凝胶渗透色谱-气相色谱-质谱法测定人乳中卤代有机化合物

Determination of Halogenated Organic Compounds in Human Milk by Gel Permeation Chromatography-Gas Chromatography-Mass Spectrometry

建立了用凝胶渗透色谱(GPC)去脂、气相色谱-负化学电离源-质谱(GC-NCI-MS)测定人乳中多溴联苯醚(PBDEs)、德克隆(DP,包括syn-DP和anti-DP)、五溴甲苯(PBT)、六溴苯(HBB)和多氯联苯(PCBs)的方法。人乳样品中加入内标13C12-BDE-139、13C12-BDE-209、13C10-syn-DP、13C12-PCBs(13C12-CB-81,77,123,118,114,105,126,167,156,157,169,189),空白样品还额外加入PBT和HBB,经过加酸去蛋白质、液液萃取、GPC去脂、酸性硅胶柱净化后,定量测定。人乳样品中13C12-BDE-139、13C12-BDE-209、13C10-syn-DP、13C12-PCBs的加标回收率分别为112.9%±14.0%、99.3%±12.7%、80.5%±17.9%、64.6%±2.4%,空白样品中PBT和HBB的加标回收率分别为102.8%±18.0%和88.1%±14.4%,各卤代化合物检出限范围为0.33~333.3pg/m L。应用本方法对人乳样品进行检测,均没有检出CB-77,81,169、BDE-154,85、syn-DP、anti-DP。∑9PCBs(CB-123,118,114,105,126,167,156,157,189)、∑8PBDEs(BDE-28,47,100,99,153,183,190,209)、PBT、HBB浓度范围分别为:0.11~0.22、4.9~7.9、0.0037~0.0056和0.0053~0.021ng/m L。

The method, using Gel Permeation Chromatography( GPC) to remove lipid and using Gas Chromatography-Negative Chemical Ionization-Mass Spectrometry( GC-NCI-MS) to detect halogenated compounds such as polybrominated diphenylethers( PBDEs), polychlorinated biphenyls( PCBs), dechlorane plus( DP,including syn-DP and anti-DP),pentabromotoluene( PBT) and hexabromobenzene( HBB),was developed. The blank and human milk samples were spiked with13C12-BDE-139,13C12-BDE-209,13C10-syn-DP,13C12-PCBs(13C12-CB-81,77,123,118,114,105,126,167,156,157,169,189) as internal standard,also PBT,HBB were added into the blank samples. All the samples were dealt with hydrochloric acid to denature protein before extracting,then the lipid was mostly removed by GPC. Samples were further cleaned up by a silica / sulfuric acid column before determined. The recoveries of13C12-BDE-139,13C12-BDE-209,13C10-syn-DP,13C12-PCBs in human milk samples were 112. 9% ± 14. 0%,99. 3% ± 12. 7%,80. 5% ± 17. 9%,64. 6% ± 2. 4%,respectively,the recoveries of PBT and HBB in blank samples were 102. 8% ± 18. 0% and 88. 1% ± 14. 4%. The limits of detection of the halogenated organic compounds were ranged from 0. 33 ~ 333. 3 ng / m L. CB-81,77,169,BDE-154,85,syn-DP,anti-DP were not detected in any blank or human milk samples,the concentrations of ∑9PCBs( CB-123,118,114,105,126,167,156,157,189),∑8PBDEs( BDE-28,47,100,99,153,183,190,209),PBT,HBB were 0. 11 ~ 0. 22,4. 9 ~ 7. 9,0. 0037 ~ 0. 0056 and 0. 0053 ~ 0. 021 ng / m L,respectively.