Analytical Constraints on the Measurement of the Sulfur Isotopic Composition and Concentration of Trace Sulfate in Phosphorites: Implications for Sulfur Isotope Studies of Carbonate and Phosphate Rocks

The aim of this study was to evaluate the existing methods for extracting trace sulfate from francolite and measuring its concentration and sulfur isotope composition. Phosphatic rocks were chemically and thermally treated to remove non‐structural SO₄^2? in francolite, which would otherwise be inadvertently included in geochemical analyses of the structurally‐bound sulfate. Acetic acid (10% v/v) proved to be effective in removing calcite, dolomite and ankerite without affecting francolite. To remove all ‘easily’ soluble sulfates, such as Ca‐sulfates and adsorbed sulfate, rinsing with 10% v/v NaCl had to be repeated several times for most samples. For subsequent S isotope determination sample combustion at 600 °C was found to be an efficient way to remove non‐francolite S‐bearing phases. From a number of SO₄^2? detection methods tested, ICP‐AES proved to be the most accurate. For francolite‐sulfate recovery, our recommended protocol involved repeated rinsing of powdered phosphorites with 10% NaCl as well as NaOCl, and testing of the filtrate for SO₄^2? in each wash. If only S isotope compositions are needed, combustion at 600 °C with a subsequent de‐ionised water rinse could be undertaken instead of repeated NaOCl rinsing for studies of both francolite and carbonate. Re‐analysis of previously published data, using the new protocol, provided evidence that the use of this protocol considerably improves data quality.