Extreme sulfur isotope fractionation in the Late Devonian Dry Creek volcanogenic massive sulfide deposit, central Alaska

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The Dry Creek Zn-Pb-Cu-Ag-Au volcanogenic massive sulfide (VMS) deposit, in east-central Alaska, occurs in a Late Devonian sequence of peralkaline rhyolite tuff, minor graphitic argillite, and local peralkaline quartz-porphyry rhyolite intrusions. Principal mineralized facies are semi-massive and massive sulfide in variably silicified and graphitic rhyolite tuff, massive sulfide in graphitic argillite, disseminated sulfides in graphitic and non-graphitic rhyolite tuff, and vein-hosted sulfides in a subvolcanic, peralkaline quartz-porphyry intrusion. In situ analysis of the sulfur isotope composition of sulfide minerals from all facies of the deposit shows a total range in δ34S values from −48.0 to 23.1‰. This remarkable 71.1‰ variation is more than twice the largest range known for sulfides in nearly all individual VMS deposits, both modern and ancient, which typically is <25‰. Based on results of geochemical reaction modeling presented here, extreme sulfur isotope systematics in the Dry Creek deposit is attributed to two main processes: low-temperature (<100 °C) kinetically controlled bacterial sulfate reduction (BSR) in anoxic to locally sulfidic bottom waters and pore fluids, and higher temperature (100–300 °C) hydrothermal sulfate reduction (HSR) of seawater sulfate during water-rock reactions. Deposition of organic-rich sediments prior to and during mineralization provided the key environment that promoted microbially mediated fractionations with Δ34Ssulfate-sulfide of up to 70‰. During BSR reaction progress modeling, residual sulfate evolved by Rayleigh distillation in pore water, producing δ34SSO4 values up to 58‰; normal Late Devonian seawater sulfate had δ34SSO4 = 22‰. BSR produced FeS precipitates with δ34S values from −50 to −15‰. Integrated textural and δ34S data also suggest that isotopically light H2S produced in pore fluids by BSR was incorporated into hydrothermal fluids and early disseminated sulfide minerals during the emplacement of peralkaline quartz-porphyry rhyolite intrusions in the shallow subsurface, broadly coeval with VMS mineralization. Modeling of moderate- to high-temperature (100–300 °C) hydrothermal sulfate reduction (HSR) of seawater-rock interaction predicts sulfide minerals with δ34S values from −8 to 19‰.High-precision CA-ID-TIMS U-Pb geochronology of zircons from a synvolcanic peralkaline quartz porphyry intrusion yields a weighted mean 206Pb/238U date of 363.02 ± 0.43 Ma (2σ total uncertainty). This date indicates that the formation of graphitic and sulfidic sediments at Dry Creek, and contemporaneous VMS mineralization, occurred at least 3.6 m.y. before, and hence are unrelated to, widespread black shale deposition during the Hangenberg Event at ca. 359 Ma.