母乳中多种含卤持久性有机污染物的联合检测方法

Simultaneous Determination of Multiple Persistent Halogenated Compounds in Human Breast Milk

建立了母乳中多种含卤持久性有机污染物(POPs)的联合检测方法,目标化合物主要包括六溴环十二烷(HBCDs)、多溴联苯醚(PBDEs)、多氯联苯(PCBs)和有机氯农药(OCPs)等。样品的前处理采用液液萃取、凝胶渗透色谱(GPC)净化和固相萃取(SPE)等技术,目标化合物经气相色谱-质谱联用仪(GC-MS)、液相色谱-三重四极杆串联质谱联用仪(LC-MS/MS)和气相色谱-三重四极杆串联质谱联用仪(GC-MS/MS)等进行检测。样品通过GPC除去脂肪,然后经SPE柱进一步净化并进行多组分分离,极大程度地减小了生物样品中复杂基质的干扰,适合样品量相对较小的人体样本中多种超痕量POPs的分析。应用灵敏度高、选择性更好的GC-MS/MS对样品中的PCBs和OCPs等进行分析,进一步降低基质的干扰。方法经过小牛血清加标实验验证,稳定可靠。POPs的加标回收率分别为88.7%~98.8%(PBDEs),88.5%~92.5%(HBCDs),67.9%~82.3%(PCBs)和81.7%~116.1%(OCPs),方法检出限分别为0.13~1.8 pg/m L(PBDEs),0.31~1.2 pg/m L(HBCDs),0.22~1.4 pg/m L(PCBs)和0.20~1.5 pg/m L(OCPs)。采用本方法对潍坊地区20例母乳样品进行分析,结果显示,潍坊市母乳中HBCDs、PBDEs、PCBs、HCHs和DDTs的中值浓度分别为2.86、7.76、8.84、140和503 ng/g脂重,此浓度水平与国内其它地区人群相当。

A method was developed for simultaneous determination of multiple persistent organic pollutants(POPs)such as hexabromocyclododecanes(HBCDs),polybrominateddiphenyl ethers(PBDEs),polychlorinated biphenyls(PCBs),and organochlorine pesticides(OCPs)in human breast m ilk.The samplepretreatment procedures included liquid-liquid extraction,gel permeation chromatography(GPC),and solid phase extraction(SPE)clean-up.Gas chromatography coupled with mass spectrometry(GC-MS),liquidchromatography coupled with tandem mass spectrometry(LC-MS/M S),and gas chromatography coupled totandem mass spectrometry(GC-MS/MS)were applied in analysis of the target compounds.By using GPC toremove high-molecular mass lipids and SPE for further clean-up and separation of target compounds,theinterferences of biological matrix were greatly reduced.The developed sample pretreatment procedure wassuitable for the multi-component analysis of POPs in human samples which had very lower POPs concentrationsand smaller sample volumes.The simultaneous determination of PCBs and OCPs by GC-MS/MS exhibitedexcellent sensitivity and selectivity.The method recoveries were tested by spiked target compounds into fetalbovine serum samples.The recoveries were88.7%-98.8%for PBDEs,88.5%-92.5%for HBCDs,67.9%-82.3%for PCBs,and81.7%-116.1%for OCPs,respectively.Limits of detection of the methodwere in the range of0.13-1.8ng^L for PBDEs,0.31-1.2ng^L for HBCDs,0.22-1.4ng^L for PCBs,and0.20-1.5ng/L for OCPs,respectively.Finally,the developed method was applied in POPs analysis of20human breast milk samples from Weifang city.The results showed that the median concentrations of HBCDs,PBDEs,PCB,HCHS and DDTs were2.86,7.76,8.84,140and503ng^g lipid weight,respectively.Levels of the target compounds were comparable to those reported in human breast milk for general populationfrom other regions in China.