Linear and Branched Perfluorooctane Sulfonate Isomers in Technical Product and Environmental Samples by In-Port Derivatization-Gas Chromatography-Mass Spectrometry
Linear and Branched Perfluorooctane Sulfonate Isomers in Technical Product and Environmental Samples by In-Port Derivatization-Gas Chromatography-Mass Spectrometry
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DOI：
10.1021/ac8027273
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发表时间：
2009-06-01
影响因子：
7.4
通讯作者：
Letcher, Robert J.
中科院分区：
文献类型：
--
作者：
Chu, Shaogang;Letcher, Robert J.
全氟辛烷磺酸（PFOS）作为一种环境污染物在全球被发现，在包括人类在内的暴露生物群中具有高度的生物蓄积性。然而，关于全氟辛烷磺酸同分异构体的环境信息缺乏，特别是在生物样品中，这需要适当的分析方法来识别和定量超痕量。在本研究中，开发了一种新的方法，结合固相萃取（SPE）蜡管清理和port衍生-气相色谱-质谱（GC/MS）来鉴定和定量测定全氟辛烷磺酸技术产品和环境相关生物样品中的线性全氟辛烷磺酸（L-PFOS）和支链（单三氟甲基和双三氟甲基）异构体。采用四丁基氢氧化铵（TBAH）在GC进样器中进行原位热解烷基化反应，生成丁基PFOS异构体衍生物。除l -全氟辛烷磺酸外，在该技术产品中还发现了10种支链全氟辛烷磺酸异构体。除了l -全氟辛烷磺酸外，支链全氟辛烷磺酸同分异构体的环境相关性还得到了证明：分别在五大湖和北极地区的代表性鲱鱼鸥和双冠鸬鹚蛋以及北极熊肝脏和血浆样本中存在六种支链和l -全氟辛烷磺酸。对于技术产品和生物群样品中的所有全氟辛烷磺酸异构体，该方法显示出高灵敏度，检测限（LOD）范围为0.05至0.25 ng/mL，但l -全氟辛烷磺酸的LOD为1.46 ng/mL。除L-PFOS （MDL = 6.87 ng/g w.w）外，生物样品的检出限（MDL）略高于lod，范围为0.09 ~ 0.46 ng/g湿重（w.w）。
Perfluorooctane sulfonate (PFOS) is found globally as an environmental contaminant and is highly bioaccumulative in exposed biota including humans. However, there is a dearth of environmental information on the isomeric profile of PFOS, especially in biological samples, which requires suitable analysis methods for the identification and quantification of ultratrace amounts. In the present study, a novel method was developed that incorporates clean up by solid-phase extraction (SPE) WAX cartridges and in-port derivatization-gas chromatography-mass spectrometry (GC/MS) to identify and quantitatively determine linear PFOS (L-PFOS) and branched (monotrifluoromethyl and bistrifluoromethyl) isomers in PFOS technical product and in environmentally relevant biological samples. Tetrabutylammonium hydroxide (TBAH) was used for derivatization via an in situ pyrolytic alkylation reaction that occurred in the GC injector and generated butyl PFOS isomer derivatives. In addition to L-PFOS, ten branched PFOS isomers were identified in the technical product. The environmental relevance of branched PFOS isomers in addition to L-PFOS was evidenced by the presence of six branched and L-PFOS in representative herring gull and double-crested cormorant egg, and polar bear liver and plasma samples from the Great Lakes and Arctic, respectively. For all PFOS isomers in the technical product and biota samples the method demonstrated high sensitivity with the limit of detection (LOD) ranging from 0.05 to 0.25 ng/mL, with exception of L-PFOS where the LOD was 1.46 ng/mL. For the biotic samples, the method detection limits (MDLs) were slightly higher than the LODs and ranged from 0.09 to 0.46 ng/g wet weight (w.w.) with exception of L-PFOS (MDL = 6.87 ng/g w.w.).