Determination of 32 Fungicide Residues in Tea by Gas Chromatography-Tandem Mass Spectrometry
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摘要: 建立了茶叶中32种杀菌剂类农药残留的气相色谱-串联质谱（GC-MS/MS）测定方法。样品经乙腈高速匀浆提取后，以N-丙基乙二胺（PSA）、石墨化碳（GCB）、C18为净化剂进行净化，在GC-MS/MS多反应离子监测（MRM）模式下进行测定，空白基质匹配标准曲线外标法定量。结果表明：27种杀菌剂在10~1 000 μg·L-1，5种杀菌剂在20~1 000 μg·L-1范围内具有良好线性关系，相关系数（R2）均大于0.99。方法检出限（S/N≥3）为0.1~8.1 μg·L-1，定量限（S/N≥10）为0.4~23.4 μg·L-1，平均添加回收率范围为70.4%~109.1%，相对标准偏差（RSD）3.4%~10.3%。该方法样品前处理操作简单、净化效果好、灵敏度高，具有良好的适用性，能够满足茶叶中多种杀菌剂残留测定分析的要求。Abstract: A gas chromatography-tandem mass spectrometry (GC-MS/MS) method was developed for detecting 32 fungicide residues in teas.The samples were extracted by acetonitrile under high-speed homogenization, purified with PSA, GCB, C18, and determined by GC-MS/MS in multi-reaction ion monitoring mode. Pesticide contents were determined by using the standard curves constructed with solutions of respective external standards. Linearity of the curves for 27 pesticides ranged from 10 μg·L-1 to 1 000 μg·L-1, and from 20 μg·L-1 to 1 000 μg·L-1 for the remaining 5 pesticides, with correlation coefficients greater than 0.99. The limits of detection were 0.1-8.1 μg·L-1 (S/N ≥ 3); and, those of quantification, 0.4-23.4 μg·L-1 (S/N ≥ 10). The average recovery rates were 70.4%-109.1%; and RSD (n=6) 3.4%-10.3%. The newly developed highly sensitive methodology that required simple pre-treatment and effective purification procedures appeared to be appropriate for the detection of fungicide residues in teas.
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Key words:
- fungicides /
- tea /
- GC-MS/MS
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图 1 32种杀菌剂(分为2组)混合标准溶液的总离子流色谱
Figure 1. TIC chromatogram of 32 pesticides in two groups
表 1 32种杀菌剂质谱信息
Table 1. Information on mass spectrum for 32 pesticides
表 2 不同提取溶剂对茶叶中32种杀菌剂的添加回收率
Table 2. Recovery rates on spiked 32 pesticides extracted with various solvents from tea
表 3 32种农药回收率及其检出限(LOD)、定量限(LOQ)、相对标准偏差(RSD)(n=6)
Table 3. Recoveries, limits of detection (LOD), limits of quantification (LOQ), and relative standard deviations (RSD) of 32 pesticides (n=6)
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[1] 刘长令.世界农药大全:杀菌剂卷[M].北京:化学工业出版社, 2005. [2] 陈佳鹏, 林刚, 周宝森.农药暴露与女性乳腺癌的相关性研究[J].中国公共卫生, 2004, 20(3):289-290. doi: 10.11847/zgggws2004-20-03-19 [3] 孔庆喜, 姚宝玉, 胡翠清.农药的致癌性评价[J].农药科学与管理, 2005, 26(7):26-28. http://www.cnki.com.cn/Article/CJFDTOTAL-NYKG200507009.htm [4] 李凤珍, 王捷, 姚宝玉, 等.氟吗啉原药大鼠慢性毒性与致癌实验[J].毒理学杂志, 2005, 19(3):260. http://cpfd.cnki.com.cn/Article/CPFDTOTAL-ZGDV200509001183.htm [5] PAN U K. A catalogue of lists of Pesticides identifying those associated with Particularly harmful health or enviromental impacts[J].Briefing Paper, 2005, (1):3. [6] 吴洁珊, 冯家望, 任永霞, 等.气相色谱测定柑橘中多种甲氧基丙烯酸酯类杀菌剂的残留量[J].农药, 2011, 50(10):754-766. doi: 10.3969/j.issn.1006-0413.2011.10.018 [7] YANG C, SALVADOR L, DOUGLAS G, et al. Determination of Multiresidue Pesticides in Botanical Dietary Supplements Using Gas Chromatography Triple-Quadrupole Mass Spectrometry (GC-MS/MS)[J].Journal of Agricultural and Food Chemistry, 2016, 64(31), 6125-6132. doi: 10.1021/acs.jafc.6b00746 [8] ANGIONI A, PORCU L, DEDOLA F. Determination of famoxadone, fenamidone, fenhexamid and iprodione residues in greenhouse tomatos[J]. Pest Management Science, 2012, 68(4):543-547. doi: 10.1002/ps.2287 [9] 丁立平, 蔡春平, 王丹红.改进的QuEChERS-气相色谱-质谱联用法测定蔬菜中的氟吗啉和烯酰吗啉残留[J].色谱, 2014, 32(8):849-854. http://www.cnki.com.cn/Article/CJFDTOTAL-SPZZ201408011.htm [10] LAGUNAS-ALLUE L, SANZ-ASENSIO J, MARTINEZ-SORIA M T.Comparison of four extraction methods for the determination of fungicide residues in grapes through gas chromatography mass spectrometry[J]. Journal of Chromatography A, 2012, 12(70):62-71. https://www.researchgate.net/publication/233772194_Comparison_of_four_extraction_methods_for_the_determination_of_fungicide_residues_in_grapes_through_gas_chromatography-mass_spectrometry [11] LI J J, LI Y Y, XU D L, et al. Determination of metrafenone in vegetables by matrix solid-phase dispersion and HPLC-UV method[J].Food Chemistry, 2017, 214(1):77-81. https://www.researchgate.net/publication/305275565_Determination_of_metrafenone_in_vegetables_by_matrix_solid-phase_dispersion_and_HPLC-UV_method [12] 周晓, 李小兰, 陈志燕, 等.高效液相色谱法测定水基胶黏剂中3种异噻唑啉酮类杀菌剂[J].色谱, 2015, 33(1):75-79. http://www.cnki.com.cn/Article/CJFDTOTAL-SPZZ201501015.htm [13] 李慧思, 黄超群, 蒋沁婷, 等.在线净化-液相色谱-串联质谱法测定茶叶中5种烟碱类农药残留[J].色谱, 2016, 34(3):263-269. http://www.cnki.com.cn/Article/CJFDTOTAL-SPZZ201603008.htm [14] 孙亚米, 吕燕, 吴银良.液相色谱-串联质谱法快速测定果蔬中16种新型酰胺类杀菌剂残留量[J].食品科学, 2015, 36(12):230-236. doi: 10.7506/spkx1002-6630-201512044 [15] DONG F S, CHEN X, LIU X G, et al. Simultaneous determination of five pyrazole fungicides in cereals, vegetables and fruits using 1iquid chromatography-tandem mass spectrometry[J].Journal of Chromatography A, 2012, 12(62):98-106. https://www.researchgate.net/publication/256742265_Simultaneous_determination_of_five_pyrazole_fungicides_in_cereals_vegetables_and_fruits_using_liquid_chromatographytandem_mass_spectrometry [16] ANNA G, IGNAZ J B, THOMAS P. Online solid phase extraction LC MS/MS method for the analysis of succinate dehydrogenase inhibitor fungicides and its applicability to surface water samples[J]. Analytical and Bioanalytical Chemistry, 2014, 406(25):6419-6427. doi: 10.1007/s00216-014-8073-4 [17] 王敬, 艾连峰, 马育松, 等.气相色谱-三重四极杆串联质谱法测定牛奶及奶粉中213种农药多残留[J].色谱, 2015, 33(11):1175-1185. http://www.cnki.com.cn/Article/CJFDTOTAL-SPZZ201511017.htm -
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