Chemical and stable isotope fractionation in manganese oxide—phosphorite mineralization, Timna Valley, Israel

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Abstract
Element, carbon and oxygen isotope fractionations have been studied in laminated deposits, manganese nodules and phosphorite lenses in clastic sediments of the Cambrian Timna Formation, southern Israel. Comparisons of element abundances show that only manganese, phosphorus and uranium were mobilized and concentrated during diagenesis: element fractionations among the diagenetic manganese components particularly resemble those observed in present-day suboxic pelagic marine sediments. Epigenetic processes involving reducing solutions reversed the diagenetic geochemical trends, with the redox-sensitive elements manganese and uranium showing considerable depletions in nodules, and iron and lead showing corresponding enrichments. The manganese oxides of nodules have calculated δ18O compositions varying from –1.6 to 3.1 ‰. These compositions are significantly lower than a δ18O value of 7.9 ‰ obtained for the manganese oxides of an ocean floor nodule and are taken to largely represent temperature differences between the ocean floor and the shallow marine Timna conditions. Slight decreases in δ18O accompany the transformation from diagenetic type A to epigenetic type B manganese nodules; corresponding shifts to lower δ18O are also inferred for the structural carbonate of apatites. Such shifts are compatible with re-equilibration accompanying a slight temperature increase and/or low temperature meteoric-water alteration. δ13C values of –7 to –12‰ obtained for the apatites of laminated deposits and phosphorite lenses are consistent with phosphorite diagenesis in suboxic to anoxic pore-waters. Early diagenetic redox conditions are indicated to be major controls governing the development of the assemblages.