Aerobic respiration controls on shale weathering

The weathering of shale exerts an important control on the hydrochemical fluxes to river systems, thus influencing the global carbon, nutrient, and geochemical cycles. However, the quantitative understanding of shale weathering and its impact on global biogeochemical cycles remains inadequate due to the complex interplay between hydrological, biogeochemical, and physical processes. In this study, we develop a novel modeling approach to quantitatively interpret the long-term chemical weathering of shale occurring since the last glaciation period (15,000 years) leading to the present geochemical conditions. The model explicitly considers processes occurring across multiple phases and involved in the weathering, including: (i) the infiltration of meteoric water, (ii) the interactions between the water and the mineral assemblage via dissolution/precipitation reactions, (iii) the microbially-mediated oxidation of organic matter, (iv) the evolution of porosity induced by mineral reactions, and (v) the exchange of gases between the subsurface and the atmosphere. To implement and test our model, we conduct this study at a well-instrumented hillslope underlain by Mancos Shale and located at the East River study site, Western Colorado. Consistent with field observations, the model successfully reproduces the stratified weathering front, the complex spatial distribution of organic carbon, and the gaseous emissions of carbon dioxide from the subsurface. Model simulations show that aerobic respiration exerts a fundamental control on the weathering of shale. While previous studies have highlighted the diffusion of oxygen from the atmosphere as the primary mechanism for shale weathering, our model simulations demonstrate that aerobic respiration limits the propagation of oxygen in the shallow subsurface, and thereby inhibits the dissolution of pyrite at depth. Aerobic respiration is particularly favored in the top soil horizon due to the constant flux of oxygen from the atmosphere, the replenishment of fresh litter/plant-derived organic matter, and to a lesser extent the presence of fossil shale-associated organic matter. The acidic pore water generated through aerobic respiration within the shallow subsurface is transported to greater depths, where it sustains the dissolution of carbonate (dolomite in this example). Overall, our results demonstrate that the evolution of pyrite and carbonate depletion fronts are significantly different, and primarily depend on the ability of microorganisms to carry out microbial respiration and the various transport pathways of reactants controlling the mineral reactions under partially saturated conditions.