Formation of carbonate chimneys in the Mediterranean Sea linked to deep-water oxygen depletion

Marine sediments at ocean margins vent substantial amounts of methane1, 2. Microbial oxidation of the methane released can trigger the precipitation of carbonate within sediments and support a broad diversity of seafloor ecosystems3, 4. The factors controlling microbial activity and carbonate precipitation associated with the seepage of submarine fluid over geological time remain poorly constrained. Here, we characterize the petrology and geochemistry of rocks sampled from metre-size build-ups of methane-derived carbonate chimneys located at the Amon mud volcano on the Nile deep-sea fan. We find that these carbonates comprise porous structures composed of aggregated spherules of aragonite, and closely resemble microbial carbonate reefs forming at present in the anoxic bottom waters of the Black Sea5. Using U-series dating, we show that the Amon carbonate build-ups formed between 12 and 7 thousand years ago, contemporaneous with the deposition of organic-rich sediments in the eastern Mediterranean, the so-called sapropel layer S1. We propose that the onset of deep-water suboxic or anoxic conditions associated with sapropel formation resulted in the development of intense anaerobic microbial activity at the sea floor, and thus the formation of carbonate chimneys

Formation of carbonate concretions in surface sediments of two mud mounds offshore Costa Rica: A stable isotope study

The surface sediments of two mud mounds (‘‘Mound 11’’ and ‘‘Mound 12’’) offshore southwest Costa Rica contain abundant authigenic carbonate concretions dominated by high-Mg calcite (14–20 mol-% MgCO3). Pore fluid geochemical profiles (sulfate, sulfide, methane, alkalinity, Ca and Mg) indicate recent carbonate precipitation within the zone of anaerobic oxidation of methane (AOM) at variable depths. The current location of the authigenic carbonate concretions is, however, not related to the present location of the AOM zone, suggesting mineral precipitation under past geochemical conditions as well as changes in the flow rates of upward migrating fluids. Stable oxygen and carbon isotope analysis of authigenic carbonate concretions yielded d18Ocarbonate values ranging between 34.0 and 37.7 % Vienna standard mean ocean water (VSMOW) and d13Ccarbonate values from -52.2 to -14.2 % Vienna Pee Dee belemnite (VPDB). Assuming that no temperature changes occurred during mineral formation, the authigenic carbonate concretions have been formed at in situ temperature of 4–5 °C. The d18Ocarbonate values suggest mineral formation from seawater-derived pore fluid (d18Oporefluid = 0 % VSMOW) for Mound 12 carbonate concretions but also the presence of an emanating diagenetic fluid (d18Oporefluid &5 %) in Mound 11. A positive correlation between d13Ccarbonate and d18Ocarbonate is observed, indicating the admixing of two different sources of dissolved carbon and oxygen in the sediments of the two mounds. The carbon of these sources are (1) marine bicarbonate (d13Cporefluid &0 %) and (2) bicarbonate which formed during the AOM (d13Cporefluid &-70 %). Furthermore, the d18Oporefluid composition, with values up to ?4.7 % Vienna standard mean ocean water (VSMOW), is interpreted to be affected by the presence of emanating, freshened and boronenriched fluids. Earlier, it has been shown that the origin of 18O-enriched fluids are deep diagenetic processes as it was indicated by the presence of methane with thermogenic signature (d13CCH4 = -38 %). A combination of present geochemical data with geophysical observations indicates that Mounds 11 and 12 represent a single fluid system interconnected by deep-seated fault(s)