The behavior of platinum-group elements (PGE) in sulfide-undersaturated primitive magmas may be controlled by crystallization of either Cr-spinel, platinum-group minerals (PGM) or olivine. Evaluation of the PGM-hosted PGE portion is challenging because PGM in volcanic rocks are small and rare. We report on the sizes and compositions of PGM associated with Cr-spinel, the PGE content of Cr-spinel and olivine, and the bulk rock PGE content from sulfide undersaturated arc volcanics of the Tumrok range (Eastern Kamchatka). Platinum-iron and Ir-Os alloys (< 30 to > 3000 nm in size) form inclusions in Cr-spinel. Their presence and composition are mostly independent of Cr-spinel chemistry. Bulk rock PGE contents are erratic and PGE concentrations in Cr-spinel are exceptionally variable (up to 2 orders of magnitude). Whereas PGM inclusions in Cr-spinel and PGE in solid solution in Cr-spinel significantly contribute to the bulk rock PGE budget, a considerable portion of the PGE must be present associated with minerals other than Cr-spinel. The variable PGE content of the rocks is attributed to a combination of: (a) disequilibrium kinetic effects at the Cr-spinel-melt boundary layer, strongly affecting PGE partitioning into Cr-spinel and crystallization of PGM in the layer; (b) the presence of some sufficiently large PGM to cause nugget effects; and (c) melt degassing.

A large hydrothermal field at depths >4300 meters was found on the east Caroline plate in the western Pacific Ocean. Here, we show that large hydrothermal pipes with steep walls and breccia-dominated bottoms suggest explosions of billion metric tons of TNT (trinitrotoluene) equivalent. More than 800 short-duration seismic events were detected within 28 days along a 150-kilometer profile, indicating widespread ongoing explosive gas release. We suggest that billions of tons of hydrogen gas were produced through serpentinization associated with fluid infiltration via fractures formed by bending of the oceanic plate. Hydrogen was retained in fractures sealed by mud and carbonate. However, hydrogen alone cannot produce the explosive capacity responsible for the formation of pipes. Oxygen released from circulating seawater can be concentrated at crustal depths and then mixed with mantle-derived hydrogen. Explosion of the gas mixture releases large amounts of heat that triggers further explosions of compressed hydrogen gas and results in the formation of hydrothermal pipes.

Iron Oxide-Apatite (IOA) deposits are a notable source of iron, and, potentially, of phosphorus and rare earth elements (REE). The vast majority of these deposits are ancient (from similar to 1900 to similar to 100 Ma), and their original textures and mineral associations are overprinted by regional and local metasomatic/metamorphic processes. In the present paper, we provide new petrographic, mineralogical and geochemical data on the poorly studied Abovyan IOA deposit in Armenia, one of the world's youngest IOA deposits. The Late Miocene magnetite-apatite Abovyan deposit is hosted by a subvolcanic andesite body located in the volcanic zone of Gegham Highland. The ore mineralization is hosted in andesite and consists of disseminated magnetite-carbonate blobs, breccia and massive magnetite-apatite bodies. Disseminated blobs mostly consist of magnetite-clinopyroxene-dolomitehematite-calcite assemblages, whereas the mineralogical diversity increases toward the massive ore bodies with the appearance of Th- (thorite, monazite) and REE-rich (monazite, REE-silicates) minerals. Abundant inclusions of halite and sylvite were also found in magnetite from massive ore. Massive magnetite-apatite ore is depleted in Rb, Ba, K, Sr and HFSE and enriched in REE, Th, U and Pb relative to host andesite. The host rocks have more radiogenic Sr-87/Sr-86 ratios of similar to 0.7053 than other volcanic rocks in the Gegham highland with ratios of similar to 0.7042. The apatite from nine ores samples have even more radiogenic Sr-87/Sr-86 ratios of similar to 0.706 for the same epsilon Nd values. These data allow us to conclude that ore formation is likely linked to liquid immiscibility triggered by the assimilation of Sr-rich and Nd-poor crustal material. The local source for such assimilated material is the K-rich evaporite of the Yerevan salt basin.

Carbonate melts are critically important for the deep carbon cycle, mantle melting, redox reactions, and transport of highly incompatible elements. The presence of carbonate melts in the cratonic mantle has been inferred from experimental studies, metasomatic transformations, and melt/fluid inclusions in xenoliths, kimberlites, and diamonds. However, the exact composition of such melts is difficult to determine due to their ephemeral nature and highly reactive properties. Once formed, they migrate away from the source and react with silicate mantle minerals, especially orthopyroxene, causing mantle metasomatism. Wehrlite is one of the products of interaction between the carbonate melt and peridotitic mantle and hence is an excellent candidate for locating in situ carbonate melts. Here, we report petrological, geochemical, and melt inclusion data for a garnet wehrlite xenolith in the Majuagaa kimberlite dike, West Greenland. The xenolith, which last equilibrated with the mantle at 4.5 GPa and 1000 degrees C, contains abundant melt pools composed of dolomite, calcite, serpentine, spinel, apatite, and phlogopite. Although the original magmatic mineralogy was largely destroyed by low-temperature alteration, remnants of the crystallized carbonatitic melt are preserved as primary melt inclusions in the liquidus Ti-Mg-Fe spinel. These melt inclusions, composed of carbonates, alkali carbonates, periclase/ brucite, and minor halides, K-sulfide, apatite, and phlogopite, are the first direct evidence for in situ alkali-carbonate melt in the deep cratonic mantle. Compositionally, they are very similar to primary Na-dolomite melt found in experiments and in fluid inclusions within diamonds.

Oceanic basalts show variation in their iron and magnesium isotope compositions. One hypothesis for the origin of this is source variation: radiogenic isotope and trace element abundance studies have long argued that the Earth's upper mantle is geochemically heterogeneous and that subducted crust is a major contributor to this diversity. In contrast, a recent hypothesis posits that stable isotopes record disequilibrium during melt transport and so provide novel insight into the melting process. In this study we investigate the first of these hypotheses, that source heterogeneity explains global Fe-Mg isotope systematics. We compile a global dataset of oceanic basalt Fe and Mg isotopes and complement this with new Fe-Mg isotope data from locations possessing some of the most extreme radiogenic isotope ratios for their setting: ocean island basalts from the Cook-Austral and Society islands and a Mid-Atlantic Ridge basalt. Despite both Fe and Mg isotope systems having the ability to trace recycled crustal material in the mantle, their global systematics are very different in this dataset. The global compilation of primitive oceanic basalts records heavier Fe (higher δ57Fe) isotope compositions than bulk silicate earth (BSE), but a mixture of heavier and lighter Mg isotope compositions than BSE. By employing a coupled Fe-Mg equilibrium isotope fractionation model during mantle melting we show that much of this isotopic variability can be generated by the mixed melts produced by melting of peridotite mantle containing moderate amounts of recycled crust as a discrete lithology. The Fe isotope composition of the melts is controlled by the bulk isotope composition of the recycled crust (expected to be considerably heavier than BSE, but variable). In contrast, the Mg isotope composition is controlled by source mineralogy. Olivine-poor lithologies such as recycled crust are able to generate large Mg isotope fractionations during melting, both positive and negative (± 0.1‰) relative to the mantle source, depending on the presence of spinel, clinopyroxene or garnet. These melt Mg isotope fractionations are consistent with the Mg isotope compositions of mid-ocean ridge basalts generated by variable depths of mantle melting. Our equilibrium model provides a baseline to test hypotheses of Fe-Mg isotope variability in basalts: our results show that contributions from recycled crust-derived melts, generated in spinel-, pyroxene-, and garnet-bearing mineral assemblages in the mantle, would be able to produce much of the Fe-Mg isotope variability seen in the global compilation of primitive oceanic basalts, without requiring isotopically extreme mantle components (e.g., carbonate with a light Mg isotope signature) or disequilibrium fractionation. However some basalt variability in ocean island settings may indeed fall outside the paradigm of pyroxenite heterogeneity – whilst we consider carbonates unlikely to be important, disequilibrium processes may in these cases play a role.

The Kerguelen Plateau is the second biggest submarine large igneous province (LIP) on Earth, however, the nature of the lithospheric mantle source underlying it remains poorly constrained. In this contribution, we provide novel insights into the oceanic lithospheric mantle underlying Heard Island (southern Indian Ocean), which represents the most recent and active phase of volcanic activity (<1 Ma) in the Kerguelen Plateau. We present petrographic and geochemical data for a suite of spinel-bearing harzburgite xenoliths hosted in basanite lavas and provide detailed constraints for distinguishing in situ mantle metasomatism from post-entrapment modification of the xenoliths following interaction with the host magma. We demonstrate that the xenolith mineral compositions and textures preserve a complex multistage history of different modal and cryptic transformations that occurred in the mantle due to: i) high degrees of partial melting that produced highly refractory whole-rock Mg# (Mg# = (Mg + Fe)/Mg x 100; 88-92), major element (FeO/MgO = 0.17) and mineral compositions (e.g. highly forsteritic olivine; Fo = (Mg + Fe)/Mg x 100; 91-92 mol %); ii) solid-state re-equilibration reactions during decompression that caused exsolution of clinopyroxene and Cr-spinel from xenolith orthopyroxene to form symplectite intergrowths; iii) cryptic metasomatism affecting the composition of xenolith clinopyroxene (i.e. enrichment in Na, Th, U and light rare earth elements, and depletion in Rb, Nb, Zr, Hf and Ti) due to interaction with carbonatitic melts in the mantle. Mantle fragments, entrapped by ascending basanite magmas as xenoliths were further modified by reactions with the host magma. This resulted in the partial dissolution of mantle orthopyroxene and replacement by newly formed and compositionally distinct assemblages of clinopyroxene (Mg# 87-91), olivine (Fo: 81-88 mol %) and Cr-spinel (i.e. 'wehrlitisation' of the xenoliths). This study highlights the utility of combining petrography and mineral chemistry to decipher the complex and sometimes overprinting and masking effects that different processes (e.g. melting events, metasomatism) exert on the lithospheric mantle, as well as constrain the processes that modify the xenoliths during transport towards the surface.

Platinum-group elements (PGE) are most effectively concentrated via sulfide-silicate melt immiscibility; however, under sulfide-undersaturated conditions, PGE may exhibit highly siderophile behavior and occur as native metals and alloys. In this case, they can form micrometer-size inclusions within Cr-spinel, but also large nuggets (up to several kilograms), found in chromitites and related placer deposits. The exact formation mechanism of such large nuggets and accumulations of PGE unrelated to sulfide melts remains controversial due to mass balance issues. In this study of multiphase inclusions in Os-Ir-Ru nuggets from the Adamsfield placer district (Tasmania, Australia), we constrain their crystallization environment. Multiphase inclusions comprise variable proportions of hornblende, enstatite, quartz, anthophyllite, anorthite, chlorite and native iridium and coexist with single-phase olivine and Cr-spinel inclusions. The heterogeneity in phase and chemical composition of the inclusions indicates a complex origin from an inhomogeneous source media. This is corroborated by grain scale disequilibrium mineral assemblages, where forsterite and quartz are both included within a single osmium grain. Our proposed multi-stage origin of Adamsfield Os-Ir-Ru nuggets involved magmatic olivine-Cr-spinel-Os-Ir-Ru cumulates in peridotite bodies that were subsequently overprinted by various hydrothermal and metamorphic processes, including serpentinization or growth of Os-Ir-Ru from supercritical fluids. The final metamorphic stage resulted in the obliteration of Os-Ir-Ru zonation, culminating in the current assemblage of inclusions.

An Erratum to this paper has been published: https://doi.org/10.1134/S1028334X23070401

Kaapvaal lamproites (aka orangeites) are a group of volatile-rich (H2O, CO2), micaceous, ultrapotassic igneous rocks that are unique to the Kaapvaal craton in southern Africa. However, the composition of the melts that give rise to these rocks remains poorly understood due to overprinting effects of contamination by mantle and crustal material, volatile exsolution, fractional crystallisation and post-magmatic alteration. Consequently, this lack of reliable data on the initial composition of the Kaapvaal lamproite melts hampers our understanding of their source, petrogenesis and ascent mechanisms.Olivine is a common mineral comprising the Kaapvaal lamproites that has both xenocrystic (i.e., mantle) and magmatic origins. Multiphase inclusions (melt/fluid) entrapped within olivine have been consistently demonstrated as an effective tool for gaining fundamental insights into the composition and evolution of melts that produce both kimberlites and lamproites, prior to processes, such as eruption, devolatization and syn-/post-magmatic alteration.In this study, multiphase inclusions of both secondary and pseudosecondary origin hosted in olivine from a Kaapvaal lamproite (Silvery Home, South Africa) provide novel insights into the composition of the melt(s) that initially transported olivine to the surface and then crystallised after emplacement to form the lamproite groundmass. The inclusions in our study contain daughter mineral assemblages consisting of diverse Ca-Mg carbonates, including K-, Na-, Ba-, and Sr-bearing varieties, moderate K-rich silicates (phlogopite, tetraferriphlogopite), and subordinate oxides, phosphates, sulphides, sulphates, and halides. Based on these daughter mineral assemblages, we suggest that the composition of the melt entrapped by olivine was SiO2-poor, Ca-Mg carbonate-rich and contained elevated concentrations of K, Na, Ba, Sr, P and Cl. The mineral and reconstructed melt compositions are in stark contrast to the mineral association of the groundmass and the bulk-rock composition of the Silvery Home lamproite, respectively. We suggest that alkali-/alkali-earth carbonates, phosphates, sulphides, sulphates, and halides represented a potentially significant, or even dominant, component of the melt that crystallised the Silvery Home lamproite but were likely removed by degassing and/or interaction with syn-/post-magmatic fluids. We show that olivine-hosted multiphase inclusions from the Silvery Home lamproite share many compositional similarities to melt inclusions hosted in olivine from kimberlites but are distinct from ‘classic’ cratonic olivine lamproites worldwide.

The sub-continental lithosphere mantle (SCLM) contains considerable amounts of carbon and is responsible for significant CO2 emissions via magmatism during major heating and rifting events. However, the role of SCLM in Earth's carbon cycle during other geological processes, such as decratonization, a process of major removal and replacement of cratonic SCLM, remains poorly understood. The North China Craton is an archetype of Archean craton having been decratonized during the Mesozoic with extensive magmatism developed. Here we show that the primary melt of Early Cretaceous Yixian basalts contained abundant CO2 (0.6 wt%), through investigating melt inclusions trapped in olivine crystals. The melt inclusions are alkalic and chemically distinct from their sub-alkalic host basalts, which could be explained by that the primary alkalic melt was reactively modified during magma ascent in the SCLM. The primary melt has geochemical characteristics consistent with partial melting of a veined carbon-rich amphibole clinopyroxenite source in the SCLM formed metasomatically during circum-craton subduction events. The findings highlight that the carbon introduced into the cratonic SCLM during subduction could be subsequently reactivated and transferred to the crust and atmosphere through decratonization-related magmatism, which might represent a major process regarding the SCLM in regulating the terrestrial carbon cycle.

Magnetite-(apatite) ore deposits are interpreted as being formed by the crystallization of iron-rich ultrabasic melts, dominantly generated by the interaction of silicate melts with oxidized P-F-SO 4 -bearing sedimentary rocks. This hypothesis is supported by geologic evidence, experimental studies, numerical modeling, stable and radiogenic isotope geochemistry, mineralogy, and melt- and mineral-inclusion data. Assimilation of crustal rocks during ascent promotes separation from a silicate magma of Fe-rich, Si-Al-poor melts with low solidus temperatures and viscosities, allowing coalescence, migration, and emplacement at deep to subaerial crustal environments. When the iron-rich melt attains neutral buoyancy, fractional crystallization leads to melt immiscibility similar to that observed in industrial blast furnaces, which promotes separation of massive magnetite ore overlain by different types of “slag” containing actinolite or diopside ± phosphates ± magnetite ± feldspar ± anhydrite ± scapolite, commonly enriched in high field strength elements. The mineralogy and morphology of this iron-depleted cap strongly depend on the depth of emplacement and composition of the iron-rich magma. Most of these systems exhibit high oxygen fugacity, which inhibits the precipitation of significant sulfide mineralization. The initially high f O 2 of these systems also promotes the formation of low-Ti (< 1 wt%) magnetite: Ti acts as an incompatible component and is enriched in the iron-poor caps and in the hydrothermal aureole. High fluid-phase pressures produced during massive crystallization of magnetite from the melt further facilitate the exsolution of magmatic-hydrothermal fluids responsible for the formation of aureoles of alkali-calcic-iron alteration with hydrothermal replacement-style iron mineralization. On the whole, these systems are dramatically different from the magmatic-hydrothermal systems related to intermediate to felsic igneous rocks; they are more akin to carbonatite and other ultramafic rocks.

The paper presents a comprehensive review of currently available data on melt inclusions entrapped in minerals of kimberlites of different age and different provenance in ancient cratons. The crystallized melt inclusions represent snapshots of kimberlite melts at different stages of their evolution. All of the inclusions are completely crystallized and consist of daughter minerals and shrinkage bubbles, which sometimes contain low-density CO2, but no aqueous fluids and quenched silicate glasses have been found so far. Although more than 60 mineral species have been identified among the daughter phases in the inclusions, all inclusions hosted in various minerals from different kimberlites have closely similar or even identical composition. The daughter minerals are various Na–K–Ca, Na–Ca, Na–Mg, K–Ca, Ca–Mg, Ca, Mg, and Na carbonates; Na–Mg and Na carbonates with additional anions Cl–, SO_4^2 - , and PO_4^3 - ; and alkali sulfates, chlorides, phosphates, sulfides, oxides, and silicates. Alkali carbonates, sulfates, and chlorides are usually absent from among the groundmass phases of most kimberlites sampled worldwide, except the Udachnaya-East kimberlite in Siberia. However, this mineral assemblage, in association with such widespread kimberlite minerals as olivine, micas, monticellite, spinel-group minerals, perovskite, rutile, ilmenite, calcite, and dolomite, is common in the crystallized melt inclusions in all studied kimberlites. Carbonates ( 30 to 85 vol

The Olympic Cu-Au Province hosts not only one of the world's largest Cu-Au-U deposits, Olympic Dam, but also Prominent Hill and Carrapateena. Additionally, REEs, other critical minerals (e.g. Sb, Bi, C, Co, W, Se, Te) plus F, S, As, Fe, Mo, Pb, Sn, Y, Zn are present at concentrations greater than mean continental crust. Other IOCGs (Fe-oxide Cu-Au) occur within a radius of similar to 150 km from Olympic Dam, which broadly defines the Olympic Cu-Au Province. These mineralised occurrences include, but are not limited to, Acropolis, Wirrda Well, Island Dam, Oak Dam East, Vulcan, Titan, Emmie Bluff, and the recently discovered Oak Dam West. Like any other global ore deposit type, IOCGs in the Olympic Cu-Au Province display similarities (e.g. hydrothermal magnetite/ hematite, hematite ages, U-Mo-Sn-W enriched hematite, Cu(+/- Fe) sulfides) and differences (e.g. host lithologies with different ages, nanoprecipitates/inclusions preserved in Fe-oxides, mineralization styles and depths of post-mineral cover). Simple down-drillhole magnetic susceptibility and total Fe concentration profiles reveal some of the complexities of these deposits. However, when coupled with micro- to nanoscale mineralogical characterisation, the macroscale trends can be articulated in terms of systematic transitions from magmatic magnetite to hydrothermal magnetite and finally to multi-generations of hematite.

Сhromite-rich rocks and monomineralic chromitites occur in mafic-ultramafic layered intrusions worldwide, and are economically important as they host major resources of chromium and platinum group elements. One of the acknowledged genetic concepts for such mineralization advocates bulk chromite crystallization in a response to hybridization of Cr-rich basic magma with felsic melts, derived from partial melting of the wall rocks. However, there has been lack of direct insights into this process and its details have been remaining largely obscured. In this study, we report data on chromite-rich assemblages of the Noril'sk-1 intrusion (Siberian LIP), with a particular focus on chromite-hosted multiphase inclusions. Composition of the latter is different from the rocks of the Noril'sk-1 intrusion and inherits geochemical fingerprints of the wall rock argillites and, therefore, represent snapshots of the heavily-contaminated medium of the magma-wall rock reaction front. Mineral relationships in chromite-rich breccias with fragments of the wall rocks also provide valuable insight into chromite mineralization mechanisms. Our results, along with geological evidence and data on other Noril'sk-type intrusions, indicate that bulk crystallization of chromite, aided by partial suppression of silicate crystallization, occurred in the hybrid medium during digestion of the wall rocks by ascending and emplacing basic magma. Continuous flow of the magma around outshoots of the wall rocks or through a “magmatic karst” in the wall rocks, allowed for a continuous precipitation of chromite. Concentration of chromite grains to form dense mineralization apparently occurred due to formation of chromite-rich blobs around the wall rock fragments, and selective collection and transport of chromite by fluid bubbles, which formed via degassing of wall rocks and then carried chromite and relics of the wall rocks (xenoliths) to the upper parts of the pluton. We propose that assimilation-driven formation of chromite-rich lithologies in intrusions requires: (1) sufficient Cr contents in magma, which allow for its oversaturation in Cr-spinel only by a sudden cooling and addition of SiO2, K2O or/and H2O; (2) efficient disintegration and digestion of the host rocks, releasing considerable amounts of these components to the magma, and (3) a mechanism ensuring accumulation of excess chromite within a small volume (e.g. continuous reaction of Cr-rich magma with the products of the host rocks' assimilation or/and mechanical concentration of chromite).

Metasomatic replacement of olivine by orthopyroxene under the influence of SiO2-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.% (similar to 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)SiO4 + 2xH(+) +SiO2 = 2(Mg,Fe)SiO3 + xNi(2+) + 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, delta S-34 = +4.5 parts per thousand, 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.

The study of melt inclusions in minerals is the only direct approach to estimate the contents of volatile components in silicate melts, which are essential to constrain the processes of magma generation and evolution. In particular, the content of sulfur in silicate melts is closely connected with the P-T-fO 2 conditions of mantle melting and the formation of sulfide deposits. Inclusions in high-Mg olivine can provide access to the composition of the most primitive melts, but these are the most susceptible to post-entrapment modification such as ‘Fe-loss’. The loss of Fe consequently decreases sulfur solubility and leads to silicate-sulfide immiscibility and formation of daughter sulfide globules, significantly affecting the initial proportions of S contained within the silicate part (glass) of melt inclusions.In this study, we investigate the influence that sulfide phase separation has on the accuracy of S content in melt estimations by performing heating experiments on natural samples at various temperatures and durations. Melt inclusions from MORB-like olivine-phyric rocks (Kamchatsky Mys, Far East Russia) heated for 30 minutes at 1200 °C and 1300 °C were compared with similar experiments on olivine-hosted melt inclusions over a 5 minute duration (at 1200 °C and 1350 °C). Average Fo content in host olivine is the same for all experimental sets, allowing for direct comparison of sulfur contents in the following types of melt inclusions: (i) both sulfide globules and shrinkage bubbles, (ii) only sulfide globules, (iii) only shrinkage bubbles, and (iv) completely homogenized. We found that the content of sulfur in shrinkage bubbles and its precipitates is negligible in reheated water-poor melt inclusions, whereas daughter sulfide globules are significant repositories of initial S content. Therefore, for restoring sulfur contents in parental melts the amounts stored in daughter sulfide and silicate glass should be combined.

Ultramafic-alkaline-carbonatite complexes (UACC), which are formed from mantle-derived carbonated alkaliultramafic melts in large igneous provinces (LIPs), are important resources of Fe, Ti, U, Th, Nb, rare earth elements (REEs), Cu, Ni and platinum group elements (PGEs). Concentration of these metals and ore formation is assumed to be largely controlled by magmatic differentiation and post-magmatic hydrothermal processes. Although basic patterns of the metals' partitioning during formation of the UACCs are constrained by geochemical and mineralogical features of the rocks, including in experimental studies, our understanding of their pathway "from primitive melt to ore deposit" is far from complete. In order to further constrain the metals' behavior during differentiation of a carbonated alkali-ultramafic melt, we studied multiphase inclusions in olivine, chromite, perovskite, pyroxene and magnetite in the ultramafic rocks from three UACCs (Guli, BorUryakh and Odikhincha), located in the Siberian LIP. Examination of both unheated and experimentally heated and quenched inclusions reveals a variety of compositions from melanephelinitic through to highly differentiated nephelinitic to alkali-rich carbonatitic. In addition, sulfide minerals, which turn into immiscible sulfide liquids during heating experiments, are widely distributed in the inclusions' assemblages. We consider these inclusions to be snapshots of intercumulus melts, which were entrained into olivine-rich cumulate mush, and use their compositions to delineate plutonic differentiation of a carbonated alkali-ultramafic melt. Highly differentiated silicate melts, entrapped in Fe-rich chromite (Guli dunites), were rich in U, Th and Nb and crystallized OsIr-Ru phases in proximity to the host chromite. Concentrations of U, Th, Nb and REEs in alkali-rich carbonatite liquids, which were present in the intercumulus of Odikhincha and Bor-Uryakh peridotites, approached levels similar to mineralized carbonatites and support the concentration of these metals in an immiscible alkalicarbonatite fraction, which was enriched in S, P and Cl. Minor sulfide liquids, which are closely associated with these carbonatite fractions, were strongly enriched in Cu and Ni, thus explaining the origin of the Phalaborwa-like sulfide ores in carbonatites as a result of magmatic differentiation. Finally, our study provides insights into the formation of peridotite-hosted types of mineralization (perovskite-magnetite ores, mineralized carbonatite veins and PGE-bearing chromitites) and shows that these ore-bearing assemblages can be formed due to the infiltration of the metal-bearing intercumulus melts through the ultramafic matrix.

Zoned plutons, composed of dunites, pyroxenites, and gabbroic rocks, have been referred to as the Ural-Alaskan type complexes (UA-complexes) and occur in numerous paleo-arc settings worldwide. Many of these complexes are source rocks for economic placers of platinum-group metals. Thus, it is important to understand how UA-complexes form and the origin and behavior of platinum-group elements (PGEs). It is widely assumed that the UA-complexes result from differentiation of supra-subduction high-Ca high-Mg sub-alkaline magmas. However, there is a lack of direct evidence for the existence and differentiation of such magmas, mainly because cases of UA-complexes being spatially and temporally linked to co-genetic volcanics are unknown. We studied an UA-complex from the Tumrok range (Eastern Kamchatka) where a dunite-clinopyroxenite-gabbro assemblage is spatially and temporary related to high-Ca volcanics (i.e., picrites and basalts). Based on the mineral and chemical composition of the rocks, mineral chemistry, and composition of melt inclusions hosted within rock-forming minerals, we conclude that the intrusive assemblage and the volcanics are co-genetic and share the same parental magma of ankaramitic composition. Furthermore, the compositions of the plutonic rocks are typical of UA-complexes worldwide. Finally, the rocks studied exhibit a full differentiation sequence from olivine-only liquidus in picrites and dunites to eutectic crystallization of diopside or hornblende, plagioclase, and K-Na feldspar in plagio-wehrlites and gabbroic rocks. All these results make the considered volcano–plutonic complex a promising case for petrological studies and modelling of UA-complex formation.

Natural Fe-Ni alloys are common in meteorites and, presumably, the Earth's core, where they host significant platinum-group elements (PGE). However, little is known on PGE concentrations in hydrothermal or metamorphic Fe-Ni alloys (i.e., awaruite Ni3Fe) from terrestrial rocks. In this work, we examine the geochemistry of awaruite and related minerals from several placer deposits sourced from the suprasubduction ophiolitic (Kamchatsky Mys, Karaginsky Island, and Mamet) and Ural-Alaskan (Galmoenan) complexes of Kamchatka and the Koryak Highlands (Far East Russia) in order to assess the abundance of PGE in awaruite and constrain their mobility under metamorphic and hydrothermal conditions. Studied awaruite from ophiolitic and Ural-Alaskan type complexes formed via desulfurization of pentlandite during serpentinization. Three groups of platinum-group minerals (PGMs) are associated with awaruite from Kamchatsky Mys: (1) Pt-Fe alloys such as ferronickelplatinum (Pt2FeNi) or unnamed Ni2FePt alloys; (2) Os-Ir-Ru alloys of various composition; (3) Pd-Sb minerals which form together with serpentine during hydrothermal alteration. Despite the abundance of PGM inclusions, no significant PGE concentrations were measured in awaruite from the Kamchatsky Mys, Karaginsky Island, or Mamet ophiolites. In contrast, pentlandite relicts in awaruite from placers related to the Galmoenan Ural-Alaskan type complex contain exceptionally high, previously unreported, Os (up to 540 ppm). Awaruite that forms on behalf of this pentlandite does not show any significant Os enrichment. Rare Galmoenan awaruite analyses yield up to 3 ppm Pd. The new data are not in complete accordance with previous studies that reported relatively high (up to first 10 ppm) PGE content in awaruite. We attribute this to low PGE concentration in precursor sulfides and preferential partitioning of PGE into discrete secondary PGM within awaruite. Nevertheless, abundant inclusions of secondary PGM in awaruite provide evidence of PGE mobility during metamorphic and hydrothermal alteration of ultramafic rocks.

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 ba-salts 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.