Decline in oceanic sulfate levels during the early Mesoproterozoic

• Multiple sulfur isotopes were analyzed for early Mesoproterozoic CAS and pyrite.
• Paired CAS and pyrite δ34S suggest low sulfur isotope fractionation (<10‰).
• Multiple lines of evidence suggest low sulfate level in early Mesoproterozoic.
• Decline in marine sulfate level might be caused by decline in pO2.
• Construction of Nuna supercontinent had significant effect on surface geochemical cycle.

Multiple-sulfur isotope compositions (32S, 33S, 34S and 36S) were analyzed for paired carbonate-associated sulfate (CAS) and disseminated pyrite (PY) from the ∼1.6-Ga Gaoyuzhuang Formation of the North China Craton to reconstruct the history of sulfate levels in Proterozoic oceans. The 200-m-thick study interval yielded relatively constant values for δ34SCAS (13.0 ± 1.8‰), δ34SPY (8.0 ± 2.3‰), and Δ34SCAS-PY (∼5‰), as well as relatively constant Δ33S (0 ± 0.05‰) and Δ36S (0.35 ± 0.15‰) for both CAS and pyrite. Limited variation in δ34SPY and slightly lower Δ33S of pyrite relative to CAS suggest water-column precipitation of pyrite. Limited fractionation of sulfur during microbial sulfate reduction (as documented by Δ34SCAS-PY) implies low seawater sulfate concentrations in the early Mesoproterozoic ocean. We quantitatively constrained paleo-seawater [SO42−] using a novel modeling approach based on measured values of Δ34SCAS-PY and ∂δ34SCAS/∂t(max). For the study unit, Δ34SCAS-PY is 5.4 ± 1.4‰ (n = 17), and ∂δ34SCAS/∂t(max) is 6.8–34‰ Myr−1 based on sedimentation rates of 30–150 m Myr−1. These data indicate early Mesoproterozoic seawater [SO42−] of ∼<0.1 to 0.35 mM (with a maximum possible concentration of 1.8 mM), a range that is lower and more tightly constrained than earlier estimates for the Mesoproterozoic. Compilation of published data suggests that low seawater sulfate concentrations began about ∼1.7 Ga and persisted until at least the mid-Mesoproterozoic (∼1.4 Ga), documenting a distinct early Mesoproterozoic perturbation in ocean chemistry that may have been related to a decline in atmospheric pO2 after Great Oxidation Event I.