A volatile sulfur sink aids in reconciling the sulfur isotope mass balance of closed basin lakes

Sedimentary rocks from the early Eocene Green River Formation comprise the largest known lacustrine oil shale deposits, contain remarkably well-preserved fossils, and provide a unique record of climate evolution across the Early Eocene Climate Optimum, a period of high atmospheric CO₂. The depositional environment of these intermountain lakes spanned from relatively fresh and fluvially influenced to expanded and stratified saline closed basin lakes under the influence of the Laramide orogeny and alternating humid and arid climatic conditions. As the surface area of the lakes expanded, alkalinity and salinity increased, with depositional cycles that linked to evaporative cycles and marked by an increasing abundance of organic matter-rich shales (TOC > 10 wt. %). Simultaneously, an intriguing 20 ‰ positive shift in the sulfur isotope composition of sulfide minerals and organic sulfur is observed. Given that this trend cannot be simply explained by a change in the source of sulfate delivered to the basin, the evolution of biogeochemical sulfur cycle and the balance of fluxes in response to basin evolution remain unresolved. Here, we combine the sulfur isotope compositions of pyrite, organic sulfur, and carbonate-associated sulfate and molecular proxies of euxinia in samples from the Uinta basin's depocenter. We find that organic matter-rich sediments reflect deposition in a stratified water column with enhanced burial of pyrite and sulfurized organic matter, while organic-lean facies present evidence of, at least transiently, euxinic conditions reaching the photic zone during arid conditions presumably because of evaporation. As the lake became both saline-stratified and euxinic, we observe that δ³⁴S values of all measured sulfur-bearing sedimentary proxies increase and evolve along a 1:1 line, a trend independent of facies that we interpret as reflecting a sulfate-limited system despite saline conditions. The isotopic mass balance of sulfur fluxes implies the existence of a sink of sulfur depleted in ³⁴S that is spatially decoupled from burial in the depocenter. Modeling sulfur biogeochemical processes in a saline stratified lake system allows us to estimate that at least 50 % of the sulfur entering the lake could have been lost from the upper part of the euxinic water column where the fractionation factor imparted by microbial sulfate reduction is expressed. We propose that the overall isotopic enrichment of the system was caused by H₂S degassing during arid climate intervals, presumably enhanced by transient water column mixing events. Further, episodic intrusion of euxinic bottom waters into the upper part of the water column might have triggered mass fish and plankton mortality, consequently facilitating the formation of these exceptionally fossiliferous and organic matter-rich rocks. Our study finds that volatile outgassing may be an underappreciated mechanism for the sulfur mass balance of stratified lacustrine systems.