Paragenesis of an Ediacaran carbonate-platform phosphorite: Constraints from optical petrography and texture-specific clumped isotope paleothermometry

The Salitre Formation is comprised of several hundred meters of primarily carbonate rocks, representing sedimentation in an intracratonic foreland basin during the Ediacaran Period (c. 600–550 Ma). The lowermost member of the Salitre Formation contains sedimentary phosphorite deposits, in which the dominant phosphate-bearing phase is cryptocrystalline carbonate-rich fluorapatite (CFA) cement. These CFA cements occur exclusively associated with digitate stromatolite buildups, decimeters to meters in vertical and lateral scale, which interfinger with cross-stratified grainstone. Notably, there are also non-phosphatic stromatolite buildups in close proximity to the phosphatic, in the same depositional facies. This implies that the mechanisms that control the distribution of phosphate cement development versus carbonate cement development are not driven by the location of depositional facies within the architecture of the Salitre paleobasin. Other models which could explain the distribution and style of phosphate mineralization there include: (1) differential diagenesis involving diagenetic fluids which infiltrate one lithofacies more pervasively than another to effect the replacement of primary cement mineralogies according to microtextural differences, and (2) differences in primary porewater chemistries over minute spatial scales which result in the formation of different primary cement phases. In this study, we present paired petrographic thin sections and novel measurements of ∆₄₇, δ¹³C_(mineral), and δ¹⁸O_(mineral). We provide a paragenetic framework for phosphatic and non-phosphatic lithofacies of the Salitre Formation which constrains the thermal and chemical alteration history of CFA, calcite, and dolomite cements. Structural carbonate in the CFA and calcite cements co-occurring in partially phosphatic digitate stromatolite buildups and adjacent carbonate grainstone generally yield similar δ¹³C_(mineral) values (0–5 ‰ VPDB), δ¹⁸O_(mineral) values (−5–0 ‰ VPDB), as well as similar ∆47 temperatures (90–115 °C) and calculated δ¹⁸O_(water) (10–19 ‰ VSMOW), supporting a scenario in which CFA and calcite formed and then both recrystallized in equilibrium with the same diagenetic fluids under low water–rock ratio conditions at depth. Dolomite cements yielded similar δ¹⁸O(mineral) values to CFA and calcite, and similar to slightly higher temperatures (85–150 °C) — supporting a scenario in which dolomite cements were recrystallized in equilibrium with a different, and isotopically lighter, generation of fluids. Given the general absence of pervasive, fabric-destructive replacement is scarce, these geochemical data do not support later stage, differential diagenesis as a mechanism for controlling the distribution of phosphatic versus non-phosphatic cements. Rather, primary differences in porewater biogeochemistry seem the likeliest explanation. This is important, as it implies that the ecology of the Ediacaran seafloor controlled the style and quality of mineralization observed today, and that the presence of CFA cements in these rocks represents a unique taphonomic window for select microbial communities.