Constraining the carbonate system in soils via testing the internal consistency of pH, pCO2 and alkalinity measurements

Inorganic carbon exists in various dissolved, gaseous and solid phase forms in natural waters and soils. It is important to accurately measure and model these forms to understand system responses to global climate change. The carbonate system can, in theory, be fully constrained and modelled by measuring at least two out of the following four parameters: partial pressure (pCO₂), total alkalinity (TA), pH and dissolved inorganic carbon (DIC) but this has not been demonstrated in soils. In this study, this “internal consistency” of the soil carbonate system was examined by predicting pH of soil extracts from laboratory measurement of TA through alkalinity titration for solutions in which pCO₂ was fixed through equilibrating the soil solution with air with a known pCO₂. This predicted pH (pH_CO2) was compared with pH measured on the same soil extracts using spectrophotometric and glass electrode methods (pH_{spec and} pH_elec). Discrepancy between measured and calculated pH was within 0.00–0.1 pH unit for most samples. However, more deviation was observed for those sample with low alkalinity (≤?0.5?meq L^?1). This is likely attributable to an effect of dissolved organic matter, which can contribute alkalinity not considered in the thermodynamic carbonate model calculations; further research is required to resolve this problem. The effects of increasing soil pCO₂ was modelled to illustrate how internally consistent models can be used to predict risks of pH declines and carbonate mineral dissolution in some soils.