Occurrence and Degradation Potential of Fluoroalkylsilane Substances as Precursors of Perfluoroalkyl Carboxylic Acids.

Abstract

Polyfluoroalkylsilanes (PFASis) are a class of artificial chemicals with wide applications in surface coating, which arouse attention due to their hydrophobic/oleophobic properties and potential biological effects. In this study, a robust high-resolution mass spectrometry method through direct injection into a Fourier transform ion cyclotron resonance instrument was established, with the aid of CF2-scaled Kendrick mass defect analysis and isotope fine structure elucidation. The occurrence of 8:2 polyfluoroalkyl trimethoxysilane (8:2 PTrMeOSi) and 8:2 polyfluoroalkyl triethoxysilane (8:2 PTrEtOSi), as well as their cationic adducts, solvent substitutions, and other compound analogues, were identified in commercial antifingerprint liquid products. In the hydroxyl radical-based total oxidizable precursor assay, differential molar yields of products were observed with regard to varied PFASi carbon-chain lengths and terminal groups. The yields of perfluoroalkyl carboxylic acids (PFCAs) from 8:2 PTrMeOSi conversion were the highest (92 ± 9%, n = 3), with the C ( n - 1) perfluoroheptanoic acid (PFHpA, 49 ± 11%, n = 3) as the dominating product. Distinct conversion of 8:2 PTrMeOSi in the simulated solar exposure experiments found that C ( n) perfluorooctanoic acid (PFOA, 0.6 ± 0.04 ‰, n = 3) was predominant, and 8:2 fluorotelomer carboxylic acid (8:2 FTCA, 0.59 ± 0.08‰, n = 3), 8:2 fluorotelomer unsaturated carboxylic acid (8:2 FTUCA, 0.09 ± 0.00‰, n = 3) intermediates were also observed. To our knowledge, this is the first report regarding the occurrence and degradation potential of several fluoroalkylsilane substances as PFCA precursors.