2011-2013年天津市售蔬菜农药残留状况监测分析

摘要:目的　了解2011-2013年天津市市售蔬菜中农药残留状况,为保障食品安全、加强监管提供科学依据。方法　2011-2013年随机采集市售蔬菜859份,按照《国家食品中化学污染物及有害因素监测工作手册》检测氨基甲酸酯类农药、拟除虫菊酯类农药、有机磷类农药、有机氯类农药;依据《食品安全国家标准食品中农药最大残留限量GB 2763-2012》进行判断。结果　2011-2013年共监测市售蔬菜859份,3年来监测农药种类17、23、49种,样本超标率依次为12.33%、16.67%、10.77%。其中,氨基甲酸酯类农药超标率依次为4.00%、9.00%、2.32%;拟除虫菊酯类农药超标率依次为0.00%、0.67%、3.86%;有机磷类农药超标率依次为8.33%、8.33%、8.89%;有机氯类农药超标率为0.00%。结论　有机磷农药使用最为普遍,超标情况比较复杂,氨基甲酸酯类农药和拟除虫菊酯类农药也存在一定的超标现象。     

QuEChERS提取-气相色谱质谱法测定蔬菜中的21种有机磷类、氨基甲酸酯类和拟除虫菊酯类农药残留量

目的建立气相色谱质谱法测定蔬菜中的21种有机磷类、氨基甲酸酯类和拟除虫菊酯类农药残留量的方法。方法样品经组织捣碎、乙腈提取、QuEChERS净化、正己烷定容,同时以环氧七氯为内标,配制成1.0μg/ml的混合标准工作液,采用GC-MS检测21种有机磷类、氨基甲酸酯类和拟除虫菊酯类农药。结果有机磷类农药的LOD为0.001 mg/kg~0.007 mg/kg,LOQ为0.003 mg/kg~0.021 mg/kg;氨基甲酸酯类农药的LOD为0.001 mg/kg~0.004 mg/kg,LOQ为0.003 mg/kg~0.012 mg/kg;拟除虫菊酯类农药的LOD为0.001 mg/kg~0.008 mg/kg,LOQ为0.003 mg/kg~0.024 mg/kg。平均加标回收率为61.9%~99.9%,相对标准偏差(RSD)为3.5%~15.0%。50份蔬菜样品中,毒死蜱检出2份,水胺硫磷检出1份,克百威检出3份,联苯菊酯检出2份,甲氰菊酯检出1份,氯氟氰菊酯检出12份,氟氯氰菊酯检出1份,氯氰菊酯检出7份,其余农药残留指标均未检出。结论该方法灵敏度高,回收率高,检出限低,符合分析要求,适合蔬菜中21种有机磷类、氨基甲酸酯类和拟除虫菊酯类农药残留检测的要求。     

吉林省市售蔬菜农药残留状况调查

目的监测分析2009年吉林省所辖的9个市(州)食品农药的污染状况。方法按照国家标准方法对本省9个市蔬菜的污染情况进行样品的检测。结果共监测10种342件蔬菜样品,获得13 680个农药检测数据,农药检出率为45.61%。所监测的样品中有机磷农药超标率为6.14%,氨基甲酸酯类农药超标率0.29%,拟除虫菊酯类农药超标率0.29%,三氯杀螨无超标样品检出。超标样品主要为鳞茎类韭菜最为严重;其次为叶菜类,以十字花科类居多;食用菌类未检出超标样品。结论本省市售蔬菜农药残留量水平总体上是安全的,但存在滥用国家禁用的农药现象,氨基甲酸酯类、拟除虫菊酯类及三氯杀螨醇残留量相对较低,安全性较高。     

孕妇孕期拟除虫菊酯类农药暴露及其对子代健康的影响

<正>拟除虫菊酯类农药(Pyrethroids)是继有机氯、有机磷和氨基甲酸酯类农药后兴起的一类新型广谱杀虫剂,由于该类农药作为卫生和农用杀虫剂具有一些独特的优点(高效、低毒、低抗性、广谱、环境兼容性、驱避性、激活作用)故被广泛用于农业领域和日常生活。近年来,农药对子代的影响一直受到国内外学者广泛关注,孕妇孕期拟除虫菊酯类农药暴露可能会影响其子代健康,本研究对孕妇孕期拟除虫菊酯类农药暴露情况及其对子代出生结局、神经精神系统和内分泌系统的影响进行回顾性总结。     

2006年陕西省六地市蔬菜水果农药残留状况

目的了解2006年陕西省蔬菜水果中有机磷农药、三氯杀螨醇、氨基甲酸酯、拟除虫菊酯类农药的残留水平。方法采用随机与定点抽样的方法采集市售蔬菜水果16个品种共265份样品，通过气相色谱法和高效液相色谱法进行定性和定量分析。结果有机磷总检出率5．97％，超标率4．65％；三氯杀螨醇检出率30．19％，超标率30．19％；氨基甲酸酯检出率2．74％，超标率0．09％；拟除虫菊酯检出率5．81％，超标率2．94％。结论该省有部分蔬菜水果有农药残留，并检出国家禁用的农药品种，三氯杀螨醇和个别拟除虫菊酯检出率较高，应加强强农药使用的监管，保证农产品安全。     

2011年鞍山市蔬菜中多种农药残留监测结果分析

目的 了解鞍山市蔬菜食品中有机磷、氨基甲酸酯及拟除虫菊酯农药残留的情况.方法 按GB/T 5009-2003《食品卫生检验方法理化部分》检测有机磷、氨基甲酸酯及拟除虫菊酯农药残留量.结果 100份蔬菜中检出甲胺磷农药残留4份,乙酰甲胺磷农药残留4份,毒死蜱农药残留10份,克百威农药残留6份,灭多威农药残留20份,氯氰菊酯农药残留14份,氯氟氰菊酯农药残留2份,均无超标样品.结论 鞍山市蔬菜中农药残留水平较低.     

QuEChERS-气相色谱-质谱联用法测定温棚蔬菜中7种氨基甲酸酯及5种拟除虫菊酯农药残留

目的建立温棚蔬菜中5种拟除虫菊酯及7种氨基甲酸酯的Qu ECh ERS-气相色谱-质谱联用测定法。方法蔬菜样品经乙腈提取,利用Qu ECh ERS法净化,GC-MS分离检测蔬菜中的农药残留。结果氨基甲酸酯在0.07~5.00μg/ml浓度范围内,拟除虫菊酯在0.05~5.00μg/ml浓度范围内,相关系数均大于0.9949%;氨基甲酸酯的检出限为0.18~0.37μg/kg,平均回收率为72.50%~98.75%,相对标准偏差在1.62%~4.13%之间;拟除虫菊酯的检出限为0.27~0.86μg/kg,平均回收率为75.00~103.6%,相对标准偏差在1.37%~5.92%之间。结论该方法简便、灵敏、准确,适用于蔬菜中氨基甲酸酯和拟菊酯类农药残留检测。     

烟台市农村饮用水水源地农药残留监测分析

摘要:目的　了解烟台市农村饮用水水源地农药污染状况,为烟台市农村水质调查提供基础数据。方法　于2012年7月-2013年6月,在烟台市12个县市区所有的55个主要水源地采集水样,采样分枯水期、丰水期两期进行。萃取后用Agilent 7890-7000A检测。共计检测105种农药。结果　共得到55个平行水样结果,55个水源地均可检出农药残留,水样检出农药种类在18～34种之间,总含量在103.0 ng/L 到345.7 ng/L。有机磷农药、拟除虫菊酯类农药在各个水源地中均可检出。各水源地农药残留含量由高到低依次为:有机磷农药＞拟除虫菊酯类＞有机氯＞氨基甲酸酯类＞二羧甲酰亚胺＞唑类。丰水期农药总含量、有机磷类、氨基甲酸酯类农药含量高于枯水期含量,差别有统计学意义（t值分别为9.674,5.577,4.320,P值均小于0.01）。结论　烟台市农村水体均受到不同种类农药的污染,不合理用药是造成污染的主要原因。     

2011年-2013年十堰市蔬菜中农药残留监测分析

目的了解十堰市近年来蔬菜中农药残留状况。方法 2011年-2013年利用气相色谱-质谱法连续对十堰市蔬菜中有机磷、拟除虫菊酯、氨基甲酸酯、有机氯等4大类共31种农药残留量进行定性和定量分析,并将监测结果进行分析。结果 294份蔬菜样品的农药残留检出率和超标率分别为13.95%和3.74%,农药残留检出和超标品种以有机磷和拟除虫菊酯类为主,不同蔬菜中叶类蔬菜的检出率较高。结论蔬菜中农药残留状况仍不容忽视,应继续做好农药监管监测工作,保障食品安全。     

自动固相萃取-气相色谱串联质谱法测定果蔬中的多组分农药残留

目的建立一种同时测定果蔬中有机磷、氨基甲酸酯类及拟除虫菊酯类等多组分农药残留的分析方法。方法果蔬样品经乙腈提取,无水硫酸钠脱水,固相萃取小柱净化,再经旋转蒸发及氮吹浓缩后,用GC-MS/MS进行测定,外标法定量。结果有机磷、氨基甲酸酯类及拟除虫菊酯类等多组分农药经过36 min后完全分离,在0.01~10.0μg/ml的线性范围内相关系数r均0.9956,平均加标回收率在72.1%~109.3%之间,相对标准偏差在4.0%~11.3%之间。结论该方法不仅前处理简便易操作,而且具有较高的灵敏度、准确度和精密度,适合于大批量样品的日常检测。     

Levels of exposure and biological monitoring of pyrethroids in spraymen.

To assess the exposure response relation of pyrethroids in spraymen, 50 adult male cotton growers were selected and divided into three groups, one group to spray pyrethroids for one day, two groups to spray for three days. Deltamethrin, fenvalerate, and a deltamethrin methamidophos mixture were sprayed by appropriate subgroups for five hours a day. Exposure levels were evaluated by measuring the air concentration, dermal exposure concentration, and urinary content of pyrethroids by gas chromatography. Air concentrations of deltamethrin at the breathing zone were 0.01-0.89 microgram/m3 in the deltamethrin exposed group. For fenvalerate, air concentrations were 0.06-1.98 micrograms/m3. Dermal exposure, particularly on the legs, feet, and hands was appreciable and indicated that this was the main route of absorption. In those spraying for one day, urinary deltamethrin was not detectable by 12 hours after the beginning of exposure whereas fenvalerate was still detectable up to 24 hours after first exposure. Both pyrethroids could be detected two days after the end of three day spraying. Health effects were investigated by interview and physical examination. Twenty nine spraymen complained of abnormal facial sensations that developed mostly two to three hours from the start of pyrethroid spraying and that disappeared by 24 hours after exposure ceased. Some had dizziness, headache, and nausea, but no subject was diagnosed as having acute pyrethroid poisoning. The symptoms showed no significant correlation with urinary pyrethroid excretion. Blood cholinesterase activity of spraymen using the pyrethroid methamidophos mixture did not change.     

Levels of exposure and biological monitoring of pyrethroids in spraymen

To assess the exposure response relation of pyrethroids in spraymen, 50 adult male cotton growers were selected and divided into three groups, one group to spray pyrethroids for one day, two groups to spray for three days. Deltamethrin, fenvalerate, and a deltamethrin methamidophos mixture were sprayed by appropriate subgroups for five hours a day. Exposure levels were evaluated by measuring the air concentration, dermal exposure concentration, and urinary content of pyrethroids by gas chromatography. Air concentrations of deltamethrin at the breathing zone were 0.01-0.89 microgram/m3 in the deltamethrin exposed group. For fenvalerate, air concentrations were 0.06-1.98 micrograms/m3. Dermal exposure, particularly on the legs, feet, and hands was appreciable and indicated that this was the main route of absorption. In those spraying for one day, urinary deltamethrin was not detectable by 12 hours after the beginning of exposure whereas fenvalerate was still detectable up to 24 hours after first exposure. Both pyrethroids could be detected two days after the end of three day spraying. Health effects were investigated by interview and physical examination. Twenty nine spraymen complained of abnormal facial sensations that developed mostly two to three hours from the start of pyrethroid spraying and that disappeared by 24 hours after exposure ceased. Some had dizziness, headache, and nausea, but no subject was diagnosed as having acute pyrethroid poisoning. The symptoms showed no significant correlation with urinary pyrethroid excretion. Blood cholinesterase activity of spraymen using the pyrethroid methamidophos mixture did not change.     

Dose-additive inhibition of chinook salmon acetylcholinesterase activity by mixtures of organophosphate and carbamate insecticides

Organophosphate and carbamate insecticides are widely detected in surface waters of the western United States. These chemicals interfere with acetylcholine-mediated synaptic transmission in the nervous systems of fish and other aquatic animals via the inhibition of AChE (acetylcholinesterase) enzyme activity. Anticholinesterase insecticides commonly co-occur in the environment. This raises the possibility of antagonistic, additive, or synergistic neurotoxicity in exposed fish, including threatened and endangered species of Pacific salmon. We extracted AChE from the olfactory nervous system of chinook salmon (Oncorhynchus tshawytscha) and investigated the inhibitory effects of organophosphates (the oxon derivatives of diazinon, chlorpyrifos, and malathion) and carbamates (carbaryl and carbofuran), alone and in two-way combinations. We found that the joint toxicity of anticholinesterase mixtures can be accurately predicted from the inhibitory potencies of individual chemicals within a mixture. This indicates that organophosphate and carbamate insecticides are noninteractive in terms of AChE inhibition and that it might be possible to estimate the cumulative neurotoxicity of mixtures by simple dose addition. Because organophosphates and carbamates are likely to have additive effects on the neurobehavior of salmon under natural exposure conditions, ecological risk assessments that focus on individual anticholinesterases might underestimate the actual risk to salmon in watersheds in which mixtures of these chemicals occur.     

固相膜萃取-高效液相色谱法测定饮用水中12种氨基甲酸酯类农药残留

目的:建立固相膜萃取-高效液相色谱法测定饮用水中灭多威、涕灭威、速灭威、残灭威、呋喃丹、甲萘威、抗杀虫威、异丙威、硫双威、仲丁威、猛杀威、杀虫威等12种氨基甲酸酯类农药残留量的方法。方法:水样经C18固相萃取膜真空抽滤,滤膜用乙酸乙酯洗脱,洗脱液经氮吹、甲醇溶解,高效液相色谱法测定。结果:12种氨基甲酸酯类农药的线性范围为0.05 mg/L～25.0 mg/L,线性相关系数大于0.999,检出限为0.31 mg/L～1.25 mg/L,水样中氨基甲酸酯类农残最低检测浓度范围为0.005 mg/L～0.019 mg/L,加标回收率为59.3%～97.3%,RSD<7.5%。结论:本方法样品前处理方便、快捷,有机试剂用量少。     

气-质谱联用法快速测定工作场所空气中多组分农药中毒

目的建立工作场所空气中有机磷农药、有机氯农药、氨基甲酸酯农药、拟除虫菊酯类农药共42种组分的快速测定方法。方法采用固体吸附剂采集空气中多种混合农药毒物，用1：1丙酮-正己烷解吸后以DB-35ms为分离柱、气相色谱-质谱仪联用分析测定。结果所有组分彼此完全分离，能同时予以定性确认；42种有机农药在一定浓度范围内线性关系良好，相关系数R≥0．99；最低检出限远低于职业化学中毒现场剂量水平。8种代表性农药组分解吸效率为86．3％～98．5％。结论本方法具有高选择性、灵敏度和准确度，完全满足工作场所空气中多种农药中毒的快速定性定量测定。     

混配农药对家兔诱发电位及脑组织ATP酶的影响

目的研究混配农药对家兔中枢神经系统功能的影响及其机制。方法将家兔随机分为混配农药染毒A组（丙溴磷与氰戊菊酯混配染毒组）、混配农药染毒B组（丙溴磷与灭多威？昆配染毒组）和1个对照组，每组6只。3个染毒组分别给予3种染毒剂量进行染毒，于染毒前后进行家兔体感染诱发电位（SEP）及染毒后大脑组织三磷酸腺苷（ATP）酶活力的测定。结果与对照组比较，2个混配农药染毒组的高剂量组染毒后SEP的N1、P1、N2波潜伏时均显著延长（P〈0．01），2个混配农药染毒组的高中剂量组染毒后的Na^＋-K^＋-ATP酶、Ca^2＋-Mg^2＋-ATP酶的活力明显下降（P〈0．05。P〈0．01）。结论一定剂量的混配农药可导致家兔中枢神经系统功能的的改变，这种改变可能与大脑组织中N^＋-K^＋-ATP酶、Ca^2＋-Mg^2^＋-ATP酶活力的下降有关．     

Piperonyl butoxide as a tool in aquatic toxicological research with organophosphate insecticides

Experiments were conducted to determine the effects of piperonyl butoxide, a synthetic methylenedioxyphenyl inhibitor of cytochrome(s) P450, on the toxicity of organophosphate insecticides to three cladoceran test species: Ceriodaphnia dubia. Daphnia magna, and Daphnia pulex. Coadministration of piperonyl butoxide effectively reduced the acute toxicity of four metabolically activated organophosphates (parathion, methyl parathion, diazinon, and malathion) and did not affect the toxicity of three organophosphates not requiring metabolic activation (dichlorvos, chlorfenvinphos, and mevinphos). These results indicate that piperonyl butoxide may be an effective tool in toxicological research focused upon identifying specific compounds responsible for toxicity in complex aqueous mixtures.     

Probabilistic risk assessment of cotton pyrethroids: I. Distributional analyses of laboratory aquatic toxicity data

This is the first in a series of five papers that assess the risk of the cotton pyrethroids in aquatic ecosystems in a series of steps ranging from the analysis of effects data through modeling exposures in the landscape. Pyrethroid insecticides used on cotton have the potential to contaminate aquatic systems. The objectives of this study were to develop probabilistic estimates of toxicity distributions, to compare these among the pyrethroids, and to evaluate cypermethrin as a representative pyrethroid for the purposes of a class risk assessment of the pyrethroids. The distribution of cypermethrin acute toxicity data gave 10th centile values of 10 ng/L for all organisms, 6.4 ng/L for arthropods, and 380 ng/L for vertebrates. For bifenthrin, cyfluthrin, lambda-cyhalothrin, and deltamethrin, the 10th centile values for all organisms were 15, 12, 10, and 9 ng/L, respectively, indicating similar or somewhat lower toxicity than cypermethrin. For tralomethrin and fenpropathrin, the 10th centiles were <310 and 240 ng/L, respectively. The distribution of permethrin toxicity to all organisms, arthropods, and vertebrates gave 10th centiles of 180, 76, and 1600 ng/L, respectively, whereas those for fenvalerate were 37, 8, and 150 ng/L. With the exception of tralomethrin, the distributions of acute toxicity values had similar slopes, suggesting that the variation of sensitivity in a range of aquatic nontarget species is similar. The pyrethroids have different recommended field rates of application that are related to their efficacy, and the relationship between field rate and 10th centiles showed a trend. These results support the use of cypermethrin as a reasonable worst-case surrogate for the other pyrethroids for the purposes of risk assessment of pyrethroids as a class.     

混配杀虫剂对小鼠学习记忆功能及大脑组织ATP酶活力的影响

[目的]研究混配杀虫剂对小鼠学习记忆功能的影响,初步探讨染毒后大脑组织ATP酶活力对小鼠学习记忆功能发生改变的作用。[方法]将小鼠随机分为混配杀虫剂染毒A组(丙溴磷与氰戊菊脂混配染毒组)、混配杀虫剂染毒B组(丙澳磷与灭多威混配染毒组)和1个对照组,每组10只。A、B组分别给予高、中、低3种染毒剂量,染毒前及染毒24h后进行跳台试验;应用化学比色法测定各组小鼠大脑组织中Na -K ATP酶、Ca2 -Mg2 -ATP酶的活力。[结果]①与对照组比较,A、B组的高剂量组跳台试验受电击次数分别为(2．90±1．45)次、(3．60±1．96)次,明显增多(P <0．05,P<0．01);总电击时间分别为(86．90±31．12)s、(101．30±38．74)s,明显增加(P<0．05,P<0．01);首次错误潜伏期分别为(74．20±27．88)s、(76．40±35．28)s,明显缩短(P<0．01)。②与对照组比较,A、B组的高剂量组大脑组织中Na -K -ATP酶活力分别为(5．50±2．17)、(5．50±2．97)μmol Pi／(mg prot·h),Ca2 -Mg2 -ATP酶的活力分别为(98．10±19．59)、(81．65±13．12)μmol Pi／(mg prot·h),明显降低(P<0．05,P<0．01)。③跳台试验各指标的改变及大脑组织ATP酶活力的降低,均以高剂量组更明显。[结论]混配杀虫剂能降低小鼠学习记忆功能,这种改变可能与大脑组织中Na -K - ATP酶、Ca2 -Mg2 -ATP酶的活力下降有关。     

Assessment of the toxicity of mixtures of nickel or cadmium with 9,10-phenanthrenequinone to Daphnia magna: impact of a reactive oxygen-mediated mechanism with different redox-active metals

Recently, we showed that reactive oxygen species (ROS) formation was involved in the toxicity of the redox-active metal Cu and mixtures of Cu plus a photomodified polycyclic aromatic hydrocarbon (PAH), phenanthrenequinone (PHQ), to Daphnia magna. It is unknown, however, if similar results can be observed for metals with lower or no redox activity and their mixtures with PHQ. In the present study using D. magna, the toxicity of Ni, a weakly redox-active metal, and of Cd, a non-redox active metal, was examined with or without PHQ. The abilities of Ni, Cd, PHQ, and binary mixtures of metal plus PHQ to generate ROS were measured using a 2',7'-dichlorofluorescein fluorescence assay. The results were compared with the results of Cu and mixtures of Cu plus PHQ from a recent study by our group. The order of metal toxicity to D. magna was found to be Cd > or = Cu > Ni. As with Cu/PHQ mixtures, synergistic toxicity was observed for mixtures of Ni and PHQ, whereas additive toxicity was observed for mixtures of Cd and PHQ. Alone, PHQ had no impact on ROS levels in D. magna. Nickel alone caused elevated ROS, which was further enhanced in the presence of PHQ. Neither Cd nor Cd/PHQ mixtures increased ROS production. Attenuation of toxicity and ROS production was observed in response to treatment with low concentrations of L-ascorbic acid. These results indicate potential toxic interactions between metals and modified PAHs. With redox-active metals, such as Cu and Ni, and modified PAHs, such as PHQ, these interactions can involve ROS formation.