Abstract
Given their extensive production volumes and potential to form persistent perfluoroalkyl acids (PFAAs), there is concern surrounding the ongoing use of side-chain fluorinated polymers (SFPs) in consumer products. Targeted SFP quantification relies on matrix-assisted laser desorption ionization time-of-flight mass spectrometry, which can suffer from poor accuracy and high detection limits. Alternatively, total fluorine (TF)-based methods may be used, but these approaches report concentrations on a “fluorine equivalent” basis (e.g., fluorine per square meter in the case of textiles) and are incapable of elucidating structure or chain length. Here a new method for comprehensive characterization of SFPs is presented, which makes use of the total oxidizable precursor assay for fingerprint-based structural elucidation and combustion ion chromatography for TF quantification. When used in parallel, quantitative determination of SFPs (in units of mass of CnF2n+1 per square meter of textile) is achieved. Expressing SFP concentrations in terms of the mass of the side chain (as opposed to fluorine equivalents) facilitates estimation of both the structure and quantity of PFAA degradation products. As a proof of principle, the method was applied to six unknown SFP-coated medical textiles from Sweden. Four products contained C6-fluorotelomer-based SFPs (concentration range of 36–188 mg of C6F13/m2), one contained a C4-sulfonamide-based SFP (718 mg of C4F9/m2), and one contained a C8-fluorotelomer-based SFP (249 mg of C8F17/m2).
Highlights
Per- and polyfluoroalkyl substances (PFAS) make up a large and diverse group of mostly anthropogenic compounds that have been synthesized since the 1940s.1 The unique properties of perfluoroalkyl chains, including combined lipophobicity and hydrophobicity, have led to the extensive use of PFAS in industrial and consumer applications.[2]
Several PFAS, including perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA), have already been added to the United Nations Stockholm Convention on Persistent Organic Pollutants,[5] while others have been restricted in the European Union (i.e., C9−C14 perfluoroalkyl carboxylic acids)[6] or are under consideration for inclusion in the Stockholm Convention [i.e., perfluorohexanesulfonate (PFHxS)]
An untreated (i.e., side-chain fluorinated polymers (SFPs)-free) PA fabric (PA 6,6 made from hexamethylenediamine and adipic acid monomers each containing six carbons) with a durable rip-stop pattern with a 115 ± 5 g/m2 (60 ± 1 threads/cm warp and 33 ± 1 threads/cm weft) fabric surface density (FOV AB Sweden) was used for the in-house durable water repellent (DWR) pad-dry-cure finishing process[10] that is similar to industrial production processes
Summary
Per- and polyfluoroalkyl substances (PFAS) make up a large and diverse group of mostly anthropogenic compounds that have been synthesized since the 1940s.1 The unique properties of perfluoroalkyl chains, including combined lipophobicity and hydrophobicity, have led to the extensive use of PFAS in industrial and consumer applications.[2]. In addition to the three reference textiles, seven medical textiles were obtained from Stockholm Healthcare (Region Stockholm) These included one surgical drape (6A), four surgical gowns (12, 17A, 21, and R10), and one ambulance jacket (35A), all determined to contain an unknown fluoropolymer coating during initial screening experiments, as well as a fluorine-free surgical drape (1A), which was used as a control.
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