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

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.

Measuring the antibiotics and pesticides in honeys by ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS)

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.