马拉硫磷和百菌清胁迫下斑马鱼行为变化的研究

以马拉硫磷和百菌清为胁迫因子,本文研究了2种污染物暴露下斑马鱼行为强度的变化。首先通过急性毒性试验确定了2种农药对斑马鱼24 h、48 h、72 h、96 h的半致死浓度(LC50),其次以LC50-48 h为1个染毒单位(TU),在0.01 TU、0.1 TU、0.5 TU、1 TU、2 TU 5个条件下,本文开展了斑马鱼行为学研究。结果显示,48 h马拉硫磷暴露斑马鱼的LC50为5 mg·L~(-1),百菌清暴露斑马鱼的LC50为0.01 mg·L~(-1)。随着污染物浓度增大,综合行为强度变化幅度增大。在设置的暴露浓度下,斑马鱼的行为强度在急剧增大或减小后都出现了明显的调节适应过程,基本符合环境压力模型。通过比较在不同频率下的影响强度,马拉硫磷和百菌清暴露斑马鱼摆鳍所受影响最大。本研究提示,水质监测中可增加斑马鱼摆鳍观察指标。     

鱼类肝脏微粒体对于硫代磷酸酯类杀虫剂活化代谢率的种间差异(Species-Related Difference of Liver Microsomes of Fish in Activation of Organothiophosphorus Insecticides)

为了弄清鱼类肝脏微粒体细胞色素P450s(CYPs)对于硫代磷酸酯类杀虫剂活化代谢率的种间差别,选用斑马鱼Brachydanio rerio、麦穗鱼Pseudorasbora parva、剑尾鱼Xiphophorus helleri、篮鳃太阳鱼Leponus macrohirus四种鱼作为受试生物,选用对硫磷、马拉硫磷、毒死蜱三种硫代磷酸酯类杀虫剂作为受试药剂,以外源乙酰胆碱酯酶(AchE)的抑制率为指标,在离体状态下间接测量了杀虫剂活化代谢物的相对生成量.离体试验表明,对于对硫磷,活化代谢物生成量的高低顺序为:斑马鱼、剑尾鱼、麦穗鱼>太阳鱼(p<0.05),最高的麦穗鱼和最低的太阳鱼之间相差10.0倍;对于马拉硫磷和毒死蜱,活化代谢物生成量的高低顺序均为:剑尾鱼>太阳鱼>斑马鱼、麦穗鱼(p<0.05),最高的剑尾鱼和最低的麦穗鱼之间的分别相差66.9和137倍.毒性测定表明,对于对硫磷、马拉硫磷和毒死蜱,四种鱼96hLC50之间的最大差别分别是45、18和77倍.对马拉硫磷而言,96hLC50的种间差异特征与活化代谢物生成量的种间差异特征比较吻合,而对于对硫磷和毒死蜱而言,两者之间的吻合度较低.研究证实了肝脏CYP在活化硫代磷酸酯杀虫剂方面具有明显的种间差异,同时也证实仅以活化代谢物的离体生成量这一指标来衡量鱼类对于硫代磷酸酯杀虫剂的敏感性,其结论可能会较大幅度地偏离生测结果.尽管如此,本研究证实在所测的鱼类当中,斑马鱼属于CYP活性较低的鱼种,而这一特性很可能是造成斑马鱼对于硫代磷酸酯杀虫剂的敏感性偏低的重要原因.     

淡水鱼脑AChE的动力学特性及抗抑制性

用PEG2000双水相萃取、DEAE-Sephadex A-50和SephadexG-200方法分离提纯麦穗鱼(Pseudorasbora parva)、金鱼(Carassius auratus)和虹鳟鱼(Salmo gairdneri)脑乙酰胆碱酯酶(AChE),比较这3种淡水鱼脑AChE纯酶液与粗酶液的动力学特性、抗抑制性及其种类之间的差异.结果表明,这3种鱼脑AChE的性质在种类间的差异要远远小于其在粗酶状态时酶活性的差异,由此得出AChE性质在种类间的差异并非影响这3种淡水鱼脑AChE活性差异的主要因素;由AChE抗抑制试验结果可知,这3种鱼脑AChE粗酶液对经溴水氧化后的马拉硫磷和三唑硫磷的敏感性及种间的差异都远大于纯酶液.     

Treatment of two insecticides in an electrochemical Fenton system

Abstract

The ability of an electrochemical Fenton system to degrade the organophosphorous insecticides malathion and methyl parathion was studied. A combination of hydrogen peroxide and electrochemically‐generated iron was found to be successful in degrading the two insecticides, and optimization of the system was pursued. Augmentation with near UV light at an intensity of 1.67xl0¹⁷ quanta/sec and centered at a wavelength of 370 nm improved the degradation of malathion at low iron concentrations but did not affect other treatments. Adding the hydrogen peroxide slowly over the course of treatment rather than all at once at the beginning of each treatment did, however, greatly improve the system. Removal efficiencies of 98.0% or greater were achieved for both pesticides.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

单扫描示波极谱法测定环境水样中马拉硫磷残留量

本文拟定了一种测定马拉硫磷残留量的极谱法，在０．１ｍｏｌ／ＬＮａＯＨ基底溶液中，用单扫描示波极谱仪制作其阴极化一阶导数极谱曲线，峰电位Ｅｐ为－０．４２Ｖ（ｖｓ．ＳＣＥ），在０．０８－０．５μｇ／ｍｌ范围内ｉ＇ｐ与浓度间呈线性关系。讨论了一些常见农药及离子的干扰情况，以及影响溶出峰电流的因素。方法应用于环境水样中马拉硫磷残留量的测定。变异系数在１０％以内。     

Malathion dermal permeability in relation to dermal load: Assessment by physiologically based pharmacokinetic modeling of in vivo human data

Estimates of dermal permeability (K_p), obtained by fitting an updated human PBPK model for malathion to previously reported data on excreted urinary metabolites after 29 volunteers were dermally exposed to measured values of [¹⁴C]malathion dermal load (L), were used to examine the empirical relationship between K_p and L. The PBPK model was adapted from previously reported human biokinetic and PBPK models for malathion, fit to previously reported urinary excretion data after oral [¹⁴C]malathion intake by volunteers, and then augmented to incorporate a standard K_p approach to modeling dermal-uptake kinetics. Good to excellent PBPK-model fits were obtained to all of 29 sets of cumulative urinary metabolite-excretion data (ave. [±1 SD] R² = 0.953 [±0.064]). Contrary to the assumption that K_p and L are independent typically applied for dermally administered liquids or solutions, the 29 PBPK-based estimates of K_p obtained for malathion exhibit a strong positive association with the 2/3rds power of L (log-log Pearson correlation = 0.925, p = ～0). Possible explanations of this observation involving physico-chemical characteristics and/or in vivo cutaneous effects of malathion are discussed. The PBPK model presented, and our observation that K_p estimates obtained by fitting this model to human experimental urinary-excretion data correlate well with L^2/3, allow more realistic assessments of absorbed and metabolized dose during or after a variety of scenarios involving actual or potential dermal or multi-route malathion exposures, including for pesticide workers or farmers who apply malathion to crops.     

Biodegradation of malathion, α- and β-endosulfan by bacterial strains isolated from agricultural soil in Veracruz,Mexico

The objective of this study was to evaluate the capacity of two bacterial strains isolated, cultivated, and purified from agricultural soils of Veracruz, Mexico, for biodegradation and mineralisation of malathion (diethyl 2-(dimethoxyphosphorothioyl) succinate) and α- and β-endosulfan (6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6-9-methano-2,4,3-benzodioxathiepine-3-oxide). The isolated bacterial strains were identified using biochemical and morphological characterization and the analysis of their 16S rDNA gene, as Enterobacter cloacae strain PMM16 (E1) and E. amnigenus strain XGL214 (M1). The E1 strain was able to degrade endosulfan, whereas the M1 strain was capable of degrading both pesticides. The E1 strain degraded 71.32% of α-endosulfan and 100% of β-endosulfan within 24 days. The absence of metabolites, such as endosulfan sulfate, endosulfan lactone, or endosulfan diol, would suggest degradation of endosulfan isomers through non-oxidative pathways. Malathion was completely eliminated by the M1 strain. The major metabolite was butanedioic acid. There was a time-dependent increase in bacterial biomass, typical of bacterial growth, correlated with the decrease in pesticide concentration. The CO₂ production also increased significantly with the addition of pesticides to the bacterial growth media, demonstrating that, under aerobic conditions, the bacteria utilized endosulfan and malathion as a carbon source. Here, two bacterial strains are shown to metabolize two toxic pesticides into non-toxic intermediates.     

凤眼莲加速水溶液中马拉硫磷降解

研究了凤眼莲对水溶液中马拉硫磷降解作用的效果及凤眼莲修复马拉硫磷污染水体的主要机理.结果表明,10～11g凤眼莲可将250mL的10mg/L马拉硫磷的降解速度提高160%.其修复机理主要是凤眼莲吸收马拉硫磷后在体内进一步降解,贡献率可达56%,微生物降解的贡献率占9%.     

毒死蜱、马拉硫磷和氰戊菊酯对赤子爱胜蚓（Eisenia foetida）的急性毒性

采用滤纸接触法和土壤培养法研究了毒死蜱(Chlorpyrifos)、马拉硫磷(Malathion)和氰戊菊酯(Fenvalerate)对赤子爱胜蚓(Eisenia foetida)的急性毒性效应.滤纸接触法试验浓度分别设置为,毒死蜱:3.14、6.28、9.42、12.56、15.70、18.84μg·cm-2;马拉硫磷:3.10、6.20、12.40、18.60、24.80、31.40μg·cm-2;氰戊菊酯:0.31、0.62、1.24、1.86、2.48、3.14μg·cm-2.土壤培养法试验浓度分别设置为,毒死蜱:100、125、150、175、200、225、250mg·kg-1;马拉硫磷:350、400、450、500、550、600mg·kg-1;氰戊菊酯:20、30、40、50、60、70、80mg·kg-1.结果表明:采用滤纸接触法测得的各农药对蚯蚓48h的半数致死浓度(LC50)分别为毒死蜱12.26μg·cm-2、马拉硫磷19.61μg·cm-2、氰戊菊酯1.03μg·cm-2;采用土壤培养法测得的各农药对蚯蚓7d的LC50分别为毒死蜱427.67mg·kg-1、马拉硫磷742.53mg·kg-1、氰戊菊酯81.81mg·kg-1,14d的LC50分别为毒死蜱182.21mg·kg-1、马拉硫磷497.29mg·kg-1、氰戊菊酯37.46mg·kg-1.根据《化学农药环境安全评价试验准则》,这3种农药对蚯蚓的毒性均为低毒级.