HPLC法和UPLC-MS/MS法检测马铃薯中调环酸钙残留量  

Residues of prohexadione calcium in potatoes determined by HPLC and UPLC-MS/MS

作　　者：刘秀[1] 席涵 唐兴 曾利红 侯连根 金晨钟[1] 欧晓明[2] LIU Xiu;XI Han;TANG Xing;ZENG Lihong;HOU Liangen;JIN Chenzhong;OU Xiaoming(Key Laboratory of Green Control of Crop Pests in Hunan Higher Education,Hunan Provincial Collaborative Innovation Center for Field Weeds Control,Hunan University of Humanities,Science and Technology,Loudi 417000,Hunan,China;National Engineering Research Center for Agrochemicals/Hunan Province Key Laboratory for Agrochemicals,Hunan Research Institute of Chemical Industry,Changsha 410014,China)

机构地区：[1]湖南人文科技学院农作物有害生物绿色防控湖南省高校重点实验室,农田杂草防控技术与应用湖南省2011协同创新中心,湖南娄底417000 [2]湖南化工研究院国家农药创制工程技术研究中心/湖南省农用化学品重点实验室,长沙410014

出　　处：《农药》2024年第9期662-667,共6页Agrochemicals

基　　金：“农药无害化应用”湖南省普通高等学校科技创新团队(2023年);湖南省自然科学基金区域联合基金项目(2024JJ7252和2023JJ50082);湖南省教育厅科学研究重点项目(22A0614)。

摘　　要：[目的]旨在建立可靠的高效液相色谱(HPLC)和超高效液相串联质谱(UPLC-MS/MS)检测方法,用于检测调环酸钙在马铃薯中的残留量,并探究调环酸钙在马铃薯中的消解动态规律和最终残留量。[方法]HPLC法测定马铃薯样品中调环酸钙残留,首先使用乙腈-0.1%磷酸水溶液振荡提取,经C_(18)柱净化后采用带DAD检测器的HPLC进行检测。UPLC-MS/MS法测定马铃薯样品中调环酸钙残留,首先使用乙腈-0.1%甲酸水溶液振荡提取,经C_(18)柱净化后进行UPLC-MS/MS检测。进一步探究了在不同施药时间下马铃薯中调环酸钙的消解动态规律和最终残留量。[结果]HPLC法测定马铃薯中添加0.05~5.0 mg/kg调环酸钙时,平均添加回收率为75%~91%,相对标准偏差(RSD)为1.0%~7.0%,定量限(LOQ)为0.05 mg/kg;UPLC-MS/MS测定马铃薯中添加0.01~1.0 mg/kg调环酸钙时,平均添加回收率为82%~90%,RSD为3.0%~12.0%,LOQ为0.01 mg/kg。试验采用的HPLC法和UPLC-MS/MS法能够检测调环酸钙,且具有较高的准确性和灵敏度。进一步研究表明调环酸钙在马铃薯中的残留消解动态不符合一级动力学方程,且有最终残留量积累,检出的最大值为0.1131 mg/kg,低于韩国规定的最大残留限量值0.2 mg/kg。[结论]建立了马铃薯中调环酸钙的HPLC和UPLC-MS/MS检测方法,且灵敏度、准确度及精密度均符合农药残留分析要求。马铃薯中调环酸钙的最终残留量低于韩国最大残留限量,为我国调环酸钙在马铃薯上的使用及最大残留限量的制定提供了参考依据。[Aims]The aim of this study is to establish reliable high-performance liquid chromatography(HPLC)and ultra-performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS)methods for detecting prohexadione calcium residues and investigate its degradation dynamics and final residue levels in potatoes.[Methods]For the HPLC method,potato samples were extracted with a mixture of acetonitrile and 0.1%of phosphoric acid aqueous solution and purified by C_(18)column,and then analyzed by HPLC with a DAD detector.Furthermore,we also explored the UPLC-MS/MS analysis method,where potato samples were extracted with a mixture of acetonitrile and 0.1%of formic acid aqueous solution,purified by C_(18)column,and then analyzed with UPLC-MS/MS.At last,we explored the residual degradation dynamics and final residue of prohexadione calcium in potatoes under different application times.[Results]For the HPLC detection method,within the concentration range of 0.05 to 5.0 mg/kg of prohexadione calcium added into potatoes,the average recovery rate was 75%to 91%,with a relative standard deviation(RSD)of 1.0%to 7.0%,and a limit of quantification(LOQ)of 0.05 mg/kg.For the UPLC-MS/MS detection method,within the concentration range of 0.01 to 1.0 mg/kg of prohexadione calcium added into potatoes,the average recovery rate was 82%to 90%,with an RSD of 3.0%to 12.0%,and an LOQ of 0.01 mg/kg.The results indicated high accuracy and sensitivity of the two detection methods.Additionally,the results showed that the residual degradation dynamics of prohexadione calcium in potatoes did not conform to the first-order kinetic equation,and the accumulated final residues were detected,with the maximum value of 0.1131 mg/kg which was lower than the maximum residue limit(MRL)of 0.2 mg/kg stipulated in South Korea.[Conclusions]HPLC and UPLC-MS/MS methods for the determination of prohexadione calcium in potato were established,and their sensitivity,accuracy and precision were in accordance with the requirements of pesticide residues analysis.The final res

关 键 词：调环酸钙 HPLC UPLC-MS/MS 残留 马铃薯 

分 类 号：TQ450.2[化学工程—农药化工]