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Enhanced Speciation of Pyrogenic Organic Matter from Wildfires Enabled by 21 T FT-ICR Mass Spectrometry

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    Enhanced Speciation of Pyrogenic Organic Matter from Wildfires Enabled by 21 T FT-ICR Mass Spectrometry
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    • Holly K. Roth
      Holly K. Roth
      Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, United States
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      Orcidhttps://orcid.org/0000-0003-2733-517X
    • Thomas Borch
      Thomas Borch
      Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, United States
      Department of Soil and Crop Sciences, Colorado State University, Fort Collins, Colorado 80523-1170, United States
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      Orcidhttps://orcid.org/0000-0002-4251-1613
    • Robert B. Young
      Robert B. Young
      Chemical Analysis & Instrumentation Laboratory, New Mexico State University, MSC 3RES, Las Cruces, New Mexico 88003, United States
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      Orcidhttps://orcid.org/0000-0001-7485-0604
    • William Bahureksa
      William Bahureksa
      Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, United States
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    • Greg T. Blakney
      Greg T. Blakney
      National High Magnetic Field Laboratory, Ion Cyclotron Resonance Facility, Florida State University,1800 East Paul Dirac Drive, Tallahassee, Florida 32310-4005, United States
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      Orcidhttps://orcid.org/0000-0002-4205-9866
    • Amelia R. Nelson
      Amelia R. Nelson
      Department of Soil and Crop Sciences, Colorado State University, Fort Collins, Colorado 80523-1170, United States
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    • Michael J. Wilkins
      Michael J. Wilkins
      Department of Soil and Crop Sciences, Colorado State University, Fort Collins, Colorado 80523-1170, United States
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    • Amy M. McKenna*
      Amy M. McKenna
      National High Magnetic Field Laboratory, Ion Cyclotron Resonance Facility, Florida State University,1800 East Paul Dirac Drive, Tallahassee, Florida 32310-4005, United States
      Department of Soil and Crop Sciences, Colorado State University, Fort Collins, Colorado 80523-1170, United States
      *Phone: +1 850 644 4809. Fax: +1 850 644 1366. Email: [email protected]
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      Orcidhttps://orcid.org/0000-0001-7213-521X
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    Analytical Chemistry

    Cite this: Anal. Chem. 2022, 94, 6, 2973–2980
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    https://doi.org/10.1021/acs.analchem.1c05018
    Published February 2, 2022
    Copyright © 2022 American Chemical Society
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    Abstract

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    Wildfires affect soils through the formation of pyrogenic organic matter (pyOM) (e.g., char and soot). While many studies examine the connection between pyOM persistence and carbon (C) composition, nitrogen (N) transformation in wildfire-impacted systems remains poorly understood. Thermal reactions in wildfires transform biomass into a highly complex, polyfunctional, and polydisperse organic mixture that challenges most mass analyzers. High-field Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) is the only mass analyzer that achieves resolving powers sufficient to separate species that differ in mass by the mass of an electron across a wide molecular weight range (m/z 150–1500). We report enhanced speciation of organic N by positive-ion electrospray ionization (ESI) that leverages ultrahigh resolving power (m/Δm50% = 1 800 000 at m/z 400) and mass accuracy (<10–100 ppb) achieved by FT-ICR MS at 21 T. Isobaric overlaps, roughly the mass of an electron (Me– = 548 μDa), are resolved across a wide molecular weight range and are more prevalent in positive ESI than negative ESI. The custom-built 21 T FT-ICR MS instrument identifies previously unresolved mass differences in CcHhNnOoSs formulas and assigns more than 30 000 peaks in a pyOM sample. This is the first molecular catalogue of pyOM by positive-ion ESI 21 T FT-ICR MS and presents a method to provide new insight into terrestrial cycling of organic carbon and nitrogen in wildfire impacted ecosystems.

    Copyright © 2022 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.analchem.1c05018.

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    Analytical Chemistry

    Cite this: Anal. Chem. 2022, 94, 6, 2973–2980
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.analchem.1c05018
    Published February 2, 2022
    Copyright © 2022 American Chemical Society
    Request reuse permissions

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