Oxidation and metal-insertion in molybdenite surfaces: evaluation of charge-transfer mechanisms and dynamics

Molybdenum disulfide (MoS₂), a layered transition-metal dichalcogenide, has been of special importance to the research community of geochemistry, materials and environmental chemistry, and geotechnical engineering. Understanding the oxidation behavior and charge-transfer mechanisms in MoS₂ is important to gain better insight into the degradation of this mineral in the environment. In addition, understanding the insertion of metals into molybdenite and evaluation of charge-transfer mechanism and dynamics is important to utilize these minerals in technological applications. Furthermore, a detailed investigation of thermal oxidation behavior and metal-insertion will provide a basis to further explore and model the mechanism of adsorption of metal ions onto geomedia.     

Sequential extraction and leaching characteristics of heavy metals in abandoned tungsten mine tailings sediments

The chemical speciation of potentially toxic elements (As, Cd, Cu, Pb, and Zn) in the contaminated soils and sulfides-rich tailings sediments of an abandoned tungsten mine in Korea was evaluated by conducting modified BCR sequential extraction tests. Kinetic and static batch leaching tests were also conducted to evaluate the potential release of As and other heavy metals by acidic rain water and the leaching behaviors of these heavy metals. The major sources of the elements were As-, Zn- and Pb-bearing sulfides, Pb carbonates (i.e., cerussite), and Pb sulfates (i.e., anglesite). The biggest pollutant fraction in these soil and tailing samples consists of metals bound to the oxidizable host phase, which can be released into the environment if conditions become oxidative, and/or to residual fractions. No significant difference in total element concentrations was observed between the tailings sediments and contaminated soils. For both sample types, almost no changes occurred in the mobility of As and the other heavy metals at 7 days, but the mobility increased afterwards until the end of the tests at 30 days, regardless of the initial pH. However, the mobility was approximately 5–10 times higher at initial pH 1.0 than at initial pHs of 3.0 and 5.0. The leached amounts of all the heavy metal contents were higher from tailings sediments than from contaminated soils at pH > 3.0, but were lower at pH < 3.0 except for As. Results of this study suggest that further dissolution of heavy metals from soil and tailing samples may occur during extended rainfall, resulting in a serious threat to surface and groundwater in the mine area.     

The effect of annealing on the luminescence decay-time of synthetic calcite:Mn

Calcite was synthesized by four methods, and the luminescence decay-time was measured for nine samples before and after heating hydrothermally in the temperature range 200–400°C. Decay-time data were collected between room temperature and approximately 15 K. The decay time at room temperature is approximately 50 ms, with little difference between a given calcite before and after hydrothermal treatment. The decay time at 15 K is always greater than at room temperature as the effect of thermal quenching diminishes. Differences in decay time before and after heating are more apparent at low temperature owing to this reduction in thermal quenching. The decay time decreased significantly in two samples, and an increase in decay time was observed in the remaining seven samples following heating. Among the latter group, the change in decay time was insignificant in three samples. The results are compared with previous data in which it was shown that the effect of heating is to increase the intensity of luminescence.     

Iron isotopic analyses of geological reference materials on MC-ICP-MS with instrumental mass bias corrected by three independent methods

Here we report iron (Fe) isotopic data of three pure Fe solution standards (IRMM-014, GSB Fe, and NIST 3126a) and five widely used geological reference materials (RMs) from the United States Geological Survey and Geological Survey of Japan obtained on a Neptune Plus multi-collector–inductively coupled plasma–mass spectrometer (MC-ICP-MS) in our laboratory over the past 3 years. The instrumental mass bias was corrected by three independent methods: sample-standard bracketing (SSB), Ni doping?+?SSB, and ⁵⁷Fe–⁵⁸Fe double spike?+?SSB. Measurements reveal that both the Ni doping and double spike methods helped calibrate short-term fluctuations in mass bias. Collectively, almost all measurements of RMs yielded δ⁵⁶Fe within?±?0.05 of recommended values, provided that each sample was measured four times on MC-ICP-MS. For the first time, new recommended values for NIST SRM3126a are reported (δ⁵⁶Fe?=?0.363?±?0.006, 2SE, 95% CI; and δ⁵⁷Fe?=?0.534?±?0.010, 2SE).     

Petrography and geochemistry of Jurassic sandstones from the Jhuran Formation of Jara dome,Kachchh basin,India: Implications for provenance and tectonic setting

Sandstones of Jhuran Formation from Jara dome, western Kachchh, Gujarat, India were studied for major, trace and rare earth element (REE) geochemistry to deduce their paleo-weathering, tectonic setting, source rock characteristics and provenance. Petrographic analysis shows that sandstones are having quartz grains with minor amount of K-feldspar and lithic fragments in the modal ratio of Q ₈₉:F ₇:L ₄. On the basis of geochemical results, sandstones are classified into arkose, sub-litharenite, wacke and quartz arenite. The corrected CIA values indicate that the weathering at source region was moderate to intense. The distribution of major and REE elements in the samples normalized to upper continental crust (UCC) and chondrite values indicate similar pattern of UCC. The tectonic discrimination diagram based on the elemental concentrations and elemental ratios of Fe₂O₃ + MgOvs. TiO₂, SiO₂ vs. log(K₂O/Na₂O), Sc/Cr vs. La/Y, Th–Sc–Zr/10, La–Th–Sc plots Jhuran Formation samples in continental rift and collision settings. The plots of Ni against TiO₂, La/Sc vs. Th/Co and V–Ni–Th ?10 reveals that the sediments of Jhuran Formation were derived from felsic rock sources. Additionally, the diagram of (Gd/Yb) _N against Eu/Eu ^? suggest the post-Archean provenance as source possibly Nagar Parkar complex for the studied samples.     

Proximal and distal styles of pegmatite-related metasomatic emerald mineralization at Ianapera,southern Madagascar

The Ianapera emerald deposit is located in the Neoproterozoic Vohibory Block of southern Madagascar. The local geology consists of intercalated migmatitic gneissic units and calcareous metasedimentary rocks, containing boudinaged metamorphosed mafic/ultramafic lenses, all intruded by pegmatite veins. These units occur near the hinge of the tightly folded Ianapera antiform, within a few kilometers of the Ampanihy shear zone. Emerald mineralization is hosted by metasomatic phlogopite veins, and bodies developed within the mafic/ultramafic rocks. Based on field and textural relationships, we distinguish proximal and distal styles of mineralization. Proximal mineralization occurs at the contact of pegmatite veins with mafic/ultramafic units; in the distal style, pegmatites are not observed. Three types of emeralds could be distinguished, mainly on the basis of color and mineral zoning. Some of these emeralds have the most Al-depleted and Cr-rich composition ever recorded. Another characteristic feature to the Ianapera deposit and, to our knowledge, yet unreported, is the association of some emeralds with scapolite in metasomatised mafic rocks. Mineral inclusions are common in most emeralds and include phlogopite, carbonates, barite, K-feldspar, quartz, pyrite, zircon, monazite, bastnaesite, phenakite, plus Fe and Cr oxides. However, feldspar and rare earth element-bearing minerals occur predominantly in proximal emeralds, which also have a more incompatible trace-element signature than distal emeralds. We propose a model related to syn- to post-tectonic magmatic-hydrothermal activity. Pegmatitic bodies intruded units of the Ianapera antiform probably during tectonic relaxation. Exsolution of fluids rich in halogens and incompatible elements from the cooling pegmatites caused hydrothermal metasomatism of Cr-bearing mafic/ultramafic rocks in direct contact with the pegmatites. Local fracturing favored fluid infiltration, permitting the formation of distal mineralization. Emerald composition was controlled by the chemistry of the host rock. The presence of carbonate mineral inclusions in the emeralds and the high F-activity indicated by elevated F-contents in newly formed minerals suggest transport of Be as a fluoride-carbonate complex. It seems likely that beryl formation was triggered by precipitation of F-rich phlogopite, which removed the complexing ligand from the fluid.     

Ionic conductivity in gem-quality single-crystal alkali feldspar from the Eifel: temperature,orientation and composition dependence

We measured the ion conductivity of single-crystal alkali feldspar originating from two different locations in the Eifel/Germany, named Volkesfeld and Rockeskyller sanidine and having potassium site fractions \(C_\mathrm{K}\) of 0.83 and 0.71, respectively. The dc conductivities resulting from electrochemical impedance spectroscopy over the temperature range of 300–900 \(^{\circ }\hbox {C}\) show a weak composition dependence but pronounced differences between the b-direction [\(\perp (010)\)] and \(c^{*}\)-direction [\(\perp (001)\)] of the monoclinic feldspar structure. Conductivity activation energies obtained from the observed linear Arrhenius plots are close to 1.2 eV in all cases, which is closely similar to the activation energies of the \(^{22}\mathrm{Na}\) tracer diffusivity in the same crystals. Taking into account literature data on K tracer diffusion and diffusion correlation effects, the present results point to a predominance of the interstitialcy mechanism over the vacancy mechanism in mass and charge transport on the alkali sublattice in potassium-rich alkali feldspar.     

Adsorption of antimony(V) on kaolinite as a function of pH,ionic strength and humic acid

The present work investigated the adsorption and mobility (desorption) of Sb(V) on kaolinite using batch experiments. The adsorption of Sb(V) on kaolinite was studied as a function of contact time, pH, ionic strength, humic acid (HA), initial Sb(V) concentration and temperature. Kinetic studies suggest that the equilibrium is achieved within 24 h. The adsorption of Sb(V) was strongly affected by changes in I at low ionic strength and unaffected at high ionic strength. The adsorption is weakly dependent on the presence of humic acid, but is strongly dependent on pH. Within the range tested, the optimal pH for Sb(V) adsorption is 3.6, and close to 75% removal can be achieved. Desorption is dependent on the original suspension pH. The addition sequence of Sb(V)/HA do not influence the adsorption of Sb(V) on kaolinite. The adsorption data fit both the Freundlich and Langmuir isotherm. The thermodynamic parameters (ΔH ⁰, ΔS ⁰ and ΔG ⁰) were calculated from the temperature dependence, and the results suggest the endothermic and spontaneous nature of the process.     

Tin partition behavior and implications for the Furong tin ore formation associated with peralkaline intrusive granite in Hunan Province,China

Tin deposits are often closely associated with granitic intrusions. In this study, we analyzed tin partition coefficients between different fluids and melts (\({\text{D}}_{Sn}^{aq.fl./melt}\)) as well as various crystals and melts \({\text{D}}_{Sn}^{aq.fl./melt}\)(\({\text{D}}_{Sn}^{crystal/melt}\)) from the Furong tin deposit associated with the Qitianling A-type granite. Our experimental results indicate that tin partition behavior is affected by the chemical compositions of fluids, melts, and minerals. Tin is prone to partitioning into the residual magma in fractional crystallization or other differential magmatic processes if the magma originated from crustal sources with high alkali content, high volatile content, and low oxygen fugacity. Highly evolved residual peralkaline granitic magma enriched in tin can lead to tin mineralization in a later stage. Furthermore, the volatiles F and Cl in the magma play important roles in tin partitioning behavior. Low F contents in the melt phase and high Cl content in the aqueous fluid phase are favorable factors for tin partitioning in the aqueous fluid phase. High Cl content in the aqueous fluid catalyzes water–rock interaction and leads to the extraction of tin from tin-bearing minerals. All these findings support a hydrothermal origin for the tin deposits. In light of the geotectonic setting, petrochemical characteristics, and mineralizing physicochemical conditions of the Furong tin deposit, it is inferred that the ore-forming fluid of the Furong tin ore deposit could have derived from the Qitianling peralkaline intrusion.     

含铁闪锌矿热容的实验测定与分析

利用美国ＤｕＰｏｎｔ公司的９９００型差示扫描量热仪对３个含铁闪锌矿样品的热容进行了实验测定,并讨论了定压摩尔热容实验值与实验温度的关系。实验结果表明,在实验条件下,含铁闪锌矿的定压摩尔热容与纯闪锌矿的定压摩尔热容存在显著差异,Ｆｅ置换Ｚｎ是造成这种差异的主要原因。