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Influence of heteroatom pre-selection on the molecular formula assignment of soil organic matter components determined by ultrahigh resolution mass spectrometry

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Abstract

Soil organic matter (SOM) is involved in many important ecosystem processes. Ultrahigh resolution mass spectrometry has become a powerful technique in the chemical characterization of SOM, allowing assignment of elemental formulae for thousands of peaks resolved in a typical mass spectrum. We investigated how the addition of N, S, and P heteroatoms in the formula calculation stage of the mass spectra processing workflow affected the formula assignments of mass spectra peaks. Dissolved organic matter extracted from plant biomass and soil as well as the soil humic acid fraction was studied. We show that the addition of S and P into the molecular formula calculation increased peak assignments on average by 17.3 % and 10.7 %, respectively, over the assignments based on the CHON elements frequently reported by SOM researchers using ultrahigh resolution mass spectrometry. The organic matter chemical characteristics as represented by van Krevelen diagrams were appreciably affected by differences in the heteroatom pre-selection for the three organic matter samples investigated, especially so for the wheat-derived dissolved organic matter. These results show that inclusion of both S and P heteroatoms into the formula calculation step, which is not routinely done, is important to obtain a more chemically complete interpretation of the ultrahigh resolution mass spectra of SOM.

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Acknowledgments

This project was supported by USDA–National Research Initiative Competitive Grant no. 2008-35107-04480 from the USDA Cooperative State Research, Education, and Extension Service, and NSF DEB-1056692. It has also been supported by Hatch funds provided by the Maine Agricultural and Forest Experiment Station. We thank Dr. Rachel Sleighter of Old Dominion University for providing the MATLAB script which is used to constrain the formula list to chemically feasible formulae and for discussion of mass spectra processing. We also thank the anonymous reviewers for valuable comments and suggestions which significantly improved this manuscript. This is Maine Agricultural and Forest Experiment Station Journal no. 3304.

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Authors and Affiliations

  1. Department of Plant, Soil, & Environmental Sciences, University of Maine, 5722 Deering Hall, Orono, ME, 04469-5722, USA

    Tsutomu Ohno

  2. Rockefeller College, Madison Hall, Princeton University, Princeton, NJ, 08544, USA

    Paul E. Ohno

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  1. Tsutomu Ohno
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  2. Paul E. Ohno
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Correspondence to Tsutomu Ohno.

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Ohno, T., Ohno, P.E. Influence of heteroatom pre-selection on the molecular formula assignment of soil organic matter components determined by ultrahigh resolution mass spectrometry. Anal Bioanal Chem 405, 3299–3306 (2013). https://doi.org/10.1007/s00216-013-6734-3

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  • DOI: https://doi.org/10.1007/s00216-013-6734-3

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