Rapid and Simultaneous Quantification of Short- and Ultrashort-Chain Perfluoroalkyl Substances in Water and Wastewater

Abstract

Per-and polyfluoroalkyl substances (PFASs) are a class of chemicals of growing concern. Recently, there has been a shift toward the use of short-and ultrashort-chain PFASs, which are difficult to measure with current analytical methods and rarely included in environment monitoring studies. In this research, we developed and optimized online solid-phase extraction, highperformance liquid chromatography, and electrospray ionization high-resolution mass spectrometry methods for the rapid and simultaneous quantification of 10 short-and ultrashort-chain PFASs. We applied our method to water samples collected from a variety of natural, engineered, industrial, and commercial water systems. We detected ultrashort-chain PFASs in every sample, including hydraulic fracturing water and wastewater samples and wastewater from electronic fabrication facilities for the first time, identifying previously unknown sources of ultrashort-chain PFASs. We also measured ultrashort-chain PFASs in a variety of drinking water sources, including what was thought to be pristine groundwater and surface water sources. The measurement of ultrashortchain PFASs in every sample type studied here raises concern over the potential ubiquity of these compounds in the environment and highlights the need for further monitoring studies, especially as longer-chain PFASs become regulated, and the industrial shift to short-and ultrashort-chain PFASs increases.

Improved Total Oxidizable Precursor Assay for Quantifying Polyfluorinated Compounds Amenable to Oxidative Conversion to Perfluoroalkyl Carboxylic Acids

“…Details on the analytical standard preparation and matrix spike for ultrashort PFCA measurements are included in Tables S14–S16. Despite using separate LCMS analytical methods here, we acknowledge that emerging techniques such as mixed-mode columns containing weak anion exchanges and reverse-phased capabilities could achieve similar results with a single method …”

“…A separate method was used to measure ultrashort PFCAs, which was adapted from Taniyasu et al 40 anion exchanges and reverse-phased capabilities could achieve similar results with a single method. 41 ■ RESULTS AND DISCUSSION Integration of a Mass-Labeled Indicator of Precursor Oxidation Efficiency. Water samples collected from landfills and wastewater treatment plants contain dissolved solutes (e.g., dissolved organic matter and reduced metals) that can scavenge • OH generated from the thermolysis of persulfate in the oxidation step of the TOP assay.…”

Exploring the Evolution of Organofluorine-Containing Compounds during Simulated Photolithography Experiments

“…We transferred 8 mL of each prepared sample into 10 mL sample vials and spiked them with 20 μL of the isotope-labeled internal standard (ILIS) mixture at a concentration of 100 μg L –1 . Six replicates of all samples were prepared so they could be measured in triplicate at each dilution level by means of two separate previously described LC-HRMS (QExactive hybrid quadrupole-orbitrap, ThermoFisher Scientific) analytical methods , needed to measure ultrashort-, short-, and long-chain PFASs.…”

“…We used a reversed-phase chromatography method for analysis of short- and long-chain PFASs and a mixed-mode chromatography method for analysis of ultrashort-chain PFASs . Details on the chromatographic and mass spectrometry experiments along with acquisition parameters of each target PFAS, quality control data, and LOQs are provided in the companion text in the Supporting Information and in Tables S8 through S11.…”

“…We used a reversed-phase chromatography method for analysis of short-and long-chain PFASs 8 and a mixed-mode chromatography method for analysis of ultrashort-chain PFASs. 34 Details on the chromatographic and mass spectrometry experiments along with acquisition parameters of each target PFAS, quality control data, and LOQs are provided in the companion text in the Supporting Information and in Tables S8 through S11. Details on mass spectrometry experiments and suspect and nontarget screening workflows are provided in the companion text in the Supporting Information and in Tables S12, S13 and Figures S1, S2.…”