Optimization and assessment of a sequential extraction procedure for calcium carbonate rocks

Sequential extraction analyses are widely used for the determination of element speciation in sediments and soils. Typical sequential extraction protocols were developed to extract from low-carbonate samples and therefore are not necessarily suitable for high-carbonate samples. In this study, we tested increased reagent to sample ratios to adjust an existing sequential extraction procedure to analyze high-CaCO₃ samples with concentrations ranging from 70 to above 90 %. Complete dissolution of the CaCO₃ phase, and a higher extraction efficiency of manganese associated with the carbonate phase, was achieved when using four times the original reagent to sample ratio in the 2nd extraction step. This increase of reagent did not compromise the extraction of subsequent phases as shown by unaffected Fe concentrations in a low-carbonate sample. Hence, an essential outcome was that increasing the solution to sample ratio did not lead to the dissolution of other sedimentary phases, such as hydrous and crystalline iron oxides or sulfides. Thus, compared to other extraction protocols that use a lower reagent to sample ratio in the carbonate dissolution step, the new protocol allowed the complete extraction of oxide and sulfide phases in the following extraction steps. Furthermore, the study demonstrated the benefit of replacing Na-acetate with NH₄-acetate to extract exchangeable ions and carbonates. We observed increased intensities for several analytes, i.e., trace metals such as Mo and As, due to less suppression of the analyte signal by NH₄-acetate than by Na-acetate during analysis by inductively coupled plasma optical emission spectrometry (ICP-OES).