, Volume 406, Issue 19, pp 4745-4755
Date: 15 May 2014

Use of high-resolution mass spectrometry to identify precursors and biodegradation products of perfluorinated and polyfluorinated compounds in end-user products

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Abstract

Structural identification of perfluoroalkyl and polyfluoroalkyl substances found in end-user products and their biodegradation products was performed using ultra-high resolution mass spectrometry. Little attention has so far been paid to the environmental burden of perfluorooctane sulfonate and perfluorooctanoic acid from compounds with a molar mass of ~2,000. Analysis of end-user waterproofing and stain repellent products revealed the presence of numerous ions with molar masses ranging from 1,000 to 2,000 and complex mass spectra. Ultra-high resolution mass spectrometry determined the accurate mass of the observed ions, allowing the cleavage position and fragment structure to be determined. The precursor structures were determined based on reconstitution of the retrieved fragments. Products of fluorochemical manufacturers before voluntary regulation comprised compounds with plural perfluorooctyl chains. In the current product lines, compounds comprising perfluorobutyl chains were detected. Biodegradation tests using activated sludge revealed that biodegradation products consistent with those reported previously were generated even from complex end-user products. For example, the biodegradation test revealed the formation of N-ethyl perfluorooctane sulfonamido acetic acid and various fluorotelomer acids in the samples. The results of the present study suggest that the environmental burden of these compounds should be reevaluated.