Technical note: In situ measurement of flux and isotopic composition of CO 2 released during oxidative weathering of sedimentary rocks

Oxidative weathering of sedimentary rocks can release carbon dioxide (CO2) to the atmosphere and is an important natural CO2 emission. Two mechanisms operate – the oxidation of sedimentary organic matter and the dissolution of carbonate minerals by sulfuric acid. It has proved difficult to directly measure the rates at which CO2 is emitted in response to these weathering processes in the field, with previous work generally using methods which track the dissolved products of these reactions in rivers. Here we design a chamber method to measure CO2 production during the oxidative weathering of shale bedrock, which can be applied in erosive environments where rocks are exposed frequently to the atmosphere. The chamber is drilled directly into the rock face and has a high surface-area-to-volume ratio which benefits measurement of CO2 fluxes. It is a relatively low-cost method and provides a long-lived chamber (several months or more). To partition the measured CO2 fluxes and the source of CO2, we use zeolite molecular sieves to trap CO2 “actively” (over several hours) or “passively” (over a period of months). The approaches produce comparable results, with the trapped CO2 having a radiocarbon activity (fraction modern, Fm) ranging from Fm = 0.05 to Fm = 0.06 and demonstrating relatively little contamination from local atmospheric CO2 (Fm = 1.01). We use stable carbon isotopes of the trapped CO2 to partition between an organic and inorganic carbon source. The measured fluxes of rock-derived organic matter oxidation (171 ± 5 mgC m−2 day−1) and carbonate dissolution by sulfuric acid (534±16 mgC m−2 day−1) from a single chamber were high when compared to the annual flux estimates derived from using dissolved river chemistry in rivers around the world. The high oxidative weathering fluxes are consistent with the high erosion rate of the study region. We propose that our in situ method has the potential to be more widely deployed to directly measure CO2 fluxes during the oxidative weathering of sedimentary rocks, allowing for the spatial and temporal variability in these fluxes to be determined.