Coal weathering and the geochemical carbon cycle

Abstract

The weathering rate of sedimentary organic matter in the continental surficial environment is poorly constrained despite its importance to the geochemical carbon cycle. During this weathering, complete oxidation to carbon dioxide is normally assumed, but there is little proof that this actually occurs. Knowledge of the rate and mechanisms of sedimentary organic matter weathering is important because it is one of the major controls on atmospheric oxygen level through geologic time. We have determined the aqueous oxidation rates of pyrite-free bituminous coal at 24° and 50°C by using a dual-cell flow-through method. Coal was used as an example of sedimentary organic matter because of the difficulty in obtaining pyrite-free kerogen for laboratory study. The aqueous oxidation rate obtained in the present study for air-saturated water (270 μM O2) was found to be on the order of 2 × 10−12 mol O2/m2/s at 25°C, which is fast compared to other geologic processes such as tectonic uplift and exposure through erosion. The reaction order with respect to oxygen level is 0.5 on a several thousand hour time scale for both 24° and 50°C experiments. Activation energies, determined under 24° and 50°C conditions, were ≈40 kJ/mol O2 indicating that the oxidation reaction is surface reaction controlled. The oxygen consumption rate obtained in this study is two to three orders of magnitude smaller than that for pyrite oxidation in water, but still rapid on a geologic time scale. Aqueous coal oxidation results in the formation of dissolved CO2, dissolved organic carbon (DOC), and solid oxidation products, which are all quantitatively significant reaction products.