Thermodynamic properties of chlorite and berthierine derived from calorimetric measurements

In the context of the deep waste disposal, we have investigated the respective stabilities of two iron-bearing clay minerals: berthierine ISGS from Illinois [USA; (Al_0.975FeIII_0.182FeII_1.422Mg_0.157Li_0.035Mn_0.002)(Si_1.332Al_0.668)O₅(OH)₄] and chlorite CCa-2 from Flagstaff Hill, California [USA; (Si_2.633Al_1.367)(Al_1.116FeIII_0.215Mg_2.952FeII_1.712Mn_0.012Ca_0.011)O₁₀(OH)₈]. For berthierine, the complete thermodynamic dataset was determined at 1 bar and from 2 to 310 K, using calorimetric methods. The standard enthalpies of formation were obtained by solution-reaction calorimetry at 298.15 K, and the heat capacities were measured by heat-pulse calorimetry. For chlorite, the standard enthalpy of formation is measured by solution-reaction calorimetry at 298.15 K. This is completing the entropy and heat capacity obtained previously by Gailhanou et al. (Geochim Cosmochim Acta 73:4738–4749, 2009) between 2 and 520 K, by using low-temperature adiabatic calorimetry and differential scanning calorimetry. For both minerals, the standard entropies and the Gibbs free energies of formation at 298.15 K were then calculated. An assessment of the measured properties could be carried out with respect to literature data. Eventually, the thermodynamic dataset allowed realizing theoretical calculations concerning the berthierine to chlorite transition. The latter showed that, from a thermodynamic viewpoint, the main factor controlling this transition is probably the composition of the berthierine and chlorite minerals and the nature of the secondary minerals rather than temperature.     

Variations in Chemical Composition of Clay Minerals and Magnetic Susceptibility of Hydrothermally Altered Rocks in the Hishikari Epithermal Gold Deposit, SW Kyushu, Japan

Hydrothermal alteration, involving chiefly chlorite and illite, is extensively distributed within host rocks of the Pleistocene Hishikari Lower Andesites (HLA) and the Cretaceous Shimanto Supergroup (SSG) in the underground mining area of the Hishikari epithermal gold deposit, Kagoshima, Japan. Approximately 60% of the mineable auriferous quartz‐adularia veins in the Honko vein system occur in sedimentary rocks of the SSG, whereas all the veins of the Yamada vein system occur in volcanic rocks of the HLA. Variations in the abundance and chemical composition of hydrothermal minerals and magnetic susceptibility of the hydrothermally altered rocks of the HLA and SSG were analyzed. In volcanic rocks of the HLA, hydrothermal minerals such as quartz, chlorite, adularia, illite, and pyrite replaced primary minerals. The amount of hydrothermal minerals in the volcanic rocks including chlorite, adularia, illite, and pyrite as well as the altered and/or replaced pyroxenes and plagioclase phenocrysts increases toward the veins in the Honko vein system. The vein‐centered variation in mineral assemblage is pronounced within up to 25 m from the veins in the peripheral area of the Honko vein system, whereas it is not as apparent in the Yamada vein system. The hydrothermal minerals in sandstone of the SSG occur mainly as seams less than a few millimeters thick and are sporadically observed in halos along the veins and/or the seams. The alteration halos in sandstone of the SSG are restricted to within 1 m of the veins. In the peripheral area of the Honko vein system, chlorite in volcanic rocks is characterized by increasing in Al in its tetrahedral layer and the Fe/Fe + Mg ratio toward the veins, while illite in volcanic rocks has relatively low K and a restricted range of Fe/Fe + Mg ratios. Temperature estimates derived from chlorite geothermometry rise toward the veins within the volcanic rocks. The magnetic susceptibility of tuff breccia of the HLA varies from 21 to less than 0.01 × 10^?3 SI within a span of 40 m from the veins and has significant variation relative to that of andesite (27–0.06 × 10^?3 SI). The variation peripheral to the Honko vein system correlates with an increase in the abundance of hematite pseudomorphs after magnetite, the percentage of adularia and chlorite with high Fe/Fe + Mg ratios, and the degree of plagioclase alteration with decreasing distance to the veins. In contrast, sedimentary rocks of the SSG maintain a consistent magnetic susceptibility across the alteration zone, within a narrow range from 0.3 to 0.2 × 10^?3 SI. Magnetic susceptibility of volcanic rocks of the HLA, especially tuff breccia, could serve as an effective exploration tool for identifying altered volcanic rocks.     

REE Mineralization of Weathered Crust and Clay Sediment on Granitic Rocks in the Sanyo Belt,SW Japan and the Southern Jiangxi Province,China

Rare earth element (REE) geochemistry and mineralogy have been studied in the weathered crusts derived from the Early Yanshanian (Jurassic) biotite granites of Dabu and Dingnan, as well as in the Indosinian (Permian) muscovite–biotite granite of Aigao in southern Jiangxi province, China, and the weathered crusts and clay sediments on biotite granites in the Sanyo belt, SW Japan, that is, Okayama, Tanakami, and Naegi areas. In all of the weathered crusts, biotite and plagioclase commonly tend to decrease toward the upper part of the profile, whereas kaolinite and residual quartz and K‐feldspar increase. The weathered crusts of the Dingnan granites and some Naegi granites, which are characterized by the enrichment in light REE (LREE) in C horizons, have higher total REE (ΣREE) content than the parent REE‐enriched granites. Weathering of LREE‐bearing apatite and fluorocarbonates in the Dingnan granites and allanite and apatite in some Naegi granites may account for the leaching of LREE at the B horizons. The leached LREE must result in subsequent enrichment of LREE in the C horizons. The enrichment is probably associated with mainly adsorption onto kaolinite and partly formation of possible secondary LREE‐bearing minerals. In Japan it was found that REE mineralization occurs not in the weathered granitic crusts but in reworked clay sediments, especially kaolinite‐rich layers, derived mainly from the weathering materials of REE‐enriched granitic rocks. The clay sediments are more enriched in LREE, which likely adsorbed onto kaolinite. Concentration of heavy REE within almost all the weathered crusts and clay sediments, however, may reflect mainly residual REE‐bearing minerals such as zircon, which originated in the parent granitic rocks. The findings of the present study support the three processes for fractionation of the REE during weathering: (i) selective leaching of rocks containing both stable and unstable REE‐bearing minerals; (ii) adsorption onto clay minerals; and (iii) presence of possible secondary LREE‐bearing minerals.     

Carbonate precipitation through photoautotrophic microorganisms at the Giza cliff in Okinawa,Japan

Environmentally friendly options for restoring limestone using microorganisms have attracted recent attention. The governing principle of this technique is to use the metabolism of microorganisms to precipitate carbonate in the gaps of mineral particles; this process is known as microbial carbonate precipitation (MCP). Here, an outcrop associated with MCP under natural conditions at the Giza cliff in Okinawa, Japan was investigated. Colonies of photoautotrophic microorganisms containing chlorophyll were found inhabiting a layer of limestone 2–4 mm below the surface of the outcrop. These microorganisms survived and photosynthesised within the limestone under favorable conditions that include an effective photon flux density of 15–75 µmol/m²/s, and some fresh calcium carbonates (i.e., calcite) were precipitated around the cell walls and extracellular polymeric substances (EPS) of the microorganisms. Furthermore, the results of powder X-ray diffraction (XRD) suggest that the synthetic calcite within the limestone may improve the mechanical strength of the outcrop. These in situ and laboratory findings indicate that these microbial functions may be applicable to some weathered rock surfaces as a self-organizing surface protection and conservation technology.