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.

New data on the mineral composition and the first data on the geochemical composition of ores of the Rogovik gold–silver deposit (Omsukchan ore district, northeastern Russia) have been obtained. Study of the regularities of the spatial distribution of ore mineralization shows that the deposit ores formed in two stages. Epithermal Au–Ag ores of typical poor mineral and elemental compositions were generated at the early volcanic stage. The major minerals are low-fineness native gold, electrum, acanthite, silver sulfosalts, kustelite, and pyrite. The typomorphic elemental composition of ores is as follows: Au, Ag, Sb, As, Se, and Hg. The content of S is low, mostly ≤1%. Silver ores of more complex mineral and elemental compositions were produced under the impact of granitoid intrusion at the late volcanoplutonic stage. The major minerals are high-Hg kustelite and native silver, silver sulfosalts and selenides, fahlore, pyrite, chalcopyrite, galena, and sphalerite. The typomorphic elemental composition of ores is as follows: Ag, As, Sb, Se, Hg, Pb, Zn, Cu, and B. The content of S is much higher than 1%. The ores also have elevated contents of Mo, Ge, F, and LREE (La, Ce, and Nd). At the volcanoplutonic stage, polychronous Au–Ag ores formed at the sites of the coexistence of silver and epithermal gold–silver mineralization. Their specific feature is a multicomponent composition and a strong variability in chemical composition (both qualitative and quantitative). Along with the above minerals, the ores contain high-Hg gold, hessite, argyrodite, canfieldite, orthite, fluorapatite, and arsenopyrite. At the sites with strongly rejuvenated rocks, the ores are strongly enriched in Au, Ag, Hg, Cu, Pb, Zn, Ge, Se, La, Ce, Nd, S, and F and also contain Te and Bi. The hypothesis is put forward that the late silver ores belong to the Ag–complex-metal association widespread in the Omsukchan ore district. A close relationship between the ores of different types and their zonal spatial distribution have been established. In the central part of the Rogovik deposit, epithermal Au–Ag ores are widespread in the upper horizons, Ag ores are localized in the middle horizons, and rejuvenated polyassociation Au–Ag ores occur at the sites (mostly deep-seated) with ore-bearing structures of different ages.

We studied the distribution and modes of occurrence of the main (Au and Ag) and major associated elements indicating mineralization (Hg, Sb, As, Pb, Zn, and Cu) in samples of loose sediments from lithochemical sediment streams of Au–Ag zones at the Dukat deposit. The major mineral and nonmineral modes of occurrence of elements indicating Au–Ag mineralization have been detected with POLAM-312 and POLAR-3 ore microscopes and by X-ray electron probe microanalysis with JCXA-733 and JXA-8200 (JEOL, Japan) microprobes. The distribution and modes of occurrence of ore elements in the loose (alluvial) sediments of streams draining the Au–Ag zones are closely related to the ore composition. As in the ores, the main elements indicating mineralization are Au and Ag, while the major associated elements are Hg, Sb, As, Cu, Pb, and Zn. Gold in alluvial sediments occurs as electrum, fine (dispersed, ultradispersed, and colloid–dispersed) particles, and the so-called “bound” (predominantly with sulfides) invisible Au (sorption component and its derivates). Silver occurs not only as hypergene forms, microinclusions, and ultrasized particles but also in native form and as partly preserved sulfides and sulfosalts. The other elements (Hg, Sb, As, Pb, Zn, and Cu) are observed as secondary minerals of complex composition and differently preserved corroded fragments of pyrite, chalcopyrite, galena, and sphalerite grains, dominated by oxides and hydroxides (mainly those of iron). Salts and water-soluble sulfates of Fe, Cu, Pb, and Zn are less widespread. In study of the conditions of sediment stream formation in cryolithogenesis zones, where physical weathering is regarded as the major process, chemical factors (first of all, chemisorption) should also be taken into account. This is proven by the enrichment of “fine” loose material in Au, Ag, and ore elements in general. The high percentage of mobile forms of elements, which are easily leached out by ordinary acids, in ores and aureoles, together with the widespread occurrence of clay minerals and hydroxides, has a significant influence on chemisorption. For example, the portion of fine and “bound” Au, the element considered to be the least prone to chemical weathering, reaches 50–60% in the riverbed sediments of the stream head. Native Au (electrum) makes up 40–50%. The material is diluted during its transport. As Au content decreases, the portion of fine and “bound” Au in the sediment stream increases to 95%. Evidently, these two Au forms are predominant in streams as compared with ores. The modes of occurrence of elements indicating Au–Ag mineralization in secondary environments, as in primary ones, serve as an effective criterion for assessment of the potential of geochemical anomalies detected in sediment streams. They are a reliable indicator of ore associations, which is of practical significance. We think that modes of occurrence can sometimes be used to estimate the erosion level of drained zones and sites (i.e., to predict mineralization to depth). This criterion can be successfully applied at all stages of geochemical study of ore-bearing areas, from the prediction of the potential of anomalies detected in sediment streams in poorly studied areas to the detailed exploration of known ore objects.

Using the methods of electron spectroscopy of the surface and SEM–EDS, it is shown that native gold of the deposit related to the epithermal Au–Ag ore formation contains oxidized gold with an...

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, Ag_2−xAu_xS, if there is enough S or S adsorption-stabilized cluster agglomerates, Ag_nAu_mS, 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.