凝胶渗透色谱柱去脂-气相色谱-质谱法测定人血清中新型卤系阻燃剂

Determination of New Halogenated Flame Retardants in Human Serum by Gel Permeation Chromatography-Gas Chromatography-Mass Spectrometry

建立了凝胶渗透色谱(GPC)去脂,气相色谱-负化学电离源-质谱(GC-NCI-MS)法测定人血清中2,2',4,4',5,5'-六溴联苯(BB-153)、1,2-二(2,4,6-三溴苯氧基)乙烷(BTBPE)和德克隆(Dechlorane plus,DP,包括syn-DP和anti-DP)的方法。人血清样本加入内标13C12BB-153和13C10syn-DP,经蛋白质变性、脂肪提取、GPC去脂、酸性硅胶柱净化后,利用气相色谱-负化学电离源-质谱法测定样品中BB-153,BTBPE,syn-DP和anti-DP,监测离子分别为m/z 627.5,629.5,m/z 79,81以及m/z 652,654。结果表明,13 C12 BB-153和13 C10syn-DP的血清加标回收率分别为91.5%±8.9%和92.3%±8.1%,检出限为0.6～1.2 ng/g脂肪。应用本方法对人血样品进行测定,BB-153和BTBPE在所有样本中均未检出,syn-DP和anti-DP的浓度范围分别是0.7～9.2 ng/g脂肪和0.6～2.0 ng/g脂肪。

A gel permeation chromatography-gas chromatography-negative chemical ionization-mass spectrometry method（GPC-GC-NCI-MS） was developed for the determination of 2,2’,4,4’,5,5’-hexabromobiphenyl（BB-153）,1,2-bis（2,4,6-tribromophenoxy）ethane（BTBPE） and Dechlorane plus（DP） in human serum sample.The serum samples were spiked with 13C12BB-153 and 13C10syn-DP as surrogate internal standard before extracting,and the serum lipid was extracted and mostly removed by gel permeation chromatography.Samples were further cleaned up with a silica/sulfuric acid column.Identification and quantification of BB-153,BTBPE,syn-DP and anti-DP were performed by Gas chromatography-Negative chemical ionization-Mass spectrometry.The monitored ions were as follows：m/z 627.5 and 629.5 for BB-153;m/z 79 and 81 for BTBPE;m/z 652 and 654 for DP.The recoveries of 13C12BB-153 and 13C10syn-DP in serum samples were 91.5%±8.9% and 92.3%±8.1%,respectively.The limits of detection were from 0.6 to 1.2 ng/g lipid.BB-153 and BTBPE were not detected in all serum samples,and the concentrations of syn-DP and anti-DP were 0.7-9.2 ng/g lipid and 0.6-2.0 ng/g lipid,respectively.