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Rapid warming of Arctic ecosystems exposes soil organic matter (SOM) to accelerated microbial decomposition, potentially leading to increased emissions of carbon dioxide (CO2) and methane (CH4) that have a positive feedback on global warming. Current estimates of the magnitude and form of carbon emissions from Earth system models include significant uncertainties, partially due to the oversimplified representation of geochemical constraints on microbial decomposition. Here, we coupled modeling principles developed in different disciplines, including a thermodynamically based microbial growth model for methanogenesis and iron reduction, a pool-based model to represent upstream carbon transformations, and a humic ion-binding model for dynamic pH simulation to build a more versatile carbon decomposition model framework that can be applied to soils under varying redox conditions. This new model framework was parameterized and validated using synthesized anaerobic incubation data from permafrost-affected soils along a gradient of fine-scale thermal and hydrological variabilities across Arctic polygonal tundra. The model accurately simulated anaerobic CO2 production and its temperature sensitivity using data on labile carbon pools and fermentation rates as model constraints. CH4 production is strongly influenced by water content, pH, methanogen biomass, and presence of competing electron acceptors, resulting in high variability in its temperature sensitivity. This work provides new insights into the interactions of SOM pools, temperature increase, soil geochemical feedbacks, and resulting CO2 and CH4 production. The proposed anaerobic carbon decomposition frame-work presented here builds a mechanistic link between soil geochemistry and carbon mineralization, making it applicable over a wide range of soils under different environmental settings.