含螺旋藻产品中多环芳烃污染状况研究

Research on pollution status of polycyclic aromatic hydrocarbons in products containing Spirulina

中文关键词:  螺旋藻产品  多环芳烃  气相色谱-串联质谱法  双指标  苯并(a)芘  苯并(a)蒽  苯并(b)荧蒽  䓛

英文关键词:Spirulina products  polycyclic aromatic hydrocarbons  gas chromatography-tandem mass spectrometry  dual indicators  benzo(a)pyrene  benz(a)anthracene  benzo(b)fluoranthene  chrysene

中文摘要:

      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1~32 μg/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4 μg/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4.1~916.0 μg/kg。在苯并(a)芘含量大于50 μg/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50 μg/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。

英文摘要:

      Objective To establish a method for the determination of polycyclic aromatic hydrocarbons residues in Spirulina products by gas chromatography-tandem mass spectrometry (GC-MS/MS). It was used to investigate the pollution status of polycyclic aromatic hydrocarbons (PAHs) represented by benzo(a)anthracene, chrysene, benzo(b) fluoranthene and benzo(a)pyrene in commercial products containing Spirulina. Methods The samples were extracted with n-hexane ultrasonically, purified by QuEChERS, separated on DB-5 MS capillary column, detected under multiple reaction monitoring (MRM) mode and quantified based on matrix external standard method. Dual index of tobenzo(a)pyrene content and the total content of benzo(a)pyrene, benz(a)anthracene, benzo(b)fluoranthene and chrysene (PAH4) was applied to analyze the pollution status of polycyclic aromatic hydrocarbons in commercial Spirulina products combined with the intake. Results The 4 types of chemical compounds possessed good linearity in the range of 1-32 μg/L with correlation coefficients (r2) all above 0.995, the limits of quantitation were 4 μg/kg, the recoveries were in the range of 64.1%-102.0% with relative standard deviations (n=6) of 2.2%-6.4%. The detection rate of polycyclic aromatic hydrocarbons in 75 samples was 76%, and the content of 4 kinds of PAHs ranged from 4.1 to 916.0 μg/kg. There was an evident positive correlation between benzo(a)pyrene and PAH4 in the samples with high levels of benzo(a)pyrene (greater than 50 μg/kg), but there was no correlation between them with low levels of benzo(a)pyrene (lower than 50 μg/kg). Conclusion The method has high accuracy and good sensitivity, and is suitable for the detection of polycyclic aromatic hydrocarbons in products containing spirulina. High-level PAH pollution in commercial products containing Spirulina may pose a safety risk to users. There is a certain correlation between benzo(a)pyrene and PAH4 especially in the samples, the correlation is significant at high pollution levels, however, benzo(a)pyrene should not be used as the only indicator of PAHs in the samples with low levels of PAHs. Relevant departments of food safety should strengthen the risk prevention and control, formulate reasonable control specifications and set appropriate residues standards.