花草茶中11种杀菌剂QuEChERS-超高效液相色谱-串联质谱快速测定法
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摘要
目的同时建立检测花草茶中11种杀菌剂的超高效液相色谱串联三重四极杆质谱(UPLC-MS/MS)测定法。方法粉碎均匀的花草茶样品经Qu EChERS试剂萃取,DisQuE净化,采用含有0.5%甲酸及乙腈为流动相进行梯度洗脱,经UPLC CORTES C18色谱柱(1.6μm,2.1×100 mm)分离,正离子模式,检测模式应用多反应监测(MRM),采用基质液配制标准系列,外标法定量。结果标准曲线范围为1.0～100.0 ng/ml时,11种杀菌剂检测得到了线性关系良好的回归方程,相关系数(r2)>0.990,检出限为0.10～1.00μg/kg,定量限为0.30～3.00μg/kg。测定回收率的样品3个添加水平分别为10、20、50μg/kg,得到78.39%～95.06%之间的回收率,1.8%～7.2%的相对标准偏差(RSD)。结论 QuEChERS-UPLC-MS/MS测定法能满足同时检测花草茶中11种杀菌剂残留的测定要求,具有操作简便、经济、快速的优点,同时具有良好的重现性、准确度和灵敏度。
[Objective] To establish a method for the determination of 11 fungicides in herbal tea by QuEChERS and ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS). [Methods]The samples were soaked with water and extracted with acetonitrile,then were extracted by QuEChERS and were purified by DisQuE. The analytes were separated on a UPLC CORTES C18 column(1.6 μm,2.1×100 mm) through a gradient elution using aqueous formic acid and acetonitrile as mobile phases. Positive electrospray ionization was used. Qualitative work was performed using select dynamic multiple reaction monitoring(MRM) mode. Quantization was performed using external standard method considering matrix effects. [Results]The correlation coefficients(r2) were greater than 0.990,which indicated that the linear dependence of the 11 fungicides were good in the range of 1.0-100.0 ng/ml. The limit of detection and limit of quantitation of all the 11 fungicides were 0.10-1.00 μg/kg and0.30-3.00 μg g/kg,respectively. with the sample addition level of 10,20 and 50 μg/kg,the recoveries were in the range of 78.39%-95.06% and the relative standard deviations(RSD) ranged from 1.8% to 7.2%. [Conclusion]QuEChERS-UPLC-MS/MS method has the advantages of rapidity,simple operation,economy,good reproducility,accuracy and sensitivity for the detection of the 11 fungicides residues in herbal tea.
[Objective] To establish a method for the determination of 11 fungicides in herbal tea by QuEChERS and ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS). [Methods]The samples were soaked with water and extracted with acetonitrile,then were extracted by QuEChERS and were purified by DisQuE. The analytes were separated on a UPLC CORTES C18 column(1.6 μm,2.1×100 mm) through a gradient elution using aqueous formic acid and acetonitrile as mobile phases. Positive electrospray ionization was used. Qualitative work was performed using select dynamic multiple reaction monitoring(MRM) mode. Quantization was performed using external standard method considering matrix effects. [Results]The correlation coefficients(r2) were greater than 0.990,which indicated that the linear dependence of the 11 fungicides were good in the range of 1.0-100.0 ng/ml. The limit of detection and limit of quantitation of all the 11 fungicides were 0.10-1.00 μg/kg and0.30-3.00 μg g/kg,respectively. with the sample addition level of 10,20 and 50 μg/kg,the recoveries were in the range of 78.39%-95.06% and the relative standard deviations(RSD) ranged from 1.8% to 7.2%. [Conclusion]QuEChERS-UPLC-MS/MS method has the advantages of rapidity,simple operation,economy,good reproducility,accuracy and sensitivity for the detection of the 11 fungicides residues in herbal tea.
引文
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[12]魏畅,傅红,郑俊超,等.QuEChERS-液质联用同步检测蘑菇中多菌灵等3种杀菌剂残留[J].中国食品学报,2016,16(11):189-193.
[13]朱松,袁晓晴,戴军,等.QuEChER/HPLC/DAD法同时检测果蔬中多种植物激素残留[J].分析测试学报,2017,36(4):513-518.
[14]秦富,邓全道,李涌,等.QuEChERS-高效液相色谱-串联质谱法测快速定罗汉果中55种杀菌剂[J].色谱,2017,35(11):1129-1136.
[15]叶江雷,金贵娥,吴云飞,等.QuEChERS法提取净化结合气-质联法快速检测茶叶中农药残留[J].食品科学,2013,34(12):265-271.
[16]孙玉玉,孙浩,董振霖,等.QuEChERS-GC-MS/MS法测定大米中20种农药残留[J].食品研究与开发,2015,36(3):121-125.
[17]王秀国,闫晓阳,宋超,等.QuEChERS高效液相色谱-质谱测定烟叶与土壤中壬菌铜法残留[J].分析测试学报,2015,34(1):91-95.
[18]平华,马智宏,王纪华,等.分散固相萃取超高效液相色谱串联质谱法同时测定土壤中12种除草剂残留[J].农药,2015,54(2):122-125.
[2]张云琳,倪蕾. 8种花草茶中六六六、滴滴涕农药残留量测定[J].海峡预防医学杂志,2013,19(4):53-54.
[3]翁贵凤.气相色谱法测定花草茶中3种农药残留量[J].农业工程,2014,4(4):86-88.
[4]黄霞,宋莹,张耀海,等.QuEChERS-GC-MS快速检测柑橘中50种农药残留[J].食品科学,2011,32(18):268-273.
[5]李芳,张静,杨中,等.QuEChERS液质联用法测定蔬菜中17种农药残留[J].吉林农业科学,2013,38(3):93-96.
[6]谢建军,陈捷,李菊,等.改良QuEChERS结合气相色谱串联质谱测定果蔬中20种杀菌剂[J].食品安全质量检测学报,2013,4(1):82-88.
[7]张雪莲,张耀海,焦必宁.气相色谱-串联质谱法结合QuEChERS方法快速检测柑橘中52种农药多残留[J].食品科学,2013,34(6):152-155.
[8]李海涛,周丽,张景然,等.QuEChERS-LC-MS/MS法检测苹果中105种农药残留[J].广东化工,2015,42(23):200-201.
[9]盖喜乐,催新仪.应用Qu EChERS方法测定苹果中有机磷[J].天津农业科学,2015,21(8):105-108.
[10]曹慧,陈小珍,张东雷,等.QuEChERS-GC-MS/MS测定饮料中邻苯二甲酸酯[J].食品研究与开发,2016,37(10):120-123.
[11]樊聪明,孙慧,谢炯炯,等.QuEChERS法测定草莓中吡虫啉农药残留[J].农业与技术,2016,36(16):6-7.
[12]魏畅,傅红,郑俊超,等.QuEChERS-液质联用同步检测蘑菇中多菌灵等3种杀菌剂残留[J].中国食品学报,2016,16(11):189-193.
[13]朱松,袁晓晴,戴军,等.QuEChER/HPLC/DAD法同时检测果蔬中多种植物激素残留[J].分析测试学报,2017,36(4):513-518.
[14]秦富,邓全道,李涌,等.QuEChERS-高效液相色谱-串联质谱法测快速定罗汉果中55种杀菌剂[J].色谱,2017,35(11):1129-1136.
[15]叶江雷,金贵娥,吴云飞,等.QuEChERS法提取净化结合气-质联法快速检测茶叶中农药残留[J].食品科学,2013,34(12):265-271.
[16]孙玉玉,孙浩,董振霖,等.QuEChERS-GC-MS/MS法测定大米中20种农药残留[J].食品研究与开发,2015,36(3):121-125.
[17]王秀国,闫晓阳,宋超,等.QuEChERS高效液相色谱-质谱测定烟叶与土壤中壬菌铜法残留[J].分析测试学报,2015,34(1):91-95.
[18]平华,马智宏,王纪华,等.分散固相萃取超高效液相色谱串联质谱法同时测定土壤中12种除草剂残留[J].农药,2015,54(2):122-125.