A pedogenic goethite record of soil CO2 variations as a response to soil moisture content

The terrestrial carbon cycle and the role of atmospheric CO2 concentrations in controlling global temperatures can be inferred from the study of ancient soils (paleosols). Soil-formed goethite and calcite have been the primary minerals used as a geochemical proxy for reconstructing atmospheric pCO2 from ancient terrestrial records. In the case of goethite, optimum sampling strategies for reconstructing pCO2 focus on the portion of the soil profile that displays steep gradients in both soil CO2 concentration and δ13C values of soil CO2 such that a keeling plot can be developed for a given soil and atmospheric pCO2 can be calculated from it. We report data from a Carboniferous paleosol that depart from the expected linear trends. The results indicate that pedogenic goethite is sensitive to variations in the isotopic composition of soil CO2, over a range of timescales, and can record these variations in the carbon isotope composition and mole fraction of Fe(CO3)OH in solid solution with goethite. We explore possible environmental conditions that can drive these changes as a function of either moisture controlled variations in soil respired CO2 or in the residence time of carbon in soils. The implications of this result are overestimation of paleoatmospheric pCO2 from pedogenic goethite.