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Matrix Effects and Solubilities of PFAS in Environmental Matrices
Citation:
Dickman, R., S. Pu, N. Sayre-Smith, J. McCord, J. Sobus, AND D. Aga. Matrix Effects and Solubilities of PFAS in Environmental Matrices. LC-MS/MS, Buffalo, NY, September 24 - 25, 2023. https://doi.org/10.23645/epacomptox.24132756
Impact/Purpose:
N/A
Description:
Per- and polyfluoroalkyl substances (PFAS) are persistent, anthropogenic chemicals that have been observed to elicit negative health effects in humans and wildlife. Due to a lack of available analytical standards, only a small fraction of PFAS contaminants (N≈40 of 12,000+) are commonly targeted in quantitative environmental analyses. Mass spectrometry (MS) based non-targeted analysis (NTA) approaches are viable for the identification of unknowns without analytical standards but are seldom applied in a quantitative capacity due to the uncertainty in chemical response factors (i.e., the relationship between chemical concentration and ionization response). Furthermore, performing standard-free, quantitative non-targeted analysis (qNTA) yields estimates that are impacted by sample matrix effects, which have poorly understood influences on PFAS solubility in liquid chromatography (LC) mobile phase and ionization efficiencies in MS. To better understand the relationships between sample matrix and PFAS solubility and ionizability, a group of nineteen stable-isotope labelled PFAS standards were spiked into five environmental matrices and then examined using liquid chromatography-high-resolution mass spectrometry (LC-HRMS). Matrix-matched calibration data (prepared in drinking water, surface water, wastewater effluent, wastewater influent, and sludge) were compared against standard calibration data prepared in LC mobile phase to assess the influence of matrices. Matrix effects were observed to have differing impacts on empirical chemical response factor (RF) values based on chemical elution time. Chemical concentrations were estimated using matrix-specific calibration curves and compared to matrix-specific semi-quantitative estimates obtained from three different qNTA approaches. Quantitative and semi-quantitative approaches were compared using accuracy, uncertainty, and reliability metrics. Accounting for the observed chemical-matrix relationships through use of matrix-matched calibration data significantly improved performance of all quantitation approaches. Based on these results, future qNTA applications for emerging PFAS should take into account chemical-matrix relationships when estimating chemical concentrations and quantitative uncertainties.
URLs/Downloads:
DOI: Matrix Effects and Solubilities of PFAS in Environmental Matrices
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