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Minerals that contain platinum-group elements (PGEs) and occur in some magmatic Cu-Ni sulfide deposits have been ascribed to crystallization from an originally PGE-rich sulfide liquid. The occurrence of PGE-bearing minerals (PGMs) in some sulfide-undersaturated primitive melts has been envisaged and recently reported, whereas direct crystallization of PGMs in sulfide-saturated silicate magmas is seemingly hindered by strong partitioning of PGE into immiscible sulfide melts. In this study, we discovered abundant nanoparticles containing noble metals in association with sulfide melt inclusions entrapped inside primitive olivine phenocrysts (Fo85-92) from the recent basaltic magma of the Tolbachik volcano (Kamchatka arc, Russia). These nuggets occur in swarms on the surface of the sulfide globules and are represented by native metals, sulfides, and alloys of Pd, Pt, Au, Pb, and Bi. The nuggets on different globules can be either Pd- or Pt-rich nuggets, and the compositions are highly variable, even among adjacent nuggets. We argue that the diffusive supply of Pd from the external nuggets can be responsible for significant uptake of Pd (up to 2 wt%) in the sulfide melt. We consider direct crystallization of PGMs in a primitive basaltic melt undergoing sulfide unmixing, and possibly sulfide breakdown due to oxidation, as another mechanism additional to their "classic" origin from the PGE-rich sulfide melt in response to solidification. [ABSTRACT FROM AUTHOR]

Subvolcanic environments in supra‐subduction zones are renowned for hosting epithermal deposits that often contain electrum and native gold, including bonanza examples. This study examined mineral assemblages and processes occurring in shallow‐crust volcanic settings using recent eruption (2012–2013) of the basaltic Tolbachik volcano in the Kamchatka arc. The Tolbachik eruptive system is characterized by an extensive system of lava tubes. After cessation of magma input, the tubes maintained the flow of hot oxidized gases that episodically interacted with the lava surfaces and sulphate‐chloride precipitates from volcanic gases on these surfaces. The gas‐rock interaction had strong pyrometamorphic effects that resulted in the formation of molten salt, oxidized (tenorite, hematite, Cu‐rich magnesioferrite) and skarn‐like silicate mineral assemblages. By analogy with experimental studies, we propose that a combination of these processes was responsible for extraction of metals from the basaltic wall rocks and deposition of Cu‐, Fe‐ and Cu‐Fe‐oxides and native gold. [ABSTRACT FROM AUTHOR]

· Mantle wedge may contain sulfide/sulfate metasomatic accumulations. · Reaction of mantle olivine with slab melt/fluid releases Ni from olivine lattice. · The released Ni reacts with S-rich slab melt/fluid to form sulfides. · Sulfur is introduced to the mantle wedge in both oxidized and reduced forms. Metasomatic replacement of olivine by orthopyroxene under the influence of SiO 2 -rich melts is a widespread process in mantle conditions responsible for the formation of pyroxenite from mantle peridotite. However, the behavior of nickel in this process remains unclear. The reaction of Ni-containing olivine with silica- and sulfur-rich metasomatic agents in the suprasubduction mantle may release nickel from olivine and subsequently form a rock containing orthopyroxene and nickeliferous sulfides. Xenoliths of mantle wedge harzburgite from the Shiveluch volcano (Kamchatka continental arc) contain abundant globules of Ni-rich MSS, pentlandite and smaller amount of copper sulfides, totaling up to 0.75 wt.% (∼2600 ppm S2–), in association with Ca-sulfates (up to 7900 ppm S6+). The process accounting for the observed mineral association can be described via simplified reactions (the coefficients are approximate): (Mg,Fe,Ni) 2 SiO 4 + 2xH+ +SiO 2 = 2(Mg,Fe)SiO 3 + xNi2+ + xH 2 O; Ni2+ + S2– = NiS. The influx of both oxidized and reduced sulfur may account for the coexistence of sulfide and sulfate phases. The presence of low-Ti chrome spinel with high Fe(II)/Fe(III) ratios, low Al, Ca and Ti in olivine, and no evidence of deserpentinization confirms the mantle origin of the sulfide/sulfate-bearing xenoliths. The mean isotopic composition of sulfur in the sulfide-sulfate assemblage, δ34S = +4.5‰, supports the contribution of slab-derived sulfur. The accumulations of Ni-(Cu)-rich sulfides and Ca-sulfate in metasomatized peridotites can serve as an intermediate host for sulfur and chalcophile metals, thereby generating magmas containing sulfur at the level of sulfide saturation and simultaneously enriched in Ni and Cu during the subsequent partial melting of the mantle. [ABSTRACT FROM AUTHOR]

A new Cu-rich variety of lyonsite has been found from fumarolic sublimates of the Tolbachik volcano (Kamchatka, Russia). The empirical formula is CuFeTiAlZn(VAsMoPS)O. The crystal structure was studied on single crystal using synchrotron radiation, R = 0.0514. The mineral is orthorhombic, Pnma, a = 5.1736(7), b =10.8929(12), c = 18.220(2) Å, V = 1026.8(2) Å, and Z = 2. The structural formula is (CuTiAlFe□)Cu(FeCu)(VAsMo)O. It is proposed to recast the simplified formula of lyonsite as Cu(FeCu)(VO), where 0 ≤ x ≤ 1. [ABSTRACT FROM AUTHOR]

A new mineral krasheninnikovite, ideally KNa2CaMg(SO4)3F, is found in the sublimates of an active fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with tenorite, thenardite, hematite, euchlorine, blödite, vergasovaite, and fluorophlogopite. Krasheninnikovite forms long-prismatic to acicular crystals up to 3 mm long and up to 20 µm thick. The crystals are combined in sheaf-like, radiating or open-work matted aggregates forming nests up to several cm³ or crusts. Krasheninnikovite is transparent, colorless in individuals and white in aggregates. The luster is vitreous. The mineral is brittle; the thinnest needles are flexible and elastic. The Mohs hardness is 2½-3. Cleavage was not observed. Dmeas is 2.68(1), Dcalc is 2.67 g/cm³. Krasheninnikovite is optically uniaxial (-), ω = 1.500(2), ε = 1.492(2). The IR spectrum is unique. The chemical composition (wt%, electron microprobe data) is: Na2O 15.48, K2O 6.92, CaO 11.51, MgO 9.25, MnO 0.15, FeO 0.04, Al2O3 0.23, SO3 53.51, F 3.22, Cl 0.16, -O=(F,Cl)2 -1.39, total 99.08. The empirical formula, calculated on the basis of 13 (O+F+Cl) apfu, is: K0.67Na2.27Ca0.93Mn0.01Mg1.04Al0.02(SO4)3.04F0.76Cl0.02O0.06. Krasheninnikovite is hexagonal, space group P63/mcm, a = 16.6682(2), c = 6.9007(1) Å, V = 1660.36(4) Å3, Z = 6. The strongest reflections of the X-ray powder pattern [d, Å I(hkl)] are: 4.286 22(121); 3.613 24(040); 3.571 17(221); 3.467 42(131); 3.454 43(002); 3.153 100(140), 3.116 22(022), 2.660 39(222), 2.085 17(440). The crystal structure was solved on a single crystal and refined on a powder sample by the Rietveld method, Rwp = 0.0485. The krasheninnikovite structure is unique. It is based upon a heteropolyhedral pseudo-framework consisting of CaO6 octahedra, MgO5F octahedra, and SO4 tetrahedra; K and Na cations are located in cavities. Krasheninnikovite is named in honor of the Russian geographer, ethnographer, and naturalist S.P. Krasheninnikov (1711-1755), one of the first scientists who researched Kamchatka. The type specimen is deposited in the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow. [ABSTRACT FROM AUTHOR]

The new mineral calciolangbeinite, ideally K2Ca2(SO4)3, is the Ca-dominant analogue of langbeinite. It occurs in sublimates at the Yadovitaya fumarole on the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure eruption, Tolbachik volcano, Kamchatka, Russia. The mineral is associated with langbeinite, piypite, hematite, rutile, pseudobrookite, orthoclase, lyonsite, lammerite, cyanochroite and chlorothionite. Calciolangbeinite occurs as tetrahedral to pseudooctahedral crystals, which are bounded by {111} and {111}, and as anhedral grains up to 1 mm in size, aggregated into clusters up to 2 mm across, and forming crusts covering areas of up to 1.5 6 1.5 cm on the surface of volcanic scoria. Late-stage calciolangbeinite occurs in complex epitaxial intergrowths with langbeinite. Calciolangbeinite is transparent and colourless with white streak and vitreous lustre. Its Mohs'' hardness is 3–3½. It is brittle, has a conchoidal fracture and no obvious cleavage. The measured and calculated densities are Dmeas= 2.68(2) and Dcalc= 2.74 g cm–3, respectively. Calciolangbeinite is optically isotropic with n= 1.527(2). The chemical composition of the holotype specimen is Na2O 0.38, K2O 21.85, MgO 6.52, CaO 16.00, MnO 0.27, FeO 0.08, Al2O30.09, SO355.14, total 100.63 wt.%. The empirical formula, calculated on the basis of twelve oxygen atoms per formula unit, is K2.01(Ca1.24Mg0.70Na0.05Mn0.02Fe0.01Al0.01)S 2.03S3.00O12. Calciolangbeinite is cubic, space group P213, a= 10.1887(4) Å, V= 1057.68(4) Å3and Z= 4. The strongest reflections in the X-ray powder pattern [listed as (d, Å (I)(hkl)] are 5.84(8)(111); 4.54(9)(120); 4.15(27)(211); 3.218 (100) (310, 130); 2.838 (8) (230, 320), 2.736 (37) (231, 321), 2.006 (11) (431, 341) , 1.658(8)(611,532,352). The crystal structure was refined from single-crystal X-ray diffraction data to R= 0.0447. The structure is based on the langbeinite-type three-dimensional complex framework, which is made up of (Ca,Mg)O6octahedra (Ca and Mg are disordered) and SO4tetrahedra. Potassium atoms occupy two sites in voids in the framework; K(1) cations are located in ninefold polyhedra whereas K(2) cations are sited in significantly distorted octahedra. Calciolangbeinite and langbeinite are isostructural and form a solid-solution series. [ABSTRACT FROM AUTHOR]

Tazieffite, ideally Pb20Cd2(As,Bi)22S50Cl10, is a new mineral from the high-temperature fumaroles of the Mutnovsky volcano, Kamchatka Peninsula, Russian Federation. It occurs as tiny, slender, needle-shaped crystals, up to 400 μm long and 10 μm across, generally forming fibrous aggregates. Tazieffite is closely associated with greenockite, galena, mutnovskite, kudriavite, and Cd-rich cannizzarite. Other minerals spatially associated are pyrite, anhydrite, and cristobalite. Tazieffite is silvery-gray in color, occasionally with a magenta tint when it forms aggregates of extremely fine needles. It has a black streak and metallic luster. In plane-polarized incident light, tazieffite is weakly bireflectant and weakly pleochroic from dark gray to a blue-gray. Between crossed polars, the mineral is weakly anisotropic, without characteristic rotation tints. Reflectance percentages measured in air (Rmin and Rmax) for a single grain are 33.9, 34.1 (471.1 nm), 32.8, 33.0 (548.3 nm), 32.4, 32.6 (586.6 nm), and 30.9, 31.1 (652.3 nm), respectively. Electron microprobe analyses yield the following ranges of concentrations: Pb 41.88-44.14 (avg. 42.90), Cd 0.87-1.16 (avg. 1.03), Sn 0.31-0.69 (avg. 0.48), Bi 20.43-22.94 (avg. 21.90), As 8.64-10.73 (avg. 9.66), S 16.10-17.48 (avg. 16.58), Se 0.82-1.28 (avg. 1.04), Cl 2.39-2.77 (avg. 2.63), Br 0.09-0.15 (avg. 0.12), I 0.27-0.58 (avg. 0.42). The empirical chemical formula, calculated on the basis of 44 cations, is Pb20.06(Cd0.89Sn0.39In0.02)Σ1.30(As12.49Bi10.15)Σ22.64 (S50.08Se1.28)Σ51.36(Cl7.18I0.32Br0.15)Σ7.65. Tazieffite is closely related to the halogen-sulfosalt vurroite, Pb20Sn2Bi22S54Cl6, both from a chemical and structural point of view. It represents the (Cd,As)-dominant of vurroite, according to the coupled heterovalent substitution Sn4+ + 2S2- → Cd2+ + 2Cl-. The crystal structure of tazieffite was refined in the space group C2/c to R = 0.0370 for 4271 reflections with I > 2σ(I). Unit-cell parameters are a = 8.3520(17), b = 45.5920(92), c = 27.2610(55) Å, β = 98.84(3)°, with V = 10257(4) Å3, and Z = 4. The structure of tazieffite consists of lozenge-shaped composite rods made of coordination polyhedra of Pb around an octahedrally coordinated (Cd,Sn,Pb) position, interconnected into layers parallel to (010). These layers are separated by ribbons of As and Bi in distorted octahedral coordination. The ribbons form wavy, discontinuous double layers of the PbS archetype. Lone electron pairs of As and Bi are accommodated in the central portions of the PbS-like layers. The possibility that small amounts of NH4+ are incorporated in the crystal structure of tazieffite is discussed. The name of this new mineral species (IMA 2008-012) honors Haroun Tazieff (Warszawa, May 11, 1914-Paris, February 6, 1998), famous Belgian/French volcanologist, who was a pioneer in the field study of volcanoes and devoted his life to the study of volcanic gases. [ABSTRACT FROM AUTHOR]

Sulfur contents in 98.5% of melt inclusions (MI) from calc-alkaline subduction basalts do not exceed 4000 ppm, whereas experimentally established limits of sulfur solubility in basaltic melts with high fO2 (characteristic of subduction zones, e.g., QFM + 2) surpass 14,000 ppm. Here we show that primitive (Mg# 62-64) subduction melts may contain high sulfur, approaching the experimental limit of sulfur solubility. Up to 11,700 ppm S was measured in olivine-hosted MI from primitive arc basalt from the 1941 eruption of the Tolbachik volcano, Kamchatka. These MI often contain magmatic sulfide globules (occasionally enriched in Cu, Ni, and platinum-group elements) and anhydrite enclosed within a brown, oxidized glass. We conclude that the ubiquitous low sulfur contents in MI may originate either from insufficient availability of sulfur in the magma generation zone or early magma degassing prior to inclusion entrapment. Our findings extend the measured range of sulfur concentrations in primitive calc-alkaline basaltic melts and demonstrate that no fundamental limit of 4000 ppm S exists for relatively oxidized subduction basalts, where the maximum sulfur content may approach the solubility limit determined by crystallization of magmatic anhydrite. [ABSTRACT FROM AUTHOR]

The geochemical variations of magmas across and along supra-subduction zones (SSZ) have been commonly attributed to profound changes in the phase and chemical compositions of the mantle source and subduction-derived melt and fluid fluxes, as well as the physical parameters (e.g. depth, temperature, oxygen fugacity etc) of slab dehydration, mineral breakdown and melting. Here we test the variability of the Late Quaternary primitive magmas in the southern and northern parts of the meridionally oriented Eastern Volcanic Belt (EVB) of Kamchatka, with a slab depth varying from 60 to 160 km. Eight high-Mg (Mg# > 60 mol%) basalts were characterized for major, trace and platinum-group element (PGE) abundances, as well as the compositions of olivine phenocrysts and olivine-hosted spinel inclusions. The basalts in our study are geochemically typical of SSZ magmas and contain similar liquidus assemblages of forsteritic olivine (Mg# 78–92 mol%), low-Ti Cr-spinel and clinopyroxene. Although the absolute abundances of major and trace elements, and their ratios, in the basalts fluctuate to some extent, the observed variability cannot be correlated with any of considered parameters in the geometry of the Kamchatka SSZ and conditions of melting. This unexpected result led to the evaluation of the platinum-group element (PGE) systematics against the lithophile and chalcophile trace element geochemistry and the compositions of phenocrysts. Total whole-rock PGE content varies from 2.3 to 11.7 ppb, whereas the normalized PGE concentration patterns are typical for supra-subduction zones magmas and broadly similar in all studied samples. They are enriched in Rh, Pd and Pt relative to mid-ocean ridge basalts (MORB) and have nearly identical concentrations of Ir-group PGE. The only parameter that correlates well with PGE contents is the average Mg# of olivine phenocrysts from 84 to 90.3 mol%. This is interpreted to result from minor cryptic fractionation of sulfide melt, together with primitive olivine, in low-to-mid crustal conditions. Negative Ru anomalies on chondrite-normalized diagrams correspond to the Fe2+/Fe3+ ratios in spinel (a proxy for magma redox conditions), which reflects a replacement of monosulfide solid solution by laurite in the mantle wedge during oxidation. • Most magnesian basalts in eastern Kamchatka arc represent primitive magmas. • No correlation found between arc system geometry and geochemistry and mineralogy. • PGE contents and systematics in studied high-Mg basalts are typical of arc magmas. • Local sulfide saturation is a common feature for primitive magmas of Kamchatka. • Laurite is a restite mineral in the sub-arc mantle that produces negative Ru anomalies. [ABSTRACT FROM AUTHOR]

Sulfide liquids that immiscibly separate from silicate melts in different magmatic processes accumulate chalcophile metals and may represent important sources of the metals in Earth's crust for the formation of ore deposits. Sulfide phases commonly found in some primitive mid-ocean ridge basalts (MORB) may support the occurrence of sulfide immiscibility in the crust without requiring magma contamination and/or extensive fractionation. However, the records of incipient sulfide melts in equilibrium with primitive high-Mg olivine and Cr-spinel are scarce. Sulfide globules in olivine phenocrysts in picritic rocks of MORB-affinity at Kamchatsky Mys (Eastern Kamchatka, Russia) represent a well-documented example of natural immiscibility in primitive oceanic magmas. Our study examines the conditions of silicate-sulfide immiscibility in these magmas by reporting high precision data on the compositions of Cr-spinel and silicate melt inclusions, hosted in Mg-rich olivine (86.9–90 mol% Fo), which also contain globules of magmatic sulfide melt. Major and trace element contents of reconstructed parental silicate melts, redox conditions (ΔQFM = +0.1 ± 0.16 (1σ) log. units) and crystallization temperature (1200–1285 °C), as well as mantle potential temperatures (~1350 °C), correspond to typical MORB values. We show that nearly 50% of sulfur could be captured in daughter sulfide globules even in reheated melt inclusions, which could lead to a significant underestimation of sulfur content in reconstructed silicate melts. The saturation of these melts in sulfur appears to be unrelated to the effects of melt crystallization and crustal assimilation, so we discuss the reasons for the S variations in reconstructed melts and the influence of pressure and other parameters on the SCSS (Sulfur Content at Sulfide Saturation). • Parental melts of sulfide-bearing KM rocks have near primary MORB-like composition. • Crystallization of these S-saturated melts occurred in near-surface conditions. • Extensive fractionation and crustal assimilation are not the causes of S-saturation. • S content in melts can be restored by accounting for daughter sulfide globules. [ABSTRACT FROM AUTHOR]

Volcanic rocks from ophiolites of Kamchatsky Mys (Kamchatka, Russia) were earlier identified as a product of the Hawaiian plume activity in the Cretaceous (Portnyagin et al., 2008, 2009). Olivine-phyric basalts found among them in 2012 (Savelyev et al., 2018) are unique because, despite their age, they contain fresh high-Mg olivine (up to Fo90) with partly crystallized inclusions of sulfide and silicate melts. Silicate melt inclusions were analyzed after reheating experiments, which allowed us to reconstruct the primary composition of melts, their crystallization and generation conditions. Temperature and oxygen fugacity of crystallization are typical for primitive MORB melts – ~1250 degrees celsius and ΔQFM ≈ 0 log units, while the trace element patterns of melts reflect highly heterogeneous source enrichment from D-DMM to OIB-like values. New high-precision data on the noble metals and other trace elements are obtained for the homogenized sulfide melt inclusions and separate sulfide phases – intermediate solid solution (ISS) and monosulfide solid solution (MSS). Obtained data can be used for modeling of sulfide saturation in primitive oceanic magmas and redistribution of noble metals and other trace elements during that process. This study was funded by the Russian Science Foundation grant #16-17-10145.References:Portnyagin, M., Savelyev, D., Hoernle, K., Hauff, F., Garbe-Schönberg, D. (2008). Mid-Cretaceous Hawaiian tholeiites preserved in Kamchatka. Geology, 36(11), 903-906.Portnyagin, M., Hoernle, K., Savelyev, D. (2009). Ultra-depleted melts from Kamchatkan ophiolites: Evidence for the interaction of the Hawaiian plume with an oceanic spreading center in the Cretaceous? Earth and Planetary Science Letters, 287(1-2), 194-204.Savelyev, D. P., Kamenetsky, V. S., Danyushevsky, L. V., Botcharnikov, R. E., Kamenetsky, M. B., Park, J. W., Portnyagin M.V., Olin P., Krasheninnikov S.P., Hauff F., Zelenski, M. E. (2018). Immiscible sulfide melts in primitive oceanic magmas: Evidence and implications from picrite lavas (Eastern Kamchatka, Russia). American Mineralogist: Journal of Earth and Planetary Materials, 103(6), 886-898. [ABSTRACT FROM AUTHOR]