Trace Element Partitioning Dualism under Mineral–Fluid Interaction: Origin and Geochemical Significance

Trace element (TE) partitioning in the system “mineral-hydrothermal solution” is studied by the method of thermo-gradient crystal growth coupled with internal sampling of a fluid phase. The analytical procedure used enables evaluating of structurally bound and superficially bound modes of TE in crystals and determining corresponding dual partition coefficients. The case of precious metals (PM—Au, Pt, Pd) at 450 and 500 °C and 100 MPa pressure is considered. The minerals are pyrite, As-pyrite, magnetite, Mn-magnetite and hematite and fluids are ammonium chloride-based hydrothermal solutions. The partition coefficients for structural and surficial modes, Dpstr and Dpsur, are found to be unexpectedly high (except for Au in pyrite). High concentrations of PM are attributed to superficial nonautonomous phases (NAPs), which can be considered as primary concentrators of PM. We also have studied the co-crystallization (exchange) coefficients (De) of REE (Ce, Eu, Er, Yb) and Fe in magnetite and hematite at 450 °C and 100 MPa. Desur is elevated to two orders of magnitude as compared to Destr. It is shown that not only physicochemical parameters affect REE distribution in hydrothermal systems, but also NAP presence and its composition. The crystal growth mechanism specified by the agency of NAP is suggested. The study of PM distribution in natural pyrite of gold-ore deposits supported the importance of differentiating between structurally and superficially bound TE modes for correct use of experimental D values to determining element concentrations in ore-forming fluids

Platinum Group Elements in Arsenopyrites and Pyrites of the Natalkinskoe Gold Deposit (Northeastern Russia)

The peculiarities of the distribution and binding forms of platinum group elements (Pt, Pd, Ru, Rh, Os and Ir) in the arsenopyrites and pyrites of the Natalkinskoe gold ore deposit (Northeastern Russia) were examined using atomic absorption spectrometry with analytical data selections for single crystals (AAS-ADSSC), a “phase” chemical analysis (PCA) based on AAS of different size-fractions of minerals, scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDX) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The arsenopyrites and pyrites of the Natalkinskoe gold deposit were found to concentrate not only Au but also platinum group elements (PGEs) such as Pt, Pd, Ru and Rh. The PCA showed that the highest contents (in ppm) were found in the monofractions of arsenopyrite—Pt up to 128, Pd up to 20, Ru up to 86 and Rh up to 21—and comparably lower in monofractions of pyrite—Pt to 29, Pd to 15, Ru to 58 and Rh to 5.9. The AAS-ADSSC method revealed two forms of uniformly distributed Pt, Pd and Ru corresponding to the chemically bound element in the structure of the mineral and in the superficial non-autonomous phase (NAP). The superficially bound form dominates over the structural form and presumably exists in a very thin surface layer of the crystal (~100–500 nm). The maximum contents of these PGE, chemically bound in the structure of arsenopyrite, reached values of (in ppm) 48, 5.9 and 48; and in pyrite structure, 68, 5.2 and 34 for Pt, Pd and Ru respectively. The contents of Pt, Pd and Ru related to NAP on the surface of the crystal were significantly higher and amounted (in ppm) for arsenopyrite to 714, 114 and 1083; and for pyrite 890, 62 and 690 for Pt, Pd and Ru, respectively. Preliminary results for the Rh form in arsenopyrite crystals suggest that the surface-related form (154–678 ppm) is more abundant than the structural form (17–45 ppm). Data from studying the surfaces of sulphide minerals by SEM-EDX and LA-ICP-MS confirmed the presence of Pt, Pd, Ru and Rh on the surface of arsenopyrite and pyrite crystals. These methods generated primary data on the content of Os and Ir in arsenopyrite and pyrite in the surface layer. The maximum content of Os and Ir found in arsenopyrites was up to 0.7 wt%. PGE-enriched fluids (up to ~3 ppm Pt) may exist in the gold ore deposit. It is assumed that there is a common mechanism of impurities uptake associated with the active role of the crystal surface and surface defects for gold-bearing arsenopyrites and pyrites. The surface enrichment is due to peculiarities in the crystal growth mechanism through the medium of NAP and the dualism of the element distribution coefficient in the system of mineral–hydrothermal solution, which is higher for NAP, compared to the volume of the crystal. Although mineral forms of Pt, Pd, Ru, Rh, Os and Ir have not been found at the Natalkinskoe gold deposit, their existence in the form of nano-scale particles is not excluded. This follows from the evolutionary model of surficial NAPs, assuming their partial transformation and aggregation with the formation of nano- and micro-sized autonomous phases of trace elements. The presence of PGE in the ores and the possibility of their extraction significantly increase the quality and value of the extracted raw gold materials at the Natalkinskoe deposit, and adds to the list of known platiniferous ore formations

Contrasting Surficial Composition of Native Gold from Two Different Types of Gold Ore Deposits

Native gold grains sampled at two different gold ore deposits in Eastern Russia have been studied by the techniques of electron spectroscopy (X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES)), electron microprobe analysis (EMPA), and scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDX). The high-fineness gold of the deposit hosted by relatively high temperature gold-quartz-sulfide mesothermal ore formation contains no oxidized Au constituents on grain surfaces, whereas the less fine gold of the epithermal Au-Ag deposit contains gold oxidized to the Au (I) state, or higher, in half of the cases. At this deposit the surface of native Au consists of a thin layer (~15 nm) with elevated Ag and S contents and an underlying SiO2–containing layer ~30–60 nm thick. Such a composite coating can perform a protective function and prevent the gold-silver sulfides in surficial parts of AuAg grains from oxidation. The sulfur-enriched marginal parts of native gold particles do not always correlate with the stoichiometry of well-known binary AuAg-sulfides and have a variable composition. This may be due to the existence of solid solutions, Ag2−xAuxS, if there is enough S or S adsorption-stabilized cluster agglomerates, AgnAumS, under sulfur deficit. The effect of the formation of nano-scale surficial zonality on the surface of native gold is quite common in nature and applicable to geological exploration and technology of gold-ore processing. It can facilitate establishing the geochemical environment and genetic type of Au mineralization

Specific features of mandible structure and elemental composition in the polyphagous amphipod Acanthogammarus grewingkii endemic to Lake Baikal.

BACKGROUND: In crustaceans, several mechanisms provide for the mechanical strength of the cuticular "tools" (dactyli, claws, jaws), which serve to catch and crush food objects. Studies on the mandibles of the endemic Baikal amphipod Acanthogammarus grewingkii by means of electron microscopy and elemental analysis have revealed specific structural features of these mouthparts. METHODOLOGY: The fine structure of the mandible has been studied by means of SEM, TEM, and AFM; methods used to analyze its elemental and phase composition include XEPMA, XPS, SEM-EDS analysis, and XRD. CONCLUSION: Functional adaptations of the mandible in A. grewingkii provide for the optimum combination of mechanical hardness and fracture resistance, which is achieved due to a complex structure and composition of its cutting parts. Teeth of the mandible are covered by a thin layer of silica (10-20 µm). Their epicuticle is characterized by a high density, consists of three layers, and increases in thickness toward the tooth apex. The epicuticle is enriched with Br, while the concentrations of Ca and P reach the peak values in the softer internal tissues of the teeth. These data broaden the view of the diversity of adaptation mechanisms providing for the strengthening of cuticular "tools" in crustaceans

Isomorphism and Mutual Transformations of S-Bearing Components in Feldspathoids with Microporous Structures

The isomorphism of S-bearing feldspathoids belonging to the cancrinite, sodalite, tugtupite, vladimirivanovite, bystrite, marinellite and scapolite structure types has been investigated using a multimethodical approach based on infrared, Raman and electron spin resonance (ESR), as well as ultraviolet, visible and near infrared (UV–Vis–near IR) absorption spectroscopy methods and involving chemical and X-ray diffraction data. Sapozhnikovite Na8(Al6Si6O24)(HS)2 and sulfite and thiosulfate analogues of cancrinite are synthesized hydrothermally and characterized by means of electron microprobe analyses, powder X-ray diffraction and Raman spectroscopy. The possibility of the incorporation of significant amounts of SO42−, S4 and SO32− in the crystal structures of cancrisilite, sulfhydrylbystrite and marinellite, respectively, has been established for the first time. Thermal conversions of S-bearing groups in the synthetic sulfite cancrinite and sapozhnikovite analogues as well as natural vladinirivanovite and S4-bearing haüyne under oxidizing and reducing conditions have been studied using the multimethodical approach. The SO42− and S2− anions and the S3•– radical anion are the most stable S-bearing species under high-temperature conditions (in the range of 700–800 °C); their ratio in the heated samples is determined by the redox conditions and charge-balance requirement. The HS− and S52− anions are stable only under highly reducing conditions