基于EMR-Lipid净化的鱼肉中多种有机磷阻燃剂超高效液相色谱-串联质谱分析法

Analytical method of organophosphorus flame retardants in fish by ultra-high performance liquid chromatography-tandem mass spectrometry based on EMR-Lipid purification

目的利用EMR-Lipid净化剂,优化样品前处理过程,结合超高效液相色谱-串联质谱技术,建立同时检测鱼肉中11种有机磷阻燃剂的方法。方法样品经0.5%甲酸乙腈溶液超声提取,使用商品化的增强型脂质去除产品EMR-Lipid进行除脂净化,用硫酸镁、N-丙基乙二胺、石墨化炭黑进一步去除共提取物,以乙腈和5 mmol/L甲酸铵溶液作为流动相梯度洗脱,目标物经ACQUITY UPLC■ BEH C_(18)色谱柱(100 mm×2.1 mm,1.7μm)分离,使用电喷雾离子源、正离子多反应监测模式进行检测,并分别对内标法与外标法定量进行了方法学评价,最终采用外标法定量。结果11种有机磷阻燃剂在0.5~50μg/L(磷酸三辛酯0.05~5μg/L)范围内线性关系良好,r均大于0.999。检出限为0.004~1.029μg/kg,定量限为0.012~3.094μg/kg。黄颡鱼低、中、高3个添加浓度水平的加标回收率为80.0%~111.2%,相对标准偏差均小于10%(n=6)。结论该方法准确可靠、灵敏度高、重现性好,覆盖的有机磷阻燃剂种类多,适用于鱼肉中痕量有机磷阻燃剂的检测。

OBJECTIVE A method for simultaneous determination of 11 kinds of organophosphorus flame retardants in fish was established by using the EMR-Lipid cleaning agent and ultra-high performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS).METHODS The samples were extracted by ultrasonic with 0.5% formic acid acetonitrile solution. The lipid removal product EMR-lipid was used for lipid purification. The co-extracts were further removed by magnesium sulfate, N-propyl ethylene amine(PSA) and graphitized carbon black(GCB) purification agent. The target compounds were separated on an ACQUITY UPLC■ BEH C_(18) column(100 mm×2.1 mm, 1.7 μm), detected by electrospray ionization(ESI) and positive ion multiple reaction monitoring mode, the internal standard method and external standard method are quantitatively evaluated, and external standard method was adopted.RESULTS The 11 kinds of organophosphorus flame retardants had a good linear relationship in the range of 0.5-50 μg/L(tris(2-ethylhexyl) phosphate 0.05-5 μg/L) with r>0.999. The limits of detection were 0.004-1.029 μg/kg and the limits of quantitation were 0.012-3.094 μg/kg. The average recoveries at three spiked levels(low, medium and high) were 80.0%-111.2% with the relative standard deviations all less than 10%(n=6).CONCLUSION The method could be used for the determination of trace organophosphorus flame retardants in freshwater fish with accurate and reliable result.