Spatially heterogenous seawater δ34S and global cessation of Ca-sulfate burial during the Toarcian oceanic anoxic event

The early Toarcian of the Early Jurassic saw a long-term positive carbon-isotope excursion (CIE) abruptly interrupted by a significant negative excursion (nCIE), associated with rapid global warming and an oceanic anoxic event (T-OAE, ∼183 Ma). However, the detailed processes and mechanisms behind widespread ocean deoxygenation are unclear. Here, we present high-resolution carbonate-associated sulfate sulfur-isotope (δ34SCAS) records spanning the late Pliensbachian–Toarcian (Pl–To) interval from the Tibetan Himalaya. We observe a large positive sulfur-isotope excursion (SIE) from ∼20‰ (around the Pl–To boundary) to ∼40‰ (around the end of the T-OAE nCIE), attributed to large-scale burial of reduced sulfur (pyrite and sulfurized organic matter) under widespread anoxic/euxinic conditions. Importantly, high δ34SCAS values were maintained into the mid–late Toarcian, even when global anoxic conditions diminished. The δ34S data confirm significant spatial heterogeneity in seawater δ34S compositions during the whole of the Toarcian, and provide strong evidence for a two-phase pattern of ocean deoxygenation. Upwelling of 34S-enriched equatorial deep water, affected by significant reduced-sulfur burial, likely caused the greatly amplified SIE in the formerly adjacent Tibetan area. By contrast, the dampened magnitude of the Toarcian SIE in Europe is attributed to a smaller, local reduced-sulfur sink. Box-modeling results indicate that the persistent post-T-OAE positive δ34S values were likely maintained because of a global reduction in Ca-sulfate (gypsum and anhydrite) burial driven by declining and continuously low seawater sulfate concentrations during and after the T-OAE. This geochemical pattern, albeit markedly reducing the total amount of global pyrite sequestration, increased the proportion of reduced to oxidized sulfur burial needed to generate the observed positive δ34S values.