT) were 13.38 ± 10.41 h. The pour-on exposure to the organophosphate chlorpyrifos significantly reduced AChE and BChE activity in steer cattle and the recovery was not reached on 50 days post-treatment.     

Determination of organochlorine and organophosphate pesticide residues in fruits,vegetables and sediments

Abstract

A method is described for the determination of organochlorine and organophosphate pesticide residues in fruits, vegetables and sediments. The concentrated solvent extract was sealed in a polymeric membrane tube, dialysed in cyclohexane and the solvent replaced with hexane. The organophosphates were analysed on a specific thermionic detector without further clean‐up. For the organochlorine pesticides the extract was eluted through 3 g of alumina and analysed on GC/ECD. The clean‐up for sediment extract was carried out on a10 g alumina column with 100 mL hexane containing 5% acetone and the eluate was concentrated to 5 mL.

The detection limit for organophosphates on a 40 g sample and a final volume of 10 mL was on the average 0.01 mg/kg. The detection limit for organochlorine pesticides, with the final volume of 25 mL, was 0.005 mg/kg for all pesticides except for p,p'‐DDT and endosulfan sulphate, which was 0.01 mg/kg.

The detection limit for oganochlorine pesticides in sediment, with the final volume of 2 mL, was less than 1 μg/kg and for organophosphate pesticides less than 10 μg/kg when the final volume was made to 0.5 mL. At the detection limits the method produced a very high coefficient of variation for both organochlorine and organophosphate pesticides.     

Photodegradation of the organophosphorus insecticide ‘Phorate’

The photolysis of Phorate(I) (0,0‐diethyl S‐ethyl thiomethyl phosphordithioate) has been studied as a thin film on a glass surface and in a solution of methanol‐water (60:40) by ultraviolet light (λ > 290 nm). The rate of disappearance of Phorate in the solution show first order Kinetics with a rate constant of 4.9 × 10^–5 S ^–1. The half‐life of (I) exposed on a glass surface is found to be 5 hours. The structure of the major photoproducts were characterised by ¹H NMR and mass spectroscopy.