Determination of Calcite and Dolomite Content In Soils and Paleosols by Continuous Coulometric Titration.

Quantitative determination of calcite/dolomite ratios in soil carbonate fractions is important for understanding the pedogenic history of a soil or paleosol.  This is particularly relevant to stable carbonate-carbon and -oxygen isotope analyses where the presence of dolomite in a carbonate fraction can lead to erroneous results and inaccurate interpretations of the paleoenvironment.  The goal of this work was to develop and test an accurate method using coulometric titration combined with differential kinetic principles for determining calcite and dolomite fractions in a sample.  An automated titrator was connected to a temperature-controlled carbonate reactor where 2 N HClO₄ was introduced to the sample and mixed by bubbling CO₂-free air at a constant rate of 100 mL min^-1.  Samples were ground to <53 μm to control for differences in particle size and reactive surface area.  The concentration of C released from the reaction was monitored and recorded every 6 s for the length of the reaction.  Data were fit with both a pseudo-first order kinetic model and a Weibull model for comparison.  The Weibull model outperformed the pseudo-first order kinetic model and it's parameter, λ, fit to titration data from unknown samples was compared to λ values from mixtures of known fractions of pure calcite and dolomite to quantitatively obtain the content of the two minerals.  Dolomite concentrations obtained by this method compared well with values obtained by XRD.  Our method allows a precise and accurate measurement for both total carbonate and the ratio of calcite to dolomite in a sample.