超高效液相色谱-四极杆-静电场轨道阱高分辨串联质谱法测定菜田土壤中甲拌磷及其代谢物残留量  

Determination of Phorate and Its Metabolites Residues in Vegetable Soil by Ultra-High Performance Liquid Chromatography-Quadrupole/Electrostatic Field Orbitrap High Resolution Tandem Mass Spectrometry

作　　者：韩梅[1] 焦颖 邱世婷[1] 侯雪[1] HAN Mei;JIAO Ying;QIU Shiting;HOU Xue(Laboratory of Risk Assessment for Agricultural Product(Chengdu),Ministry of Agriculture and Rural Affairs,Analytical and Testing Centre,Sichuan Academy of Agricultural Sciences,Chengdu 610066,China)

机构地区：[1]四川省农业科学院分析测试中心农业农村部农产品质量安全风险评估实验室(成都),成都610066

出　　处：《理化检验（化学分册）》2021年第11期1005-1010,共6页Physical Testing and Chemical Analysis(Part B:Chemical Analysis)

基　　金：国家蔬菜产品质量安全风险评估项目(GJFP2019009)。

摘　　要：建立了超高效液相色谱-四极杆-静电场轨道阱高分辨串联质谱法测定菜田土壤中甲拌磷及其5种代谢物(甲拌磷砜、甲拌磷亚砜、氧甲拌磷、氧甲拌磷砜、氧甲拌磷亚砜)残留量的方法。用含1%(体积分数)乙酸的乙腈溶液涡旋提取样品溶液中的目标物,加入氯化钠盐析后离心,上清液用乙二胺-N-丙基硅烷(PSA)净化,离心后过0.22μm有机滤膜。滤液中的目标物用CAPCELL CORE AQ型色谱柱固定,用不同体积比的含5 mmol·L^(-1)甲酸铵的0.1%(体积分数,下同)甲酸溶液和含0.1%甲酸和5 mmol·L^(-1)甲酸铵的甲醇溶液的混合溶液进行梯度洗脱。采用四极杆-静电场轨道阱高分辨串联质谱仪在加热电喷雾离子源正离子模式和平行反应监测(PRM)模式下检测,以基质匹配混合标准溶液系列制作工作曲线。结果显示,6种农药的质量浓度均在一定范围内与其对应的峰面积呈线性关系,测定下限(10S/N)为0.10~10μg·kg^(-1);对实际样品进行3个浓度水平的加标回收试验,回收率为90.2%~109%,测定值的相对标准偏差(n=5)为0.33%~10%;方法用于39个菜田土壤的分析,仅在两个样品中检出了目标物,未检出甲拌磷和氧甲拌磷,甲拌磷砜的检出量较高(8.09,8.55μg·kg^(-1))。A method for determination of residues of phorate and its 5 metabolites(phorate sulfone,phorate sulfoxide,phorate oxon,phoratoxon sulfone and phoratoxon sulfoxide)in vegetable soil by ultra-high performance liquid chromatography-quadrupole/electrostatic field orbitrap high resolution tandem mass spectrometry.Targets in sample were extracted with acetonitrile solution containing 1%(φ)acetic acid by vortex,and sodium chloride was added for salting out.After centrifuging,the supernatant was purified with ethylenediamine-N-propylsilane(PSA)and centrifuged subsequently.The supernatant was passed through 0.22μm organic filter membrane.The targets in the filtrate were fixed with a CAPCELL CORE AQ chromatographic column and mixed solutions composed of 0.1%(volume fraction,the same below)formic acid solution(containing 5 mmol·L^(-1) ammonium formate)and methanol solution(containing 0.1%fromic acid and 5 mmol·L^(-1) ammonium formate)with various volume ratios were used for gradient elution.Quadrupole/electrostatic field orbitrap high resolution tandem mass spectrometer was adopted for detection in the positive ion mode and parallel reaction monitoring(PRM)mode of the heated electrospray ion source,and mixed standard solution series prepared by matrix matching method were used for making the working curves.The results showed that mass concentrations of the 6 pesticides were in linear relationships with their corresponding peak areas within certain ranges,and lower limits of determination(10 S/N)were found in the range of 0.10-10μg·kg-1,the spiked recovery test was made on actual samples at 3 concentration levels,giving values of recovery in the range of 90.2%-109%,and RSDs(n=5)of the determined values were ranged from 0.33%to 10%,the proposed method was used for the analysis of 39 vegetable soils samples,and targets were detected in two samples,phorate and phorate oxon were not detected,and the detected amount of phorate sulfone was relatively high(8.09,8.55μg·kg-1).

关 键 词：超高效液相色谱-四极杆-静电场轨道阱高分辨串联质谱法 甲拌磷 甲拌磷代谢物 残留量 菜田土壤 

分 类 号：O657.63[理学—分析化学]