超高效液相色谱-串联质谱法检测小龙虾中7种有机磷酸酯类阻燃剂

Determination of 7 kinds of organophosphate flame retardants in Procambarus clarkii by ultra performance liquid chromatography-tandem mass spectrometry

中文关键词:  小龙虾  有机磷酸酯类阻燃剂  超高效液相色谱-串联质谱法  同位素稀释内标法

英文关键词:Procambarus clarkii  organophosphate flame retardants  ultra performance liquid chromatography- tandem mass spectrometry  isotope dilution internal standard method

中文摘要:

      目的 建立超高效液相色谱-串联质谱法(ultra performance liquid chromatography-tandem mass spectrometry, UPLC-MS/MS)测定小龙虾中7种有机磷酸酯类阻燃剂(organophosphate flame retardants, OPFRs)的分析方法, 探究湖北省不同地区小龙虾中的OPFRs污染水平。方法 以二氯甲烷为提取溶剂, 采用超声辅助提取及固相萃取和QuEChERS技术进行前处理, 利用超高效液相色谱-串联质谱法定量分析小龙虾中7种OPFRs的含量。结果 该方法线性系数r2>0.999; 各物质定量限在0.08~4.68 μg/kg; 回收率在62.39%~113.31%; 相对标准偏差(relative standard deviations, RSDs)不大于9.70%。7种OPFRs在样品中检出率为100%, ∑OPFRs范围在34.09~41.45 μg/kg。其中, 磷酸三乙酯(triethyl phosphate, TEP)和磷酸三(2-氯丙基)酯[tris (1-chloro-2-propyl) phosphate, TCPP]总体占比最多, 达到13.43~18.14 μg/kg和9.72~13.67 μg/kg; 磷酸三(2-氯乙基)酯[tris (2-chloroethyl) phospate, TCEP]、磷酸三苯酯(triphenyl phosphate, TPHP)和磷酸三丁酯(tributyl phosphate, TnBP)次之, 达到3.08~3.83 μg/kg、2.86~5.30 μg/kg和2.63~3.63 μg/kg, 磷酸三丙酯(tripropyl phosphate, TPP)和磷酸三(2-丁氧基乙基)酯[tris (2-butoxyethyl) phosphate, TBEP]含量最少, 分别为0.17~0.20 μg/kg和1.28~1.75 μg/kg。结论 该方法准确、可靠、简便, 可用于小龙虾中有机磷酸酯类阻燃剂检测。湖北省小龙虾中OPFRs污染现象普遍存在。因OPFRs市场使用前景广阔, 后续仍需持续关注其在小龙虾中的含量变化。

英文摘要:

      Objective To establish a method for the determination of 7 kinds of organophosphate flame retardants (OPFRs) in Procambarus clarkii samples by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), and explore the levels of OPFRs pollution of Procambarus clarkii in different regions of Hubei Province. Methods With dichloromethane as the extraction solvent, ultrasound-assisted extraction, solid phase microextraction and QuEChERS were used for pre-treatment, the content of 7 kinds of OPFRs in Procambarus clarkii were quantitatively analyzed by UPLC-MS/MS. Results The linear coefficients r2＞0.999; the limits of quantification were 0.08?4.68 μg/kg; the recoveries were 62.39%?113.31%; and the relative standard deviations (RSDs) were less than 9.70%. The detection rate of 7 kinds of OPFRs in Procambarus clarkii samples was 100%, and the ∑OPFRs ranged from 34.09 to 41.45 μg/kg. Among them, triethyl phosphate (TEP) and tris (1-chloro-2-propyl) phosphate (TCPP) content accounted for the most in total, reaching 13.43?18.14 μg/kg and 9.72?13.67 μg/kg, tris (2-chloroethyl) phosphate (TCEP), triphenyl phosphate (TPHP) and tributyl phosphate (TnBP) were the next, reaching 3.08?3.83 μg/kg and 2.86?5.30 μg/kg and 2.63?3.63 μg/kg, tripropyl phosphate (TPP) and tris (2-butoxyethyl) phosphate (TBEP) content were the least, 0.17?0.20 μg/kg and 1.28?1.75 μg/kg, respectively. Conclusion The method is accurate, reliable and handy, and can be used for the detection of organophosphate flame retardants in Procambarus clarkii. The pollution of OPFRs in Procambarus clarkii in Hubei Province is widespread. Due to the broad prospect of OPFRs market, it is necessary to pay continuous attention to its content change in the future.