液相色谱–质谱联用测定咖啡中肟菌酯及代谢物残留
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摘要
【目的】建立一种同时测定咖啡中肟菌酯及其代谢物肟菌酸残留量的液相色谱–质谱检测方法。【方法】样品中待测农药组分采用含φ为1%乙酸的乙腈匀浆后超声提取,氯化钠和无水硫酸镁盐析及高速离心后,取上清液经C18分散固相萃取净化,采用液相色谱–质谱联用检测,ESI (+)电离和多反应监测(MRM)定量测定。【结果】添加肟菌酯质量分数为0.01～2.00 mg·kg–1时,肟菌酯在咖啡全果中的添加回收率为87.8%～106.7%,相对标准偏差(RSD)为1.3%～5.8%;在咖啡豆中添加回收率为83.2%～88.1%,RSD为2.0%～6.2%。肟菌酸在咖啡全果中的添加回收率为71.5%～106.0%,RSD为1.0%～6.1%;在咖啡豆中的添加回收率为84.4%～105.2%,RSD为1.0%～5.2%。肟菌酯及肟菌酸在咖啡中的最小检出量均为2.5×10–12 g,最低检出限均为0.01 mg·kg–1。【结论】该方法操作简便、快速和稳定,可以满足咖啡实际样品中肟菌酯及其代谢物肟菌酸的残留检测要求。
【Objective】To develop a method for determining trifloxystrobin and its metabolite trifloxystrobin acid simultaneously in coffee by liquid chromatography-mass spectrometry(LC-MS).【Method】The sample was ultrasonically extracted with acetonitrile(including φ=1% acetic acid), and salted out with sodium chloride and anhydrous magnesium sulfate. After high-speed centrifugation, the supernatant was purified by C18 dispersive solid-phase extraction and detected by LC-MS. The quantitative determination was conducted by ESI(+) ionization mode and multi-reaction monitoring(MRM).【Result】The recovery rates of trifloxystrobin in coffee fruits ranged from 87.8% to 106.7%, and the relative standard deviation(RSD) ranged from 1.3% to 5.8%when the additive amount of trifloxystrobin ranged from 0.01 to 2.00 mg·kg–1. The recovery rates of trifloxystrobin in coffee beans ranged from 83.2% to 88.1%, and the RSD ranged from 2.0% to 6.2%. The recovery rates of trifloxystrobn acid in coffee fruits ranged from 71.5% to 106.0%, and the RSD ranged from1.0% to 6.1%. The recovery rates of trifloxystrobn acid in coffee beans ranged from 84.4% to 105.2%, and the RSD ranged from 1.0% to 5.2%. The minimum detectable amounts of both trifloxystrobin and trifloxystrobin acid in coffee were 2.5 × 10–12 g, and the minimum limits of quantitation were 0.01 mg·kg–1.【Conclusion】This method is simple, rapid and stable, and can meet the requirement for detecting the residues of trifloxystrobin and its metabolites in coffee samples.
【Objective】To develop a method for determining trifloxystrobin and its metabolite trifloxystrobin acid simultaneously in coffee by liquid chromatography-mass spectrometry(LC-MS).【Method】The sample was ultrasonically extracted with acetonitrile(including φ=1% acetic acid), and salted out with sodium chloride and anhydrous magnesium sulfate. After high-speed centrifugation, the supernatant was purified by C18 dispersive solid-phase extraction and detected by LC-MS. The quantitative determination was conducted by ESI(+) ionization mode and multi-reaction monitoring(MRM).【Result】The recovery rates of trifloxystrobin in coffee fruits ranged from 87.8% to 106.7%, and the relative standard deviation(RSD) ranged from 1.3% to 5.8%when the additive amount of trifloxystrobin ranged from 0.01 to 2.00 mg·kg–1. The recovery rates of trifloxystrobin in coffee beans ranged from 83.2% to 88.1%, and the RSD ranged from 2.0% to 6.2%. The recovery rates of trifloxystrobn acid in coffee fruits ranged from 71.5% to 106.0%, and the RSD ranged from1.0% to 6.1%. The recovery rates of trifloxystrobn acid in coffee beans ranged from 84.4% to 105.2%, and the RSD ranged from 1.0% to 5.2%. The minimum detectable amounts of both trifloxystrobin and trifloxystrobin acid in coffee were 2.5 × 10–12 g, and the minimum limits of quantitation were 0.01 mg·kg–1.【Conclusion】This method is simple, rapid and stable, and can meet the requirement for detecting the residues of trifloxystrobin and its metabolites in coffee samples.
引文
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[10]CAO M,LI S,WANG Q,et al.Track of fate and primary metabolism of trifloxystrobin in rice paddy ecosystem[J].Sci Total Environ,2015,518/519:417-423.
[11]陈莉,贾春虹,朱晓丹,等.超高效液相色谱-电喷雾串联质谱法测定戊唑醇、肟菌酯及代谢物肟菌酸在西瓜和土壤中的残留[J].农药,2013,52(2):119-121.
[12]王林.肟菌酯及其代谢物在水稻和稻田中的残留研究[D].郑州:河南农业大学,2014.
[13]WANG L,LI W,LI P,et al.Residues and dissipation of trifloxystrobin and its metabolite in tomatoes and soil[J].Environ Monit Assess,2014,186(11):7793-7799.
[14]CHEN X X,XU J,LIU X G,et al.Simultaneous determination of trifloxystrobin and trifloxystrobin acid residue in rice and soil by a modified quick,easy,cheap,effective,rugged,and safe method using ultra high performance liquid chromatography with tandem mass spectrometry[J].J Sep Sci,2014,37(13):1640-1647.
[15]陈祎平,林昭华,梁振益,等.咖啡渣油脂的提取及其脂肪酸组成研究[J].食品科技,2005(12):84-86.
[16]FOTOPOULOU A.Matrix effect in gas chromatographic determination of insecticides and fungicides in vegetables[J].Int J Environ An Ch,2004,84(1/2/3):15-27.
[17]方旭元,夏高峰,石巧巧,等.QuEChERS-GC-MS法检测当归中9种除草剂残留[J].华南农业大学学报,2017,38(6):79-83.
[18]中华人民共和国农业部.农药残留试验准则:NY/T788-2004[S].北京:中国农业出版社,2004:5.
[2]WANG L,LI W,LI P,et al.Residues and dissipation of trifloxystrobin and its metabolite in tomatoes and soil[J].Environ Monit Assess,2014,186(11):7793-7799.
[3]ZHU J,DAI X J,FANG J J,et al.Simultaneous detection and degradation patterns of kresoxim-methyl and trifloxystrobin residues in citrus fruits by HPLC combined with QuEChERS[J].J Environ Sci Heal B,2013,48(6):470-476.
[4]LIKAS D T,TSIROPOULOS N G.Residue screening in apple,grape and wine food samples for seven new pesticides using HPLC with UV detection:An application to trifloxystrobin dissipation in grape and wine[J].Intern JEnviron Anal Chem,2009,89:857-869.
[5]周凤霞,陈存.气相色谱法同时测定蔬菜中醚菌酯和肟菌酯残留量的方法研究[J].农业环境与发展,2009(4):81-84.
[6]钱训,陈勇达,张少军.固相萃取-气相色谱测定马铃薯中肟菌酯残留量[J].食品安全质量检测学报,2016,14(2):535-539.
[7]CHEN J,LOO B,RAY C.Determination of trifloxystrobin and its metabolites in Hawaii soils by ASE-LC-MS/MS[J].J Agric Food Chem,2008,56(6):1829-1837.
[8]SANNINO A,BOLZONI L,BANDINI M.Application of liquid chromatography with electrospray tandem mass spectrometry to the determination of a new generation of pesticides in processed fruits and vegetables[J].J Chromatogr A,2004,1036(2):161-169.
[9]MOHAPATRA S.Residue levels and dissipation behaviors for trifloxystrobin and tebuconazole in mango fruit and soil[J].Environ Monit Assess,2015,187(3):95.
[10]CAO M,LI S,WANG Q,et al.Track of fate and primary metabolism of trifloxystrobin in rice paddy ecosystem[J].Sci Total Environ,2015,518/519:417-423.
[11]陈莉,贾春虹,朱晓丹,等.超高效液相色谱-电喷雾串联质谱法测定戊唑醇、肟菌酯及代谢物肟菌酸在西瓜和土壤中的残留[J].农药,2013,52(2):119-121.
[12]王林.肟菌酯及其代谢物在水稻和稻田中的残留研究[D].郑州:河南农业大学,2014.
[13]WANG L,LI W,LI P,et al.Residues and dissipation of trifloxystrobin and its metabolite in tomatoes and soil[J].Environ Monit Assess,2014,186(11):7793-7799.
[14]CHEN X X,XU J,LIU X G,et al.Simultaneous determination of trifloxystrobin and trifloxystrobin acid residue in rice and soil by a modified quick,easy,cheap,effective,rugged,and safe method using ultra high performance liquid chromatography with tandem mass spectrometry[J].J Sep Sci,2014,37(13):1640-1647.
[15]陈祎平,林昭华,梁振益,等.咖啡渣油脂的提取及其脂肪酸组成研究[J].食品科技,2005(12):84-86.
[16]FOTOPOULOU A.Matrix effect in gas chromatographic determination of insecticides and fungicides in vegetables[J].Int J Environ An Ch,2004,84(1/2/3):15-27.
[17]方旭元,夏高峰,石巧巧,等.QuEChERS-GC-MS法检测当归中9种除草剂残留[J].华南农业大学学报,2017,38(6):79-83.
[18]中华人民共和国农业部.农药残留试验准则:NY/T788-2004[S].北京:中国农业出版社,2004:5.