手性杀菌剂在有机蔬菜中的残留特征
Residual characteristics of 9 chiral fungicides in organic vegetables
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摘要:
本文建立了基于QuEChER-超高效液相色谱-串联质谱分析有机蔬菜中联苯三唑醇、苯霜灵、己唑醇、戊唑醇、粉唑醇、三唑酮、腈菌唑、甲霜灵和多效唑等9种手性杀菌剂的分析方法，该方法定量限为6.4-270.3 ng·kg-1鲜重（fw），相对回收率为77.1%-110.3%.随后运用该方法对有机番茄、苦瓜、黄瓜和胡萝卜等4种有机蔬菜中的手性杀菌剂残留及其对映体特征进行了分析.研究结果显示，9种杀菌剂中，联苯三唑醇未检出，甲霜灵残留量最高，中值为4.9 μg·kg-1 fw，有机黄瓜中的甲霜灵残留量（1.1-1.4 mg·kg-1 fw）超标（中国食品安全国家标准，最大残留限量0.5 mg·kg-1 fw）.在4种有机蔬菜中，胡萝卜和黄瓜检测出的手性杀菌剂种类最多，且黄瓜的手性杀菌剂残留总量最高，达1.1-1.4 mg·kg-1 fw，主要为甲霜灵.不同蔬菜种类的杀菌剂残留有明显差异，但有机蔬菜的杀菌剂残留远低于常规蔬菜.手性杀菌剂对映体的残留与蔬菜种类有关.
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关键词:
- 手性杀菌剂 /
- 有机蔬菜 /
- 对映体 /
- QuEChERS /
- UPLC-MS/MS
Abstract:A method was developed to detect 9 chiral fungicides including bitertanol, benalaxyl, hexaconazole, tebuconazole, flutriafol, triadimefon, myclobutanil, metalaxyl and bonzi in vegetables based on QuEChERS coupling with UPLC-MS/MS. The method quantitation limits ranged from 6.4 to 270.3 ng·kg-1 fresh weight (fw). The relative recoveries were 77.1%-110.3% for the analytes. This method was applied to detect the 9 chiral fungicides in four organic vegetables including tomatoes, bitter gourds, cucumbers and carrots. Bitertanol was not detected in all samples. Metalaxyl was the fungicide with the highest residue of 4.9 μg·kg-1 fw (median). The residue of metalaxyl in organic cucumbers (1.1-1.4 mg·kg-1 fw) exceeded the recommended standard. The highest levels for the total residue of the 9 chiral fungicides were detected in cucumber with a range of 1.1-1.4 mg·kg-1 fw, to which metalaxyl was the major contributor. Significant differences in fungicide residues were observed among various organic vegetables, but the fungicide residues in organic vegetables were much lower than those in conventional vegetables. The residual characteristics were vegetable species-specific for enantiomers of the chiral fungicides.
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Key words:
- chiral fungicides /
- organic vegetables /
- enantiomers /
- QuEChERS /
- UPLC-MS/MS
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[1] LIU W P, GAN J Y, SCHLENK D, et al. Enantioselectivity in environmental safety of current chiral insecticides[J]. Proceedings of the National Academy of Sciences of the United States of America, 2005, 102(3):701-706. [2] WILLIAMS A. Opportunities for chiral agrochemicals[C]. Pesticide Science, 1996, 46(1):3-9. [3] LIU H, HUANG R, XIE F, et al. Enantioselective phytotoxicity of metolachlor against maize and rice roots[J]. Journal of Hazardous Materials, 2012, 217:330-337. [4] GRIFFITHS K M, BACIC A, HOWLETT B J. Sterol composition of mycelia of the plant pathogenic ascomycete Leptosphaeria maculans[J]. Phytochemistry, 2003, 62(2):147-153. [5] CIMEN I, BASBAG S, TEMIZ M, et al. The effect of paclobutrazol, growth retardant, on cotton growth and verticillium wilt (Verticillium dahliae Kleb.)[J]. Plant Pathology Journal, 2004, 3(1):35-39. [6] BLAEDOW R A, CHANEY W R, PECKNOLD P C, et al. Investigation of fungicidal properties of the tree growth regulator paclobutrazol to control apple scab[J]. Journal of Arboriculture, 2006, 32(2):67-73. [7] LI Y B, DONG F S, LIU X G, et al. Enantioselective determination of triazole fungicide tebuconazole in vegetables, fruits, soil and water by chiral liquid chromatography/tandem mass spectrometry[J]. Journal of Separation Science, 2012, 35(2):206-215. [8] LI Y B, DONG F S, LIU X G, et al. Development of a multi-residue enantiomeric analysis method for 9 pesticides in soil and water by chiral liquid chromatography/tandem mass spectrometry[J]. Journal of Hazardous Materials, 2013, 250:9-18. [9] LI Y B, DONG F S, LIU X G, et al. Enantioselective separation and transformation of metalaxyl and its major metabolite metalaxyl acid in tomato and cucumber[J]. Food Chemistry, 2013, 141(1):10-17. [10] LI Y B, DONG F S, LIU X G, et al. Studies of enantiomeric degradation of the triazole fungicide hexaconazole in tomato, cucumber and field soil by chiral liquid chromatography-tandem mass spectrometry[J]. Chirality, 2013, 25(3):160-169. [11] CHEN J H, WANG H L, GUO B Y, et al. LC-MS/MS method for simultaneous determination of myclobutanil, hexaconazole, diniconazole, epoxiconazole and tetraconazole enantiomers in soil and earthworms[J]. International Journal of Environmental Analytical Chemistry, 2014, 94(8):791-800. [12] ZHANG Q, TIAN M M, WANG M Y, et al. Simultaneous enantioselective determination of triazolefungicide flutriafol in vegetables, fruits, wheat, soil, and water by reversed-phase high-performance liquid chromatography[J]. Journal of Agricultural and Food Chemistry, 2014, 62:2809-2815. [13] YU P Z, JIA C H, SONG W C, et al. Dissipation and residues of flutriafol in wheat and soil under field conditions[J]. Bulletin of Environmental Contamination and Toxicology, 2012, 89(5):1040-1045. [14] GARRISON A W. Probing the enantioselectivity of chiral pesticides[J]. Environmental Science & Technology, 2006, 40:16-23. [15] SEKHON B S. Chiral pesticides[J]. Journal of Pesticide Science, 2009, 34(1):1-12. [16] DONG F S, LIU X G, ZHENG Y Q, et al. Stereoselective degradation of fungicide triadimenol in cucumber plants[J]. Chirality, 2010, 22:292-298. [17] YE J, ZHAO M R, LIU J, et al. Enantioselectivity in environmental risk assessment of modern chiral pesticides[J]. Environmental Pollution, 2010, 158(7):2371-2383. [18] LIU H G, XU L H, ZHAO M R, et al. Enantiomer-specific, bifenthrin-induced apoptosis mediated by MAPK signalling pathway in Hep G2 Cells[J]. Toxicology, 2009, 261(3):119-125. [19] 王新茹. 两种酰胺类手性农药在动物体内及体外的代谢及毒性研究[D]. 北京:中国农业大学,2016. WANG X R. Enantioselective metabolism and toxic effects of two chiral amide pesticides in animals[D]. Beijing:China Agriculture University, 2016(in Chinese). [20] DING G D, WANG P, TIAN Y, et al. Organophosphate pesticide exposure and neurodevelopment in young Shanghai children[J]. Environmental Science & Technology, 2012, 46:2911-2917. [21] CRESSEY P, VANNOORT R, MALCOLM C. Pesticide residues in conventionally grown and organic New Zealand produce[J]. Food Additives and Contaminants:Part B, 2009, 2(1):21-26. [22] 赵悦臣. 水果和茶叶中四种手性农药对映体多残留分析方法研究[D]. 天津:天津农学院,2016. ZHAO Y C. The research of multiple residue analysis of four chiral pesticides in fruit and tea[D]. Tianjin:Tianjin Agricultural University, 2016(in Chinese). [23] 陈胜文,刘维屏,张大同. 手性检测器及手性对映体圆二色光谱标识[J]. 环境化学,2006,25(03):331-335. CHEN S W, LIU W P, ZHANG D T. Chiral detector and characterization with circular dichroism of chiral pesticides[J]. Environmental Chemistry, 2006, 25(3):331-335(in Chinese).
[24] 张荧,吴江平,罗孝俊,等. 生物样品中甲磺基多氯联苯的测定及手性拆分[J]. 环境化学,2012,31(08):1165-1170. ZHANG Y, WU J P, LUO X J, et al. Determination of methyl sulfonyl polychlorinated biphenyls and their chiral atropisomers in biota samples[J]. Environmental Chemistry, 2012, 31(8):1165-1170(in Chinese).
[25] 王伟,李兴红,陆海,等. 多介质环境样品中有机氯农药及其手性成分的分析方法[J]. 环境化学,2009,28(02):293-297. WANG W, LI X H, LU H, et al. Determination method of organochlorine pesticides and their chiral components in environmental samples[J]. Environmental Chemistry, 2009, 28(2):293-297(in Chinese).
[26] WINTER C K, DAVIS S F. Organic foods[J]. Journal of Food Science, 2006, 71(9):117-124. [27] WINTER C K. Pesticide residues in imported, organic and "suspect" fruits and vegetables[J]. Journal of Agricultural and Food Chemistry, 2012, 60(18):4425-4429. [28] 中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会. GB/T 19630.1-2011有机产品第1部分:生产[S]. 北京,2011. General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China, Standardization Administration. GB/T 19630.1-2011 Organic products-Part 1:Production[S]. Beijing, 2011(in Chinese).
[29] 中华人民共和国国际卫生和计划生育委员会,中华人民共和国农业部,国家食品药品监督管理总局. GB 2763-2016食品安全国家标准[S]. 北京,2016. National Health Commission of the People's Republic of China, Ministry of Agriculture and Rural Affairs of the People's Republic of China, China Food and Drug Administration. GB 2763-2016 National food safety standard[S]. Beijing, 2016 (in Chinese).
[30] 徐真真,姬泓巍,刘修园,等. 甲霜灵在黄瓜和土壤中的残留分析及消解动态[J]. 农药,2015,54(10):755-758. XU Z Z, JI H W, LIU X Y, et al. Residue analysis and decline dynamics of metalaxyl in cucumber and soil[J]. Agrochemicals, 2015, 54(10):755-758(in Chinese).
[31] 王美云. 手性农药甲霜灵的立体选择性降解研究[D]. 南京:南京农业大学,2014. WANG M Y. Studies on stereoselective degradation of chiral pesticide metalaxyl[D]. Nanjing:Nanjing Agriculture University, 2014(in Chinese). [32] MALHAT F M. Persistence of metalaxyl residues on tomato fruit using high performance liquid chromatography and QuEChERS methodology[J]. Arabian Journal of Chemistry, 2017, 10:S765-S768. [33] 王雪松. 三唑类手性农药反相拆分及戊唑醇选择性残留行为[D]. 哈尔滨:东北农业大学,2011. WANG X S. Enantiomeric sepparation of triazole pesticides under reversed phase and enantioselective residue study of tebuconazole[D]. Haerbin:Northeast Agricultural University, 2011(in Chinese). [34] LIN C M, ZHANG L J, ZHANG H, et al. Enantioselective degradation of myclobutanil and famoxadone in grape[J]. Environmental Science and Pollution Research, 2018, 25(3):2718-2725. -
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