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Thermodynamically controlled preservation of organic carbon in floodplains

Nature Geoscience volume 10, pages 415–419 (2017)Cite this article

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Abstract

Organic matter decomposition in soils and terrestrial sediments has a prominent role in the global carbon cycle. Carbon stocks in anoxic environments, such as wetlands and the subsurface of floodplains, are large and presumed to decompose slowly. The degree of microbial respiration in anoxic environments is typically thought to depend on the energetics of available terminal electron acceptors such as nitrate or sulfate; microbes couple the reduction of these compounds to the oxidation of organic carbon. However, it is also possible that the energetics of the organic carbon itself can determine whether it is decomposed. Here we examined water-soluble organic carbon by Fourier-transform ion-cyclotron-resonance mass spectrometry to compare the chemical composition and average nominal oxidation state of carbon—a metric reflecting whether microbial oxidation of organic matter is thermodynamically favourable—in anoxic (sulfidic) and oxic (non-sulfidic) floodplain sediments. We observed distinct minima in the average nominal oxidation state of water-soluble carbon in sediments exhibiting anoxic, sulfate-reducing conditions, suggesting preservation of carbon compounds with nominal oxidation states below the threshold that makes microbial sulfate reduction thermodynamically favourable. We conclude that thermodynamic limitations constitute an important complement to other mechanisms of carbon preservation, such as enzymatic restrictions and mineral association, within anaerobic environments.

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Figure 1: Conceptual model of the evolution of anaerobic environments and thermodynamic constraints on carbon (C) fate in the subsurface of floodplains.
Figure 2: Sediment profiles of the five examined cores from the four floodplains in the Upper Colorado River Basin, USA.
Figure 3: Chemical signature induced by thermodynamic constraints on C oxidation in sulfidic samples acting to selectively preserve highly reduced C.

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Acknowledgements

This work was supported by the US Department of Energy (DOE) Office of Science, Office of Biological and Environmental Research (BER), through the SLAC National Accelerator Laboratory Scientific Focus Area (SFA) (Contract No. DE-AC02-76SF00515). Work by S.F. was supported by the US DOE BER Terrestrial Ecosystem Program (Award Number DE-FG02-13ER65542). Work by M.M.T. was conducted at EMSL, a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Field operations at the Rifle site and work by K.W.H. was supported through the Lawrence Berkeley National Laboratory’s Sustainable Systems SFA (US DOE BER, contract DE-AC02-05CH11231). Additional funding for field operations was provided by the DOE Office of Legacy Management (DOE-LM). This study could not have been completed without the logistical support of the DOE-LM staff and contractors. Special thanks to R. Bush, R. H. Johnson and W. L. Dam. The authors are very grateful for sampling and analytical efforts provided by J. S. L. Pacheco, E. Cardarelli, L. Barraghan, G. Li, D. Turner, L. Pasa-Tolic, R. Chu, T. Z. Regier and J. J. Dynes.

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Authors and Affiliations

  1. Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA

    Kristin Boye, Vincent Noël, Sharon E. Bone & John R. Bargar

  2. Earth System Science Department, Stanford University, Stanford, California 94305, USA

    Kristin Boye & Scott Fendorf

  3. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richmond, Washington 99354, USA

    Malak M. Tfaily

  4. Climate and Ecosystem Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

    Kenneth H. Williams

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  1. Kristin Boye
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Contributions

This work was originally conceived by K.B. and S.F., with substantial contributions from J.R.B.; field activities were designed and coordinated by K.H.W., S.E.B., J.R.B. and V.N., with input from K.B. and S.F.; V.N. designed and carried out the inorganic chemical characterization activities, with input from J.R.B.; K.B. designed and carried out the organic matter characterization approach, with input from S.E.B., S.F., J.R.B. and M.M.T.; M.M.T. performed the FT-ICR-MS analyses and data processing; K.B. compiled the data and performed statistical analyses. The manuscript and supporting information was written by K.B. with input from all co-authors, particularly S.F.

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Correspondence to Kristin Boye.

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Boye, K., Noël, V., Tfaily, M. et al. Thermodynamically controlled preservation of organic carbon in floodplains. Nature Geosci 10, 415–419 (2017). https://doi.org/10.1038/ngeo2940

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