CHEN Guo-feng,LI Xue-ru,LIU Feng,et al.Detection Methods of 82% Metolachlor?Metribuzin?2,4-D-Ethylhexyl EC on Soybean and Its Dietary Risk Assessment[J].Soybean Science,2020,39(05):781-789.[doi:10.11861/j.issn.1000-9841.2020.05.0781]
82%嗪·异丙甲·滴辛酯乳油在大豆上残留的检测方法及膳食风险评估
- Title:
- Detection Methods of 82% Metolachlor?Metribuzin?2,4-D-Ethylhexyl EC on Soybean and Its Dietary Risk Assessment
- Keywords:
- Soybean; Residues; Dietary risk assessment; Metolachlor; Metribuzin; 2; 4-D-ethylhexyl
- 文献标志码:
- A
- 摘要:
- 为评价异丙甲草胺、嗪草酮和2,4-滴异辛酯的复配农药82%嗪?异丙甲?滴辛酯乳油在大豆生产上的安全性，本研究使用改进的QuEChERS前处理方法，并通过超高效液相色谱串联质谱和气相色谱对大豆、青豆、大豆秸秆和青豆秸秆中的异丙甲草胺、嗪草酮和2,4-滴异辛酯及其中间代谢物2,4-滴进行定量测定。并依据国家估算的每日摄入量与可接受的每日摄入量，评估这些农药的风险系数。结果表明：异丙甲草胺、嗪草酮、2,4-滴异辛酯及2,4-滴在不同样品中的平均回收率为72.3%~105.7%，相对标准偏差为0.9%~14.0%；4种除草剂成分在大豆和青豆中的最低检出浓度分别为0.02,0.005,0.005和0.005 mg?kg-1，在大豆秸秆中的最低检出浓度均为0.04 mg?kg-1，在青豆秸秆中的最低检出浓度均为0.02 mg?kg-1。该方法可应用于测定大豆田间试验样品中异丙甲草胺、嗪草酮、2,4-滴异辛酯及2,4-滴的含量。良好农业规范条件下，大豆、青豆、大豆秸秆和青豆秸秆中的异丙甲草胺、嗪草酮、2,4-滴异辛酯和2,4-滴最终残留量均未检出。普通人群异丙甲草胺、嗪草酮和2,4-滴异辛酯的国家估计每日摄入量分别为0.083 73，0.011 6和0.279 5 mg?(kg bw)-1，风险系数分别为1.33％、1.41%和44.36%，这表明在良好农业规范条件下以2 460 g a.i. hm-2用量浓度施用3种除草剂复合的82%嗪?异丙甲?滴辛酯乳油对消费者的健康风险较低。
- Abstract:
- To evaluate the safety of compound pesticide 82% metolachlor?metribuzin?2,4-D-ethylhexyl EC of metolachlor, metribuzin and 2,4-D-ethylhexyl in soybean, this study used an improved QuEChERS pretreatment method coupled with Ultra Performance Liquid Chromatography Tandem Mass Spectrometry (UPLC-MS/MS) and Gas Chromatography (GC) to determine metolachlor, metribuzin, 2,4-D-ethylhexyl and intermediate metabolite 2,4-D in soybean, immature soybean, soybean straw and immature soybean straw. The risk factors (Risk Quotients, RQ) of these pesticides were evaluated by comparing the national estimated daily intake with the acceptable daily intake. The results showed that the average recovery of metolachlor, metribuzin, 2,4-D and 2,4-D-ethylhexyl in samples were 72.3%-105.7%, and the Relative Standard Deviation (RSD) was 0.9%-14.0%. The limit of quantitation (LOQ) of metolachlor, metribuzin, 2,4-D and 2,4-D-ethylhexyl in soybean and immature soybean were repectively 0.02, 0.005, 0.005 and 0.005 mg?kg-1, in soybean straw was 0.04 and in immature soybean straw was 0.02 mg?kg-1. This method has been successfully applied to determine the concentration of metolachlor, metribuzin, 2,4-D-ethylhexyl and 2,4-D in soybean field test samples. Under the conditions of Good Agricultural Practices (GAP), the terminal residues of metolachlor, metribuzin, 2,4-D-ethylhexyl and 2,4-D in soybean, immature soybean, soybean straw and immature soybean straw were not detected. The National Estimated Daily Intake (NEDI) of metolachlor, metribuzin and 2,4-D for the general population was 0.083 73, 0.011 6 and 0.279 5 mg?(kg bw)-1, respectively, and the RQs were 1.33%, 1.41% and 44.36%, which showed that the application of 82% metolachlor?metribuzin?2,4-D-ethylhexyl EC compound of the three herbicides under GAP conditions had a lower health risk for consumers.
参考文献/References:
［1］郑宇宏, 马铃铃, 邱红梅, 等. 东北大豆种质不同多胺组分含量分析［J］. 大豆科学, 2019, 38(6): 856-861. (Zheng H Y, Ma L L, Qiu H M, et al. Preliminary analysis of polyamine composition content in soybean germplasm of the northeast China［J］. Soybean Science, 2019, 38(6): 856-861.)［2］Hymowitz T. On the domestication of the soybean［J］. Economic Botany, 1970, 24: 408-421.［3］Athow K L. Soybean pest management［J］. Journal of The American Oil Chemists′ Society, 1981, 58(3): 130-135.［4］刘宝元, 阎百兴, 沈波, 等. 东北黑土区农地水土流失现状与综合治理对策［J］.中国水土保持科学, 2008, 6(1): 1-8. (Liu B Y, Yan B X, Shen B, et al. Current status and comprehensive control strategies of soil erosion for cultivated land in the Northeastern black soil area of China［J］. Science of Soil and Water Conservation, 2008, 6(1): 1-8.)［5］马增林. 黑龙江省大豆产业发展问题［D］. 哈尔滨: 东北农业大学, 2009. (Ma Z L. Development of soybean industry in Heilongjiang province［D］. Harbin: Northeast Agricultural University, 2009.)［6］许晶晶, 王兰腾, 赖玉健, 等. 除草剂异丙甲草胺特异性抗体制备及免疫检测方法的建立［J］. 现代食品科技, 2019, 35(10): 246-252. (Xu J J, Wang L T, Lai Y J, et al. An immunoassay based on the antibody specific for herbcide metolachlor［J］. Modern Food Science and Technology, 2019, 35(10): 246-252.)［7］范伟彦, 宋文钰, 吴彩兰, 等. 精异丙甲草胺对甜菜田主要杂草的防除效果和甜菜幼苗的安全性评价［J］. 石河子大学学报(自然科学版), 2019, 37(6): 677-681. (Fan W Y, Song W Y, Wu C L, et al. Control of weeds in sugarbeet field and safety assessment of sugarbeet seedling stage with S-methachlor［J］. Journal of Shihezi University(Natural Science), 2019, 37(6): 677-681.)［8］刘萌萌, 侯志广, 赵晓峰, 等. 降解嗪草酮微生物菌剂的制备及稳定性研究［J］. 安全与环境学报, 2015, 15(1): 245-249. (Liu M M, Hou Z G, Zhao X F, et al. Preparation and stability analysis of the degradable metribuzin bacterium microorganism agent［J］. Journal of Safety and Environment, 2015, 15(1): 245-249.)［9］王海燕, 曲政, 李晶, 等. 乙草胺?莠去津?2,4-滴异辛酯66%悬乳剂的气相色谱分析初探［J］. 辽宁农业科学, 2014, 1: 67-69. (Wang H Y, Qu Z, Li J, et al. Gas chromatographic analysis of acetochlor?atrazine?2,4-diisooctyl ester emulsion 66%［J］. Liaoning Agricultural Sciences, 2014, 1: 67-69.)［10］张双, 刘娜, 程功, 等. 利用QuEChERS-GC-ECD法测定2,4-滴异辛酯在土壤中的残留及消解［J］. 农药, 2018, 57(4): 290-293. (Zhang S, Liu N, Cheng G, et al. Determination of 2,4-D isooctyl ester residues in soil and dissipation process in soil by QuEChERS-GC-ECD［J］. Agrochemicals, 2018, 57(4): 290-293.)［11］王二琼, 陈飞, 张维博. 40％喹草酮?异丙甲草胺悬浮乳剂的反相高效液相色谱测定［J］. 安徽化工, 2019, 45(6): 106-108. (Wang E Q, Chen F, Zhang W B. Determination of 40% quinotrione and metolachlor SE by RP-HPLC［J］. Anhui Chemical Industry, 2019, 45(6): 106-108.)［12］梁林, 任玉鹏, 李文平, 等. 嗪草酮在马铃薯和土壤中的残留分析方法及消解动态［J］. 农药, 2017, 56(12): 908-911. (Liang L, Ren Y P, Li W P, et al. Dissipation dynamics and residue analysis of metribuzin in potato and soil［J］. Agrochemicals, 2017, 56(12): 908-911.)［13］张双, 纪明山, 谷祖敏, 等. 2,4-滴异辛酯的水解及光解特性［J］. 农药学学报, 2019, 21(1): 125-130. (Zhang S, Ji M S, Gu Z M, et al. The hydrolytic and photolytic properties of 2,4-D isooctyl ester［J］. Chinese Journal of Pesticide Science, 2019, 21(1): 125-130.)［14］杜鹏飞, 金茂俊, 石梦琪, 等. 分散固相萃取-气相色谱-质谱法同时测定玉米中乙草胺、莠去津和2,4-滴异辛酯［J］. 农药, 2015, 54(10): 748-751. (Du P F, Jin M J, Shi M Q, et al. Simultaneous determination of acetochlor, atrazine and 2,4-D-ethylhexyl residues in corn by dispersive solid phase extraction and gas chromatography-mass spectrometry［J］. Agrochemicals, 2015, 54(10): 748-751.)［15］中华人民共和国卫生部. 中国居民营养与健康状况2002［M］. 北京: 人民卫生出版社, 2002. (Ministry of Health of the People′s Republic of China. Nutrition and health status of Chinese residents 2002［M］. Beijing: People′s Medical Publishing House, 2002.)［16］钱永忠, 李耘. 农产品质量安全风险评估: 原理、方法和应用［M］. 北京: 国标准出版社, 2007: 20-61. (Qian Y Z, Li Y. Risk assessment for quality and safety of agrofoods: Principles, methodologies and applications［M］. Beijing: Standards Press of China, 2007: 20-61.)［17］European Food Safety Authority. Conclusion on the peer review of the pesticide risk assessment of the active substance tembotrione［J］. EFSA Journal, 2011, 9(1):1969.［18］Chen X, He S, Gao Y, et al. Dissipation behavior, residue distribution and dietary risk assessment of field incurred boscalid and pyraclostrobin in grape and grape field soil via MWCNTs-based QuEChERS using an RRLC-QqQ-MS/MS technique［J］. Food Chemistry, 2019, 274: 291-297.［19］Malhat F, Badawy H M A, Barakat D A, et al. Residues, dissipation and safety evaluation of chromafenozide in strawberry under open field conditions［J］. Food Chemistry, 2014, 152: 18-22.［20］Nougadère A, Merlo M, Héraud F, et al. How dietary risk assessment can guide risk management and food monitoring programmes: The approach and results of the French Observatory on Pesticide Residues (ANSES/ORP)［J］. Food Control, 2014, 41: 32-48.［21］Li X, Chen X, Hu J. Dissipation behavior, residue distribution and dietary risk assessment of chlorfenapyr and clothianidin in leek using RRLC-QqQ-MS/MS technique［J］. Chinese Chemical Letters, 2018, 30(1): 107-110.［22］周芹, 吴玉梅, 许庆轩. 超高效液相色谱-串联质谱法测定甜菜中除草剂残留含量［J］. 中国农学通报, 2017,33(36):152-156. (Zhou Q, Wu Y M, Xu Q X. Determination of herbicide residue in sugar beet by ultra high performance liquid chromatography-tandem mass spectrometry［J］. Chinese Agricultural Science Bulletin, 2017,33(36):152-156.)［23］Chen X, Li X, Pang K, et al. Dissipation behavior and residue distribution of fluazaindolizine and its seven metabolites in tomato ecosystem based on SAX SPE procedure using HPLC-QqQ-MS/MS technique［J］. Journal of Hazardous Materials, 2018, 342: 698-704.［24］Li S, Yu P, Zhou C, et al. Analysis of pesticide residues in commercially available chenpi using a modified QuEChERS method and GC-MS/MS determination［J］. Journal of Pharmaceutical Analysis, 2020, 10(1): 60-69.［25］Wilkowska A, Biziuk M. Determination of pesticide residues in food matrices using the QuEChERS methodology［J］. Food Chemistry, 2011, 125(3): 803-812.［26］陈春红, 逯忠斌, 侯志广. 嗪草酮在土壤和大豆中的残留动态研究［J］ .江苏农业科学, 2011(1): 332-335. (Chen C H, Lu Z B, Hou Z G. Study on the residual dynamics of metribuzin in soil and soybean［J］. Jiangsu Agricultural Sciences, 2011(1): 332-335.)
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