Vol 55, No 9 (2017)

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.

Late Vendian (540–550 Ma) U–Pb age was established for zircon from postcollisional granites of the Osinovsky Massif located among island-arc complexes of the Isakovka terrane in the northwestern Sayan–Yenisei accretionary belt. The granites were formed 150 Ma after the formation of the host island-arc complexes and 50–60 Ma after the beginning of their accretion to the Siberian Craton. These events mark the final stage of the Neoproterozoic history of the Yenisei Ridge related to the end of accretion of oceanic fragments and the beginning of the Caledonian Orogeny. The granites are subalkaline leucoractic Na–K rocks enriched in Rb, U, and Th. The petrogeochemical and Sm–Nd isotope data (T_Nd(DM)-2st = 1490–1650 Ma and ε_Nd(T) from–2.5 to–4.4) indicate that their source was highly differentiated continental crust of the SW margin of the Siberian Craton. Therefore, the host Late Riphean island-arc complexes were thrust over the craton margin for distance significantly exceeding the size of the Osinovsky Massif.

The paper reports original thermochemical data on six natural amphibole samples of different composition. The data were obtained by high-temperature melt solution calorimetry in a Tian–Calvet microcalorometer and include the enthalpies of formation from elements for actinolite Ca_1.95(Mg_4.4Fe_0.5²⁺Al₀₁)[Si_8.0O₂₂](OH)₂(–12024 ± 13 kJ/mol) and Ca_2.0(Mg_2.9Fe_1.9²⁺Fe_0.2³⁺)[Si_7.8Al_0.2O₂₂](OH)₂, (–11462 ± 18 kJ/mol), and Na_0.1Ca_2.0(Mg_3.2Fe_1.6²⁺Fe_0.2³⁺)[Si_7.7Al_0.3O₂₂](OH)₂ (–11588 ± 14 kJ/mol); for pargasite Na_0.5K_0.5Ca_2.0-(Mg_3.4Fe_1.8²⁺Al_0.8)[Si_6.2Al_1.8O₂₂](OH)₂ (–12316 ± 10 kJ/mol) and Na_0.8K_0.2Ca_2.0(Mg_2.8Fe_1.3³⁺Al_0.9) [Si_6.1Al_1.9O₂₂](OH)₂ (–12 223 ± 9 kJ/mol); and for hastingsite Na_0.3K_0.2Ca_2.0(Mg_0.4Fe_1.3²⁺Fe_0.9³⁺Al_0.2) [Si_6.4Al_1.6O₂₂](OH)₂ (‒10909 ± 11 kJ/mol). The standard entropy, enthalpy, and Gibbs free energy of formation are estimated for amphiboles of theoretical composition: end members and intermediate members of the isomorphic series tremolite–ferroactinolite, edenite–ferroedenite, pargasite–ferropargasite, and hastingsite.

Zircon hosted in granite, which crystallized from local pools of anatectic melt among migmatites, in the Rikolatvi structure, Belomorian Mobile Belt, contains minute inclusions of various minerals, biotite and garnet among others. The compositions of the biotite and garnet in the microinclusions differ from those of the same minerals in the granite containing the zircon. The crystallization temperature of the anatectic melt was estimated by the biotite–garnet geothermometer and the composition of the biotite and garnet inclusions at ~800°C.