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1 Geowissenschaftliches Zentrum der Universität Göttingen, Goldschmidtstrasse 1, D-37077 Göttingen, Germany
2 Dipartimento di Biologia e Chimica Agro-Forestale ed Ambientale, Università di Bari, Via Amendola, 165/A, I-70126 Bari, Italy
3 Faculty of Earth and Life Sciences, Vrije Universiteit, De Boelelaan 1085, 1081 HV Amsterdam, Netherlands
4 Institut für Radiochemie, Forschungszentrum Rossendorf, P.O. Box 510119, D-01314 Dresden, Germany
5 Dipartimento di Biologia e Chimica Agro-Forestale ed Ambientale, Università di Bari, Via Amendola, 165/A, I-70126 Bari, Italy
Intracrystalline organic compounds, enclosed within in situ–precipitated marine microcrystalline calcite (automicrite), might represent either an inclusion or the catalyst of such precipitation. We use evidence from a Lower Cretaceous deep-water carbonate mound to show (1) the original source, (2) the degree of condensation, (3) the redox conditions involved, and (4) the catalytic role of natural organic matter for the precipitation of automicrite. Fluorescence spectrometry of the intracrystalline organic fraction extracted from these carbonates identifies a marine fulvic acid–like organic compound with a low degree of polycondensation. This finding points to a temporal correlation of the initial stage of geopolymer formation with the precipitation of automicrite. Furthermore, the rare earth element (REE) distribution patterns in the mineral show a consistent positive Ce anomaly, suggesting an episode of reductive dissolution of iron-manganese oxyhydroxides during automicrite formation. In general, a relative enrichment of middle-weight REEs is observed, resulting in a convex distribution pattern typical for, e.g., phosphate concretions or humic acid material. By merging the results of spectrometry and REE geochemistry we thus conclude that the marine calcite precipitation was catalyzed by marine fulvic acid–like compounds during the early stages of humification under suboxic conditions. This indicates that humification, driven by the presence of a benthic biomass, is more important for calcite authigenesis than any site-specific microbial metabolism. The Neoproterozoic rise of carbonate mounds supports this hypothesis; there is molecular evidence for early metazoan divergence then, but not for a major evolutionary episode of microorganisms.
Key Words: carbonate mud mound • authigenesis • fulvic acids • rare earth elements
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