头发中多种新型有机污染物检测方法的建立

The establishment of a new method for the detection of emerging organic contaminants in hair

本研究基于超声提取-分散固相萃取技术,建立了同时分析头发中多溴联苯醚(PBDEs)、有机磷系阻燃剂(OPFRs)、全氟及多氟烷基化合物(PFASs)、邻苯二甲酸酯(PAEs)及其代谢物(mPAEs)等5类有机污染物的前处理方法.头发样品(0.1 g)研磨成粉/絮状后经4 mL正己烷:丙酮:乙酸乙酯:乙腈(1:1:1:1,V/V/V/V)混合溶液提取3次,加入20 mg无水硫酸钠(Na2SO4)和100 mg十八烷基硅烷键合硅胶(C18)净化除杂,氮吹浓缩后分别采用GC-MS、GC-MS/MS和LCMS/MS进行分析.实验采用内标法定量,所有目标化合物在其相应的质量浓度范围内线性关系良好,相关性系数大于0.995;5类化合物检出限介于0.042—364.7 ng·g^(−1),加标回收率在53.6%—138%之间,相对标准差及日内/间精密度均小于20%.采用该方法对广州市10例男性头发进行了检测,所有样品均检出全氟辛烷磺酸(PFOS)、邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二异丁酯(DIBP)、邻苯二甲酸二丁酯(DNBP)、邻苯二甲酸二(2-乙基)己酯(DEHP)、邻苯二甲酸单异丁酯(miBP)、邻苯二甲酸单(2-乙基己基)酯(mEHP)、磷酸三苯酯(TPHP)、磷酸三(2-乙基己基)酯(TEHP)、2-乙基己基二苯基磷酸酯(EHDPP)、磷酸三(2-氯乙基)酯(TCEP)、磷酸三(2-氯丙基)酯(TCIPP)及十溴联苯醚(BDE 209),检出浓度介于1.09—4951 ng·g^(−1)之间.该方法简单安全,有较高灵敏度和精确度,仅用少量样品和有机溶剂即可同步分析头发多种痕量新型有机污染物,可为人体多种有机污染物长期暴露研究提供技术参考.

In this study,a pretreatment method was established for the simultaneous analysis of polybrominated diphenyl ethers(PBDEs),organophosphorus flame retardants(OPFRs),perfluorinated and polyfluorinated alkyl compounds(PFASs),phthalate esters(PAEs)and their metabolites(mPAEs)in human hair based on ultrasonic extraction-dispersed solid phase extraction.Hair sample(0.1 g)was ground into powder/flocculent and then extracted with 4 mL hexane:acetone:ethyl acetate:acetonitrile(1:1:1:1,V/V/V/V)for three times,and 20 mg anhydrous sodium sulfate(Na2SO4)and 100 mg octadecyl bonded silica(C18)were added to purify and remove impurities.The extract was concentrated and reconstituted,and the target chemicals were analyzed by using GC-MS,GC-MS/MS and LC-MS/MS,respectively.The linearity of individual target chemicals was good in the corresponding concentration range,with correlation coefficient higher than 0.995.The detection limits of the target chemicals were 0.042—364.7 ng·g^(−1),the recoveries were 53.6%—138%,and the relative standard deviation and the intraday and interday precision were less than 20%.The developed method was applied to analyze target chemicals in 10 male hair samples.Perfluorooctane sulfonic acid(PFOS),dimethyl phthalate(DMP),diethyl phthalate(DEP),di-iso-butyl phthalate(DIBP),di-N-butyl phthalate(DNBP),dis(2-ethyl)hexyl phthalate(DEHP),mono-isobutyl phthalate(miBP),mono-(2-ethylhexyl)phthalate(mEHP),triphenyl phosphate(TPHP),tri2-ethylhexyl phosphate(TEHP),2-ethylhexyl diphenyl phosphate(EHDPP),tri(2-chloroethyl)phosphate(TCEP),tri(2-chloropropyl)phosphate(TCIPP)and decabromodiphenyl ether(BDE 209)were detected in all samples,with concentrations as 1.09—4951 ng·g^(−1).Only a small amount of hair sample and low volume of organic solvents were needed to simultaneously analyze a variety of trace emerging organic contaminants in hair,which can provide technical support for the study of long-term exposure to a variety of organic pollutants in human body.