We studied the mineralization and sulfur isotopic composition of sulfides of gold–palladium ores in olivine clinopyroxenites from the Dzelyatyshor massif made up of a continuous layered series of rocks: olivine-free clinopyroxenite–olivine clinopyroxenite–wehrlite. The primary igneous layering of rocks, manifested as different quantitative ratios of clinopyroxene and olivine in them, controls the local trends of variability in the chemistry of mineral-forming medium and the concentrations of ore components, including noble metals, and sulfur in each separate layer during its cooling. The replacement of primary rock-forming minerals by secondary minerals, when the temperature decreases, is a characteristic trend for pyroxenites: (a) olivine → serpentine, secondary magnetite, and (b) clinopyroxene → amphibole, secondary magnetite → chlorite. The deposition of native gold in parageneses with PGM and sulfides at the Ozernoe occurrence took place during the replacement of earlier rock-forming minerals by chlorite. This process completed mineral formation at the deposit and took place at temperatures 150–250 °C and at the high activity of S, Te, Sb, and As of fluid. The variability of mineral formation conditions during chloritization is reflected in the change of native-sulfide forms of Pd by arsenide-antimonide forms and the sulfur isotopic composition of sulfides. The Pd content in native gold increases in the series—Au-Ag solid solution (<1.5 wt.% Pd)—Au-Cu intermetallides (to 6 wt.% Pd)—Cu-Au-Pd solid solutions (16.2–16.9 wt.% Pd). The sulfur isotopic composition of pyrite, chalcopyrite, and bornite varies from −2.1 to −2.9‰. It is assumed that a deep-seated magmatic basic melt was the source of fluid, ore components, and sulfur.

This paper reviews and summarizes the available information on the composition of palladian gold with various contents and sets of isomorphic impurities (Ag, Cu, Hg) at 50 deposits and ore occurrences with Au-Pd mineralization. It is revealed that Palladian gold is represented by the systems Au–Pd, Au–Pd–Hg, Au–Pd–Cu, and Au–Pd–Ag–Hg, but more frequently corresponds to Au–Pd–Ag, Au–Pd–Ag–Cu, and Au–Pd–Ag–Cu–Hg. Objects with palladian gold belong to different types of gold deposits and to the deposits at which the main components of ores are PGE, Cr, Cu, Ni, V, and Ti. We propose a classification of the types of deposits with palladian gold: (1) PGE ore deposits related to mafic–ultramafic magmatic complexes (two subtypes—(a) low-sulfide-grade (less than 2%–5% sulfides) Alaskan, and (b) high-sulfide-grade (more than 5% sulfides) Norilsk); (2) orogenic gold deposits (OG); (3) epithermal (porphyry) gold–copper deposits (EPGC); (4) iron oxide copper gold deposits (IOCG); (5) ferruginous quartzite deposits; (6) volcanic exhalation; and (7) gold-PGE placers of five subtypes corresponding to the types of 1–5 primary sources. Physicochemical conditions of the formation of palladian gold at some deposits of type 1 cover two areas—magmatic high-temperature and hydrothermal low-temperature. At the majority of deposits of types 2–4, its formation proceeds with the participation of hydrothermal fluids (300–60 °C) of various salinities (0.2–30 wt.% NaCl eq.). Palladian gold is mainly high-fineness (910‰–990‰), is less frequently medium-fineness, and contains Ag and Cu, but does not contain Hg at the deposits of types 1, 3, and 4. The only exception is the Au-Pd-Hg Itchayvayam ore occurrence (Kamchatka, Russia), for which two varieties of Pd,Hg-bearing native gold (fineness 816‰–960‰ and 580‰–660‰) are determined. Low-fineness palladian gold with the major content of Ag is typical of OGD deposits. Medium-fineness palladian gold occurs at ferruginous quartzite deposits and in volcanic exhalations. Hg, Ag, Cu-bearing high-fineness palladian gold is present mainly in placer deposits (type 7). The most common minerals in association with palladian gold are arsenides, stibioarsenides, sulfides, stannides, bismuthides, tellurides, and selenides of Pd and Pt. These are typical of deposit types 1 and 7. The minerals of Au, Ag, and Cu (tetra-auricupride, aurostibite, chalcopyrite, bornite, chalcocite, eucairite, etc.) are in association with palladian gold at OG, EPGC, and IOCG deposits. Hg minerals (cinnabar, tiemannite, coloradoite, potarite) are at some deposits (types 1, 2, 7-1, 7-4). Cu, Fe, and Pd oxides (tenorite, hematite, magnetite, PdO, (Pd,Cu)O) and Fe and Pd hydroxides (goethite, (Fe,Pd)OOH) occur at the deposits of the 3, 4, and 7 groups and indicate the highly oxidizing conditions of ore formation. The most common minerals among host minerals are quartz and muscovite, including fuchsite (Cr-Ms), chlorite, albite, K-feldspar, hornblende, and carbonates (calcite, siderite, etc.). The fineness, content, and set of impurities in palladian gold and minerals in association with it reflect the mineralogy of Au-Pd ores and allow them to be used as indicators for the deposit types.

Heterogeneous grains in the heavy fractions of the placers of the Olkhovaya-1 river (Kamchatka Cape Peninsula, Eastern Kamchatka, Russia) containing Au-Ag, Au-Cu, and Au-Ag-Cu particles were analyzed using scanning electron microscopy, electron-probe microanalysis, and X-ray powder diffractometry. The analyses showed that auricupride dominates in some grains, whereas in others, the main phases are tetra-auricupride or Ag-rich and (or) Au-rich alloys. It was revealed that in the central parts of some grains of exsolution structures, auricupride Cu_3.04–2.74Au_0.96–1.26 (Ag < 1 wt.%) occurs in intergrowths with low-fineness Ag_0.86–0.67Au_0.09–0.33Cu_<0.05 solid solutions (160‰–480‰), and tetra-auricupride Cu_1.12–0.87Au_0.88–1.11Ag_<0.02 (Ag < 2 wt.%) occurs with higher-fineness Au_0.73–0.62Ag_0.2–0.38Cu_<0.07 solid solutions (520‰–850‰). We also observed, mainly in the peripheral parts of the grains, insignificant amounts of secondary phases that were compositionally similar to Cu₂Au, Cu₃Au₂, Au₃Cu₂, Au₂Cu, Au₃Cu, high-fineness gold with impurities of Cu and occasionally Ag (>850‰), and pure gold. In intergrowths with auricupride and tetra-auricupride, we also observed earlier-formed silicates (garnet, pyroxene, chlorite, epidote, titanite), syngenetic sulfides (pyrrhotite, bornite, galena), and later minerals (chalcocite, covellite, anilite, cuprite, goethite, etc.). The XRD analysis of the peripheral parts of some grains showed the presence of auricupride (Cu₃Au), tetra-auricupride CuAu (I) and Cu(Au_0.92Ag_0.08) (II), and gold. The profiles show the absence of peaks of the Au₃Cu phase and other Au-Ag-Cu phases identified by the EMPA, which is likely due to their low concentrations in the samples or their structural similarity to gold. It is assumed that the probable source of Au-Ag-Cu mineralization in the Olkhovaya-1 river placers is located in the upper reaches of watercourses that erode the ultrabasic massif of Mounts Soldatskaya and Golaya (Kamchatka Cape Peninsula).

The unique minerals of the Au-Pd-Hg system in gold grains from heavy concentrates of the Itchayvayam placers and watercourses draining and ore samples of the Barany outcrop at the Itchayvayam mafic–ultramafic complex (Kamchatka, Russia) were investigated. Gold grains from watercourses draining and heavy concentrates of the Itchayvayam placers contain substitution structures formed by Pd,Hg-rich low-fineness gold (Au_0.59–0.52Pd_0.24–0.25Hg_0.17–0.23, 580‰–660‰) and Pd,Hg-poor high-fineness gold (Au_0.94–0.90Pd_0.02–0.04Hg_0.03, 910‰–960‰). Potarite (PdHg) without and with impurities (Au < 7.9, Cu < 3.5, Ag < 1.2 wt.%), Ag-poor high-fineness gold (Au_0.91Ag_0.09, 950‰), Ag,Pd,Hg-bearing middle-fineness gold (Au_0.75Ag_0.08Pd_0.09Hg_0.08—Au_0.88Ag_0.09Pd_0.02Hg_0.01, 820‰–930‰), and Pd,Hg-rich low-fineness gold with minor contents Ag and Cd (Au_0.51–0.55Pd_0.25–0.22Hg_0.21–0.16Ag_0.03–0.06Cd_0.01, fineness 580‰–630‰) were observed as individual microinclusions in the ore samples of the Barany outcrop. XRD and EBSD study results show that the Pd,Hg-rich low-fineness gold is isotypic to gold and has the same structure type, but different cell dimensions. According to data obtained for the Itchayvayam and some deposits and ore occurrences with Pd,Hg-bearing gold, the stable ternary phases and solid solutions of the following compositions in the Au-Pd-Hg system have been identified: Pd,Hg-poor gold (Au_0.94–0.90Pd_0.02–0.04Hg_0.03), Pd,Hg-rich gold (Au_0.59–0.52Pd_0.24–0.25Hg_0.17–0.23), Au-potarite (PdHg_0.62Au_0.38—Pd_1.04Hg_0.96—Au_0.80Pd_0.68Hg_0.52), and Au,Hg-bearing palladium (Pd_0.7Au_0.3Hg_0.1). The genesis of Pd,Hg-rich gold is insufficiently studied. We supposed that the meteoric waters or low-temperature hydrotherms rich in Pd and Hg could lead to the replacement Pd,Hg-poor gold by Pd,Hg-rich gold. High concentrations of Pd in Pd,Hg-bearing gold indicate a genetic relationship with mafic–ultramafic rocks.

—We have studied the mineral composition of ores from the Pepenveem epithermal Au–Ag deposit, which is a promising new object of the Chukchi Peninsula. It has been found that the ore formation process was developed in the following sequence: Pyrite, arsenopyrite, and marcasite were deposited at the early stage, next were Pb, Zn, and Cu sulfides; at the late stage, native gold, pyrargyrite, stephanite, proustite, minerals of the pearceite–polybasite series, acanthite, and other Ag minerals were deposited. The results of fluid inclusion studies indicate that the Au–Ag mineralization formed from low-temperature (236–137 °C) low-concentration chloride hydrotherms (0.18–1.57 wt.% NaCl eq.). The results of calculation of thermodynamic equilibria have shown that in the temperature range from 200 to 100 °C, there were a decrease in the fugacity of sulfur (lg fS₂ from –10 to –21) and oxygen (lg fO₂ from <–36 to <–48) and a change from near-neutral to acidic solutions. Compared to other Au–Ag deposits on the Chukchi Peninsula (Corrida and Valunistoe), which are characterized by wide distribution of Se- and Te-bearing Au–Ag chalcogenides (naumannite, cervelleite, and hessite), ore formation with gold–silver–sulfosalt mineralization at the Pepenveem deposit took place at lower temperatures and lower selenium, tellurium, and oxygen fugacity. The data obtained permit us to refer the Pepenveem deposit to the group of epithermal low-sulfidation (LS) deposits.