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Carbon Cycling and the Coupling Between Proton and Electron Transfer Reactions in Aquatic Sediments in Lake Champlain

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Abstract

We used fine-scale porewater profiles and rate measurements together with a multiple component transport–reaction model to investigate carbon degradation pathways and the coupling between electron and proton transfer reactions in Lake Champlain sediments. We measured porewater profiles of O2, Mn2+, Fe2+, HS−, pH and pCO2 at mm resolution by microelectrodes, and profiles of NO3 −, SO4 2−, NH4 +, total inorganic carbon (DIC) and total alkalinity (TA) at cm resolution using standard wet chemical techniques. In addition, sediment–water fluxes of oxygen, DIC, nitrate, ammonium and N2 were measured. Rates of gross and net sulfate reduction were also measured in the sediments. It is shown that organic matter (OM) decomposes via six pathways: oxic respiration (35.2%), denitrification (10.4%), MnO2 reduction (3.6%), FeOOH reduction (9.6%), sulfate reduction (14.9%), and methanogenesis (26.4%). In the lake sediments, about half of the benthic O2 flux is used for aerobic respiration, and the rest is used for the regeneration of other electron acceptors produced during the above diagenetic reactions. There is a strong coupling between O2 usage and Mn2+ oxidation. MnO2 is also an important player in Fe and S cycles and in pH and TA balance. Although nitrate concentrations in the overlying water were low, denitrification becomes a quantitatively important pathway for OM decomposition due to the oxidation of NH4 + to NO3 −. Finally, despite its low concentration in freshwater, sulfate is an important electron acceptor due to its high efficiency of internal cycling. This paper also discusses quantitatively the relationship between redox reactions and the porewater pH values. It is demonstrated here that pH and pCO2 are sensitive variables that reflect various oxidation and precipitation reactions in porewater, while DIC and TA profiles provide effective constraints on the rates of various diagenetic reactions.

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Acknowledgments

This research was supported through a collaborative NSF grant from DEB. We greatly appreciate the assistance of the following individuals in data collection: Pingsan Zhao, Yongchen Wang, Jane Tucker, and Andrew Bono, Steve Theberge and Amy Witter. Discussions of modeling issues with Dr. F. Meysman and Dr. P. Van Cappellen during the modeling effort (1999–2001) were helpful. We apologize for possible missing of recent literature.

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Authors and Affiliations

  1. Department of Marine Sciences, University of Georgia, Athens, GA, 30602, USA

    Wei-Jun Cai

  2. College of Marine Studies, University of Delaware, Lewes, DE, 19958, USA

    George W. Luther III

  3. University of Maryland/Center for Environmental Sciences, Horn Point Laboratory, Cambridge, MD, 21613, USA

    Jeffrey C. Cornwell

  4. The Ecosystem Center, Marine Biological Laboratory, Woods Hole, MA, 02543, USA

    Anne E. Giblin

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  1. Wei-Jun Cai
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Correspondence to Wei-Jun Cai.

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Cai, WJ., Luther, G.W., Cornwell, J.C. et al. Carbon Cycling and the Coupling Between Proton and Electron Transfer Reactions in Aquatic Sediments in Lake Champlain. Aquat Geochem 16, 421–446 (2010). https://doi.org/10.1007/s10498-010-9097-9

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