Significant fluctuation in the global sulfate reservoir and oceanic redox state during the Late Devonian event.

Ocean sulfate concentration might have fluctuated greatly throughout the Earth's history and may serve as a window into perturbations in the ocean-atmosphere system. Coupling high-resolution experimental results with an inverse modeling approach, we, here, show an unprecedented dynamic in the global sulfate reservoir during the Frasnian-Famennian (F-F) boundary event, as one of the "Big five" Phanerozoic biotic crises. Notably, our results indicate that, in a relatively short-time scale (∼200 thousand years), seawater sulfate concentration would have dropped from several mM before the Upper Kellwasser Horizon (UKH) to an average of 235 ± 172 μM at the end of the UKH (more than 100 times lower than the modern level) as the result of evaporite deposition and euxinia, and returned to around mM range after the event. Our findings indicate that the instability in the global sulfate reservoir and nutrient-poor oceans may have played a major role in driving the Phanerozoic biological crises.