The speciation of mercury in hydrothermal systems, with applications to ore deposition

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Hg in hydrothermal systems is generally thought to be transported as Hg-S complexes. However, the abundance of Hg 0 vap , in geothermal emissions suggests that Hg 0 eq , is present in the liquid phase of geothermal systems. Calculations for reducing fluids (HS - dominant over SO = 4 ) in equilibrium with cinnabar indicate that Hg 0 eq , can be quite abundant relative to other species at temperatures above 200°C. Increasing pH and temperature, and decreasing total S, ionic strength, and p O 2 all promote the abundance of Hg 0 eq . When a vapor phase develops from a geothermal liquid, Hg partitions strongly into the vapor as Hg 0 vap . Vapor transport at shallow level then results in the formation of Hg halos around shallow aquifers as well as in a flux of Hg to the atmosphere. Hg deposition may occur in response to mixing with oxidizing or acidic water, turning Hg 0 eq , into Hg ++ , with subsequent cinnabar precipitation. When pyrite is the stable Fe-sulfide, cinnabar solubility is at its lowest, so cinnabar + pyrite assemblages are common. Cinnabar + hematite ± pyrite can precipitate from more oxidized or S-poor water. Hg 0 liq , can occur as a primary mineral, in coexistence with all common Fe-sulfides and oxides. Cinnabar ± Hg 0 liq cannot coexist with pyrrhotite or magnetite at temperatures between 100° and 250°C. Evidence from Hg deposits indicates that many formed from dilute hydrothermal fluids in which Hg probably occurred as Hg 0 eq . In S-rich systems, Hg may occur as Hg-S complexes, and in saline waters it can occur as Hg-Cl complexes.

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