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.