17O-depleted barite from two Marinoan cap dolostone sections, South China

Distinct, non-mass-dependent 17O depletion was reported in barite from Marinoan cap dolostones (~ 635 Ma) in South China, and has been interpreted as an indication of an extremely high-pCO2 atmosphere (Bao et al., 2008). There is a significant variation in the magnitude of the 17O anomaly even among samples from the same outcrops. Understanding the origins of this barite and particularly the source of sulfate is critical to interpreting the anomalous 17O signature and its implication on sulfur and oxygen cycles at the aftermath of Marinoan glacial meltdown. In this study, we analyzed 160 micro-sampled barite samples from 20 hand specimens collected from two cap dolostone sections in South China. Together with field, petrographic, and Sr isotope data, the expanded dataset 1) confirms the large variability in ∆17O (from − 0.09‰ to − 0.87‰, VSMOW), δ18O (+ 13.3‰ to + 23.5‰, VSMOW), and δ34S (+ 20.0‰ to + 45.5‰, VCDT) of barite; 2) demonstrates a hyperbolic relationship between the ∆17O and δ34S of various barite samples with more negative Δ17O values generally corresponding to lower δ34S values; 3) reveals that individual barite crystal fans and fans of the same layer possess a well-clustered set of δ18O, Δ17O, and δ34S values; and 4) shows, correspondingly, that barite crystal fans of different layers bear different sets of Δ17O, δ18O, and δ34S values. The study suggests that 17O-depleted barite crystals were formed under supersaturation when Ba2+ from sulfate-free deepwater came to mix with sulfate-bearing shallow water. There were multiple upwelling episodes which resulted in multiple barite layers. The large variability in sulfur and triple-oxygen isotope composition and the high 87Sr/86Sr ratios indicate that the two sites from South China were sufficiently close to the continent so that the isotopic composition of sulfate was easily influenced by changes in riverine flux when seawater sulfate concentration at that time was exceedingly low. Our depositional model for the barite is consistent with the proposed sequence of events after the meltdown of Marinoan glaciation in South China by Zhou et al. (2010), and is also consistent with the proposed atmospheric origin of sulfate 17O depletion by Bao et al. (2008).

Research Highlights
► Sea-floor barite from two Marinoan cap dolostone sections in South China.
► High-spatial-resolution sampling and isotope analysis (δ18O, Δ17O, δ34S) on barite.
► Multiple episodes of deepwater Ba2+ came to mix with SO42−-bearing shallow water.
► Support the sequence of events after Marinoan glacial meltdown (Zhou et al. 2010).
► Support atmospheric origin of anomalous sulfate 17O depletion (Bao et al., 2008 and Bao et al., 2009).