Molecular Characterization of Organophosphorus Compounds in Wildfire Smoke Using 21-T Fourier Transform-Ion Cyclotron Resonance Mass Spectrometry

Ijaz, Amna; Kew, William; China, Swarup; Schum, Simeon K.; Mazzoleni, Lynn R.

doi:10.1021/acs.analchem.2c00916

Molecular Characterization of Organophosphorus Compounds in Wildfire Smoke Using 21-T Fourier Transform-Ion Cyclotron Resonance Mass Spectrometry

Journal Article · Mon Oct 10 00:00:00 EDT 2022 · Analytical Chemistry

DOI:https://doi.org/10.1021/acs.analchem.2c00916· OSTI ID:1898425

^[1]; ^[2]; ^[2]; Schum, Simeon K. ^[1]; Mazzoleni, Lynn R. ^[1]

Michigan Technological University, Houghton, MI (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)

Here, we present a detailed molecular characterization of organophosphorus compounds in ambient organic aerosol influenced by wildfire smoke. Biomass burning organic aerosol (BBOA) is an important source of phosphorus (P) to surface waters, where even a small imbalance in the P flux can lead to substantial effects on water quality, such as eutrophication, algal blooms, and oxygen depletion. We aimed to exploit the ultrahigh resolving power, mass accuracy, and sensitivity of Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) to explore the molecular composition of an ambient BBOA sample collected downwind of Pacific Northwest wildfires. The 21-T FT-ICR MS yielded 10533 distinct formulae, which included molecular species comprising C, H, O, and P with or without N, i.e., organophosphorus compounds that have long been quantified in wildfire smoke but have not yet been characterized at the molecular level. The lack of detailed molecular characterization of organophosphorus compounds in BBOA is primarily due to their inherently low concentrations in aerosols and poor ionization efficiency in complex mixtures. We demonstrate that the exceptional sensitivity of the 21-T FT-ICR MS allows qualitative analysis of a previously uncharacterized fraction of BBOA without its selective concentration from the organic matrix, exemplifying the need for ultrahigh-resolution tools for a more detailed and accurate molecular depiction of such complex mixtures.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830; SC0021168

OSTI ID:: 1898425

Alternate ID(s):: OSTI ID: 2000837

Report Number(s):: PNNL-SA-170743

Journal Information:: Analytical Chemistry, Journal Name: Analytical Chemistry Journal Issue: 42 Vol. 94; ISSN 0003-2700

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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