浙江居民毒死蜱和氯氰菊酯的长期膳食暴露与风险评估

基于2007 -2008年浙江省市场销售农产品中毒死蜱和氯氰菊酯残留的监测数据及浙江不同人群的各类食物摄入量和体重数据,采用分布点评估的方法,评估了浙江省20个不同年龄、性别组人群毒死蜱和氯氰菊酯的长期膳食暴露风险水平。结果表明,浙江省不同年龄、性别组人群毒死蜱长期膳食暴露带来的慢性风险仍控制在较低水平范围内,只有当长期食用毒死蜱残留超过监测资料中的99th百分位点值(蔬菜、水果和大米分别为0.395,0.165和0.011 mg/kg)的食物时,才可能产生不可接受的较大风险。而氯氰菊酯的膳食暴露风险更低,即使长期持续食用的果蔬产品中氯氰菊酯残留都达到监测资料中的最大残留值(蔬菜和水果分别为1.830和0.519 mg/kg),其膳食暴露风险仍属于可接受水平。对膳食暴露的贡献率分析结果显示,蔬菜类食品仍是浙江居民毒死蜱和氯氰菊酯膳食暴露的主要来源,控制蔬菜 中毒死蜱和氯氰菊酯残留是降低这2种农药膳食暴露风险的关键。     

基于点评估方法的渤海湾产区苹果中农药残留膳食暴露风险研究

为评估渤海湾产区苹果中主要农药的残留情况及其产生的风险,在山东、辽宁及河北3个主要省份的150个生产基地进行了苹果样品采集与测定分析,并对我国不同人群的膳食暴露风险进行了评估。结果表明:93.3%的苹果样品检出有低浓度农药残留,经最大残留限量值(MRL)判定后100%合格,82.0%的样品中农药残留种类在3种及以下;共检出17种农药残留,大多为低毒或无毒农药,无禁用和高毒农药。采用点评估方法,选择检出率在20%以上的多菌灵、毒死蜱、啶虫脒和戊唑醇进行不同消费人群暴露点评估。结果显示:4种农药的急性和慢性摄入风险均为儿童高于成年人,绝大多数女性人群的摄入风险高于男性;4种农药急性摄入风险均高于慢性摄入风险,风险水平由高到低为多菌灵毒死蜱戊唑醇啶虫脒,但点评估结果均远低于100%,说明通过食用苹果摄入的农药残留极其微量,不会对人体产生急性或慢性风险。     

三唑类杀菌剂在蔬菜中的残留分布及对不同人群的累积性膳食摄入风险

为探明蔬菜中残留的三唑类杀菌剂可能存在的累积性膳食摄入风险,本研究基于蔬菜样品检测获得的三唑类杀菌剂残留数据,分析了来自江苏省、浙江省、上海市、安徽省及福建省 5 个地区的 1612 批次蔬菜样本中 8 种三唑类杀菌剂的残留分布,并采用相对效能因子法以及概率评估方法的蒙特卡罗 (Monte Carlo) 模拟技术和 Bootstrap 抽样技术,对目标人群通过蔬菜摄入三唑类杀菌剂的累积急性及慢性暴露风险进行了评估。结果显示:检出较多的农药及产品组合为芹菜和西红柿中的苯醚甲环唑,检出率分别达到 23.1% 和 20.4%,其他检出率较高的农药还有三唑酮、戊唑醇、氟硅唑、烯唑醇、丙环唑、抑霉唑及腈菌唑。各类蔬菜中,黄瓜中三唑类杀菌剂残留对不同人群累积暴露量的贡献率最大,为 50%~70%。在第 97.5 百分位点处,蔬菜中残留的三唑类杀菌剂对各年龄段人群的累积慢性暴露量均低于慢性参考剂量 (ADI),其中 0~35 个月婴幼儿的累积慢性膳食摄入风险商 (%ADI) 值最高,平均为 34.6%,但仍低于100%;在第 99.9 百分位点处,蔬菜中残留的三唑类杀菌剂对各年龄段人群的累积急性暴露量均低于急性参考剂量 (ARfD),0~35 个月婴幼儿的累积急性膳食摄入风险商 (%ARfD) 值最高,平均为 51.7%,但也低于100%。研究表明,江苏、浙江、上海、安徽及福建 5 个地区蔬菜中三唑类杀菌剂残留的累积急性及慢性膳食摄入风险皆在可接受范围内。     

南方五省辣椒农药残留膳食暴露风险评估

为了促进辣椒产业的良性发展和维护消费者生命健康安全,本研究分别使用确定性、概率性和累积暴露评估方法评估了2016年我国南方5省辣椒中农药残留的膳食暴露风险。确定性方法的结果表明6种农药对8组人群的急慢性暴露量仅占安全阈值的0.0%～12.0%;考虑到累积暴露风险的问题,本文还评估了吡虫啉和啶虫脒的累积暴露风险并与两种农药单一暴露风险(概率性暴露评估)的结果进行了比较,结果表明两种农药的急慢性累积暴露量仅占安全阈值的0.90%～33.32%,但要高于各自的单一暴露量;同时三种方法的结果皆表明辣椒中6种农药残留对儿童的暴露风险要高于其他人群。综上,2016年我国南方5省辣椒中6种农药残留对8类人群的急慢性膳食暴露风险皆可接受。     

冬季蔬菜中有机磷农药残留状况分析

2016年冬季随机抽取湖北省主要蔬菜生产基地的蔬菜,共抽取177份蔬菜样品,采用气相色谱法,测定蔬菜中18种有机磷农药残留。结果表明,有机磷农药残留检出样品5份,检出率为2.8%,其中检出超标样品0份,合格率为100%;叶菜类蔬菜中有机磷农药残留检出率最高,其他类蔬菜无检出;有机磷农药残留检出全部为乐果农药。     

中国食品中农药MRL标准对急性膳食暴露评估需求的研究

为了评估当前国内相关农药最大残留限量(MRL)标准及我国居民的急性膳食暴露风险水平,采用FAO/WHO农药残留专家联席会议(JMPR)推荐的农药残留急性膳食暴露评估方法,利用我国居民大份额膳食消费数据、国内登记农药的规范残留试验数据和JMPR推荐的农药毒理学数据,对我国普通人群、0~6岁儿童和育龄妇女的农药残留摄入情况进行了急性膳食暴露评估。结果表明:白菜中的虫螨腈和丙森锌、甘蓝中的高效氯氰菊酯和灭多威对三类人群的国家估算急性暴露水平(NESTI)均大于急性参考剂量(ARf D);香蕉中的氟硅唑对0~6岁儿童和普通人群的NESTI分别为ARf D值的300%和160%;苹果中的二氰蒽醌、甘蓝中的高效氯氟氰菊酯、花椰菜中的阿维菌素及番茄中的丙森锌仅对0~6岁儿童有较高的急性膳食暴露风险;儿童相比其他人群摄入农药残留的急性膳食暴露风险更高、概率更大。建议我国采取相应的风险管理措施,降低农药残留摄入的急性膳食风险,同时尽快完善短期膳食消费数据库和农药残留数据库,在制定农药MRL标准时进行相应的急性膳食暴露评估,以保障消费者的农药急性膳食暴露风险在可接受水平。     

浙江省芹菜中农药多残留水平及累积急性膳食摄入风险初评

为明确浙江省各地区芹菜中农药残留水平以及对人群的膳食摄入风险,采用蔬菜中农药残留的标准检测方法,对在浙江省各地区采集的210个芹菜样品进行了检测,并就其累积急性膳食摄入风险开展了初步评估。结果表明:210个芹菜样品中共检出35种农药,检出率为94.8%,其中杀虫剂23种,杀菌剂11种,除草剂1种;97.1%的样品中的农药残留量低于其在芹菜中的最大残留限量 (MRL),残留水平整体较低;检出4种及4种以上农药残留的样品占总样品量的54%,存在农药多残留现象。采用相对强度系数 (RPF) 法将具有相同作用机制的农药分组,依据各农药的毒理学数据计算了各组农药的累积当量浓度,并针对不同人群进行了累积急性膳食摄入风险评估。结果显示:拟除虫菊酯类、三唑类、有机磷类、烟碱类及氨基甲酸酯类农药对儿童的急性膳食摄入风险 (%ARfD) 分别为60.35%、46.96%、20.15%、20.76%和12.40%;对一般人群分别为51.70%、40.20%、17.25%、17.77%和10.65%;所检出5类农药对各群体的%ARfD值均小于100%,表明芹菜中农药残留量及膳食摄入风险总体处于可接受水平。     

叶菜类农药残留快速检测方法

利用有机磷和氨基甲酸酯农药对乙酰胆碱酯酶的活性的抑制作用,使这种酶在含有有机磷和氨基甲酸酯农药残留的蔬菜样品中不能被水解,从而无显色反应原理,采用吸光度对比法计算抑制率,判断叶菜类蔬菜中是否存在有机磷和氨基甲酸酯类农药的残留,方法简便、快捷、经济,是保障农产品质量安全的重要手段。     

块茎类植物酯酶对有机磷农药残留的检测

采用酶抑制法,选用五种块茎土豆、红薯、茨菇、芋头、莲藕提取植物酯酶,测定了总酯酶活力和比活力大小,结果显示土豆、茨菇、莲藕的酯酶活力分别高达8.462 3、8.743 7、7.491 0,显著高于其他几种。探索其检测有机磷农药的最佳条件,对5种有机磷农药进行了敏感性试验,并测定3种植物酯酶对这5种有机磷农药的最低检测限(LOD)。3种植物酯酶对受试的5种有机磷农药均有良好的敏感性,且最低检测限远低于国家规定的最大残留限量(MRL)。因此,这几种酶可作为有机磷农药残留检测用酶。     

福建省主产区普通白菜中农药残留水平及膳食暴露风险评估

为评估福建省主产区普通白菜中农药残留水平及对人体的膳食暴露风险,采用现有的标准检测方法,对在福建省主产区采集的88个普通白菜样品中的68种农药残留进行了检测分析,并对检出农药进行了短期和长期膳食暴露风险评估。结果显示：88个普通白菜样品中,共有68个样品检出了农药残留,总检出率为77.27%;共检出27种农药,其中杀虫剂18种,杀菌剂9种;检出2种及2种以上农药残留的样品占检出农药残留样品总量的83.82%,存在农药多残留现象。利用相关农药的毒理学数据——急性参考剂量(ARfD)和每日允许摄入量(ADI)、农药残留数据和普通白菜的膳食消费量数据,评估了所检出农药的短期和长期膳食暴露风险。其中,短期膳食暴露风险值(%ARfD)范围为0～90%,长期膳食暴露风险商贡献率(RQc%)范围为0～46%。研究表明,福建省主产区普通白菜中的农药残留水平较低,通过食用该地区生产的普通白菜对消费者的农药残留膳食暴露风险整体在可接受范围内。     

两种蔬菜中甲胺磷、氧乐果和克百威的残留量分析

分别选取一种瓜菜 (黄瓜 )和一种叶菜 (生菜 ) ,选择了两种有机磷 (甲胺磷、氧乐果 )和一种氨基甲酸酯类 (克百威 )农药 ,对这 3种农药在两种蔬菜中的残留测定方法进行了研究。采用弗罗里硅土柱提取的方法进行前处理 ,淋洗液浓缩后用 GC- NPD测定 ,建立了一种简便快速的检测方法 ,并采用该方法对实际处理样本进行了测定。从方法添加回收率和实测数据可以看出 ,该方法净化提取效果好 ,结果平行性好 ,灵敏度较高 ,是一次快速准确测定蔬菜中农药残留的成功尝试。     

化学发光酶联免疫分析法同时检测3种有机磷农药残留

利用能同时识别对硫磷、甲基对硫磷和杀螟硫磷的宽谱特异性单克隆抗体,建立了同时测定这3种有机磷农药残留的化学发光酶联免疫分析方法（chemiluminescence enzyme immunoassay,CLEIA）,比较了间接竞争（ic-CLEIA）和直接竞争（dc-CLEIA）2种反应模式,优化了相关理化参数,确立了最适反应条件。结果表明:间接竞争CLEIA法检测对硫磷、甲基对硫磷和杀螟硫磷的抑制中浓度（IC₅₀）分别为5.57、2.30和2.62 μg/kg,检测线性范围分别为0.39~100、0.39~25和0.39~25 μg/kg;直接竞争CLEIA法检测对硫磷、甲基对硫磷和杀螟硫磷的抑制中浓度（IC₅₀）分别为5.43、1.34和1.24 μg/kg,检测线性范围分别为0.39~100、0.10~25和0.10~25 μg/kg。所建立的CLEIA方法基本能满足对硫磷、甲基对硫磷和杀螟硫磷在谷物和果蔬中最大残留限量的检测要求,为研制有机磷农药多残留检测试剂盒提供了技术依据。     

农药对两栖动物的生态风险评估研究进展

农药的环境污染问题一直备受关注。两栖动物在农业区域及附近的水体中活动和繁殖,其个体发育和种群生存易受到农药的威胁,因此评估农药对两栖动物的生态风险显得尤为重要。本文主要综述了近几年来不同国家和组织关于农药对两栖动物的暴露评估、效应评估以及风险表征领域的研究进展。其中,美国和欧盟的两栖动物农药风险评估方法体系相对较为完善,在暴露模型研发及毒性 效应测试等方面更加科学化,评价工具更为模型化,评估方法为定性和定量相结合,并且已进入到大尺度空间的区域生态风险评估阶段。我国的两栖动物生态风险评估还处于初级阶段,慢性评估基础数据资料匮乏,评估方法尚不完善,定量评估模型研发还有待加强。因此,我国应积极完善两栖动物生态风险评估体系,以满足未来生态风险评估的发展趋势,为保护两栖动物种群的健康发展以及农药的合理应用和有效管理提供参考方案。     

Comparing ecological risks of pesticides: the utility of a Risk Quotient ranking approach across refinements of exposure

Environmental risk assessment of pesticides and other chemicals often uses the Risk Quotient (RQ) method to characterize risk quantitatively. An RQ is calculated by dividing an environmental exposure value by a toxicity end-point value. Tier 1 RQs, which are characterized by highly conservative toxicity and exposure assumptions, are used primarily for screening out negligible risks in regulatory decision making. It has been argued that the tier 1 RQ approach is valuable for making direct comparisons of quantitative risk between pesticides. However, an outstanding question is whether relative risks among pesticides would change if refinements of exposure are incorporated into the RQ calculations. This study tested that hypothesis. Aquatic ecological risk assessments were conducted for 12 herbicide and 12 insecticide active ingredients used on agricultural crops in the USA. The pesticides were chosen because surface-water monitoring data for them were available as part of the United States Geological Survey's National Water-Quality Assessment Program (NAWQA). Ecological receptors and effects evaluated were aquatic non-vascular plants (acute risk), aquatic vertebrates (acute risk) and aquatic invertebrates (acute risk) for the herbicides and aquatic vertebrates (acute and chronic risk) and aquatic invertebrates (acute and chronic risk) for the insecticides. The data indicate that there were significant statistical correlations between numerical rankings of tier 1 RQs and RQs using refined environmental exposures. The results support the hypothesis that numerical ranking of RQs for the purpose of comparing potential ecological risks is a valid approach because the rankings are significantly correlated regardless of the degree of exposure refinement.     

Pesticide residues in human milk, Alberta, Canada--1966-70, 1977-78

Organochlorine pesticide residues were determined in human milk of residents of Alberta, Canada, during 1966-70 and 1977-78. Levels of polybrominated biphenyls (PBBs), polychlorinated biphenyls (PCBs), and some common organophosphorus pesticides were also monitored during 1977-78. Average residue levels were generally lower in 1977-78 samples, whereas the percent incidence of residues was generally lower in 1966-70 samples. beta-BHC was found in all 1977-78 samples, but was not detected in 1966-70 samples. PCBs were detected in all but two of the 1977-78 samples. Average levels of p,p'-DDT and is metabolites were substantially lower during the second period than during the first. Large increases in the average levels and percent incidences of heptachlor epoxide and o,p'-DDT have been attributed to refinements in both cleanup and gas chromatographic analysis. Although no PBBs or organophosphorus pesticides were detected in 1977-78 samples, an unidentified hydrocarbon similar to dicofol was found in all samples of that period. No correlation between donor age groups and average pesticide residue levels could be inferred.     

Pesticide residue levels in soils and crops from 37 states, 1972--National Soils Monitoring Program (IV).

Residue data from the 1972 (FY--73) National Soils Monitoring Program are summarized. Composite samples of agricultural soil and mature crops were collected from 1,483 of the 1,533 selected 4-hectare sites in 37 states. Analyses were performed for organochlorine and organophosphorus compounds, trifluralin and polychlorinated biphenyls (PCBs); analysis for atrazine was performed only when pesticide application data indicated current-year use. Organochlorine pesticides were detected in 45 percent of the soil samples. The most frequently detected compound was dieldrin, found in 27 percent of all soil samples. Other compounds detected, in order of frequency, included DDT, aldrin, chlordane, and heptachlor epoxide, found, respectively, in 21, 9, 8, and 7 percent of all soil samples. Crop samples were collected from 727 sites. All were analyzed for organochlorines; analyses were performed for organophosphates and atrazine only when pesticide application data indicated current-year use. For all crops, 40 percent of the samples contained detectable levels of organochlorines and 10 percent contained detectable levels of organophosphates. Atrazine was not detected.     

Evaluation of inexpensive thin-layer chromatographic procedures for the estimation of some organophosphorus and carbamate insecticide residues in fruit and vegetables

Modified versions of previously published procedures for the extraction and clean-up of some organophosphorus insecticide residues in fruits and vegetables are described, and their usefulness in combination with selected thin-layer chromatographic procedures is experimentally assessed for several pesticides in apples, oranges, tomatoes, carrots and peas. A simple extraction procedure for insecticidal carbamates is similarly evaluated for carbaryl and propoxur residues in apples, carrots and peas. Semi-quantitative estimation, by visual comparison with standards, is shown to be possible in many cases at residue levels as low as 0.4 mg kg^?1, and the combined procedures should be useful in the screening of fruits or vegetables for compliance with maximum residue limits.