三种常用氨基甲酸酯类农药人工抗原合成方法的设计与优选

农药人工抗原的合成直接影响制备抗体的质量,是建立农药分子特异性强、灵敏度高的免疫分析方法的关键。本文综述了国内外对于氨基甲酸酯类广泛使用的3种农药甲萘威、克百威、涕灭威人工抗原合成过程中的农药分子半抗原的设计原则、合成方法,人工抗原的设计、优选及影响因素等方面的研究进展。     

Biotransfer of persistent organic pollutants from a large site in China used for the disassembly of electronic and electrical waste

Samples of groundwater, river water, river sediment, paddy soil, rice seeds, hen eggs, fish, umbilical cord blood, and newborn meconium were collected from October 2002 to October 2003 near a large site in China used for the disassembly of obsolete transformers and other electronic or electrical waste. Six indicator PCB congeners, three non-ortho dioxin-like PCB congeners, and six organochlorine pesticides were determined in the samples by GC with electron capture detector. The results demonstrated that the local environment and edible foods had been seriously polluted by toxic PCBs and organochlorine pesticides. The actual daily intakes (ADIs) of these pollutants were estimated for local residents living in the area. The intake data showed that the contents of PCBs in these local residents were substantial, as the ADI estimates greatly exceed the reference doses set by the World Health Organization and the United States Agency for Toxic Substances and Disease Registry. The presence of the indicator PCB congeners in the cord blood and the meconium samples, as well as significant correlations (r ² > 0.80, p < 0.05) between these levels, suggests a potential biotransfer of these indicators from mothers to their newborns. This preliminary study showed that obsolete transformers and other electronic or electrical waste can be an important source for the emission of persistent organic pollutants into the local environment, such as through leakage, evaporation, runoff, and leaching. Contamination from this source appears to have reached the level considered to be a serious threat to environmental and human health around the disassembly site.     

上海市稻米中有机氯农药残留水平及健康风险评价

中国作为农药的生产和使用大国,曾大量使用滴滴涕(DDTs)、六六六(HCHs)等有机氯农药.水稻是上海市的主要粮食作物,青浦和崇明区是其重要的水稻种植基地.本研究检测了上海市青浦和崇明区稻米样品中24种有机氯农药的残留水平,分析了OCPs的组成特征并对上海地区稻米中的OCPs残留进行了健康风险评价.结果表明,研究区稻米中OCPs以DDTs和HCHs为主要残留物.青浦和崇明稻米中24种OCPs的总平均残留量分别为6.53 ng·g-1和4.70 ng·g-1,低于食品安全国家标准中对应OCPs的再残留限值.青浦区稻米中4,4-DDE和β-HCH的残留水平最高,崇明区稻米则以2,4-DDT和β-HCH为主要成分.来源解析显示,上海市区域内近期可能仍有三氯杀螨醇和林丹的使用.健康风险评价结果表明,食用本研究区稻米因OCPs所产生的致癌与非致癌风险较低,处于可接受水平.     

自动固相萃取-气相色谱质谱法测定饮用水源地水中有机氯农药的研究

建立了自动固相萃取-气相色谱质谱仪测定饮用水源地水体中8种痕量有机氯农药的检测法.采用Supelclean ENVI-18固相萃取柱以10 mL/min流速富集500 mL水样,再依次用7.5 mL乙酸乙酯和10 mL二氯甲烷进行洗脱.8种物质在0.188 mg/L~2.04 mg/L范围内线性良好,相关系数均在0.997以上;检出限为0.011μg/L~0.034μg/L;实际水样加标回收率为82.9%~103%,相对标准偏差为0.7%~8.3%.该方法自动化程度高、检出限低、灵敏度高、结果准确,适用于饮用水源地水体中痕量有机氯农药的测定.     

白洋淀多环芳烃与有机氯农药季节性污染特征及来源分析

为研究白洋淀表层水体中多环芳烃(polycyclic aromatic hydrocarbons,PAHs)和有机氯农药(organochlorine pesticides,OCPs)的季节性污染特征及来源,分析了白洋淀12个监测断面春、夏两季表层水体中17种PAHs和15种OCPs的浓度.结果表明,白洋淀春季表层水体中PAHs总浓度范围是35.38~88.06 ng·L~(-1),平均值为46.57 ng·L~(-1),夏季表层水体中PAHs总浓度范围是25.64~301.41 ng·L~(-1),平均值为76.23 ng·L~(-1);白洋淀春季表层水体中OCPs总浓度范围是0.69~4.50 ng·L~(-1),平均值为1.77 ng·L~(-1);夏季表层水体中OCPs总浓度范围是0.11~3.20 ng·L~(-1),平均值为0.90 ng·L~(-1).白洋淀春、夏两季表层水体中PAHs季节性污染特征表现为前塘、关城和安新桥等3个断面夏季PAHs总浓度要远高于春季,而其他9个断面则均表现为春季略高于夏季;OCPs季节性污染特征表现为关城断面夏季OCPs总浓度高于春季,而其他11个监测断面均表现为春季高于夏季.从白洋淀春、夏两季表层水体PAHs和OCPs组成特征来看,春季各监测断面PAHs主要以三环芳烃为主,占PAHs总浓度的比例为45.92%~61.36%(平均为52.60%);夏季安新桥、前塘和关城等3个监测断面主要以二环芳烃萘(Naphthalene,Nap)为主,其浓度分别占PAHs总浓度的比例高达84.91%、91.04%和78.10%,其他9个监测断面主要以三环芳烃为主,占PAHs总浓度的比例为37.14%~53.90%(平均为48.94%);白洋淀表层水体中只有HCHs和DDTs有不同程度检出,且呈现出以HCHs为主的污染特征,其中,春季各监测断面表层水体中HCHs均以β-HCH为主,占HCHs总浓度的29.94%~100%,平均比例为59.87%,而夏季大张庄、郭里口等5个监测断面表层水体中HCHs以β-HCH为主,占HCHs总浓度的57.55%~80.23%,平均比例为61.98%,其他断面以α-HCHs和δ-HCH为主.分析白洋淀春、夏两季表层水体中PAHs和OCPs的来源,PAHs同分异构体比值显示其PAHs主要来源于燃烧源,部分监测断面还存在石油源;而OCPs同分异构体比值显示其OCPs主要来源于环境残留和大气的长距离传输.白洋淀表层水体中PAHs和OCPs浓度不超过不同国家和组织制定的相关水质标准,但安新桥和圈头两个监测断面表层水体中α-HCH、p,p'-DDD浓度超过了美国环保署制定的人体健康水质基准,表明α-HCH和p,p'-DDD可能会对白洋淀淀区居民产生潜在有害影响.     

气相色谱法同时测定地表水中的百菌清、环氧七氯和有机氯农药

用正己烷一次同时萃取地表水中的百菌清、环氧七氯和有机氯农药,萃取液脱水后进气相色谱仪进行测定。当取样体积为500ml时,方法检出限为0．01～0．02μg,／L,标准曲线相关系数大于0．999,方法精密度的相对标准偏差为1．5％-4．0％,加标回收率为81．6％～109．6％。该方法用于实际样品测定,结果令人满意。     

福建戴云山脉土壤有机氯农药残留及空间分布特征

为研究有机氯农药(OCPs)在福建戴云山脉表层土壤中的残留水平、来源和空间分布特征,采集福建戴云山脉101个表层代表性土壤样品,并用气相色谱(GC-ECD)法分析其20种OCPs的含量.结果表明,研究区域土壤中20种OCPs均被检出,除Endrin和β-HCH外,OCPs检出率均在90%以上.HCHs、DDTs、硫丹及硫丹硫酸脂的含量之和占OCPs总含量的79.51%,是主要的污染物.土壤中OCPs的含量范围为2.56~465.99 ng·g-1,平均值为38.00 ng·g-1.与国内外相比,HCH和DDT的残留水平相对较低,属于低污染区域;研究区内硫丹硫酸脂及硫丹存在一定的污染.来源分析显示研究区近期可能存在林丹和三氯杀螨醇的输入,硫丹的污染来源于历史使用.不同种植类型土壤对比结果表明,土壤中OCPs(HCHs+DDTs+硫丹硫酸脂+硫丹)的平均含量依次为水田>菜地>果园,果园土壤污染主要源于林丹的输入,DDTs主要为三氯杀螨醇型污染.水田耕作中输入的硫丹类农药是土壤污染的主要原因.     

Comparative analysis of tolerance to pesticides in annelids

The tolerance of annelids (11 oligochaete and 13 leech species) to several organophosphate pesticides, polychloropinene, phenol, and copper sulfate was compared in an acute experiment. The dependence of pesticide resistance on specific biological and ecological features of the annelid species and their position in the phylogenetic series is discussed.     

Magnetic polyamidoamine dendrimers for magnetic separation and sensitive determination of organochlorine pesticides from water samples by high-performance liquid chromatography

Organochlorine pesticides (OCPs) have received much attention due to their toxicity. Reliable methods to monitor their residues in the environment are needed. Here, magnetic polyamidoamine dendrimers were prepared by co-precipitation, Michael addition, and amidation. The magnetic polyamidoamine dendrimers demonstrated good adsorption ability for OCPs—this feature was utilized to construct a sensitive tool for monitoring OCPs in water samples. The proposed method provided remarkable linearity from 0.1 to 500 μg/L and satisfactory limits of detection from 0.012 to 0.029 μg/L. The spiked recoveries of the four target analytes were 91.8%?103.5% with relative standard deviations less than 4.5%. The magnetic materials had good reusability. The results indicated that the resulting method was an efficient, easy, rapid, economical, and eco-friendly tool for monitoring OCPs in aqueous samples.     

华北四城市生活污水中农药残留及健康风险

分析了华北地区北京、太原、呼和浩特和石家庄4个城市生活污水中的21种农药浓度,计算了污水中的农药残留量,结合蔬果加工因子和蔬果消费量,近似推算城市蔬果上的农药残留量,评价农药残留的健康风险.结果显示,4个城市的生活污水中,石家庄21种农药的综合千人均残留量最高,为454.89mg/（千人·d）,呼和浩特最低,为63.69mg/（千人·d）.所检测的21种农药中,多菌灵的残留浓度相对较高,为224.22~1328.07ng/L,千人均残留量为49.98~424.98mg/（千人·d）,多菌灵在4个城市的农药残留中占比均最高,为51.35%（北京）~93.43%（石家庄）,其他占比较高的农药包括吡虫啉和氯虫苯甲酰胺,这体现出华北地区蔬果农药使用具有相似的结构特征.根据生活污水中的农药残留推算蔬果农药残留量,石家庄多菌灵的蔬果残留量最高,为5.04mg/kg.北京吡虫啉和氯虫苯甲酰胺的蔬果残留量也相对较高.通过日均潜在摄入量与每日允许摄入量比较,这些农药残留的长期健康风险相对较低.