离子液体与有机磷农药间的毒性相互作用

"绿色"溶剂离子液体(ILs)与其他污染物之间的毒性相互作用已有报道,但相关数据仍较为缺乏。以7种具有不同阴阳离子组成的ILs:溴化丁基吡啶(IL1)、氯化丁基-2,3-二甲基咪唑(IL2)、丁基-3-甲基咪唑翁磷酸盐(IL3)、丁基-3-甲基咪唑正辛基硫酸(IL4)、丁基-2,3-二甲基咪唑二乙二醇单甲醚硫酸盐(IL5)、辛基-3-甲基咪唑二乙基醚单甲磺硫酸(IL6)和氯化己基-3-甲基咪唑(IL7),与5种有机磷农药(OPs):敌敌畏(DIC)、乐果(DIM)、草甘膦(GLY)、久效磷(MON)和磷胺(PHO),作为混合物组分,以等效应浓度比射线法设计7种ILs分别与5种OPs等EC_(50)配比的35组二元混合物,应用微板毒性分析法(MTA)测定这些混合物对青海弧菌Q67的毒性,以浓度加和(CA)和独立作用(IA)为参考模型分析毒性相互作用。结果表明,不同的IL-OP混合物呈现的作用类型不同:如IL1-DIM、IL2-DIM、IL3-DIM、IL6-DIM、IL2-MON和IL7-DIM的混合物呈明显的拮抗作用;IL3-DIC和IL2-GLY的混合物呈明显的协同作用;IL5-DIM和IL4-MON的混合物在较高浓度区呈拮抗作用;而IL3-GLY和IL6-DIC的混合物在较高浓度区呈协同作用;其余的混合物则为加和作用。     

有机磷农药的构效关系及其对浮游生物的毒性效应

以定量构效关系理论和实验室内急性毒性试验相结合研究了六种有机磷农药对四尾栅藻（S.quadricanda）和多刺裸腹溞（Moina macrocopa）的生态毒性。有机磷农药的毒性取决于磷原子的电正性,各取代基种类和构象对电荷分布作用显著。根据构效关系原理,磷氧双键（P=O）被磷硫双键（P=S）取代后毒性降低;羟基（-OH）被甲、乙、丙氧基（-CH3O、-CH3CH2O、-CH3CH2CH2O）取代后有机磷农药毒性依次增强;磷氧单键（P-O）毒性高于磷碳单键（P-C）。该实验中毒死蜱、辛硫磷（-CH3CH2O）毒性高于其它四种（-CH3O）,敌敌畏和敌百虫（P=O）毒性高于乐果（P=S）,敌敌畏（P-O）又高于敌百虫（P-C）,甘氨酸异丙胺盐取代羟基（-OH）的草甘膦毒性最低。毒性试验结果表明,毒死蜱、辛硫磷、敌百虫、敌敌畏、乐果、草甘膦异丙胺盐对四尾栅藻的96 h EC50分别为6.34、6.62、59.53、82.12、141.37和7.25 mg.L-1。它们对多刺裸腹溞的48 h LC50分别为0.20、0.12、0.28、0.17、1.12和5.03 mg.L-1。六种有机磷农药对多刺裸腹溞的毒性强度结果与QSAR分析具有较高的一致性,即表征有机磷农药毒性特征的取代基团作用的毒性强弱顺序为：-OH〉=O〉-O;对四尾栅藻毒性试验结果中,由于草甘膦异丙胺盐作用于植物类靶位点的特殊性,导致其对四尾栅藻毒性显著增强。综合以上研究,以构效关系理论和浮游生物毒性试验相结合进行有机磷农药的生态风险评价将更加便捷和准确。     

利用实验塘及原位生物群落(mesocosm)开展农药生态毒理学研究

能接受必要的控制,并可设置重复的实验塘及原位生物（ｍｅｓｏｃｏｓｍ）是开展农药水生生态毒理学研究的理想选择。通过对该系统的研究,农药生产者可阐明复杂系统对药剂毒性的缓冲能力,污染管理者可获得农药对水生生态系统不良影响的信息。本文根据现有资料从池塘设计和建造、规格、生物构成、测定参数和结果分析等方面对该测试系统加以介绍。     

农药对藻类的生态毒理学研究Ⅱ:毒性机理及其富集和降解

随着对农药污染认识的深入,农药对生态系统的初级生产者———藻类毒性以及毒性机制的研究不断增多。农药对藻类的毒性在于破坏藻类生物膜的结构和功能、影响藻类的光合作用、改变呼吸作用以及固氮作用,影响藻类的生理进程并改变其生化组分。开展农药对藻类毒性机理的研究,揭示农药结构—活性关系,对农药的研制和应用,评价农药的生态风险,减少农药对藻类的毒害是重要的。在自然环境中还发现藻能富集和降解农药。因此,对于这些藻来说,农药对藻类的毒害作用和藻类对农药的富集和降解作用可能同时存在。本文综述了农药对藻类的毒性机理以及藻类对农药的富集和降解作用。     

TRANSPORT OF SEDIMENT-BOUND ORGANOCHLORINE PESTICIDES TO THE SAN JOAQUIN RWER,CALIFORNIA1

ABSTRACT: Suspended sediment samples were collected in west-side tributaries and the main stem of the San Joaquin River, California, in June 1994 during the irrigation season and in January 1995 during a winter storm. These samples were analyzed for 15 organochiorine pesticides to determine their occurrence and their concentrations on suspended sediment and to compare transport during the irrigation season (April to September) to transport during winter storm runoff (October to March). Ten organochiorine pesticides were detected during the winter storm runoff; seven during the irrigation season. The most frequently detected organochlorine pesticides during both sampling periods were p,p'-DDE, p,p'-DDT, p,p'-DDD, dieldrin, toxaphene, and chiordane. Dissolved samples were analyzed for three organochiorine pesticides during the irrigation season and for 15 during the winter storm. Most calculated total concentrations of p,p-DDT, chlordane, dieldrin, and toxaphene exceeded chronic criteria for the protection of freshwater aquatic life. At eight sites in common between sampling periods, suspended sediment concentrations and streamfiow were greater during the winter storm runoff - median concentration of 3,590 mg/L versus 489 mg(L and median streamfiow of 162 ft³/s versus 11 ft³/s. Median concentrations of total DDT (sum of p,p'-DDD, p,p-DDE, and p,p'-DDT), chlordane, dieldrin, and toxaphene on suspended sediment were slightly greater during the irrigation season, but instantaneous loads of organochlorine pesticides at the time of sampling were substantially greater during the winter storm. Estimated loads for the entire irrigation season exceeded estimated loads for the January 1995 storm by about 2 to 4 times for suspended transport and about 3 to 11 times for total transport. However, because the mean annual winter runoff is about 2 to 4 times greater than the runoff during the January 1995 storm, mean winter transport may be similar to irrigation season transport. This conclusion is tentative primarily because of insufficient information on long-term seasonal variations in suspended sediment and organochlorine concentrations. Nevertheless, runoff from infrequent winter storms will continue to deliver a significant load of sediment-bound organochiorine pesticides to the San Joaquin River even if irrigation-induced sediment transport is reduced. As a result, concentrations of organochlorine pesticides in San Joaquin River biota will continue to be relatively high compared to other regions of the United States.     

四种农药对土壤微生物的影响Ⅰ:土壤呼吸的变化

研究了不同浓度的农药氯氰菊酯,高效氯氰菊酯,多菌灵和丁硫克百威对两种土壤的呼吸强度的影响．结果表明;农药对土壤呼吸强度的影响随农药的品种而异;四种农药可刺激或抑制土壤微生物的活性,其作用随浓度增加而增大,但这种影响是非持续性影响     

洪湖表层沉积物中有机氯农药的含量及组成

利用GC-ECD测定了洪湖表层(0~2cm)、次表层(2~10cm)沉积物中有机氯农药的含量,并对其分布、组成及来源进行了探讨.结果表明,HCHs在表层、次表层沉积物中的含量分别为2.05~19.0ng/g和0.66~11.3ng/g,DDTs在表层、次表层沉积物中的含量分别为2.39~25.8ng/g和1.22~27.5ng/g.次表层沉积物中的有机氯农药含量低于表层沉积物,可能是因为有部分已发生迁移或转化.HCHs和DDTs呈现出在河流入湖口处含量较高,近长江处含量降低的趋势,其污染来源主要是河流输入及洪湖市的工农业排污.组分特征表明沉积物中的HCHs主要来源于林丹的使用,而DDTs则主要来源于环境早期残留.     

海南东寨港表层沉积物中有机氯农药的组成特征

利用GC-ECD对海南东寨港海湾表层沉积物中有机氯农药进行分析,结果表明,研究区总有机氯农药浓度为0.31～7.36ng/g(层深0～2cm),0.38～5.38ng/g(层深2～10cm).HCHs浓度为0.04～2.30ng/g,DDTs浓度为0.07～4.56ng/g,说明海南东寨港沉积物有机氯农药处于低生态风险状态.港内湾红树林国家自然保护区内有机氯农药浓度较高,其DDTs农药主要来自于历史积累,γ-HCH农药有近期输入.     

Distribution and bioaccumulation of organochlorine pesticides along the Black Sea coast

Sediment, mussel, and seawater samples were collected three times during 2001–2003 at nine sampling stations along the mid-Black Sea coast of Turkey. The samples were analyzed with GC-ECD for contents of various organochlorine pesticides (OCPs) in the environment. DDT and its metabolites were detected at concentrations significantly above the detection limits. The highest concentrations of DDT metabolites measured in the sediment and mussel samples were 35.9 and 14.0 ng/g wet weight respectively. Considerable levels of aldrin, dieldrin, endrin, heptachlor epoxide, lindane, endosulfan sulphate, and HCB were also detected in the sediment, mussel, or seawater samples. Although these persistent toxic compounds have been banned for some years in Turkey, they may still be used illegally in some regions, contributing to their significant levels in the environment. The biota–sediment accumulation factor (BSAF) estimated for DDT and its metabolites in mussels was 2.9, which is nearly two times higher than the benchmark of 1.7. In spite of such high BSAF values observed for these toxic compounds, their levels in mussels were significantly below the international legal limits recommended by the Food and Agriculture Organization of the United Nations. Edible biota from the waterbodies examined may thus still be considered safe for human consumption at this time. However, as pollutants can biomagnify through the food chain over time, further routine sampling and analysis of biota along the Black Sea coast are warranted in order to better assess the threat of OCPs to public health in the region.     

华北典型污灌区有机氯农药残留特征及健康风险评价

在我国华北地区由于水资源的匮乏及农业生产的需要,采用污水灌溉与施用有机氯农药(OCPs)结合的农业管理方式普遍存在。大量OCPs则被引入到当地环境中,进而可能对该地区的居民产生潜在的健康风险。本研究分析石家庄市汪洋沟污灌区OCPs的残留状况,探讨污水灌溉条件下土壤-作物系统OCPs残留对土壤质量影响,并评价经口摄入及皮肤接触两种暴露途径下对人体产生的健康风险。结果表明:汪洋沟污灌区地表水、沉积物、土壤和玉米籽粒中检出了14种OCPs,其平均残留浓度分别为36.5 ng·L~(-1)、62.9 ng·g~(-1)、57.3 ng·g~(-1)和27.0 ng·g~(-1),滴滴涕(DDTs)是其最主要的污染物,占OCPs的73%以上,其次是六六六(HCHs)和甲氧滴滴涕。р,р'-DDT是DDTs的最主要成分,其主要来源于污水灌溉或近期DDTs的使用。γ-HCH是环境HCHs残留的主要成分,其主要来源于林丹的输入和使用。此外,在该地区污灌条件下OCPs残留对土壤中C、N循环及有机S的矿化产生一定的负面影响。研究区OCPs残留对人体产生的非致癌风险和致癌风险均不超过控制标准,但经口摄入所引致的非致癌风险应予以关注,其中р,р'-DDT与γ-HCH为主要风险物质。