Assessing potential diagenetic alteration of primary iodine-to-calcium ratios in carbonate rocks

Abstract:

We have evaluated iodine-to-calcium (I/Ca) ratios from a series of carbonate samples with well-constrained histories of diagenetic alteration to assess the likelihood of overprints on primary water column-derived signals. Because only the oxidized iodine species, iodate, is incorporated during carbonate precipitation, I/Ca ratios have strong potential as proxies for both marine redox and carbon cycling. This utility lies with the combination of iodate’s redox sensitivity as well as the close association between iodine and marine organic matter. However, despite the possibility of large pore water iodine enrichments relative to overlying seawater, carbonate alteration under reducing diagenetic conditions, and iodate-to-iodide reduction, no study has assessed the prospect of diagenetic alteration of primary I/Ca ratios. Here, we evaluated aragonite-to-calcite transformations and dolomitization within the Key Largo Limestone of South Florida and the Clino and Unda drill cores of the Bahamas Bank. Also, early burial diagenesis was studied through analysis of I/Ca ratios in short cores from a variety of shallow settings within the Exuma Bay, Bahamas. Further, we evaluated authigenic carbonates through analysis of iodine in concretions constrained to have formed during varying stages of evolving pore fluid chemistry. In all cases, I/Ca ratios show the potential for diagenetic iodine loss relative to water-column derived values, consistent with observations of quantitative reduction of dissolved iodate to iodide in pore waters before or synchronous with carbonate alteration. In no case, however, did we observe an increase in I/Ca during diagenetic transformation. Our results suggest both that primary I/Ca values and trends can be preserved but that maximum I/Ca ratios should be considered a minimum estimate of seawater iodate. We recommend that ancient carbonates with distinct I/Ca trends not indicative of diagenetic iodine loss reflect preservation of or very early diagenetic alteration of primary mineralogies.