Total and class-specific analysis of per- and polyfluoroalkyl substances in environmental samples using nuclear magnetic resonance spectroscopy

Camdzic, Dino; Dickman, Rebecca A.; Aga, Diana S.

doi:10.1016/j.hazl.2021.100023

Cited by 30 publications

(52 citation statements)

References 60 publications

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“…Comparison of computational and experimental values, along with differences, between (A) C 7 38 and (B) C 8 17 perfluorocarboxylic acids (PFCAs) using the ωB97XD/6–31+ G ( d , p ) level of theory in the gas phase with one explicit deuterated water molecule (not shown).…”

Section: Resultsmentioning

confidence: 99%

“…F I G U R E 2 Comparison of computational and experimental values, along with differences, between (A) C 7 38 and (B) C 8 17 perfluorocarboxylic acids (PFCAs) using the ωB97XD/6-31+G(d,p) level of theory in the gas phase with one explicit deuterated water molecule (not shown). We first computed 19 F NMR shifts for N-methyl perfluorobutane sulfonamide (NMeFBSA) and N-methyl perfluorooctane sulfonamide (NMeFOSA), whose literature values for 19 F NMR are unknown.…”

Section: (A) (B)mentioning

confidence: 99%

“…Recent reports suggest that several thousands of PFAS may be present in the environment 14 . In addition, matrix effects and extensive clean‐up procedures increase the complexity in detecting various PFAS 15–17 . 19 F NMR is recently being utilized to detect PFAS, since 19 F is 100% abundant and because NMR chemical shifts of various groups of fluorines can serve as diagnostic tools for detecting the structure of certain PFAS over others 10,17,18 .…”

Section: Introductionmentioning

confidence: 99%

“…In addition, matrix effects and extensive clean‐up procedures increase the complexity in detecting various PFAS 15–17 . 19 F NMR is recently being utilized to detect PFAS, since 19 F is 100% abundant and because NMR chemical shifts of various groups of fluorines can serve as diagnostic tools for detecting the structure of certain PFAS over others 10,17,18 . In order for this tool to be effective, we need to distinguish the chemical shifts corresponding to different types of structures.…”

Section: Introductionmentioning

confidence: 99%

“…15-17 19 F NMR is recently being utilized to detect PFAS, since 19 F is 100% abundant and because NMR chemical shifts of various groups of fluorines can serve as diagnostic tools for detecting the structure of certain PFAS over others. 10,17,18 In order for this tool to be effective, we need to distinguish the chemical shifts corresponding to different types of structures. Computational methods can be used to obtain 19 F NMR signatures of PFAS families in the absence of standards, but an accurate protocol must be developed.…”

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confidence: 99%

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Computational protocol for predicting ¹⁹F NMR chemical shifts for PFAS and connection to PFAS structure

2022

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Per‐ and polyfluoroalkyl substances (PFAS) are robust “forever” chemicals that have become global environmental contaminants due to their inability to degrade using traditional techniques. In addition to the persistent nature of PFAS, the structural and functional diversity in PFAS creates a unique challenge in identification and remediation. Their identification is further complicated by the absence of standards for many PFAS. This work is aimed at developing a protocol for computing and establishing accurate 19F NMR chemical shifts for PFAS using density functional theory (DFT), which can aid in the identification of PFAS. The impact of solvation and basis sets was evaluated by comparing the computed data with the experimental measurements. Results showed the addition of dispersion corrections in the methodology improve the accuracy of calculated NMR parameters within 4 ppm of the experimental values. Adding a second diffuse function and additional polarization did not improve the accuracy, likely because of the electronegativity of fluorine which does not allow the electron density of fluorine atoms to be polarized. The inclusion of various implicit solvation (DMSO, chloroform, and water) yielded negligible differences in accuracy, and were overall less accurate than the gas phase calculations. The most accurate methodology was then applied to more environmentally relevant PFAS, and the impact of helical nature on the NMR signatures was evaluated. The implication of this work is to be able to improve the identification of structurally diverse PFAS using the 19F NMR.

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Section: Resultsmentioning

confidence: 99%

Section: (A) (B)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Computational protocol for predicting ¹⁹F NMR chemical shifts for PFAS and connection to PFAS structure

2022

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Chemically Tailored Metal‐Organic Frameworks for Enhanced Capture of Short‐ and Long‐Chain Per‐ and Polyfluoroalkyl Substances from Water

Loukopoulos,

Marugán‐Benito,

Raptis

et al. 2024

Adv Funct Materials

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Per‐ and polyfluoroalkyl substances (PFAS) are emerging as bioaccumulative and toxic water pollutants, posing a large threat to human and aquatic organisms. This threat is aggravated by their extreme persistence to common degradation methods. Adsorption is regarded as the most conventional method to treat these contaminants, however, existing sorbents present considerable limitations on performance. The development of more efficient PFAS adsorbents is therefore of urgent need. The class of metal‐organic frameworks (MOFs) can hold great promise for these purposes, featuring porous materials with high tailoring potential. Herein, a series of functionalized Zr‐MOFs have been designed with boosted capacities for the adsorption of short‐ and long‐chain perfluorinated carboxylic acids of environmental interest. The approach relies on chemistry‐based concepts to introduce targeted post‐synthetic modifications that promote PFAS···MOF interactions, specifically through coordinative bonding and hydrophobic effects. In particular, the framework TFA‐MOF‐808 (TFA = trifluoroacetic acid) displays the highest capture capacities reported for MOF materials in this pollutant class. Mechanistic studies, assisted by advanced synchrotron characterization techniques and theoretical calculations, support a ligand exchange process occurring during the adsorption phenomena. The results demonstrate the potential of this design approach in developing advanced PFAS sorbents with optimal performance.

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Comprehensive review of combustion ion chromatography for the analysis of total, adsorbable, and extractable organic fluorine

Shelor,

Warren,

Odinaka

et al. 2024

J of Separation Science

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Poly‐ and perfluoroalkyl substances (PFAS) are a class of persistent organic pollutants whose high stability and appreciable water solubility have led to near‐global contamination. PFAS are bioaccumulative toxins that have been linked to a myriad of disorders and have been detected nearly universally in human blood. Liquid chromatography‐tandem mass spectrometry is the most frequent method used for quantitation, though this typically only measures a few dozen of the >14 000 known PFAS and has been shown to account for a small portion of the total organic fluorine present. Sum parameter methods such as total, extractable, and adsorbable organic fluorine have emerged as alternative measurements for PFAS determination. Combustion ion chromatography has become the preferred method for organofluorine measurement where the sorbent or extract containing PFAS is combusted and the emitted hydrofluoric acid (HF) is a measure of the cumulative organofluorine present. Herein we critically review the types of organofluorine measurement, their separation from the sample matrix, and key parameters of the analytical instrument that affect sensitivity, reproducibility, and recovery with regards to PFAS analysis.

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Total and class-specific analysis of per- and polyfluoroalkyl substances in environmental samples using nuclear magnetic resonance spectroscopy

Cited by 30 publications

References 60 publications

Computational protocol for predicting ¹⁹F NMR chemical shifts for PFAS and connection to PFAS structure

Computational protocol for predicting ¹⁹F NMR chemical shifts for PFAS and connection to PFAS structure

Chemically Tailored Metal‐Organic Frameworks for Enhanced Capture of Short‐ and Long‐Chain Per‐ and Polyfluoroalkyl Substances from Water

Comprehensive review of combustion ion chromatography for the analysis of total, adsorbable, and extractable organic fluorine

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Total and class-specific analysis of per- and polyfluoroalkyl substances in environmental samples using nuclear magnetic resonance spectroscopy

Cited by 30 publications

References 60 publications

Computational protocol for predicting 19F NMR chemical shifts for PFAS and connection to PFAS structure

Computational protocol for predicting 19F NMR chemical shifts for PFAS and connection to PFAS structure

Chemically Tailored Metal‐Organic Frameworks for Enhanced Capture of Short‐ and Long‐Chain Per‐ and Polyfluoroalkyl Substances from Water

Comprehensive review of combustion ion chromatography for the analysis of total, adsorbable, and extractable organic fluorine

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Computational protocol for predicting ¹⁹F NMR chemical shifts for PFAS and connection to PFAS structure

Computational protocol for predicting ¹⁹F NMR chemical shifts for PFAS and connection to PFAS structure