O. Yu. Belozerova

Dualistic distribution coefficients of elements in the system mineral-hydrothermal solution. I. Gold accumulation in pyrite

The use of trace elements (TE) as geochemical indicators is complicated by the dualism of their distribution coefficients D due to the additional (i.e., above the concentrations of an isomorphic component) incorporation of elements at structural defects of various nature (including the surface of the crystal). A pressing problem in this situation is to determine the true D values that pertain to the structural component of an admixture Dstr and evaluate effects of other modes of TE occurrence. Only upon distinguishing Dstr in the bulk coefficient Dbulk it is possible to evaluate the ore potential of fluid in terms of certain TE from the composition of a mineral containing the TE. Pyrite synthesized in solutions of variable pH at 450°C and 1 kbar (100 MPa) at fluid portions sampled in a trap is utilized to demonstrate the role of a surface nonautonomous phase (NP) in the incorporation of gold in this mineral. The distribution coefficient of gold between pyrite and hydrothermal solution is 0.14 for “pure” pyrite and 0.05 for As-bearing pyrite (containing 0.02–0.05 wt % As), and these coefficients for NP are 310 and 170, respectively. This increases the Dbulk for evenly distributed (“invisible”) gold by factors of four and nine. In contrast to the results of earlier studies conducted at room temperature and pressure or parameters close to them, our data demonstrate that the accumulation of “invisible” Au in pyrite is controlled not only by reducing adsorption with the development of Au(0) particles and films but also by Au incorporation in NP developing in the surface layer of the crystal approximately 500 nm thick as chemically bound Au [most likely as Au(I)]. The possible reason for the high absorption capacity of NP is the defect (pyrrhotite-like) structure, which is not saturated with bonds of excess S and sulfoxi onions.

Dualistic Distribution Coefficients of Elements in the System Mineral-Hydrothermal Solution. II. Gold in Magnetite

The system magnetite-Au-hydrothermal solution was employed to continue studying the distribution coefficients of trace elements in system with real crystals. The role of surface nonautonomous phase (NP) is elucidated. The distribution coefficient of an Au structural admixture between magnetite and hydrothermal solution at the experimental conditions [450°C, 1 kbar (100 MPa), and fluid sampling by a trap] is, according to the most representative data, 1.0 ± 0.3, and Au is thus not an incompatible element in magnetite, in contrast to pyrite and arsenopyrite [1], minerals for which this coefficient is much lower than one. The NP is enriched in Au with respect to the rest of the crystal by a factor of more than 4000, and this results in an one order of magnitude increase in the bulk distribution coefficient. Similar to pyrite, the reason for the dualistic nature of the distribution coefficient is the presence of an NP, which contains ∼2000 ± 500 ppm Au. The NP occupies the approximately 330-nm surface layer of the crystal, and the chemically bound Au [Au(III), according to XPS data] admixture is evenly distributed with depth within the layer, which is the reason for the strongly determinate dependences of the concentrations of the evenly distributed Au admixture on the size and specific surface area of the crystal. The occurrence of an NP is controlled by the chemistry of the system. The partial substitution of Fe for Mn and the synthesis of a phase close to jacobsite MnFe2O4 results in the disappearance of both the NP itself and the size dependence of the Au concentration. The XPS spectra of O 1s and Fe 2p are used to analyze two models: (i) a single goethite-like (O2−/OH−∼ 1) phase of variable composition and Fe in more than one valence state and (ii) a heterogeneous structure of alternating domains of wuestite- and goethite-like NP. The reason for the “excess” admixture in the former instance can be vacancies at Fe sites, whereas that in the latter one is the interaction of the admixture with nanometer-in-size nanometer in-size strained domains on the surface of the crystal.

Electron-probe X-ray microanalysis of individual particles of solid snow sediment with size factor correction.

A technique is proposed for X-ray electron-probe microanalysis (EPMA) of individual particles of solid snow sediment. Two sample preparation procedures were used to analyze the sediments. The PAP-method and the original bi-exponential model were used for matrix correction and the calculation of elemental composition. A method of calculating composition has been developed for approximately spherical individual particles, comparable in size with an area of X-ray generation. An analytical expression is proposed for determining the composition of these particles, taking account of their size. Including the size factor reduces the error of composition determination from 0.5-45 to 0.2-22% relative percent, for particles in the size range 1-3 microm.

Biogeochemistry of encrusting sponges of the family Lubomirskiidae in Southern Lake Baikal

ICP-MS analyses of encrusting sponges indicate that their predominant chemical elements are, along with Si, by P, Al, Fe, Ca, S, Mg, K, Na, Cu, Mn, Zn, Ti, Ba, and Br. The sponges are most significantly enriched in Al > Cu > Ti > REE > Mn > P relative to their aqueous habitat and in Cu > I > Cd > P > Br > As ≥ S relative to the relatively rudaceous bottom sediments. One of the sources of elements occurring the aqueous habitat and being of vital importance for the activity of the sponges was proved to be the rock substrates.

Assessment of the homogeneity of the synthesized beryllium-bearing silicate glass for its use as a quality control material in the X-ray electron probe microanalysis of silicates

Results of assessment of the stability and homogeneity of the Be−Mg−Al−silicate glass synthesized by the authors and possibilities of its use as a quality control material (QCM) in the X-ray electron probe microanalysis (EPMA) of Be-bearing silicate materials, i.e., crystals and quenched melts (glasses), and also silicates and oxides are presented. The homogeneity of the samples was studied at the macro- (10–100 μm) and microlevels (1–10 μm) and assessed according to the scheme of dispersion analysis. A possibility of using the Be–silicate glass as a certified reference material for the determination of the concentrations of Mg, Al, Si was estimated using international reference materials of glasses and QCM of minerals of the known composition. The metrological performance of the experimental data obtained suggest that the studied glass can be used as a QCM in the EPMA of Be-bearing silicate materials, silicates, and oxides. The use of the Be-silicate glass as a certified reference material of composition in EPMA ensures acquisition of satisfactory data on the composition of minerals including cordierite and beryllium cordierite, beryllium indialite, beryl and also of metastable phases of chrysoberyl and compounds with the structure of β-quartz and petalite.

Dualistic distribution coefficients of trace elements in the system mineral–hydrothermal solution. IV. Platinum and silver in pyrite

The FeS2–Ag–Pt–As system was studied using hydrothermal thermogradient synthesis (with internal sampling) of pyrite crystals at a temperature of 500°C and pressure of 1 kbar in ammonium chloridebased solutions. The modes of occurrence of precious metals (PM) were determined using atomic absorption spectrometry (AAS) in its version of statistical selections of analytical data on single crystals (SSADSC), electron microprobe analysis (EMPA), scanning electron microscopy with energy-dispersive spectrometry (SEM-EDS), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The concentration of Pt in its structural mode in pyrite is as high as 10–11 ppm and is practically not correlated with the As concentration. The dualistic distribution coefficient of Pt between pyrite and hydrothermal solution is 21 ± 7 for the structural mode and 210 ± 80 for the surface-related mode of this element. No inclusions of either any Pt-bearing minerals or Pt itself was detected. Platinum is an element highly compatible with hydrothermal pyrite and is different in this sense from gold, and pyrite is underestimated as a potential concentrator of platinumgroup elements (PGE). The distribution of Ag in pyrite is highly heterogeneous. The likely reason for this is that the Ag solid solution cannot be quenched, and hence, the Ag concentrations broadly vary and are very unsystematically distributed in natural pyrite crystals. Assuming this hypothesis, the limit for Ag accommodation in FeS2 can be estimated using SSADSC at 0.09 ± 0.06 wt % under the experimental parameters, and the distribution coefficient of the structural Ag mode is thereby evaluated at 1400 ± 700. When crystallizing together with FeS2 proustite (Ag3AsS3) near its melting point, forms mixtures with dervillite (Ag2AsS2), in which Ag deficit is counterbalanced by excess divalent As. The limit of As incorporation into pyrite under these conditions is ≤0.1 wt %. SEM-EDS and XPS data indicate that the surface phases are of three types. In the course of crystal growth, practically two-dimensional nonautonomous phases (NP) are aggregated into submicroscopic and micrometer-sized crystalline bodies (mesocrystals) that largely inherit their unusual minor-element composition from NP and are enriched in Ag, Pt, As, and other minor elements. NP and mesocrystals are enriched in Al, which was transferred into them from the Al-bearing Ti alloy of the reaction containers. Silver occur in the volume of the crystals and on their surface as monovalent silver sulfide. Arsenic was detected mostly in the form of di- and trivalent arsenic sulfides. Pentavalent arsenic oxide was identified only on the surface of the crystals and can be easily eliminated by ion milling.

Crystallochemical aspect of the substance in the amorphous gel-crystalline Mg-Be-Al silicate series under solid-state conditions

It is established that solid-phase crystallization of beryllian indialite (BI), obtained by heating a sol-gel precursor of the initial compound of nonstoichiometric composition Mg1.81Be1.09Al2.27Si5.85O18, occurs through the following successive reconstructive transformation: phase with a quartz structure → phase with a petalite structure → BI. It is found that metastable phases with quartz and petalite structures, filled with excess cations, are transformed into equilibrium BI, which has no cationic excess, during this process. It is revealed that the structural aspect of the relationship between the phases involved in the transformation is in the inheritance of a hollow Si6O18 ring of preceding phase by subsequent phases and in the edge aggregation of polyhedra. The chemical relationship is in the approximately identical amounts of all species-forming components in the phase compositions.

On the Coexistence of Chemically Similar Stable and Metastable Phases in the BeO–MgO–Al2O3–SiO2 System

The joint crystallization of the stable phase (a number of solid solutions of chromium-containing beryllian indialite) and metastable phases (crystalline modifications) of the compound with β-quartz structure (Si0.64Al0.28Mg0.21Be0.09)IVO2 ~ Mg1.89Be0.81Al2.52Si5.76O18 admixed with Cr2O3 phases of khmaralite Mg1.21Cr0.01Be0.46Al1.78Si3.38O20 and spinel {(Mg0.95Be0.045Si0.005)IV(Al1.31Cr0.67Mg0.02)VI}O4 is performed using melted chromium–beryllian indialite preliminarily obtained by solid-phase synthesis as a precursor. Simultaneously, the residual X-ray amorphous melt of composition Mg1.83Cr0.01Be1.04Al2.64Si5.57O18 is hardened. Thus, a reconstructive transition from the beryllian indialite melt to a phase with the β-quartz structure is implemented, and the chemical similarity of these compounds is demonstrated. The rate of change in the crystallization isotherm of 2°С/h and increased heat outflow through the highly heat-conducting walls of the Pt–Rh crucible (taper) contribute to this process.

Occurrence Forms of Carbon, Sulfur, and Noble Metals in Deposits of the Black-Shale Formation by the Example of the Degdekan Gold-Ore Deposit (Northeastern Russia)

Pyrite crystals and ore-bearing shales of the Degdekan deposit were studied by means of XPS, SEM–EDX, EPMA, and AAS. Five peaks of carbon organic forms were identified, conforming to polymer compounds containing either double bonds of carbon or alkyne groups and compounds containing C–OH and C=O bonds, as well as, probably, small amounts of S-containing compounds and those with functional groups of carboxylic acids. Sulfate prevails over sulfite in pyrites; among the surface sulfide forms, disulfide prevails over monosulfide; the presence of polysulfide is registered. The occurrence of various chemical forms of sulfur on the surface might provide for concentrating of microelements including the noble metals (NMs) in their surface-bound forms. The regular behavior of NMs (Au, Pt, Pd, and Ru) depending on the grain sizes (specific surfaces) of pyrite crystals along with the narrow range of the ratios of structural and surface components of the concentrations of different NMs points to NM coprecipitation with pyrite during the same productive stage. No capture of NM-containing carbonaceous phases took place, which should violate the regularity of Au distribution in pyrites of the Sukhoi Log deposit.

Effect of microabsorption heterogeneity in the X-ray fluorescence analysis of ultrafine particles

The dependence of the intensity (Ii) of X-ray fluorescence on the size (D) of finely ground particles was studied for saturated and unsaturated samples. It was found that even at the wet grinding (addition of ethanol) of powders with D < 10 μm, the aggregation and covering of larger grains (α) with smaller grains of different compositions occur, which changes the character of the dependence Ii = f(D), particularly, if fluorescence is emitted by the grains α. The nature of the observed effects is proved by the results of granulometric analysis and by electron probe X-ray analysis. In the transition from saturated to unsaturated samples, the discussed effects are enhanced.