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Contribution of ketone/aldehyde-containing compounds to the composition and optical properties of Suwannee River fulvic acid revealed by ultrahigh resolution mass spectrometry and deuterium labeling

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Abstract

A prior method of mass labeling ketone-/aldehyde-containing species in natural dissolved organic matter (DOM) is further developed and applied. This application involved the treatment of Suwannee River fulvic acid (SRFA) with increasing concentrations of sodium borodeuteride (NaBD4), followed by detection of reduced species via negative mode electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR MS). The extent of reduction, as determined by ESI FTICR MS, resulting from increasing concentrations of NaBD4 correlated well with changes in the absorption and emission spectra of the corresponding untreated and borodeuteride-reduced samples, providing evidence that ketone/aldehyde functional groups contribute substantially to the bulk optical properties of SRFA. Furthermore, the differences in the reactivity and abundance of ketone-/aldehyde-containing species for various regions in Van Krevelen plots were revealed, thus showing how this mass labeling method can be used to provide more detailed structural information about components within complex DOM samples than that provided by the determination and analysis of molecular formulae alone.

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Acknowledgments

We thank Mourad Harir for the assistance with mass spectrometry data acquisition.

Funding

This work was supported by the National Science Foundation grant (OCE-1357411) awarded to NVB and RDV.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, University of Maryland, College Park, MD, 20742, USA

    Marla R. Bianca & Neil V. Blough

  2. Department of Chemistry and Biochemistry, Western Connecticut State University, Danbury, CT, 06810, USA

    Daniel R. Baluha

  3. Chesapeake Biological Laboratory, University of Maryland Center for Environmental Science, Solomons, MD, 20688, USA

    Michael Gonsior

  4. Department of Environmental Sciences, Helmholtz Zentrum Muenchen, German Research Center for Environmental Health, 85764, Neuherberg, Germany

    Philippe Schmitt-Kopplin

  5. Technical University Munich, Chair of Analytical Food Chemistry, 85354, Freising-Weihenstephan, Germany

    Philippe Schmitt-Kopplin

  6. Earth System Science Interdisciplinary Center, University of Maryland, College Park, 20740, USA

    Rossana Del Vecchio

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  1. Marla R. Bianca
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Correspondence to Neil V. Blough.

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Rossana Del Vecchio regrettably passed away on July 4, 2019.

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Bianca, M.R., Baluha, D.R., Gonsior, M. et al. Contribution of ketone/aldehyde-containing compounds to the composition and optical properties of Suwannee River fulvic acid revealed by ultrahigh resolution mass spectrometry and deuterium labeling. Anal Bioanal Chem 412, 1441–1451 (2020). https://doi.org/10.1007/s00216-019-02377-x

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