Stable isotope (C, O, S) systematics of the mercury mineralization at Idrija, Slovenia: constraints on fluid source and alteration processes

The world-class Idrija mercury deposit (western Slovenia) is hosted by highly deformed Permocarboniferous to Middle Triassic sedimentary rocks within a complex tectonic structure at the transition between the External Dinarides and the Southern Alps. Concordant and discordant mineralization formed concomitant with Middle Triassic bimodal volcanism in an aborted rift. A multiple isotopic (C, O, S) investigation of host rocks and ore minerals was performed to put constraints on the source and composition of the fluid, and the hydrothermal alteration. The distributions of the δ13C and δ18O values of host and gangue carbonates are indicative of a fracture-controlled hydrothermal system, with locally high fluid-rock ratios. Quantitative modeling of the δ13C and δ18O covariation for host carbonates during temperature dependent fluid-rock interaction, and concomitant precipitation of void-filling dolomites points to a slightly acidic hydrothermal fluid (δ13C≈−4‰ and δ18O≈+10‰), which most likely evolved during isotopic exchange with carbonates under low fluid/rock ratios. The δ34S values of hydrothermal and sedimentary sulfur minerals were used to re-evaluate the previously proposed magmatic and evaporitic sulfur sources for the mineralization, and to assess the importance of other possible sulfur sources such as the contemporaneous seawater sulfate, sedimentary pyrite, and organic sulfur compounds. The δ34S values of the sulfides show a large variation at deposit down to hand-specimen scale. They range for cinnabar and pyrite from −19.1 to +22.8‰, and from −22.4 to +59.6‰, respectively, suggesting mixing of sulfur from different sources. The peak of δ34S values of cinnabar and pyrite close to 0‰ is compatible with ore sulfur derived dominantly from a magmatic fluid and/or from hydrothermal leaching of basement rocks. The similar stratigraphic trends of the δ34S values of both cinnabar and pyrite suggest a minor contribution of sedimentary sulfur (pyrite and organic sulfur) to the ore formation. Some of the positive δ34S values are probably derived from thermochemical reduction of evaporitic and contemporaneous seawater sulfates