节点文献
有机磷、有机氯等多项农药残留检测方法研究
【作者】 李建军；
【作者基本信息】 山东大学 ， 应用化学， 2008， 硕士
【摘要】 2003年5月,日本修订了《食品卫生法》,于2006年5月29日实施食品中农业化学品“肯定列表制度”。该制度的实施已对我国食品对日出口造成重大影响。“肯定列表制度”是日本为加强食品中农业化学品(包括农药、兽药和饲料添加剂)残留管理而制定的一项新制度。2005年日本出台“肯定列表制度”讨论稿,把原有限量标准提高到799种农、兽药,53862个限量标准。限量之多、限量之严格,前所未有,该制度已于2006年5月开始实行。此项贸易壁垒实行之后,仅2006年6月至8月,全国出口日本蔬菜数量、货值均下滑30%多,造成的经济损失惨重。日本是我国食品、农产品的第一大市场,就潍坊市来说,2005年,对日出口保鲜蔬菜10829批、重量27.4万吨、货值1.3亿美元,占全国出口保鲜蔬菜总量的58%、56%、56%。日本市场对我们山东省的农业发展、经济发展具有不可替代的地位。山东作为农产品出口大省,研究日本贸易壁垒对促进出口贸易具有重要作用。目前在“肯定列表制度”所涉及的799种农业化学品中,尚有391种农药、155种兽药我国还没有制定检测方法,占62.1%,检测标准的制定工作迫在眉睫。缺少的检测标准如此之多,一一制定人力、物力、财力均有极大困难。为使应对肯定列表工作更有针对性,我们对列表中的农药项目和现在市场上流通及使用的农药品种进行了统计汇总,共有113种农药,尚有56种(甲胺磷、DDV、EPTC、茵草敌、速灭磷、丁草敌、乙酰甲胺磷、克草敌、禾草敌、氧化乐果、四氯硝基苯、环草敌、久效磷、甲拌磷、α-六六六、乐果、β-六六六、五氯硝基苯、γ-六六六、地虫硫磷、百菌清、嘧霉胺、乙拌磷、δ-六六六、抗芽威、异稻瘟净、甲基毒死蜱、甲基对硫磷、杀螟硫磷、马拉硫磷、艾试剂、毒死蜱、乙霉威、对硫磷、喹硫磷、p,p′-DDE、p,p′-滴滴伊、狄氏剂、氟硅唑、异狄氏剂、o,p′-滴滴涕、p,p′-滴滴滴、乙硫磷、三唑磷、三硫磷、p,p′-滴滴涕、联苯菊酯、甲氰菊酯、高效氯氰菊酯、氯菊酯、氟氯氰菊酯、氯氰菊酯、氟氰戊菊酯、氰戊菊酯、氟胺氰菊酯、溴氰菊酯)没有或标准的检测精度偏低,而且都是国际上重点关注和检测的农药,尤其是“肯定列表制度”重点关注的项目,各国对蔬菜中上述农药的限量进行了严格规定并重点监控,近两年来日方时有预警,对我国出口蔬菜带来极大困难。为使我国蔬菜产品顺利出口,有针对性地探索蔬菜中上述农药残留快速准确的分析方法显得极为迫切。2003年,美国宾西法尼亚州的化学家Steven J.Lehotay和来自德国的访问学者Michelangelo Anastassiadas提出了QuEChERS农药多残留同时分析方法[8],目前应用较多的作用是QuChERS前处理技术,QuEChERS的意思是“quick,easy,cheap,effective,rugged,and safe”,是一种快速、简单、低成本的样品处理方法,该方法的关键是采用分散型固相萃取(dispersire-SPE)净化法,将乙腈振荡提取后的部分提取液,直接加入无水硫酸镁和PSA吸附剂粉末进行净化,离心后取上清液进行仪器分析。此方法代替了相应的SPE小柱净化,优点是快速、简单、经济,缺点则是方法检测限难以满足要求,水分去除可能不完全,提取效率有可能降低,净化效果不理想。由于QuEChERS是近几年新出现的样品处理技术以及其自身的局限性,目前在国内实际应用较少针对此方法的局限性,结合肯定列表,对样品的提取及净化均进行了改进,除用PSA粉外,考虑加入石墨炭黑粉、ODSC18和氨丙基粉等多种吸附剂,对具体的操作步骤和针对不同的样品基质进行了细化,使提取效率和净化效果得到明显改善,净化前先进行氮吹或旋蒸浓缩,使方法方法灵敏度提高了4～5倍,并且通过溶剂置换,使此技术可以结合更多的分析仪器进行检测。我们首先开发了狄氏剂、异狄氏剂、艾氏剂三重农残的检测项目的开发,将此改进后的QuEChERS样品处理技术分别结合GC-FPD、GC-ECD进行了果蔬中有机磷农药检测、有机氯农药检测;结合GC-MS进行了有机磷、有机氯等多种农药化合物的多残留同时检测、结合均取得了满意结果。而后进一步将此方法应用到兽药残留的分析,结合HPLC进行了禽肉中磺胺类、地克珠利、克球酚的同时检测,结果同样令人满意。通过此项目开发及运用,2007年,山东出口食品106.65亿美元,同比增长21.6%,占全国食品农产品的四分之一,连续六年持续实现高门槛下的高增长。解决劳动就业1400多万人,有力促进了“三农问题”的解决。
【Abstract】 At May 2003, Japan revised Food Sanitation Law and began to implement agricultural chemicals Positive List System in food from May 29, 2006. The implementation of this system has caused great influences on our country’s food export to Japan. The Positive List System is a new system set by Japan in order to strength agricultural pesticide (including pesticide, veterinary medicine and feed additive) residue management in food. In the draft of Positive List System announced at 2005, Japan raised original limit standard to 799 kinds of pesticides and veterinary medicines and 53862 limit standards. The amount and strictness of limits is unprecedented. This system had been implemented at May 2006. After the implementation of this trade barrier, only from June to August 2006, the whole amount and value of vegetables export to Japan both slip more than 30%, which resulted in great economic losses.Japan is the biggest market to our country’s food and agricultural products. In the case of Weifang City, at 2005 the fresh vegetables exported to Japan reached 10829 batches, 274 thousand tons in weight and 130 million US dollars in value, which accounted for 58%, 56% and 56% of the total amount of exported fresh vegetables respectively. Japan market has irreplaceable effect on agricultural development and economic development of Shandong province. As a large agricultural products-export province, it has important effects for promoting import and export trade of Shandong province to study the Japanese trade barriers.Among the 799 agricultural chemicals involved in current Positive List System, there still are 391 kinds of pesticides and 155 kinds of veterinary medicines that have not been set up detection methods, which account for 62.1%. So the standard-setting work is extremely Urgent. It is very difficult to set up so many absent detection standards in labor resources, materials and money. In order to make the Positive List coping work to be more targeted, we carried out statistic collection to the pesticide items in the list and pesticide varieties that are circulated and used at current market. There are 113 kinds of pesticides. Among these pesticides, 56 kinds (methamidophos, ddv, eptc, eradicane, mevinphos, butylate, acephate, pebulate, molinate, dimethoxon, tetrachloronitrobenzene, cycloate, monocrotophos, phorate,α-benzene hexachloride, dimethoate,β-benzene hexachloride,γ-benzene hexachloride, fonofos, chlorothalonil, pyrimethanil, disulfoton,δ-benzene hexachloride, pirimicarb, iprobenfos, chlorpyrifos-methyl, parathion-methyl, sumithion, malathion, aldrin, chlorpyrifos, diethofencarb, parathion, quinalphos, p, p’-dde, p, p’-dichloroethylene, dieldrin, endrin, flusilazole, o,p’-ddt, p,p’-ddd, ethion, triazophos, carbophenothion, p, p’-ddt, bifenthrin, fenpropathrin, beta-cypermethrin, permethrin, baythroid, cypermethrin, flucythrinate, fenvalerate, tau-fluvalinate, decamethrin) are still have not detection standards or the detection precision of standards is comparatively low. All these pesticides are the emphasis being focused and detected by the international plane, especially by Positive List System. Every country has strictly stipulated the limit of the above-mentioned pesticides in vegetables and monitored emphatically. In recent years, Japan gave warnings from time to time, which brought great difficulties to our country’s vegetables export. For the sake of successfully exporting of our country’s vegetable products, it is extremely urgent to investigate the rapid and accurate analysis methods targetedly to analyze the above-mentioned pesticide residues in vegetables.At 2003, the chemist Steven J.Lehotay at Pennsylvania, USA and visiting scholar Michelangelo Anastassiadas from Germany put forward QuEChERS multiple pesticide residues simultaneous analysis method. At present, the major action applied is QuEChERS pre-treatment technology. QuEChERS means "quick, easy, cheap, effective, rugged and safe", which is a quick, simple and low-cost sample treatment method. The key of this method is to adopt dispersive solid-phase extraction (dispersive-SPE) purification method, mix magnesium sulfate and PSA absorbing agent powder directly into partial extracting solution after acetonitrile oscillation extraction for purification, then analyze the supernatant fluid after centrifugation with instruments. This method replaces the corresponding SPE cartridge purification, has the advantages of quickness, simpleness and economy, and also has the shortcomings that detection limit could not meet the requirements, moisture may not be removed thoroughly, extraction rate might be low and purification effects may be less than ideal. Because QuEChERS is the newly appeared sample treatment technology in recent years and it has limitations, at present only less application has been carried out in our country. On account of the limitations of this method and combined with Positive List, we improved the sample extraction and purification. Besides PSA powder, we took into account the mixture several absorbing agents including graphite carbon black powder, ODSC18 and amino-propyl powder and divided the specific operation procedures according to different sample substance, which significantly improved the extraction rate and purification effects. Through nitrogen evaporation and revolving steaming condensation, the sensitivity got 4-5 fold increases and through solvent replacement, this technology could integrate more analysis instruments for detection. We firstly developed the pesticide residue detection project development of three pesticides, dieldrin, endrin and aldrin, carried out the detection of organic phosphorus pesticide and organic chlorine pesticide with improved QuEChERS sample treatment technology combined with GC-FPD and GC-ECD separately, and carried out multiple residues simultaneous detection of many kinds of pesticide chemicals such as organic phosphorus pesticide and organic chlorine. All the combinations obtained satisfying results. We further applied this method into the analysis of veterinary residue and carried out simultaneous detection of sulfa, diclazuril and clopidol in poultry meat combined with HPLC. The result is equally satisfactory.Through the development and application of this project, the exported food value of Shandong province amounted to 10.665 billion US dollars, increased 21.6% accounting for one-quarter of countrywide food and agricultural products export, and constantly realized high growth under high-entry barrier for six years. The food export has settled the employment of 14 million people and strongly boosts the resolve of agriculture, countryside and farmers issues.