Pyrite geochemistry in the Toarcian Posidonia Shale of south‐west Germany: Evidence for contrasting trace‐element patterns of diagenetic and syngenetic pyrites

Authigenic pyrite grains from a section of the Lower Toarcian Posidonia Shale were analysed for their trace‐element contents and sulphur‐isotope compositions. The resulting data are used to evaluate the relationship between depositional conditions and pyrite trace‐element composition. By using factor analysis, trace‐elements in pyrite may be assigned to four groups: (i) heavy metals (including Cu, Ni, Co, Pb, Bi and Tl); (ii) oxyanionic elements (As, Mo and Sb); (iii) elements partitioned in sub‐microscopic sphalerite inclusions (Zn and Cd); and (iv) elements related to organic or silicate impurities (Ga and V). Results indicate that trace‐element contents in pyrite depend on the site and mechanism of pyrite formation, with characteristic features being observed for diagenetic and syngenetic pyrites. Diagenetic pyrite formed within anoxic sediments generally has a high heavy metals content, and the degree of pyritization of these elements increases with increasing oxygen deficiency, similar to the degree of pyritization of reactive Fe. The highest gradient in the increase of the degree of trace element pyritization with bottom‐water oxygenation was found for the elements Ni < Cu < Mo = As < Tl. In contrast, syngenetic pyrite formed within a euxinic water column typically is enriched in As, Mo and Sb, but is low in heavy metals, and the geochemical variation reflects changes in sea water composition.     

Role of carbonates in mitigation of metal release from mining waste. Evidence from humidity cells tests

 Leaching of two contrasting types of sulphidic tailings in humidity cells has been performed. The release of heavy metals and the oxidation rate have been studied. Tailings from the Laver mine contain a few percent sulphides and lack carbonates, whereas tailings from the Stekenjokk mine are both sulphide- and carbonate-rich. The results showed that in the leachates from the Laver samples, the metal concentrations increased and pH decreased with time, indicating an increased oxidation rate. In the Stekenjokk samples, pH remained high during the experiment, thereby keeping the metal concentrations low in the leachates. The oxidation rate also decreased with time, probably due to Fe-hydroxide coatings on sulphide surfaces. The results show that addition of carbonates and the maintenance of a high pH not only reduce the solubility of heavy metals, but also decrease the oxidation rate of sulphides. Received: 20 January 1998 · Accepted: 2 April 1998     

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

Hg in hydrothermal systems is generally thought to be transported as Hg-S complexes. However, the abundance of Hg⁰_vap, in geothermal emissions suggests that Hg⁰_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 Hg⁰_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 pO₂ all promote the abundance of Hg⁰_eq. When a vapor phase develops from a geothermal liquid, Hg partitions strongly into the vapor as Hg⁰_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 Hg⁰_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. Hg⁰_liq, can occur as a primary mineral, in coexistence with all common Fe-sulfides and oxides. Cinnabar ± Hg⁰_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 Hg⁰_eq. In S-rich systems, Hg may occur as Hg-S complexes, and in saline waters it can occur as Hg-Cl complexes.