Structural relaxation in the MnCO3–CaCO3 solid solution: a Mn K-edge EXAFS study

Mn K-edge EXAFS spectroscopy of solid-solution samples encompassing the complete MnCO₃–CaCO₃ series shows that first-shell Mn–O distances deviate little from the 2.19-Å distance observed in pure MnCO₃. Very slight lengthening is observed only in the limiting case of dilute Mn(II) calcite solid solutions, where the Mn–O distance is 2.21 Å. The observed nearly complete structural relaxation and the composition independence of the Mn–O distance are consistent with the Pauling model behavior of solid solutions, and agree with previous studies showing a high degree of relaxation around hetero-sized substituents in the calcite structure. Strain occurs through bond bending, which is facilitated by the exclusively corner-sharing topology of calcite. Observed distances from Mn to more distant neighbors show significant variation across the solid-solution series that resembles Vegard's law-type behavior but reflects averaging. The high degree of relaxation suggests modest enthalpies of mixing in the solution, consistent with calorimetric studies.     

Stability,transformations and stabilizing potential of an amorphous manganese oxide and its surface-modified form in contaminated soils

A surface-modified amorphous manganese oxide (SM-AMO) was prepared to increase the stability of a previously studied promising stabilizing agent and to compare its immobilizing efficiency with respect to contaminating metals with the original material. To synthesize the SM-AMO, the AMO surface was synthetically covered with a coating of MnCO₃ because newly formed rhodochrosite precipitates were previously found to increase the stability of AMO particles in soils. A preliminary experiment evaluating the long-term stability of both materials in pure water suggested higher stability for the SM-AMO particles, showing a smaller release of Mn compared to the original AMO. An adsorption kinetics study focused on As, Cd, Pb and Zn showed lower adsorption rates and adsorption capacity for Zn, probably as a result of partial surface passivation. In comparison to these results for simple controlled systems, different effects were recorded when the two materials were applied to contaminated soils. When incubated in soil, a constantly lower mass loss was recorded in the case of SM-AMO. There were no significant differences in the release of Mn and DOC into the soil solution or in the stabilizing efficiency with regard to contaminating metal(loid)s between the original and surface-modified materials. Concerning the potential solid phase transformations in soil conditions, we observed a gradual equilibration between the surface composition of both materials. While the newly formed rhodochrosite precipitated on the AMO surface, the MnCO₃ coatings on SM-AMO gradually dissolved. Both amendments also effectively supported microbial activity, especially in the more contaminated soil sample. Thus, despite the smaller mass loss, the effectiveness of both materials is comparable in the long term.     

Geochemistry of Flooded Underground Mine Workings Influenced by Bacterial Sulfate Reduction

Unlike the majority of the water in the flooded mine complex of Butte Montana, which includes the highly acidic Berkeley pit lake, groundwater in the flooded West Camp underground mine workings has a circum-neutral pH and contains at least 8 μM aqueous sulfide. This article examines the geochemistry and stable isotope composition of this unusual H₂S-rich mine water, and also discusses problems related to the colorimetric analysis of sulfide in waters that contain FeS_(aq) cluster compounds. The West Camp mine pool is maintained at a constant elevation by continuous pumping, with discharge water that contains elevated Mn (90 μM), Fe (16 μM), and As (1.3 μM) but otherwise low metal concentrations. Dissolved inorganic carbon in the mine water is in chemical and isotopic equilibrium with rhodochrosite in the mineralized veins. The mine water is under-saturated with mackinawite and amorphous FeS, but is supersaturated with Cu- and Zn-sulfides. However, voltammetry studies show that much of the dissolved sulfide and ferrous iron are present as FeS_(aq) cluster molecules: as a result, the free concentration of the West Camp water is poorly constrained. Concentrations of dissolved sulfide determined by colorimetry were lower than gravimetric assays obtained by AgNO₃ addition, implying that the FeS_(aq) clusters are not completely extracted by the Methylene Blue reagent. In contrast, the clusters are quantitatively extracted as Ag₂S after addition of AgNO₃. Isotopic analysis of co-existing aqueous sulfide and sulfate confirms that the sulfide was produced by sulfate-reducing bacteria (SRB). The H₂S-rich mine water is not confined to the immediate vicinity of the extraction well, but is also present in flooded mine shafts up to 3 km away, and in samples bailed from mine shafts at depths up to 300 m below static water level. This illustrates that SRB are well established throughout the southwestern portion of the extensive (>15 km³) Butte flooded mine complex.     

Standard thermodynamic data for Rhodochrosite from equilibrium decomposition curve

Hydrothermal equilibrium decomposition curve for MnCO₃⇌MnO + CO₂ in the total CO₂ pressure range of 100–1700 bars and temperature range of 500–800°C was studied. The standard thermodynamic data obtained are: ΔH⁰ _f= − 894.382 ± 0.74 kj/mol and ΔG⁰ _f = − 822.170 ± 0.74 kj/mol. These values are more negative than the reported calorimetric data.     

川北高燕锰矿的锰质岩类型和生物成矿作用

川北高燕陡山沱组锰矿的锰质岩有四种主要类型：由富藻层和碎屑层组成的叠层石锰质岩，由藻屑，鲕屑组成的藻屑锰质岩和由锰质内碎屑与各种基质组成的内碎屑锰质岩。根据矿层中赋存的大量藻类遗体及其与矿石的密切共生关系来看．生物特别是藻类参与了锰矿的成矿作用。     

The Sweet Home rhodochrosite specimen mine,Alma District,Central Colorado: the porphyry molybdenum–fluorine connection

Intermediate sulfidation veins containing quartz–sphalerite–tetrahedrite–rhodochrosite–fluorite in the Sweet Home Mine, Alma District, Colorado were originally mined for silver starting in 1873. For the last 13 years up until 2004, however, the mine has produced world-class rhodochrosite specimens. Some of these specimens are considered to be among the finest mineral specimens ever produced and the finest of their species with values well over $1 million US dollars. The extraction, preparation, and marketing techniques pioneered at the Sweet Home operation have revolutionized the minerals specimen industry. The Sweet Home deposit is interpreted as a single pulse variant of a Climax-type hydrothermal system. Evidence for this includes (1) an age of mineralization (25.8 ± 0.3 Ma) that coincides with the age of the end stages of mineralization of the Climax molybdenum deposit approximately 7.5 km to the northeast; (2) a geochemical (Mn, W, F) and mineralogical (topaz, fluorite, hubnerite, greisen muscovite) signature typically associated with Climax-type systems; (3) the presence of porphyry rhyolite dikes, a breccia dike, and local quartz–molybdenite veins in the nearby area; (4) a small pegmatite within the mine with an age (25.9 ± 0.3 Ma) coincident with mineralization, which also contains minor amounts of disseminated molybdenite; and (5) the presence of similar-appearing gemmy, red rhodochrosites at Climax and other high-silica rhyolite systems. A significant difference is that unlike Climax-type systems, the Sweet Home hydrothermal system appears to have consisted of a single, relatively small pulse of magmatic fluid that slowly cooled and diluted with groundwater. This is inferred to have occurred at moderate depths in the order of 1.5–2.5 km below the surface. The fluids that formed the Sweet Home veins were dilute (salinity in the order of 2–4 wt% NaCl equivalent), high-temperature (temperatures of homogenization up to 370°C), and initially of magmatic origin. Gem quality ruby-red rhodochrosite at the Sweet Home Mine is nearly pure manganese carbonate with minimal solid solution with Fe⁺², Ca, or Mg. It formed at higher temperatures and salinities in comparison to lower value, pink rhodochrosite. Gemmy, ruby-red rhodochrosite is distinctly associated with highly evolved silica-rich igneous/hydrothermal systems. The high fluorine content typical of such systems suggests that Mn was transported in solution as fluoride complexes, which, in turn, favored rhodochrosite deposition at above-average temperatures and with minimal cation contamination. An erratum to this article can be found at     

A geochemical study of the Sweet Home Mine,Colorado Mineral Belt,USA: hydrothermal fluid evolution above a hypothesized granite cupola

Deposition of quartz–molybdenite–pyrite–topaz–muscovite–fluorite and subsequent hübnerite and sulfide–fluorite–rhodochrosite mineralization at the Sweet Home Mine occurred coeval with the final stage of magmatic activity and ore formation at the nearby world-class Climax molybdenum deposit about 26 to 25 m.y. ago. The mineralization occurred at depths of about 3,000 m and is related to at least two major fluid systems: (1) one dominated by magmatic fluids, and (2) another dominated by meteoric water. The sulfur isotopic composition of pyrite, strontium isotopes and REY distribution in fluorite suggest that the early-stage quartz–molybdenite–pyrite–topaz–muscovite–fluorite mineral assemblage was deposited from magmatic fluids under a fluctuating pressure regime at temperatures of about 400°C as indicated by CO₂-bearing, moderately saline (7.5–12.5 wt.% NaCl equiv.) fluid inclusions. LA-ICPMS analyses of fluid inclusions in quartz demonstrate that fluids from the Sweet Home Mine are enriched in incompatible elements but have considerably lower metal contents than those reported from porphyry–Cu–Au–Mo or Climax-type deposits. The ore-forming fluid exsolved from a highly differentiated magma possibly related to the deep-seated Alma Batholith or distal porphyry stock(s). Sulfide mineralization, marking the periphery of Climax-type porphyry systems, with fluorite and rhodochrosite as gangue minerals was deposited under a hydrostatic pressure regime from low-salinity ± CO₂-bearing fluids with low metal content at temperatures below 400°C. The sulfide mineralization is characterized by mostly negative δ³⁴S values for sphalerite, galena, chalcopyrite, and tetrahedrite, highly variable δ¹⁸O values for rhodochrosite, and low REE contents in fluorite. The Pb isotopic composition of galena as well as the highly variable ⁸⁷Sr/⁸⁶Sr ratios of fluorite, rhodochrosite, and apatite indicates that at least part of the Pb and Sr originated from a much more radiogenic source than Climax-type granites. It is suggested that the sulfide mineralization at the Sweet Home Mine formed from magmatic fluids that mixed with variable amounts of externally derived fluids. The migration of the latter fluids, that were major components during late-stage mineralization at the Sweet Home Mine, was probably driven by a buried magmatic intrusion.     

湖南桃江奥陶系磨刀溪组锰质岩的内碎屑结构和重力流沉积

湖南桃江一带的奥陶纪锰质碳酸盐岩,具有清晰的内碎屑结构和一些粒度递变沉积构造。锰质岩或锰矿层呈薄层或条带夹在含有笔石的黑色泥页岩中,表现出它们在成因或沉积环境方面的极不协调。以砂屑和藻屑为主组成的白色、灰白色锰质碳酸盐岩是清洁、浅水、碱性环境中的产物;以细粉砂级颗粒为主并含有硅质、碳质的泥页岩则是污浊、深水、酸性环境中的沉积。这种不协调的沉积组合是由于浅水锰质碳酸盐沉积物以重力流方式进入深水盆地与黑色泥质沉积物混合、交互沉积结果。     

Spessartine Garnets in a Manganiferous Carbonate Formation from Nsuta, Ghana

Abstract: Manganese carbonate ore beds and host rock manganiferous phyllites at the Nsuta mine, western Ghana, contain well developed garnet crystals. Individual crystals are idioblastic, sometimes porphyroblastic, and homogeneous, and are associated with rhodochrosite (with or without kutnahorite), quartz and muscovite. The conspicuous absence of chlorite in garnet-rich assemblages, and of garnet in chlorite-rich rocks, suggest chemical constraints may have been important in the formation of the two minerals. Gondite bands within carbonate ores are interpreted to have resulted from localised processes in which manganese carbonates, in environments rich in alumino-silicate minerals, may have been completely exhausted during metamorphic reactions.