高效液相色谱串联质谱法测定喹啉铜在葡萄和土壤中残留及消解动态  

Residues and Dissipation of Oxine-Copper in Grape and Soil Using HPLC-MS/MS Methodology

作　　者：尹绍静 柳亚男 于遒功[2] 鲁雪莉 孔庆仙 尤祥伟[1] 李义强[1] YIN Shao-jing;LIU Ya-nan;YU Qiu-gong;LU Xue-li;KONG Qing-xian;YOU Xiang-wei;LI Yi-qiang(Tobacco Research Institute,Chinese Academy of Agricultural Sciences,Qingdao 266101,Shandong,China;Qingdao Academy of Agricultural Sciences,Qingdao 266101,Shandong,China)

机构地区：[1]中国农业科学院烟草研究所,山东青岛266101 [2]青岛市农业科学研究院,山东青岛266101

出　　处：《农药》2021年第5期357-360,378,共5页Agrochemicals

基　　金：国家重点研发计划项目(2016YFD0200206);山东省自然科学基金(ZR2019BC082)。

摘　　要：[目的]建立葡萄和土壤中喹啉铜的残留分析方法并研究其在葡萄和土壤中的消解动态与残留水平。[方法]采用硫化钠对喹啉铜解络合后,甲醇涡旋提取,分散固相萃取净化,结合高效液相色谱串联质谱(HPLC-MS/MS)检测,建立了葡萄和土壤中喹啉铜的残留分析方法。采用所建方法研究了喹啉铜在山东和河北2地葡萄和土壤中的消解动态和残留水平。[结果]在0.05~2.00 mg/L质量浓度范围内不同基质中喹啉铜解络产物8-羟基喹啉的线性关系良好,线性系数均大于0.999。在0.05、2.00、5.00 mg/kg添加质量分数水平下,喹啉铜在葡萄中的平均回收率为86.87%~98.24%,相对标准偏差(RSD)为2.80%~6.48%;在0.03、2.00、5.00 mg/kg添加质量分数水平下,喹啉铜在土壤中的平均回收率为82.71%~88.45%,相对标准偏差(RSD)为3.17%~10.08%。以最小添加质量分数确定喹啉铜在土壤和葡萄中的定量限(LOQ)分别为0.03、0.05 mg/kg。田间残留试验结果表明:喹啉铜在葡萄中降解半衰期为6.5~10.6 d,在土壤中降解半衰期为20.1~32.5 d,2年2地试验表明:末次施药7 d后,2年2地葡萄中喹啉铜的最终残留量0.068~1.53 mg/kg,土壤中喹啉铜的最终残留量0.031~0.36 mg/kg。[结论]建议使用防治效果更好的53%喹啉·噻灵可湿性粉剂防治葡萄黑痘病,有效成分用量331.28~496.88 g a.i./hm^(2),施药4次,安全间隔期7 d。试验为喹啉铜在葡萄上的安全使用提供了理论依据。[Aims]This paper aims to study the dissipation and residue levels of oxine-copper in grape and soil.[Methods]After being decomplexated with sodium sulfide,the residues of oxine-copper in grape and soil were extracted with methanol by vortexing,and cleaned up with primary secondary amine by dispersive solid phase extraction,thereafter,determined with high performance liquid chromatography-mass spectrometry(HPLC-MS/MS).The dissipation and residue levels of oxine-copper in grape and soil in Shandong and Hebei provinces were investigated with the established method.[Results]Good linearity between the mass concentration of the oxine-copper decomplexation product8-hydroxy-quinoline and the corresponding peak area was achieved from 0.05 to 2.00 mg/L,with a coefficient of determination higher than 0.999.At the fortification levels of 0.05,2.00 and 5.00 mg/kg,the recoveries of oxine-copper in grape ranged from 86.87 to 98.24%,with the relative standard deviation(RSD)was 2.80-6.48%.At the fortification levels of 0.03,2.00 and 5.00 mg/kg,the recoveries oxine-copper in soil were 82.71-88.45% with the RSD of 3.17-10.08%.The limit of quantitation(LOQ),which was defined as the lowest spiked concentration with satisfactory recovery,of oxine-copper in soil and grape were 0.03 and 0.05 mg/kg,respectively.The results showed that the half-lives of oxine-copper in grape and soil were 6.5-10.6 and 20.1-32.5 d,respectively.The terminal residues of oxine-copper in grapes and soil with the pre-harvest interval of 7 days were 0.068-1.53,0.031-0.36 mg/kg,respectively.[Conclusions]A more effective quinoline·thialin 53% wettable powder is recommended for control of grape black pox with the dosage of 331.28-496.88 g a.i./ha with spraying application not more than 5 times and preharvest interval 7 d.The experiment results provide data support for the safe use of oxine-copper in grape.

关 键 词：喹啉铜 葡萄 高效液相色谱-串联质谱法 土壤 降解 残留 

分 类 号：TQ450.2[化学工程—农药化工]