Geochemical evidence for the link between sulfate reduction, sulfide oxidation and phosphate accumulation in a late cretaceous upwelling system

Background: On Late Cretaceous Tethyan upwelling sediments from the Mishash/Ghareb Formation (Negev, Israel),bulk geochemical and biomarker analyses were performed to explain the high proportion of phosphates in thelower part and of organic matter (OM) preserved in upper parts of the studied section. The profile is composed ofthree facies types; the underlying Phosphate Member (PM), the Oil Shale Member (OSM) and the overlying MarlMember (MM).
Results: Total organic carbon (TOC) contents are highly variable over the whole profile reaching from 0.6% in theMM, to 24.5% in the OSM. Total iron (TFe) varies from 0.1% in the PM to 3.3% in the OSM. Total sulfur (TS) rangesbetween 0.1% in the MM and 3.4% in the OSM, resulting in a high C/S ratio of 6.5 in the OSM section. A meanproportion of 11.5% total phosphorus (TP) in the PM changed abruptly with the facies to a mean value of only 0.9% in the OSM and the MM. The TOC/TOC${}_{OR}$ ratios argue for a high bacterial sulfate reduction activity and in addition, results from fatty acidanalyses indicate that the activity of sulfide-oxidizing activity of bacteria was high during deposition of the PM,while decreasing during the deposition of the OSM.
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Conclusions: The upwelling conditions effected a high primary productivity and consequently the presence of abundant OM. This, in combination with high sulfate availability in the sediments of the PM resulted in a higher sulfide production due to the activity of sulfate-reducing bacteria. Iron availability was a limiting factor during the deposition of the whole section, affecting the incorporation of S into OM. This resulted in the preservation of a substantial part of OM against microbial degradation due to naturally-occurring sulfurization processes expressed by the high C/S ratio of 6.5 in the OSM. Further, the abundant sulfide in the pore water supported the growth of sulfide-oxidizing bacteria promoting the deposition of P, which amounted to as much as 15% in the PM. These conditions changed drastically from the PM to the OSM, resulting in a significant reduction of the apatite precipitation and a high concentration of reactive S species reacting with the OM.