ALBERT

Description: A one-dimensional reactive transport model including mass, momentum and volume conservation for the solid, aqueous, and gaseous phases is developed to explore the fate of free methane gas in marine sediments. The model assumes steady–state compaction for the solid phase in addition to decoupled gas and aqueous phase transport, instigated by processes such as buoyancy, externally impressed flows and compaction. Chemical species distributions are governed by gas advection, dissolved advection and diffusion as well as by reaction processes, which include organoclastic sulfate reduction, methanogenesis and anaerobic oxidation of methane (AOM). The model is applied to Eckernförde Bay, a shallow-water environment where acoustic profiles confirm a widespread occurrence of year-round biogenic free methane gas within the muddy regions of the sediment, and where subsurface methanogenesis, overlaid by a zone of AOM has been reported. The model results reveal that, under steady-state conditions, upward gas migration is an effective methane transport mechanism from oversaturated to undersaturated intervals of the sediment. Furthermore, sensitivity tests show that when methanogenesis rates increase, the gas flux to the AOM zone becomes progressively more important and may reach values comparable to those of the aqueous methane diffusive flux. Nevertheless, the model also proves that the gas transport rates always remain smaller than the removal rates by combined gaseous methane dissolution and oxidation. Consequently, for the range of environmental conditions investigated here, the AOM zone acts as an efficient subsurface barrier for both aqueous and gaseous methane, preventing methane escape from the sediments to the water column.

Description: A kinetic-bioenergetic reaction model for the anaerobic oxidation of methane (AOM) in coastal marine sediments is presented. The model considers a fixed depth interval of sediments below the zone of bioturbation (the window-of-observation), subject to seasonal variations of temperature and inputs of organic substrates and sulfate. It includes (1) nine microbially-mediated reaction pathways involved in CH4 production/consumption; (2) an explicit representation of five functional microbial groups; and (3) bioenergetic limitations of the microbial metabolic pathways. Fermentation of organic substrates is assumed to produce hydrogen (H2) and acetate (Ac) as key reactive intermediates. Competition among the metabolic pathways is controlled by the relative kinetic efficiencies of the various microbial processes and by bioenergetic constraints. Model results imply that the functional microbial biomasses within the window-of-observation undergo little variation over the year, as a result of kinetic and thermodynamic buffering of the seasonal forcings. Furthermore, the microbial processes proceed at only small fractions of their maximum potential rates. These findings provide a theoretical justification for the approximation of steady-state microbial biomasses, which is frequently used in diagenetic modeling. In contrast, AOM rates show a strong seasonal evolution: AOM only becomes spontaneous in winter, when hydrogenotrophic sulfate reduction (hySR) sufficiently reduces the local H2 concentration. The bioenergetic limitation of AOM is thus a critical factor modulating this process in seasonally-forced nearshore marine sediments. A global sensitivity analysis based on a 2-level factorial design reveals that AOM rates are most sensitive to the kinetic parameters describing hySR and acetotrophic methanogenesis (acME). The growth and substrate uptake kinetics of AOM are unimportant, whereas the threshold value of ATP energy conservation for AOM is the most sensitive thermodynamic parameter. These results confirm that anaerobic methane oxidizing microorganisms are metabolizing close to their thermodynamic limit, with the energetic balance being controlled by the relative rates of hySR and acME. The removal of Ac by acME primarily allows more sulfate (SO42−) to be utilized for H2 oxidation, thereby promoting AOM.