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浙江大学学报（理学版）
浙江大学学报（理学版）  2018, Vol. 45 Issue (3): 330-342    DOI: 10.3785/j.issn.1008-9497.2018.03.010
化学     
超高效液相色谱-串联质谱法测定蜂蜜中抗生素和农药浓度
汪建妹, 杨华, 曾银欢, 吴俐勤, 李锐, 袁玉伟, 钱鸣蓉
浙江农业科学院 农产品质量标准研究所, 浙江 杭州 310014
Measuring the antibiotics and pesticides in honeys by ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS)
WANG Jianmei, YANG Hua, ZENG Yinhuan, WU Liqin, LI Rui, YUAN Yuwei, QIAN Mingrong
Institute of Quality Standards for Agricultural Products, Zhejiang Academy of Agricultural Sciences, Hangzhou 310014, China
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摘要： 基于快速有效的基质净化方法，结合超高效液相色谱-串联质谱技术，建立了测定蜂蜜中39种抗生素及25种农药的检测方法.蜂蜜样品经乙腈+水（v/v=8：2）提取，用PRiME HLB净化，超高效液相色谱-串联质谱（ultra-performance liquid chromatography tandem mass spectrometry，UPLC-MS/MS）分析测定，通过多反应监测模式（MRM）分析目标化合物，并进行基质标准曲线定量.在测定浓度范围内呈良好线性关系，相关系数大于0.99；农兽药的检出限为0.02~3.8 μg·kg-1，定量限为0.1~11.5 μg·kg-1；在3档浓度的添加回收实验中，39种抗生素的回收率在72%~119%内，25种农药的回收率在72%~115%内，相对标准偏差均小于15%.随机抽取浙江市场上在售的52份蜂蜜样进行检测分析和膳食暴露评估，共检出罗红霉素、诺氟沙星和环丙沙星3种抗生素，检出率分别为2.6%，8.6%和3.9%，浓度分别为59.6~214.4，4.7~1 486.3和5.9~215.1 μg·kg-1.膳食暴露评估结果表明，蜂蜜中抗生素残留对10岁以下组群的风险高于其他组群、女性消费者高于男性消费者；% ADI<100，说明膳食暴露评估风险水平尚可接受.因在计算中存在诸多不确定性因素，对组群的风险评估尚需进一步分析.
关键词： 抗生素;  农药;  蜂蜜;  UPLC-MS/MS;  风险评估    
Abstract: A rapid and effective matrix cleanup method was used for the simultaneous detection of 39 antibiotics and 25 pesticides in honey samples by UPLC-MS/MS. After honey was extracted by acetonitrile + water (v/v=8:2), the extract was quickly purified by PRiME HLB and analyzed by UPLC-MS/MS. The qualitative and quantitative analysis of the compounds was carried out under the multi-reaction monitoring (MRM) mode in matrix-matched standard method. It shows a good linearity (r2>0.99) for all compounds. The LOD values of antibiotics and pesticides were in the range of 0.02~3.8 μg·kg-1. The LOQs of antibiotics and pesticides were in the range of 0.1~11.5 μg·kg-1. At the three spiking levels, the recoveries ranged in 72%~119% and 72%~115% for antibiotics and pesticides, respectively, with the relative standard deviations less than 15%. The method was used to analysis the honey samples that were on sale on the market in Zhejiang province. Three kinds of antibiotics (roxithromycin, norfloxacin and ciprofloxacin) were detected in 52 honey samples. The detection rate of roxithromycin, norfloxacin and ciprofloxacin is 2.6%, 8.6% and 3.9%. The corresponding concentrations were respectively 59.6~214.4, 4.7~1 486.3 and 5.9~215.1 μg·kg-1. The obtained data were then used to assess the potential health risks associated with a human when he/she is exposed to these drugs. The outcome indicates that the exposure of antibiotics in honey to children (below 10 year-old) is higher than that to the adults (above 10 year-old), and the risk of exposure to female consumers was higher than that to male consumers. Based on of the probabilistic assessment at high percentile (P99.9),% ADI of the dietary exposure assessment was below 100. Although, there is no risk in theory, but a more detailed study is required due to the great uncertainty in these calculations.
Key words: antibiotics    pesticides    honey    UPLC-MS/MS    risk assessment
收稿日期: 2017-12-06 出版日期: 2018-03-15
CLC:  O657  
基金资助: 浙江省财政厅专项（ZJNY2017001）.
通讯作者: 钱鸣蓉,ORCID:http://orcid.org/0000-0001-6011-872X,E-mail:qianmr@mail.zaas.ac.cn.     E-mail: qianmr@mail.zaas.ac.cn
作者简介: 汪建妹(1967-),ORCID:http://orcid.org/0000-0002-1126-0612,女,本科,实验师,主要从事畜产品质量安全研究.
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引用本文:

汪建妹, 杨华, 曾银欢, 吴俐勤, 李锐, 袁玉伟, 钱鸣蓉. 超高效液相色谱-串联质谱法测定蜂蜜中抗生素和农药浓度[J]. 浙江大学学报（理学版）, 2018, 45(3): 330-342.

WANG Jianmei, YANG Hua, ZENG Yinhuan, WU Liqin, LI Rui, YUAN Yuwei, QIAN Mingrong. Measuring the antibiotics and pesticides in honeys by ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS). Journal of Zhejiang University (Science Edition), 2018, 45(3): 330-342.

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https://www.zjujournals.com/sci/CN/10.3785/j.issn.1008-9497.2018.03.010    或    https://www.zjujournals.com/sci/CN/Y2018/V45/I3/330

[1] CUI X, ZHANG P, YANG X, et al. β-CD/ATP composite materials for use in dispersive solid-phase extraction to measure (fluoro)quinolone antibiotics in honey samples[J]. Analytica Chimica Acta, 2015, 878:131-139.
[2] LI Y, KELLEY R A, ANDERSON T D, et al. Development and comparison of two multi-residue methods for the analysis of select pesticides in honey bees, pollen, and wax by gas chromatography-quadrupole mass spectrometry[J]. Talanta, 2015, 140:81.
[3] KUJAWSKI M W, NAMIES'NIK J. Levels of 13 multi-class pesticide residues in polish honeys determined by LC-ESI-MS/MS[J]. Food Control, 2011, 22(6):914-919.
[4] 卢坤,童群义. 高效液相色谱法同时检测蜂蜜中的5类抗生素残留[J].分析测试学报,2011, 30(11):1320-1323. LU K, TONG Q Y. Simultaneous determination of 5 classes of antibiotics residues in honey using high performance liquid chromatography[J]. Journal of Instrumental Analysis,2011, 30(11):1320-1323.
[5] LI J, CHEN L, WANG X, et al. Determination of tetracyclines residues in honey by on-line solid-phase extraction high-performance liquid chromatography.[J]. Talanta, 2008, 75(5):1245-52.
[6] 周碧青,张金彪,陈万灵. 蜂蜜中8种有机磷农药残留量的气相色谱法测定[J]. 福建分析测试, 2012(6):9-12. ZHOU B Q, ZHANG J B,CHEN W L. Determination of eight organophosphorus pesticide residues in honey by gas chromatography[J]. Fujian Analysis &Testing, 2012(6):9-12.
[7] ZHENG W, PARK J A, ABD El-ATY A M, et al. Development and validation of modified QuEChERS method coupled with LC-MS/MS for simultaneous determination of cymiazole, fipronil, coumaphos, fluvalinate, amitraz, and its metabolite in various types of honey and royal jelly[J]. J Chromatogr B Analyt Technol Biomed Life Sci, 2018, 1072:60-69. DOI:10.1016/j.jchromb-2017.11.011.
[8] DEBAYLE D, DESSALCES G, GRENIER-LOUSTALOT M F. Multi-residue analysis of traces of pesticides and antibiotics in honey by HPLC-MS-MS[J]. Analytical & Bioanalytical Chemistry, 2008, 391(3):1011-1020.
[9] SHENDY A H, AL-GHOBASHY M A, GAD ALLA S A, et al. Development and validation of a modified QuEChERS protocol coupled to LC-MS/MS for simultaneous determination of multi-class antibiotic residues in honey[J]. Food Chemistry, 2016, 190:982-989.
[10] ORSO D, FLORIANO L, RIBEIRO L C, et al. Simultaneous determination of multiclass pesticides and antibiotics in honey samples based on ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Food Analytical Methods, 2016, 9(6):1638-1653.
[11] 苗琼晨,聂晶,吴慧珍,等. QuEChERS净化-高效液相色谱-串联质谱法测定蜂蜜中农药及抗生素的含量[J]. 理化检验:化学分册, 2017, 53(7):745-752. MIAO Q C, NIE J, WU H Z, et al. Determination of Pesticides and antibiotics in honey by QuEChERS-HPLC-MS/MS[J]. Physical Testing and Chemical Analysis Part B:Chemical Analysis, 2017, 53(7):745-752.
[12] SHENDY A H, ALGHOBASHY M A, MOHAMMED M N, et al. Simultaneous determination of 200 pesticide residues in honey using gas chromatography-tandem mass spectrometry in conjunction with streamlined quantification approach[J]. Journal of Chromatography A, 2016, 1427:142.
[13] SHAMSIPUR M, YAZDANFAR N, GHAMBARIAN M. Combination of solid-phase extraction with dispersive liquid-liquid microextraction followed by GC-MS for determination of pesticide residues from water, milk, honey and fruit juice[J]. Food Chemistry, 2016, 204:289.
[14] 庄明亮,崔敬德,朱方群,等. 一种用微生物法检测蜂蜜中环丙沙星的尝试[J].中国蜂业,2013, 64(z1):122-122. ZHUANG M L,CUI J D,ZHU F Q, et al. An experiment on the detection of antibiotic ciprofloxacin in honey by TTC[J].Apiculture of China, 2013, 64(z1):122-122.
[15] 刘津涛. 四环素酶联免疫检测方法的研究[D]. 天津:天津科技大学, 2012. LIU J T. Study on an Enzyme-Linked Immunosorbent Assay for the Detection of Tetracycline[D]. Tianjin:Tianjin University of Science&Technology, 2012.
[16] 王兴如,钟文英,李周敏,等. 微孔板生物芯片测定蜂蜜中四环素残留方法的研究及应用[J]. 药物分析杂志, 2015(7):1240-1244. WANG X R, ZHONG W Y, LI Z M, et al. Visual microplate biochip for determination of tetracycline residues in honey[J]. Chinese Journal of Pharmaceutical Analysis, 2015(7):1240-1244.
[17] 冯强. 浙江省
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