作者：朱霞萍¹, 王勇¹, 安艳¹, 张传峰¹, 王泽鹏²

作者单位：1. 成都理工大学材料与化学化工学院，四川 成都 610059;
2. 贵州省地质矿产勘查开发局一0五地质大队，贵州 贵阳 550018

关键词：环境样品;前处理方法;总结;有机磷农药

摘要：

有机磷农药在我国农业生产使用的农药中占有很大的比例，施用的有机磷农药经过一系列的迁移、转化最终残留在大气、水体和土壤中，严重威胁着人类的健康。环境样品基体复杂且农残含量极低，基本无法直接测定，因此，针对不同环境样品、不同类型农药选择合适的前处理技术是准确测定有机磷农药的关键。目前有机磷农药残留检测的前处理技术主要有固相萃取、液相萃取、新型搅拌棒吸附萃取、超声辅助萃取、微波辅助萃取、加速溶剂萃取、超临界流体萃取、分子印迹聚合物法、免疫亲和层析法和QuEChERS法等。固相萃取和液相萃取应用广泛，已开发的新型萃取方式很多。微波辅助萃取、超声辅助萃取和加速溶剂萃取是借助外力加快萃取速率。分子印迹聚合物法和免疫亲和层析法是针对某一种农药合成具有高度识别能力的聚合物和抗体来提高萃取选择性。该文总结近年来国内、国外环境样品中有机磷农药残留检测的前处理技术的分类、原理、应用现状及优劣，指出未来前处理时间短，富集倍数高，使用材料和试剂量少、毒性小的绿色前处理技术是今后发展的方向。

Development on pretreatment techniques for detection of organophosphorus pesticide residues in environmental samples
ZHU Xiaping¹, WANG Yong¹, AN Yan¹, ZHANG Chuanfeng¹, WANG Zepeng²
1. College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu 610059, China;
2. 105 Geological Brigade, Guizhou Bureau of Geology and Mineral Exploration and Development, Guiyang 550018, China
Abstract: Organophosphorus pesticides account for a large proportion of the pesticides used in agricultural production in our country. The residues of the organophosphorus pesticides finally remain in the atmosphere, water and soil after a series of migration and transformation, which seriously threaten human health. The matrix of environmental samples is complex with extremely low content of pesticide residues, which is almost impossible to directly determine. Therefore, choosing appropriate pretreatment techniques for different environmental samples and different types of pesticides is the key to accurate determination of organophosphorus pesticides. At present, the pre-treatment technologies for the detection of organophosphorus pesticide residues mainly include solid phase extraction, liquid phase extraction, new type of stirring rod adsorption extraction, ultrasonic assisted extraction, microwave assisted extraction, accelerated solvent extraction, supercritical fluid extraction, molecularly imprinted polymer method, immunology affinity chromatography and QuEChERS method. Solid phase extraction and liquid phase extraction are widely applied, and many new extraction methods have been developed. Microwave-assisted extraction, ultrasonic-assisted extraction and accelerated solvent extraction use external force to accelerate the extraction rate. The molecularly imprinted polymer method and immunoaffinity chromatography method are to synthesize polymers and antibodies with high recognition ability for a certain pesticide to improve extraction selectivity. This paper summarizes the classification, principle, application situation, advantages and disadvantages of the pretreatment technologies used in the detection of organophosphorus pesticide residues in environmental samples domestically and overseas in recent years. In the future, the green pretreatment technology with shorter process time, higher enrichment factor, fewer using of the materials and reagents and lower toxicity will be the development trend.
Keywords: environmental samples;pretreatment methods;summarize;organophosphorus pesticides
2021, 47(9):52-60  收稿日期: 2020-08-10;收到修改稿日期: 2020-10-06
基金项目: 贵州省科技厅应用基础重点项目（[2019]1424）
作者简介: 朱霞萍(1968-),女,江西萍乡市人,教授,硕士生导师,主要从事环境分析化学,土壤、水体环境污染防控与修复技术
参考文献
[1] 2019~2025年中国化学农药制造市场分析与投资前景研究报告[EB/OL]. 博思网: 博思数据, 2019[2020-8-1]. http://www.bosidata.com/data/K24775TCGQ.html.
[2] 束放, 李永平, 魏启文. 2018年种植业农药使用情况及2019年需求分析[J]. 中国植保导刊, 2019, 39(4): 75-78
[3] 张骥, 杨土保. 有机磷农药与再生障碍性贫血发病关系的Meta分析[J]. 中华流行病学杂志, 2015, 36(9): 1005-1009
[4] YU R, LIU Q, LIU J S, WANG Q C, et al. Concentrations of organophosphorus pesticides in fresh vegetables and related human health risk assessment in Changchun, Northeast China[J]. Food Control, 2016, 60: 353-360
[5] 陈卫明, 邓天龙, 张勤, 等. 土壤中有机氯农药残留的分析技术研究进展[J]. 岩矿测试, 2009, 28(2): 151-156
[6] JORDAN T B, NICHOLS D S, KERR N I. Selection of SPE cartridge for automated solid-phase extraction of pesticides from water followed by liquid chromatography-tandem mass spectrometry[J]. Analytical & Bioanalytical Chemistry, 2009, 394(8): 2257-2266
[7] 刘鹏. 饮用水中有机磷农药的样品前处理与HPLC分析[J]. 环境化学, 2004, 23(1): 117-118
[8] 万译文, 康天放, 张雁. 固相萃取气相色谱法测定地表水中有机磷农药[J]. 中国环境监测, 2008, 24(6): 40-43
[9] 陈烨, 许秀艳, 吕怡兵, 等. 固相萃取-双柱气相色谱法测定水中多种有机磷农药残留[J]. 中国测试, 2011, 37(5): 53-55
[10] 顿咪娜, 刘莉, 王永朝, 等. 固相萃取-气相色谱法测定饮用水中5种有机磷农药[J]. 化学分析计量, 2016, 25(2): 12-15
[11] 杨元, 高玲, 景露, 等. SPE-GC/MS法测定水中有机磷和氨基甲酸酯农药[J]. 中国测试, 2009, 35(2): 86-89
[12] 林得平. 水环境和土壤中56种农药的残留分析[D]. 济南: 山东大学, 2014.
[13] BALLESTEROS E, PARRADO M J. Continuous solid-phase extraction and gas chromatographic determination of organophosphorus pesticides in natural and drinking waters[J]. Journal of Chromatography A, 2004, 1029(1-2): 267-273
[14] MOLINA C, HONING M, BARCELO D. Determination of organophosphorus pesticides in water by solid-phase extraction followed by liquid chromatography/high-flow pneumatically assisted electrospray mass spectrometry[J]. Analytical Chemistry, 1994, 66(24): 4444-4449
[15] 任丽萍, 田芹, 刘丰茂, 等. 用固相萃取和气相色谱技术测定环境水体中痕量农药[J]. 中国农业大学学报, 2004, 9(2): 93-96
[16] 陈明, 任仁, 王子健, 等. 北京工业废水和城市污水环境激素污染状况调查[J]. 环境科学研究, 2007, 20(6): 1-7
[17] 伍亮, 钟非, 吴娟, 等. 环境介质中三唑磷农药残留分析方法[J]. 环境化学, 2014, 33(6): 1038-1039
[18] 王若苹. 固相微萃取-毛细管气相色谱法快速同步分析水中有机氯及有机磷农药[J]. 中国环境监测, 2004, 20(3): 23-27
[19] 王一龙, 曾昭睿, 杨敏, 等. 固相微萃取联用气相色谱测定有机磷农药[J]. 武汉理工大学学报, 2005, 27(10): 37-39+46
[20] 王新平, 杨云, 栾伟, 等. 固相微萃取-气相色谱-质谱联用分析环境水样中痕量有机磷农药[J]. 分析试验室, 2003, 22(5): 5-9
[21] 穆仁, 何秀丽, 高晓光, 等. 基于固相微萃取-离子迁移率谱的敌敌畏快速检测方法[J]. 分析试验室, 2017, 36(11): 1247-1250
[22] 吴科盛, 许恒毅, 郭亮, 等. 磁性固相萃取在检测分析中的应用研究进展[J]. 食品科学, 2011, 32(23): 324-327
[23] SHAKOURIAN M, YAMINI Y, SAFARI M. Facile magnetization of metal-organic framework TMU-6 for magnetic solid-phase extraction of organophosphorus pesticides in water and rice samples[J]. Talanta, 2020: 121-139
[24] XIE J, LIU T, Song G, et al. Simultaneous analysis of organophosphorus pesticides in water by magnetic solid-phase extraction coupled with GC-MS[J]. Chromatographia, 2013, 76(9-10): 535-540
[25] MIGUEL ÁNGEL G, ANTONIO V, JAVIER H, et al. Analysis of pesticides residues in environmental water samples using multiwalled carbon nanotubes dispersive solid-phase extraction[J]. Journal of Separation Science, 2013, 36(3): 556-563
[26] KERMANI M, JAFARI M T, SARAJI M. Porous magnetized carbon sheet nanocomposites for dispersive solid-phase microextraction of organophosphorus pesticides prior to analysis by gas chromatography-ion mobility spectrometry[J]. Microchimica Acta, 2019, 186(2): 88-98
[27] SUN T, JIN Y, YANG J, et al. Dispersive solid-phase extraction of organophosphorus pesticides from apple, cucumber and water samples using reduced graphene oxide coated with ZnO nanocomposites as a sorbent[J]. Analytical Methods, 2015, 7(15): 6095-6102
[28] 胡小键, 刘达峰, 丁新良, 等. 全自动固相萃取LC/MS/MS测定水中6种有机磷农药[J]. 环境卫生学杂志, 2012, 2(1): 38-40+47
[29] 王艳丽, 李利荣, 高璟赟, 等. 全自动固相萃取-气相色谱/质谱联用法测定水中多种有机磷农药[C]. 中国环境科学学会2013年学术年会, 2013: 631-635.
[30] 陈晓秋. 圆盘固相萃取-GC/MS/SIM法在水体有机氮磷农药测定中的应用研究[J]. 分析测试技术与仪器, 2005, 11(2): 123-127
[31] 胡骢. 新型搅拌棒吸附萃取涂层的研制及其在环境和食品分析中的应用[D]. 武汉: 武汉大学, 2013.
[32] United States. Environmental Protection Agency. Office of Solid Waste, Emergency Response. Test methods for evaluating solid waste: physical/chemical methods[M]. US Environmental Protection Agency. Office of Solid Waste and Emergency Response, 1986.
[33] 王祎亚, 饶竹. 大口径毛细管柱气相色谱法测定水中15种有机磷农药[J]. 岩矿测试, 2007, 26(1): 17-20
[34] 郭虹, 刘闯, 杨玉竹. 毛细管柱气相色谱法测定水中13种有机磷农药的方法研究[J]. 环境与职业医学, 2009, 26(2): 216-218
[35] 陈蓓蓓, 刘鸣, 吴诗剑. 气相色谱法测定土壤和沉积物中12种有机磷农药[J]. 中国环境监测, 2013, 29(6): 134-138
[36] 王建伟, 张彩香, 潘真真, 等. 江汉平原地下水中有机磷农药的分布特征及影响因素[J]. 中国环境科学, 2016, 36(10): 3089-3098
[37] FARAJZADEH M A, SEYEDI S E, SHALAMZARI M S, et al. Dispersive liquid-liquid microextraction using extraction solvent lighter than water[J]. Journal of Separation Science, 2009, 32(18): 3191-3200
[38] 李晓晶, 陈安, 黄聪, 等. 分散液液微萃取-气相色谱法快速测定水中23种有机磷农药[J]. 分析测试学报, 2011, 30(3): 326-329
[39] SOISUNGNOEN P, BURAKHAM R, SRIJARANAI S. Determination of organophosphorus pesticides using dispersive liquid-liquid microextraction combined with reversed electrode polarity stacking mode-micellar electrokinetic chromatography[J]. Talanta, 2012, 98: 62-68
[40] YANG Z, LIU Y, LIU D, et al. Determination of organophosphorus pesticides in soil by dispersive liquid-liquid microextraction and gas chromatography[J]. Journal of Chromatographic Science, 2012, 50(1): 15-20
[41] SANZ C P, HALKO R, FERRERA Z S, et al. Micellar extraction of organophosphorus pesticides and their determination by liquid chromatography[J]. Analytica Chimica Acta, 2004, 524(1-2): 265-270
[42] PENG G, HE Q, LU Y, et al. Dispersive solid phase extraction followed by low-toxicity vortex-assisted liquid-liquid microextraction for the determination of organophosphorus pesticides by high-performance liquid chromatography[J]. Analytical Methods, 2016, 8(12): 2684-2690
[43] PENG G, HE Q, MMEREKI D, et al. Vortex‐assisted liquid-liquid microextraction using a low‐toxicity solvent for the determination of five organophosphorus pesticides in water samples by high‐performance liquid chromatography[J]. Journal of Separation Science, 2015, 38(20): 3487-3493
[44] 陈子键, 王宇, 李美英, 等. 食品基质有机磷农药残留的前处理新方法研究进展[J]. 分析测试学报, 2015, 34(11): 1315-1323
[45] FUENTES E, BÁEZ M E, LABRA R. Microwave-assisted extraction through an aqueous medium and simultaneous cleanup by partition on hexane for determining pesticides in agricultural soils by gas chromatography: A critical study[J]. Analytica Chimica Acta, 2006, 578(2): 122-130
[46] FUENTES E, MARÍA E B, LABRA R. Parameters affecting microwave-assisted extraction of organophosphorus pesticides from agricultural soil[J]. Journal of Chromatography A, 2007, 1169(1-2): 40-46
[47] MERDASSA Y, LIU J F, MEGERSA N. Development of a one-step microwave-assisted extraction method for simultaneous determination of organophosphorus pesticides and fungicides in soils by gas chromatography-mass spectrometry[J]. Talanta, 2013, 114: 227-234
[48] ZHANG W, LV J G, SHI R G, et al. A rapid screening method for the determination of seventy pesticide residues in soil using microwave-assisted extraction coupled to gas chromatography and mass spectrometry[J]. Journal of Soil Contamination, 2012, 21(4): 407-418
[49] 赵欣, 汪子明. 微波辅助微固相萃取-气相色谱/质谱法测定河水中5种有机磷农药[J]. 分析科学学报, 2016, 32(6): 865-868
[50] 杨敏娜, 孙成, 塔娜. 环境介质中有机磷农药残留分析方法[J]. 环境科学与技术, 2006, 29(6): 46-48
[51] WANG Q, YIN J, PAN H, et al. A novel method based on combining ultrasonic-assisted dispersive solid-phase extraction and low-density solvent dispersive liquid-liquid microextraction (UA-DSPE-LDS-DLLME) for the determination of organophosphorus pesticides in soil[J]. Analytical Methods, 2014, 6(18): 7335-7342
[52] AHMADI K, ABDOLLAHZADEH Y, ASADOLLAHZADEH M, et al. Chemometric assisted ultrasound leaching-solid phase extraction followed by dispersive-solidification liquid-liquid microextraction for determination of organophosphorus pesticides in soil samples[J]. Talanta, 2015, 137: 167-173
[53] 聂春林. 色谱-色质联用技术在土壤及中药农残中的应用研究[D]. 长沙: 中南大学, 2009.
[54] GARCÍA-VALCÁRCEL A I, TADEO J L. A combination of ultrasonic assisted extraction with LC-MS/MS for the determination of organophosphorus pesticides in sludge[J]. Analytica Chimica Acta, 2009, 641(1-2): 117-123
[55] 赵海香, 袁光耀, 邱月明, 等. 加速溶剂萃取技术(ASE)在农药残留分析中的应用[J]. 农药, 2006, 45(1): 15-17+21
[56] WU S, ZHANG H, CHEN B, et al. Multiresidue determination of organophosphorus pesticides in solid waste environmental samples by gas chromatography[J]. Journal of AOAC International, 2014, 97(5): 1463-1469
[57] BØWADT S, HAWTHORNE S B. Supercritical fluid extraction in environmental analysis[J]. Journal of Chromatography A, 1995, 703(1-2): 549-571
[58] BARNABAS I J, DEAN J R, HITCHEN S M, et al. Selective extraction of organochlorine and organophosphorus pesticides using a combined solid phase extraction-supercritical fluid extraction approach[J]. Analytica Chimica Acta, 1994, 291(3): 261-267
[59] NAEENI M H, YAMINI Y, REZAEE M. Combination of supercritical fluid extraction with dispersive liquid-liquid microextraction for extraction of organophosphorus pesticides from soil and marine sediment samples[J]. Journal of Supercritical Fluids, 2011, 57(3): 219-226
[60] ANASTASSIADES M, LEHOTAY S J, STAJNBAHER D,et al. Fast and easy multiresidue method employing acetonitrile extraction/partitioning and “dispersive solid-phase extraction” for the determination of pesticide residues in produce[J]. AOAC Int., 2003, 86(2): 412-431.
[61] 蔡霖, 席普宇, 谢晴, 等. QuEChERS方法联合HPLC-MS/MS和GC-MS测定土壤中110种农药残留[J]. 农业环境科学学报, 2017, 36(8): 1680-1688
[62] 吴茂, 范亚军, 郭亚平, 等. 有机磷农药残留分子印迹聚合物研究现状与展望[J]. 农药学学报, 2018, 20(6): 689-703
[63] 左海根, 苗珊珊, 杨红. 分子印迹技术在农药残留检测中的研究进展[J]. 南京农业大学学报, 2012, 35(5): 175-182
[64] 蔡亚岐, 牟世芬. 分子印迹固相萃取及其应用[J]. 分析测试学报, 2005, 24(5): 116-121
[65] ZHU X, YANG J, SU Q, et al. Selective solid-phase extraction using molecularly imprinted polymer for the analysis of polar organophosphorus pesticides in water and soil samples[J]. Journal of Chromatography A, 2005, 1092(2): 161-169
[66] 苗珊珊. 硅胶表面分子印迹聚合物及新型电化学发光生物传感器在农药残留分析中的应用[D]. 南京: 南京农业大学, 2016.
[67] 胡艳云, 徐慧群, 姚剑, 等. 分子印迹固相萃取-液相色谱-质谱法测定果蔬中20种三唑类农药残留[J]. 分析化学, 2014, 42(2): 227-232
[68] 高文惠, 刘博, 庞军, 等. 虚拟模板分子印迹固相萃取-高效液相色谱法检测食品中联苯三唑醇与烯唑醇[J]. 现代食品科技, 2013, 29(10): 2504-2508+2497
[69] XU Z L, DENG H, DENG X F, et al. Monitoring of organophosphorus pesticides in vegetables using monoclonal antibody-based direct competitive ELISA followed by HPLC-MS/MS[J]. Food Chemistry, 2012, 131(4): 1569-1576
[70] 吴芸茹. 三种有机磷农药残留免疫检测方法的建立与应用[D]. 南京: 南京农业大学, 2008.