Ge-Hg-Rich Sphalerite and Pb, Sb, As, Hg, and Ag Sulfide Assemblages in Mud Volcanoes of Sakhalin Island, Russia: An Insight into Possible Origin

Abstract

We characterize the mineralogy and geochemistry of Fe, Zn, Pb, Sb, As, Hg, Ag sulfide assemblages from mud masses currently extruded by the onshore South Sakhalin and Pugachev mud volcanoes (Sakhalin Island, Russia). Abundant Tl-rich pyrite in sulfide concentrate samples from the mud volcanoes coexists with common Hg- and Ge-rich sphalerite, as well as with sporadic boulangerite, robinsonite, bournonite, galena, realgar, metacinnabar, cinnabar, acanthite, and chalcopyrite. Sphalerites are remarkably enriched in Hg (locally reaching 27 wt%) and coupled zwith permanent abnormal enrichment in Ge (3008–3408 ppm). According to single-crystal XRD analyses and Raman spectroscopy, both Hg-poor and Hg-rich sphalerites are single-phase (Zn,Hg)Scub compounds. Pyrite is of diagenetic origin, judging by its trace-element chemistry, particular morphology, and heavy S isotope composition. Another assemblage, composed of Pb-Sb-(Hg) sulfide minerals and lesser As, Cu, Ag, and Bi compounds, results from hydrothermal alteration and is genetically related to Neogene volcano-sedimentary rocks found among the ejecta of the mud volcanoes. The composition of impurities in sphalerite from mud masses indicates crystallization at temperatures lower than ~100 °C, under the leaching effect of mud volcano waters.

Keywords

• sphalerite
• metacinnabar
• cinnabar
• ZnS-HgS series
• Pb-Sb sulfosalts
• LA-ICPMS