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.

This study presents the typomorphic features of native gold grains from three different geological-industrial types (GIT) of gold deposits in the North-East of Russia: (1) gold–arsenic-sulfide in black shale strata (Natalka, Degdekan, Karalveem, Maldyak deposits), (2) gold–quartz veins in granitoids (Dorozhnoye, Butarnoye, Shkolnoye, Maltan deposits), and (3) gold–silver adularia in volcanogenic strata (Kupol, Olcha, Kubaka, Burgali, Primorskoe, Dalnee deposits). The reliability of the geological interpretation is directly related to mineral associations, fineness variations, its internal structure and the content of microimpurities. Native gold is a reliable indicator for identifying various GIT of gold deposits at the early geological-prospecting stages of studying gold-bearing areas. Typomorphic features of native gold for each of the considered GIT are stable and do not depend on the age and scale of mineralization. It is shown that using an integrated approach obtains genetic information about a particular ore object, which makes it possible to predict the vertical range of mineralization and outline the technology for processing ores. The information obtained can also be effectively used in the search for placer deposits in nearby watercourses. Identification of typomorphic features of ore and placer native gold opens up wide opportunities for delineating the distribution areas of placer deposits.

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 study focused on the forms of occurrence and distribution of hidden (“invisible”) noble metals (NMs = Au, Ag, Pt, Pd, Ru) in the coexisting pyrites and arsenopyrites of four samples of mineral associations from three Au deposits in the north-east of Russia. The unique nature of our approach was the combination of methods of local analysis and statistics of the compositions of individual single crystals of different sizes. This allowed us to take into account the contribution of the surface component to the total NM content and to distinguish the structurally bound form of the elements. The following estimates of the distribution coefficients of the structural (str) and surficial (sur) forms of elements were obtained: D ¯ P y / A s p s t r = 2.7 (Au), 2.5 (Pd), 1.6 (Pt), 1.7 (Ru) and D ¯ P y / A s p s u r = 1.6 (Au), 1.1 (Pd), 1.5 (Pt and Ru). The data on Ag in most cases indicated its fractionation into pyrite ( D ¯ P y / A s p s t r = 17). Surface enrichment was considered as a universal factor in “invisible” NM distribution. A number of elements (i.e., Pt, Ru, Ag) tended to increase their content with a decrease in the crystallite size in pyrite and arsenopyrite. This may be due to both the phase size effect and the intracrystalline adsorption of these elements at the interblock boundaries of a dislocation nature. The excess of metal (or the presence of S vacancies) in pyrite increased Ag and Pt content in its structure and, to a lesser extent, the content of Ru, Pd and Au. Arsenopyrite exhibited a clear tendency to increase the content of Pt, Ru and Pd in samples with excess As over S. Sulphur deficiency was a favourable factor for the incorporation of Ag and platinoids into the structures of the mineral associations studied. Perhaps this was due to the lower sulphur fugacity. Pyrite with excess Fe was associated with higher contents of some NMs. The presence of other impurity elements was not an independent factor in NM concentration.

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.

The interfacial crystal layer of poorly soluble mineral grown under hydrothermal conditions is modified chemically into a surficial nonautonomous phase (SNAP) and, in this capacity, takes part in growth process, doing several important functions. This paper considers some of them related to geochemistry and mineralogy. The new interpretation is given to the following phenomena: (1) selection of components during crystal growth in multiphase associations; (2) stability of multiphase parageneses having a common chemical component; (3) dual character of the distribution coefficients due to different properties of the crystal volume and SNAP; (4) formation of nano- and microinclusions of unusual composition different from the basic mineral phase; (5) spatial ordering of nano- and microparticles during their directed aggregation at the growing crystal face; (6) accumulation of valuable components (primarily noble metals), incompatible in most of mineral matrixes, in the surficial layer; and (7) effect of “hidden” metal content, associated with the presence of noble metals in the SNAP or of nano- and microinclusions formed during the SNAP evolution.

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.

A method for estimating the native gold composition in micron‐ and submicron‐sized inclusions in the matrix of a sulfide mineral with electron probe X‐ray microanalysis is proposed. Such inclusion sizes are comparable with or less than the X‐ray generation volume, and therefore, the analytical signal is a mixture of signals from the matrix elements and the inclusion elements, which significantly complicates the quantification. The proposed procedure is based upon the extrapolation of the trend of the dependence of the measured elemental contents in the inclusions, for example, Au or Ag, versus the content of matrix elements, namely, S, Fe, and As. To define the influence of the inclusion size on the intensity of the excited X‐rays, the trajectories of the electrons in a sample were simulated by the Monte Carlo method. It was found that the trends in the behavior calculated by the Monte Carlo method are consistent with the data measurements of an artificial pyrite sample with a sprayed pure gold layer (approximately 1 μm thick) arranged perpendicular to the sample surface. The measurements were performed on a Superprobe JXA‐8200 microanalyzer. The proposed method was demonstrated by analyzing natural, finely dispersed gold inclusions in arsenopyrite. This approach made it possible to evaluate the Au and Ag contents in the approximately 1 μm inclusions and assess the uncertainty of the measurement.

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.

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.

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.