目的 建立QuEChERS-气相色谱-串联质谱(QuEChERS-GC-MS/MS)法快速测定地黄中菲(Phe)、蒽(Ant)、荧蒽(Flua)、芘(Pyr)、苯并[a]蒽(BaA)、艹屈(Chr)、苯并[b]荧蒽(BbF)、苯并[k]荧蒽(BkF)、苯并[a]芘(BaP)、茚并[1,2,3-c,d]芘(IcdP)、二苯并[a,h]蒽(DahA)、苯并[g,h,i]芘(BghiP)的含量.方法 正己烷超声提取后,提取液经PSA、C18粉末净化,氮吹浓缩后进行测定.分析采用DB-5MS石英毛细管柱(30 m×0.25 mm,0.25 μm);体积流量 1.5 mL/min;电子轰击离子源;多反应监测模式.结果 12 种多环芳烃在 1～32 ng/mL范围内线性关系良好(R2＞0.999),平均加样回收率70.4%～108.6%,RSD 0.8%～7.5%.在23 批样品中均检出多环芳烃,含量范围 32.7～3 628.9 μg/kg.结论 该方法简便快速,实用性强,适合地黄中多环芳烃的定量分析.

Objective: The purpose of this study was to systematically establish a gas chromatography-mass spectrometry (GC-MS/MS) analysis method for polycyclic aromatic hydrocarbons in Spirulina, and empirically analyze the new risk of polycyclic aromatic hydrocarbons found in Spirulina. Method: The polycyclic aromatic hydrocarbons of the sample were extracted twice with n-hexane ultrasonically, purified by QuEChERS, and tested after being concentrated by nitrogen blowing. Qualitative and quantitative: Separation using DB-5 MS capillary chromatographic column, multiple reaction monitoring mode (MRM) combined with matrix-matched external standard method for analysis. Results: The recovery rate was 68.8%～101.9%, the relative standard deviation was 1.8%～8.4% (n=6), the correlation coefficient of the equation reached above 0.999 within the linear range of 1～32 ng/mL, and the limit of quantitative (LOQ) was 2 μg/kg. Polycyclic aromatic hydrocarbons were detected in all 69 commercially available Spirulina samples, with the content in the range of 2.4 μg/kg to 3491 μg/kg. Conclusion: The QuEChERS detection method for 15 polycyclic aromatic hydrocarbons in Spirulina established in this paper is fast, accurate and highly sensitive, and can provide scientific technical support for daily supervision. It is necessary to pay attention to the risk of polycyclic aromatic hydrocarbons in Spirulina products, and further identify the source of pollution to establish prevention and control measures.

基于GB 5009.191-2016《食品安全国家标准食品中氯丙醇及其脂肪酸酯含量的测定》,对3-氯-1,2-丙二醇脂肪酸酯和2-氯-1,3-丙二醇脂肪酸酯及其内标绝对响应值较低、多个实验室间数据差异较大等问题进行了研究,重点对正己烷、不同酯键断裂试剂和反应时间进行了验证和优化.结果 表明:正己烷对测试结果无影响,最佳的酯键断裂试剂为0.5 mol/L甲醇钠-甲醇溶液,最佳酯键断裂反应时间为2 min.通过国际比对和多品牌标准品比较,确定了多个实验室间数据差异较大原因主要来自于内标物质的纯度差异以及标准曲线内标物质与样品中加入的内标物质不同.建议样品测试时,应尽可能使标准曲线使用的标准物质及内标物质与样品中添加的内标物质相同,并同法处理,从而提高数据准确性.

目的 建立气相色谱-串联质谱法(gas chromatography-tandem mass spectrometry,GC-MS/MS)测定含螺旋藻产品中多环芳烃(polycyclic aromatic hydrocarbons,PAHs)残留量的方法,并以此法探究市售含螺旋藻产品中以苯并(a)蒽 ?、、苯并(b)荧蒽和苯并(a)芘为代表的多环芳烃污染状况.方法 样品采用正己烷超声提取,经QuEChERS净化,选择DB-5 MS毛细管色谱柱,在多反应监测(multiple reaction monitoring,MRM)模式下采用基质匹配外标法定量.采用4种多环芳烃总含量(PAH4)和苯并(a)芘含量进行双指标分析,并结合摄入量对市售含螺旋藻产品中多环芳烃污染情况进行分析.结果 4种化合物在1～32μg/L的范围内具有良好的线性关系,相关系数r2>0.995,方法定量限4μg/kg,平均回收率为64.1％～102.0％,相对标准偏差(relative standard deviations,RSD)为2.2％～6.4％(n=6).75个受试样本的多环芳烃检出率为76％,检出的4种多环芳烃含量范围为4.1～916.0μg/kg.在苯并(a)芘含量大于50μg/kg时,苯并(a)芘含量与PAH4含量之间呈现明显的正相关,但在低于50μg/kg时,两者未显示出相关性.结论 建立的方法准确度高,灵敏度好,适用于含螺旋藻产品中多环芳烃的检测.市售含螺旋藻产品中存在高水平多环芳烃污染的情况,可能对服用者产生安全风险.样品中苯并(a)芘与PAH4总量之间存在一定相关性,在高污染水平两者相关性明显,但在低污染水平苯并(a)芘不宜作为螺旋藻中多环芳烃污染的唯一指标.建议食品安全相关部门应加强风险防控,制定合理的控制规范、设立恰当的指标限量.