The content, distribution and speciation of gold in ores of the Natalka deposit (North East Russia) were studied. According to atomic absorption spectrometry (AAS), the vein and veinlet-vein ores are highest grade in gold, whereas veinlet-disseminated ores are lower grade and disseminated ores are poor in gold. According to light microscopy and electron probe microanalysis, up to 85% of gold in the Natalka ores is represented by large and small grains of free native gold associated with gangue and sulfide minerals. The gold grains of 0.01 to 2 mm in size are dominated and their fineness vary from 720 to 860 ‰. Up to 20% of native gold is represented by finely dispersed particles < 0.01 mm in size and a fineness of 750–990‰. Most of this gold is fixed and bounded mainly to with sulfides. According to “phase” chemical analysis with AAS, arsenopyrite is richest in gold whereas pyrite is poorer in gold. Using AAS with analytical data selections for single crystals, two non-mineral forms of “invisible” gold were found in these sulfides, namely the structurally bound (structural) and surficially bound (surficial) forms. The structural gold is incorporated into the mineral structure. The surficial form is confined to nano-sized non-autonomous phases on the sulfide mineral surfaces and often dominates over the structural form. The maximum gold concentrations on the surface of arsenopyrite and pyrite were confirmed by LA-ICP-MS data. It is expected that not all “invisible” gold is a refractory gold. The major part of gold contained in arsenopyrite and pyrite as finely dispersed, micron- and submicron-sized particles, as well as the surficially bound gold, can be extracted with modification of current flowsheet, which enhances the value of the gold ores at the Natalka deposit.

Comprehensive research has been implemented to raise the efficiency of the geochemical survey of stream sediments (SSs) that formed under the cryolithogenesis conditions. The authors analysed the composition, structure and specific features of the formation of exogenous anomalous geochemical fields (AGFs) identified through SSs of large river valleys of IV order. In our case, these were the valleys of Maly Ken, Ken and Tap Rivers. These rivers are located in the central and southern parts of the Balygychan–Sugoy trough enclosed in the Magadan region, North–East of Russia. The authors proposed a new technique to sample loose alluvium of SSs in the large river valleys along the profiles. The profiles were located across the valleys. The AGFs of Au, Ag, Pb, Zn, Sn, Bi, Mo and W were studied. Correlations between elements have been established. These elements are the main indicator elements of Au–Ag, Ag–Pb, Sn–Ag, Mo–W and Sn–W mineralization occurring on the sites under study. The results obtained were compared with the results of geochemical surveys of SSs. It is concluded that the AGFs recognized along the profiles reflect the composition and structure of eroded and drained ore zones, uncover completely and precisely the pattern of element distribution in loose sediments of large water flows. The alluvium fraction < 0.25 mm seems to be most significant in a practical sense, as it concentrated numerous ore elements. Sampling of this fraction in the river valleys of IV order does not cause any difficulty, for this kind of material is plentiful. The developed technique of alluvium sampling within large river valleys is efficient in searching for diverse mineralization at all stages of prognostic prospecting. It is applicable for geochemical survey of SSs performed at different scales both in the North–East of Russia, as well as other regions with similar climatic conditions, where the SSs are formed under the cryolithogenesis conditions.

Existing and recently acquired data on the isotope age and composition of volcanogenic Au-Ag deposits and occurrences of the Evensk group (Okhotsk-Chukotka volcanogenic belt, Northeast Russia) are summarized. The K-Ar isotopic and Rb-Sr isochron ages of Au-Ag ores from the deposits and occurrences studied is 82.7 ± 3–77.5 ± 3 Ma and 84.1 ± 2–79.7 ± 5, respectively. Au-Ag mineralization formed during a 5 million-year time interval. Au-Ag mineralization, typical of productive ore stages and practically unaffected by later thermal processes, is characterized by low values of primary 87Sr/86Sr(0) = 0.7055–0.7059 ratios close to primary 87Sr/86Sr(0) ratios in wall-rock metasomatites (0.7033–0.7082) and unaltered host rocks (0.7045–0.7048) indicative of a pronounced predominance of mantle Sr in the ores. The composition points of ore Pb on the 207Pb/204Pb – 206Pb/204Pb evolution diagram are grouped in close proximity to the Pb isotope composition points in the exhausted (depleted) mantle with a trend towards the volcanic rocks formed in subduction zones typical of the continental margin. A close genetic relationship between ore and magmatic processes is confirmed. It is assumed that this relationship is due to the functioning of a single mantle basaltoid chamber, a source of metal-bearing fluids and, probably, the primary source of Au and Ag.

The distribution and speciation features of gold in ores and minerals of the Natalkinskoe gold deposit (North-East Russia) are studied using light microscopy (LM), scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDX), X-ray electron probe microanalysis (EPMA), "phase" chemical analysis with atomic absorption spectrometry (PCA-AAS) and atomic absorption spectrometry with analytical data selections for single crystals (AAS-ADSSC). The vein and streaky-vein ores are high-grade ores, whereas veinlet-disseminated ores are less rich and disseminated ores are poor in gold. Up to 85 % of the gold in the ores is in a free native state, associated with quartz and sulfide minerals. LM, SEM-EDX and EPMA reveal that the predominant gold grains are 0.01 to 2.00 mm in size and at a fineness of 720 to 900 ‰. The finely dispersed and submicron elemental gold particles (Au0) amounted to 20 % and are mainly enclosed into arsenopyrite and pyrite. According to PCA-AAS data, the highest Au concentrations (up to 1383 ppm) are recorded in arsenopyrite; lower contents are typical of pyrite (up to 158.2 ppm). In these sulfides, two non-mineral species of "invisible" Au are the structurally bound and surface-bound species recognized by AAS-ADSSC. The structural Au is included in the mineral structure. The surface-bounded Au prevails and is confined to nano-sized, non-autonomous phases (NAPs) on the sulfide surface. In common with "invisible" Au, the micro-sized particles of native gold are often observed on the surface and within the surface layers of sulfide crystals. This is consistent with the model of post-growth transformations of nano-sized NAPs, resulting in the formation of nano and micro-sized Au0 particles. It is expected that the major part of gold contained in arsenopyrite and pyrite as finely dispersed and submicron particles, as well as the surface-bound gold in NAPs, can be won with modified current schemes of gold concentration, which enhances the value of the gold ore mining.

The composition, structure, and formation features of the exogenous anomalous geochemical fields (AGCFs) identified through stream sediments (SSs) are considered here within the Pestrinsk silver-bearing system and the Goltsovy silver-polymetallic deposit. The research was performed in the southern part of the Balygychan-Sugoy trough (northeastern Russia). The exogenous AGCFs of the main indicator elements of ores, formed in cryolithogenesis zone conditions, were studied. We used the results of multi-scale areal geochemical surveys of SSs. A survey of SSs at 1:200,000 scale was found to be effective at the stage of regional forecasting. Indeed, it is characterized by simplicity and the possibility of obtaining information operatively regarding the metallogeny of the area. It was found that at the local forecast stage, when prospecting for mineralization, the most effective was a survey of SSs at 1:50,000 scale. The AGCFs identified during this survey were distinguished by a richer component composition, higher contrast, and closer relationship with ores. During the lithochemical sampling of the watercourse heads, where alluvial sediments were found to be almost completely absent, a positive result was obtained by the bryolithochemical method, which is based on moss sampling together with a fine fraction of alluvium held by a moss cushion. The method enabled the sampling of watercourse heads and thus yielded information about the presence or absence of anomalous concentration fields of ore elements.

The paper presents newly acquired data on the mineral and chemical composition of the crystal surface layers of arsenopyrite and pyrite from the Natalkinskoe gold deposit, northeastern Russia. Data on arsenopyrite and pyrite grains from metasomatites and from quartz veins and veinlets were obtained using a scanning electron microscope equipped with an energy dispersive X-ray spectrometer (SEM-EDX). The surface layers of the sulfide crystals from the metasomatites contain no admixtures, except only As (up to 2.48 wt %) in the pyrite. The surface layers of arsenopyrite crystals from the vein and veinlets contains the following admixtures (wt %): Pt (up to 2.11), U (up to 2.03), Hg (up to 1.11), Au (up to 0.96), and more rarely Ru (up to 1.44), Ir (up to 0.67), Os (up to 0.64), Ag (up to 0.71), and Cu (up to 0.56). The surface layers of the pyrite crystals contain (wt %): As (up to 2.24), Pt (up to 2.88), and Cu (up to 0.69). The detected elevated concentrations of the admixtures are thought to be explained primarily by the presence of nonautonomous phases.

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.

The composition, structure and formation features of the exogenous anomalous geochemical fields (AGFs) identified by lithochemical stream sediments (LSSs) are considered using the examples of the Dukat gold–silver ore-forming system and the deposit with the same name. The research was carried out in the Balygychan–Sugoy trough (Magadan region, north–east of Russia). Areal geochemical surveys on the 1:200,000 and 1:50,000 scales were conducted. Exogenous AGFs of basic element indicators of all known mineralization types were studied. It is shown that the surveys on the 1:200,000 scale are characterized by simplicity, relative depth and the possibility to obtain information operatively about the metallogeny of the area as a whole. At the same time, the anomalies were revealed as a result of surveys often making a relatively poor component composition and low contrast compared with ores. The violation of quantitative and sometimes qualitative relationships can be seen between elements, especially those related to gold–silver mineralization. In this situation, the most informative are surveys of LSSs on the 1:50,000 scale. The AGFs were revealed as a result of their performance to have a richer component composition and high contrast, conforming to different ore types. It is shown that, while prospecting for gold–silver mineralization with LSSs in cryolithogenesis zone conditions, the binding forms study of mineralization element indicators is effective. In watercourse heads, where alluvium is practically absent, mosses are proposed for sampling, as they hold the sandy silt material firmly. The obtained results are recommended for use at all stages of prospecting, not only in the north–east of Russia but also in other similar climatic regions.

The first bryolithochemical studies have been carried out within the Dukat ore field (Balygychan-Sugoi trough, northeastern Russia), in its northeast (Dukat Au-Ag deposit, Chaika site) and on its eastern flank (Au-Ag ore occurrence, Piritovyi site). Sampling was made along primary water streams draining Au-Ag ore zones, because the headstreams localized in the permafrost zone are poor in alluvial sediments or lack them, whereas the stream banks and beds are overgrown with aquatic and semiaquatic mosses. We examined samples of moss cushions with loose sediments (fine silt suspension and sand-silt material). The study has shown that moss cushions are an effective natural trap extracting finely dispersed, ultradisperse, and colloid-dispersed particles, including ore ones, from water stream suspension. The contents of major elements indicating Au-Ag mineralization (Au, Ag, Hg, Sb, As, Pb, and Zn) in the bryolithochemical and lithochemical samples were compared. The highest contents of these elements have been revealed in the bryolithochemical samples. Scintillation analysis shows a predominance of finely dispersed Au and Ag particles. The chemical composition of lithoparticles and probable species of elements indicating mineralization were studied by energy-dispersive X-ray microanalysis. It has been concluded that the bryolithochemical stream sediments are an integral part of the lithochemical ones and can also be effectively used to reveal geochemical anomalies and identify the corresponding ores. It is shown that the bryolithochemical sediment streams bear important information about the chemical composition of primary ores, as they have the same major indicator elements (Au, Ag, Hg, Sb, As, Pb, and Zn) and nearly the same mineral composition (finely dispersed gold and silver, electrum, silver sulfosalts, and simple sulfides). The proposed bryolithochemical research is promising not only for northeastern Russia but also for other areas with similar landscapes, primarily areas where lithochemical and bryolithochemical stream sediments form in the northern subarctic and arctic environments. (C) 2018, V.S. Sobolev IGM, Siberian Branch of the RAS. Published by Elsevier B.V. All rights reserved.

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 oxidation degree of Au (I) or higher on the surface. A thin layer (~15 nm) with high concentrations of Ag and S and an underlying SiO 2 -bearing layer with a thickness of ~30–60 nm play a protective role providing preservation of Ag and Au sulfides in the surface parts of the Au–Ag grains under the oxidizing conditions. S-rich marginal parts of native gold particles may be represented by solid solutions Ag 2– x Au x S or (with a lack of S) by agglomerates of Ag n Au m S clusters. The formation of surface zoning in the nanoscale on the surface of native Au is abundant in nature and may be applied in prospecting.

The first data on native silver from the Rogovik Au–Ag deposit in northeastern Russia are presented. The deposit is situated in central part of the Okhotsk–Chukchi Volcanic Belt (OCVB) in the territory of the Omsukchan Trough, unique in its silver resources. Native silver in the studied ore makes up finely dispersed inclusions no larger than 50 μm in size, which are hosted in quartz; fills microfractures and interstices in association with küstelite, electrum, acanthite, silver sulfosalts and selenides, argyrodite, and pyrite. It has been shown that the chemical composition of native silver, along with its typomorphic features, is a stable indication of the various stages of deposit formation and types of mineralization: gold–silver (Au–Ag), silver–base metal (Ag–Pb), and gold–silver–base metal (Au–Ag–Pb). The specificity of native silver is expressed in the amount of trace elements and their concentrations. In Au–Ag ore, the following trace elements have been established in native silver (wt %): up to 2.72 S, up to 1.86 Au, up to 1.70 Hg, up to 1.75 Sb, and up to 1.01 Se. Native silver in Ag–Pb ore is characterized by the absence of Au, high Hg concentrations (up to 12.62 wt %), and an increase in Sb, Se, and S contents; the appearance of Te, Cu, Zn, and Fe is notable. All previously established trace elements—Hg, Au, Sb, Se, Te, Cu, Zn, Fe, and S—are contained in native silver of Au–Ag–Pb ore. In addition, Pb appears, and silver and gold amalgams are widespread, as well as up to 24.61 wt % Hg and 11.02 wt % Au. Comparison of trace element concentrations in native silver at the Rogovik deposit with the literature data, based on their solubility in solid silver, shows that the content of chalcogenides (S, Se, Te) exceeds saturated concentrations. Possible mechanisms by which elevated concentrations of these elements are achieved in native silver are discussed. It is suggested that the appearance of silver amalgams, which is unusual for Au–Ag mineralization not only in the Omsukchan Trough, but also in OCVB as a whole, is caused by superposition of the younger Dogda–Erikit Hg-bearing belt on the older Ag-bearing Omsukchan Trough. In practice, the results can be used to determine the general line of prospecting and geological exploration at objects of this type.

The T,X-parameters of the main ore-forming stages of the Rogovik epithermal gold-silver deposit (northeastern Russia) were determined using microthermometric techniques on fluid inclusion assemblages. On the basis of these data we carried out thermodynamic calculations that model the formation conditions of three types of ore mineral assemblages: gold-silver – at the early volcanic stage, silver-polymetallic and silver-gold-polymetallic – at the late volcanoplutonic stage. The silver-gold-polymetallic mineralization is located at the sites where silverpolymetallic and gold-silver zones overlap. The calculations were made using the “Selektor-C” software within a complex geochemical multicomponent system. Several scenarios of formation of gold-silver mineralization at an early volcanic stage were considered: 1) boiling of a hydrothermal solution; 2) interaction of residual aqueous solution with host rocks; 3) mixing of an ore-bearing gas phase with meteoric waters. For the late volcanoplutonic stage, we modeled formation of “silver mineralization” using an ore-forming solution genetically related to a deep-seated granite massif and its interaction with host rocks and gold-silver zones of early volcanic stage. These physicochemical models substantially improve our understanding of formation of the three types of mineral assemblages at the Rogovik deposit and can be applied to other epithermal deposits with similar mineralization styles.

New data on mercurial mineralization are presented, and a detailed characteristic is given for the first discovery of mercurous silver in ores of the Rogovik gold–silver deposit (the Omsukchan trough, Northeastern Russia). It was found that native silver in the examined ores occurs as finely-dispersed inclusions in quartz filling microcracks and interstitions. It also occurs in associations with kustelite, Ag sulfosalts and selenides, selenitic acanthite, and argyrodite. The mercury admixture varies from “not detected” in the central parts of grains to 0.22–1.70 wt % along the edges, or, in independent grains, to the appearance of Ag amalgams containing 10.20–24.61 wt % of Hg. The xenomorph form of grains of 50 μm or less in size prevails. It is assumed that the appearance of mercurial mineralization is caused by the superposition of products of the young Hg-bearing Dogda–Erikit belt upon the more ancient Ag-bearing Omsukchan trough.

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.