Resolving unknown isomers of emerging per- and polyfluoroalkyl substances (PFASs) in environmental samples using COSMO-RS-derived retention factor and mass fragmentation patterns
| Autor: | Scott Simpson, Mary Grace E. Guardian, Jonathan P. Antle, Diana S. Aga, Paul A. Vexelman |
|---|---|
| Rok vydání: | 2021 |
| Předmět: |
021110 strategic
defence & security studies Environmental Engineering Chemistry Health Toxicology and Mutagenesis No reference 0211 other engineering and technologies Analytical chemistry 02 engineering and technology 010501 environmental sciences Mass spectrometry 01 natural sciences Pollution Industrial effluent Partition coefficient COSMO-RS Fragmentation (mass spectrometry) Structural isomer Environmental Chemistry Density functional theory Waste Management and Disposal 0105 earth and related environmental sciences |
| Zdroj: | Journal of Hazardous Materials. 402:123478 |
| ISSN: | 0304-3894 |
| Popis: | Chromatographic retention factors (k) and mass spectral fragmentation patterns of per- and polyfluoroalkyl substances (PFASs) were determined using the optimized parameters in liquid chromatography with tandem high-resolution mass spectrometry (LC-HRMS) analysis. Characteristic fragment ions obtained at various collision energies (MS2 fragmentation) were used to determine the structures of newly discovered (emerging) PFASs detected from industrial effluent and surface water samples. Moreover, COnductor-like Screening MOdel for Realistic Solvents (COSMO-RS) derived octanol-water partition coefficients (Kow), along with mean isotropic polarizabilities calculated from Density Functional Theory (DFT), of known PFASs were plotted against their experimental k values (kexp) to obtain a multivariable regression model that can be used to predict k values of unknown PFASs. The k values of different structural isomers of unknown PFASs were calculated and compared to kexp. The predicted k value for the isomer that matches the MS2 fragmentation observed was found to be within 4.2 % of kexp. This study demonstrates the applicability of an approach that combines the observed MS2 fragmentation patterns and k values, together with computationally-derived log Kow and polarizabilities, in assigning the structures of unknown PFASs at environmentally relevant conditions when no reference standards are available. |
| Databáze: | OpenAIRE |
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