Mineralization of organic matter in boreal lake sediments: rates, pathways, and nature of the fermenting substrates

The complexity of organic matter (OM) degradation mechanisms represents a significant challenge for developing biogeochemical models to quantify the role of aquatic sediments in the climate system. The common representation of OM by carbohydrates formulated as CH2O in models comes with the assumption that its degradation by fermentation produces equimolar amounts of methane (CH4) and dissolved inorganic carbon (DIC). To test the validity of this assumption, we modelled using reaction-transport equation vertical profiles of the concentration and isotopic composition (δ13C) of CH4 and DIC in the top 25 cm of the sediment column from two lake basins, one whose hypolimnion is perennially oxygenated and one with seasonal anoxia. Furthermore, we modelled solute porewater profiles reported in the literature for four other seasonally anoxic lake basins. A total of 17 independent porewater datasets are analyzed. CH4 and DIC production rates associated with methanogenesis at the five seasonally anoxic sites collectively show that the fermenting OM has a mean (± SD) carbon oxidation state (COS) value of −1.4±0.3 . This value is much lower than the value of zero expected from carbohydrate fermentation. We conclude that carbohydrates do not adequately represent the fermenting OM in hypolimnetic sediments and propose to include the COS in the formulation of OM fermentation in models applied to lake sediments to better quantify sediment CH4 outflux. This study highlights the potential of mass balancing the products of OM mineralization to characterize labile substrates undergoing fermentation in sediments.