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氟在新型消防员灭火防护服上的沉积

Disposition of Fluorine on New Firefighter Turnout Gear.

作者信息

Muensterman Derek J, Titaley Ivan A, Peaslee Graham F, Minc Leah D, Cahuas Liliana, Rodowa Alix E, Horiuchi Yuki, Yamane Shogo, Fouquet Thierry N J, Kissel John C, Carignan Courtney C, Field Jennifer A

机构信息

Department of Chemistry, Oregon State University, Corvallis, Oregon 97331, United States.

Department of Environmental and Molecular Toxicology, Oregon State University, Corvallis, Oregon 97331, United States.

出版信息

Environ Sci Technol. 2022 Jan 18;56(2):974-983. doi: 10.1021/acs.est.1c06322. Epub 2021 Dec 27.

Abstract

Firefighter turnout gear is essential for reducing occupational exposure to hazardous chemicals during training and fire events. Per-and polyfluoroalkyl substances (PFASs) are observed in firefighter serum, and possible occupational sources include the air and dust of fires, aqueous film-forming foam, and turnout gear. Limited data exist for nonvolatile and volatile PFASs on firefighter turnout gear and the disposition of fluorine on the individual layers of turnout gear. Further implications for exposure to fluorine on turnout gear are not well understood. Three unused turnout garments purchased in 2019 and one purchased in 2008, were analyzed for 50 nonvolatile and 15 volatile PFASs by liquid chromatography quadrupole time-of-flight mass spectrometry (LC-qTOF-MS) and gas chromatography-mass spectrometry (GC-MS), respectively. Particle-induced gamma ray emission (PIGE), a surface technique, and instrumental neutron activation analysis (INAA), a bulk technique, were used to measure total fluorine. Bulk characterization of the layers by pyrolysis-GC/MS (py-GC/MS) was used to differentiate fluoropolymer (e.g., PTFE) films from textile layers finished with side-chain polymers. The outer layer, moisture barrier, and thermal layers of the turnout gear all yielded measured concentrations of volatile PFASs that exceeded nonvolatile PFAS concentrations, but the summed molar concentrations made up only a small fraction of total fluorine (0.0016-6.7%). Moisture barrier layers comprised a PTFE film, as determined by py-GC-MS, and gave the highest individual nonvolatile (0.159 mg F/kg) and volatile PFAS (20.7 mg F/kg) as well as total fluorine (122,000 mg F/kg) concentrations. Outer and thermal layers comprised aromatic polyamide-based fibers (aramid) treated with side-chain fluoropolymers and had lower levels of individual nonvolatile and volatile PFASs. Equal concentrations of total fluorine by both PIGE and INAA on the outer and thermal layers is consistent with treatment with a side-chain fluoropolymer coating. New turnout gear should be examined as a potential source of firefighter occupational exposure to nonvolatile and volatile PFASs in future assessments.

摘要

消防员灭火防护服对于减少训练和火灾事故期间职业接触有害化学物质至关重要。在消防员血清中观察到了全氟和多氟烷基物质(PFASs),可能的职业来源包括火灾产生的空气和灰尘、水成膜泡沫以及灭火防护服。关于消防员灭火防护服上非挥发性和挥发性PFASs以及灭火防护服各层上氟的分布情况的数据有限。灭火防护服上氟暴露的进一步影响尚未得到充分了解。分别采用液相色谱四极杆飞行时间质谱(LC-qTOF-MS)和气相色谱-质谱(GC-MS)对2019年购买的三件未使用过的灭火防护服和2008年购买的一件灭火防护服进行了50种非挥发性和15种挥发性PFASs的分析。采用粒子诱导γ射线发射(PIGE,一种表面技术)和仪器中子活化分析(INAA,一种体相技术)来测量总氟含量。通过热解-气相色谱/质谱(py-GC/MS)对各层进行体相表征,以区分含氟聚合物(如聚四氟乙烯)薄膜与用侧链聚合物整理的纺织层。灭火防护服的外层、防潮层和隔热层测得的挥发性PFASs浓度均超过非挥发性PFASs浓度,但总的摩尔浓度仅占总氟的一小部分(0.0016-6.7%)。通过py-GC-MS确定,防潮层包含聚四氟乙烯薄膜,其非挥发性PFASs(0.159 mg F/kg)、挥发性PFASs(20.7 mg F/kg)以及总氟(122,000 mg F/kg)的个体浓度最高。外层和隔热层由用侧链含氟聚合物处理的芳族聚酰胺基纤维(芳纶)组成,其非挥发性和挥发性PFASs的个体含量较低。外层和隔热层通过PIGE和INAA测得的总氟浓度相等,这与用侧链含氟聚合物涂层处理一致。在未来的评估中,应将新的灭火防护服作为消防员职业接触非挥发性和挥发性PFASs的潜在来源进行检查。

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