Silicate Melts Research Articles

Non‐destructive quantitative analysis of melt inclusions in extraterrestrial samples: Case study of chassignite via nanoscale X‐ray computed tomography

AbstractEstimation of the composition of planetary rocks and minerals is crucial for understanding their formation processes. In this study, we present the application of X‐ray nano‐computed tomography (nano‐XCT) for non‐destructive three‐dimensional (3‐D) phase analysis and estimation of phase abundances in rare Martian meteorite samples, specifically chassignite Northwest Africa (NWA) 2737. We determined the most suitable laser power for minimizing artifacts and maximizing phase contrast. By utilizing nano‐XCT, we successfully identified and segmented primary phases in the bulk meteorite sample. Additionally, we were able to locate and segment crystallized silicate melt inclusions within the meteorite. The phase abundances in bulk NWA 2737 and within melt inclusions calculated using nano‐XCT were in good agreement with previous studies that used thin section calculations, demonstrating the reliability of nano‐XCT as a non‐destructive alternative for estimating bulk phase abundances in rare samples. This study develops a benchmarking protocol and demonstrates the efficacy of nano‐XCT as a non‐destructive technique for generating an overview of phase distribution and assemblages of melt inclusions within rare samples. Future research can benefit from combining non‐destructive 3‐D phase assemblage estimations with non‐destructive 3‐D chemical analysis techniques to achieve a fully non‐destructive parental magma composition estimation of rare cumulate samples.

Studying the features of complex beryllium-containing silicate phases co-crystallization in zonal samples using the x-ray electron probe microanalysis method

Research subject. Silicate ingots containing four species-forming components Be, Mg, Al, and Si and belonging to the crystallization region of beryllium indialite (with the formula of Mg2BeAl2Si6O18 and a beryl-type structure). Aim. To investigate the fundamental problem of identifying the patterns of matter differentiation and the stable and metastable phase formation in silicate matrices. Methods. The evolution of the phase composition of silicate melts was registered using a temperature gradient method. Results. New data on the features of phase transformations in silicate melts belonging to the region of beryllium indialite were obtained by electron probe microanalysis (EPMA). Co-existing metastable and stable mineral phases were identified, and the similarity of their compositions with different structures was shown. The nature of impurity phases at each stage of crystallization was established. Conclusions. The evolutionary sequence of phase associations ensuring the crystallization of beryllium indialite and metastable phases of a similar composition, the nature of which is determined by the initial ratio of components, was experimentally recorded. The range of possible phase associations that co-crystallize or replace a stable phase with a beryl structure in melts from the region of existence of beryllium indialite in the BeO–MgO–Al2O3–SiO2 system was extended. The selectivity of the coloring element chromium entry into various phases of the studied system is shown depending on the capabilities of their structure. The addition of a chromophore is a reliable criterion for visualizing successive layers, zones, and areas of changing phase associations in the final ingot.

Magmatic-Hydrothermal Evolution at the Barren Wushan Pluton, Southeast China: Insight into Controls on Mineralization Potential

Abstract A-type granites typically exhibit enrichment and mineralization of critical metals such as molybdenum and tin, essential for emerging technologies. However, the key factors influencing their mineralization potential remain elusive. The scarcity of studies on barren systems impedes the understanding of this question. Here, a detailed melt and fluid inclusion study was conducted on the barren Wushan pluton to reconstruct its magmatic evolution and magmatic-hydrothermal transition and to explore the factors controlling the metallogenic potential of Mo and Sn in A-type granites. The Wushan pluton displays apparent lithological zoning consisting of two major phases, i.e., medium-grained seriate to porphyritic alkali feldspar granite and fine-grained porphyritic granite. Miarolitic cavities are widely developed in each lithofacies. The silicate melt inclusions from two granitic phases are rhyolitic, with moderate F contents (0.06–0.53 wt %) and depleted H2O contents (2.0–3.5 wt %). Melt inclusions show a wide range of incompatible element contents, such as Cs (9–1977 μg/g) and Rb (268–2601 μg/g), suggesting that Wushan has undergone a high degree of magma evolution. Mo behaves incompatibly in the magmatic evolution, and its content is enriched with the increasing degree of fractional crystallization, but remains constant after the Cs content exceeds 50 μg/g. Rayleigh fractionation model suggests a large amount of Mo is extracted from fluid exsolution, which restrains Mo from further enrichment. In contrast, Sn behaves as a mildly incompatible element during the entire magmatic evolution history. The contents of Sn increase slowly compared to the trend of Mo, and the maximum contents reach ~30 μg/g in the highly evolved melts. The separation and crystallization of Sn-bearing minerals such as biotite, magnetite, and titanite inhibit the enrichment of Sn. Intermediate-density (ID-type) fluid inclusions hosted in the miarolitic quartz, representing the initial fluid exsolving from magma, display high Mo but low Sn concentrations. Constrained from two assemblages of coexisting ID-type fluid and melt inclusions, the fluid/melt partition coefficients of metals are obtained, with DMo, fluid/melt at 16–19, while DSn, fluid/melt is only about 1. The comparison between Mo-mineralized and barren intrusions worldwide shows that the metal contents in melts and fluids are not fundamentally different. The mineralized intrusions are characterized by the lower melt viscosity and the development of apophyses, both of which facilitate the extraction of metals and fluids from large magma chambers, followed by their concentration into a small rock volume. Consequently, it appears that physical and structural conditions rather than chemical compositions play a crucial role in the Mo mineralization process. Enrichment of Sn in melts is necessary but not decisive for Sn mineralization, whereas Sn enrichment in the initial exsolving fluid determines the Sn mineralization potential of a given granitic system. Compared to Sn enrichment in source melting and fractional crystallization which commonly enhance final Sn fertility in the highly-evolved melts, the efficiency of Sn partitioning between melt and fluid plays a fundamental role in converting melt fertility into Sn-enriched fluids and thereby high mineralization potential of the magmatic-hydrothermal system. Our findings suggest a prospect for Mo exploration in the coastal A-type granite belt in South China, while the potential for Sn mineralization is expected to be limited.

Are Clay Minerals Systematically the Products of Aqueous Alteration in Cosmic Bodies?

The formation of chondrite materials represents one of the earliest mineralogical processes in the solar system. Phyllosilicates are encountered at various stages of the chondrule formation, from the initial stages (IDP agglomerates) to the final steps (chondrule internal alteration). While typically linked to aqueous alteration, recent studies reveal that phyllosilicates could precipitate directly from residual fluids in post-magmatic or deuteric conditions and under a wide range of temperatures, pressures, water/rock ratios, and H2/H2O ratio conditions. This study re-examined the formation of hydrated phyllosilicates in chondrules and associated fine-grained rims (FGRs) using published petrographical, mineralogical, and chemical data on carbonaceous chondrites. Given that chondrules originate from the melting of interplanetary dust particles, the water liberated by the devolatilization of primary phyllosilicates, including clay minerals or ice melting, reduces the melting temperature and leads to water dissolution into the silicate melt. Anhydrous minerals (e.g., olivine and diopside) form first, while volatile and incompatible components are concentrated in the residual liquid, diffusing into the matrix and forming less porous FGRs. Serpentine and cronstedtite are the products of thermal metamorphic-like mineral reactions. The mesostasis in some lobated chondrules is composed of anhydrous and hydrous minerals, i.e., diopside and serpentine. The latter is probably not the alteration product of a glassy precursor but rather a symplectite component (concomitant crystallization of diopside and serpentine). If so, the symplectite has been formed at the end of the cooling process (eutectic-like petrographical features). Water trapped inside chondrule porosity can lead to the local replacement of olivine by serpentine without external water input (auto-alteration). In the absence of water, hydrated phyllosilicates do not crystallize, forming a different mineral assemblage.

The evolution of crystal‐poor rhyolite in the middle Okinawa Trough and its implications for the state of magma chamber

The crystal‐poor rhyolitic pumice is the product of extreme magma differentiation and is characterized by highly vesicular, honeycomb‐like structure. However, little is known about the evolutionary history and the time of volatile saturation of the pumice‐forming melt. A crystal‐poor rhyolitic pumice (TVG7‐1) has been collected from the Yoron Hole hydrothermal field in the middle Okinawa Trough, a young continental margin back‐arc basin in the western Pacific. This study conducted a detailed analysis on the texture and in situ chemical composition of plagioclase, orthopyroxene and Fe‐Ti oxides to reveal the evolution process, storage state and eruption triggers of eruptible silicic melt. Texture and zoning of specific minerals and mineral populations suggest a magmatic evolution history of open system. Additionally, the hollow reentrant texture, as well as results from plagioclase‐liquid hygrometers, confirm a water‐rich melt pocket. The exsolution of volatiles (H2O, etc.), in this melt pocket, will contribute to local oxidation conditions, which may have been recorded by the concordant behaviour of FeO and An in plagioclase. Then, the overpressure caused by volatile exsolution would destabilize the magma chamber, which will eventually be broken by magma mixing/recharge, and lead to violent melt evacuation. Consequently, crystal size distribution (CSD) provides a new perspective on understanding the kinetic effect of magma mixing/recharge in the Okinawa Trough, especially on the mineral populations. Our study reveals the petrogenesis of crystal‐poor rhyolite within the framework of the mush model, refines the magma evolution history and demonstrates that pumice magma reaches volatile saturation before the eruption.

Zircon and Whole-Rock Trace Element Indicators of Magmatic Hydration State and Oxidation State Discriminate Copper Ore-Forming from Barren Arc Magmas

Abstract To meet surging requirements of copper for the green energy revolution, minable resources subequal to all copper production in history must be found in the next two decades. We show that trace elements in zircon and whole-rock samples that are diagnostic of unusually high-pressure magmatic differentiation and high hydration state and oxidation state of their parent silicate melt are effective for discriminating copper sulfide-ore-productive arc magmas from infertile arc magmas. Tests on our database of 5,777 zircons from 80 igneous complexes, including 2,220 zircons from ore-generative intrusions in 37 major porphyry and high-sulfidation epithermal Cu(-Au-Mo) deposits worldwide, demonstrate that our magmatic copper fertility discriminants apparently perform equally well in intraoceanic arcs, continental margin arcs, and continental collision orogens of Ordovician to Quaternary age. That performance consistency means that the tectono-magmatic controls on development of magmatic-hydrothermal copper ore-forming fertility are essentially the same in all those plate-convergence settings. The ratio Ce/√(U × Ti) in zircon is a quantitative indicator of the relative oxygen fugacity of the silicate melt and its sulfur-carrying capacity. The ratio of the europium anomaly to ytterbium in granitoid melts and zircon is an uncalibrated but empirically useful indicator of the melt’s hydration state and ability to provide chloride-complexed metals to exsolving hydrothermal fluids. Plots of (EuN/Eu*)/YbN vs. Ce/√(U × Ti) in zircon are remarkably effective for discriminating igneous complexes, arc segments, and time intervals within them that can generate and are likely to host magmatic-hydrothermal Cu(-Au-Mo) ore deposits. Arrays of cognate zircons on such plots have slopes that vary with pressure-dependent chlorinity of exsolving fluid and its efficacy in scavenging CuCl from the melt. Our zircon indicators of Cu metallogenic fertility are applicable to detrital as well as in situ zircons and can assist with ore discovery in watersheds upstream from a sediment sampling site. We formulated a composite zircon copper fertility index (ZCFI) that can be applied to each microbeam spot analysis—ZCFI = 104 (EuN/EuN*)/YbN + 5 Ce/√(Ui × Ti)—and substantially decreases the number of zircon analyses needed for reliable prospectivity assessment in a detrital grain population, thereby making this watershed-scale exploration tool cost-competitive with other methods of geochemical exploration.

Trace element (Be, Zn, Ga, Rb, Nb, Cs, Ta, W) partitioning between mica and Li-rich granitic melt: Experimental approach and implications for W mineralization

Mica is the most important carrier of rare alkalis (Li, Rb and Cs) and volatiles, and also a major host of rare metals such as Sn, W, Nb and Ta. Thus, the knowledge of trace element partitioning between mica and silicate melt is crucial to understand enrichment mechanisms of ore metals in evolved silicic systems. However, experimental data are scarce, mainly because the synthesis of large mica grains which can be analyzed with laser ablation techniques is challenging. To address this issue, we conducted two-step experiments, using a high-temperature step at 800 °C, and a low-temperature step at 600 °C with a temperature cycling interval of 30 °C, and variable run durations from 21 to 60 days. The experimental products, at 600 °C, 200 MPa, are mainly composed of mica and alkali feldspars. Ferroholmquistite (Fhlm; a Li-bearing amphibole) was also observed in the Li-bearing systems.Beryllium, Zn and Cs are highly incompatible in all run products with mineral/melt partitioning of mineral/meltDBe between 0.01 and 0.08, mineral/meltDZn between < 0.01 and 0.24 and mineral/meltDCs between <0.01 and 0.19. Gallium is mildly incompatible in mica and feldspars with mica/meltDGa, K-feld/meltDGa and Na-feld/meltDGa of 0.24 ∼ 0.35, 0.60 ∼ 0.67 and 0.69 ∼ 0.72, respectively, whereas Fhlm/meltDGa is nearly 1. Rubidium is characterized by a slight enrichment in mica and K-rich feldspar with respect to melt. Niobium and Ta are highly incompatible in feldspars, while they are compatible in ferroholmquistite. Li-mica crystallization would cause Nb/Ta fractionation with mica/meltDNb and mica/meltDTa of 4.46 and 0.88, respectively. Tungsten is preferentially incorporated in Li-rich mica with mica/meltDW > 22. The strong partitioning of W into Li-rich mica implies that minor Li-rich mica fractionation (>5 %) will strongly deplete W in the residual melt, thus inhibiting transfer to the magmatic fluid at the magmatic-hydrothermal transition. Based on the observed mineral/meltD value, a multi-stage quantitative fractionation model for the behavior of metals during the crystallization of Li-bearing granitic magmas was developed. The results suggest that crystal fractionation is an effective mechanism that could further enrich Be, Ga, Rb, Cs, Nb and Ta in residual melts. Li-rich mica and muscovite are more effective in causing Nb/Ta fractionation as compared with biotite. The very low Nb/Ta ratios found in natural granite may have resulted via extreme, i.e., >99 wt% of fractional crystallization, even if without the precipitation of columbite-group minerals or increasing hydrothermal activity. Due to the very high Li-mica/meltDW value, water saturation in the melt and subsequent magmatic fluid exsolution should occur before Li-mica starts to crystallize to avoid W sequestration in the magma. At 175 MPa, the efficiency of extracting W from Li-poor granitic system is at least 15 % higher than that from Li-rich granitic system. Li-poor granitic systems are thus expected to have a greater W-mineralization potential than Li-rich system, which is consistent with the fact that most parental magmas of large/giant W deposits are Li-poor in composition.

Crustal conductivity footprint of the Miocene porphyry copper polymetallic deposits in the Gangdese metallogenic belt, Tibetan Plateau

New evidence worldwide has linked the surface locations of mineral deposits and their crustal-scale electrical conductivity footprint. We examine the relationship between the Gangdese Miocene porphyry copper deposits, Tibetan Plateau, and the electrical conductivity signature from a three-dimensional model generated from 311 magnetotelluric measurements. The distribution of electrical resistivity throughout the crust and the conductance within the mid-lower crust (depth range of 25–70 km) is analyzed. The results clearly show that the large and ultra-large Miocene porphyry copper deposits coincide spatially with conductive zones and areas of very-high conductance (>10,000S) in the mid-lower crust. Computations are undertaken to determine the influence of water-bearing silicate melts and alkali-bearing (Na+ and K+) fluids on conductivity. Based on this, the bulk conductivity is interpretated to be caused by a system of alkali-rich volatile-rich partial melt. The alkali-rich volatile-rich magmatic-hydrothermal fluids facilitate the migration and concentration of metal ions originating in deep areas. The volumes necessary are much less than partial melt alone and can thus help to reconcile large conductivity variations with small seismic velocity variations. The electrical structure indicates the magma source area of anatexis in the lower crust, a multi-stage magmatic system with large mid-crustal and small upper-crustal magma reservoirs, and complex pathways related to rift zones. We determine that the conductive zones in the mid-lower crust have an influence on the development of the mineralization and the location of the mineral belt.

Contrasting Tectonomagmatic Conditions for Coexisting Iron Oxide-Apatite Deposits and Porphyry and Skarn Cu ± Au Deposits in the Middle-Lower Yangtze River Metallogenic Belt, China

Abstract Porphyry Cu ± Mo ± Au and iron oxide-apatite (IOA) deposits rarely occur in spatial and temporal proximity in Phanerozoic arc-related settings, and the formation of these mineral deposit types in an evolving arc setting remains poorly understood. Specifically, the roles of magma composition and the tectonic regime remain the subject of some debate. Here, we systematically estimated the P-T-fO2 conditions and H2O-S-Cl contents for dioritic to granodioritic source magmas for porphyry and skarn Cu ± Au (150–135 Ma) and IOA deposits (~130 Ma) that formed in transpressional and transtensional settings in the Middle-Lower Yangtze River metallogenic belt, China. Our estimates show that, compared to IOA deposits, the porphyry- and skarn-related magmas were relatively felsic, cooler, and more hydrous. These geochemical features are consistent with the tectonic transition from subduction to slab rollback of the paleo-Pacific plate in the East Asia continental margin at &amp;lt;135 Ma and concomitant crustal extension and steepening of the regional geothermal gradient. Apatite data reveal that the silicate melts associated with the porphyry and skarn Cu ± Au and IOA deposits had comparable predegassed S concentrations (~0.13 ± 0.06 wt % vs. ~0.16 ± 0.09 wt % on average), but that IOA-related melts contained higher predegassed Cl/H2O ratios (~0.11 ± 0.03 vs. ~0.04 ± 0.03 for porphyry- and skarn-related magmas) that decreased by one order of magnitude after magmatic degassing. Magmatic fO2 estimated using zircon and amphibole, reported in log units relative to the fayalite-magnetite-quartz (FMQ) redox buffer, gradually increased during cooling of the porphyry- and skarn-related magmas (ΔFMQ +0.7 to +2.5) at 950° to 800°C and decreased to ΔFMQ +1 at 700°C owing to fractionation of Fe2+-rich minerals and subsequent S degassing, respectively. In contrast, the magmatic fO2 values for the IOA-related source magmas varied significantly from ΔFMQ –1.5 to ΔFMQ +2.5 but generally show an increasing trend with cooling from 970° to 700°C that probably resulted from variable degrees of evaporite assimilation, fractionation of Fe2+-rich minerals, and Cl degassing. These results are consistent with the hypothesis that Cl enrichment of the IOA-related source magmas played a determinant role in their formation. We propose that the porphyry and skarn Cu ± Au deposits in the Middle-Lower Yangtze River metallogenic belt formed in a transpressional setting in response to paleo-Pacific flat-slab subduction that favored storage and evolution of S-rich hydrous ore-forming magmas at variable crustal levels. A subsequent extensional setting formed due to slab rollback, leading to rapid degassing of Cl-rich IOA-related magmas. For the latter scenario, assimilation of evaporite by mafic to intermediate magmas would lead to an enrichment of Cl in the predegassed magmas and subsequent exsolution of hypersaline magmatic-hydrothermal fluid enriched in Fe as FeCl2. This Fe-rich ore fluid efficiently transported Fe to the apical parts of the magma bodies and overlying extensional normal faults where IOA mineralization was localized. The concomitant loss of S, H2O, and Cu with Cl by volcanic outgassing may have inhibited sulfide mineralization at lower temperatures.

Carbon-rich polyphasic inclusions in postcollisional mafic magmatic rocks from the Dabie Shan, China: Implications for the carbon cycle in continental subduction zones

Subduction is a fundamental geodynamic process that transfers carbon from Earth’s surface into the mantle. However, current understanding of the migration mechanisms, final storage region, and species involved in carbon recycling from continental crust remains limited. Here, we investigated the compositions of polyphasic inclusions and Mg isotopes in postcollisional mafic magmatic rocks from the Dabie Shan region of China. The main rock-forming minerals contained two distinct types of polyphasic inclusions, which displayed systematic differences in daughter mineral/gaseous phase assemblages, including host-like silicates ± carbonates (magnesite, dolomite, and calcite) + CH4 and carbonates + talc ± SiO2 (aqueous) + CH4, respectively. These inclusions indicate that carbon-rich silicate melts and carbon-rich magmatic fluids were trapped by host minerals during magmatic processes. The abundant carbonates and CH4 in both types of inclusions suggest that the mantle source of these postcollisional mafic magmatic rocks was rich in carbon, most likely existing in the forms of CO2 and CH4. Moreover, the studied postcollisional mafic magmatic rocks have mantle-like Mg isotope compositions, with δ26Mg values ranging from −0.23‰ to −0.16‰. The combined observations of polyphase inclusions and Mg isotopes indicate that a substantial carbon-rich mantle domain arose from the metasomatism of silicate melts derived from subducted continental slabs that had dissolved a certain quantity of CO2 and CH4. We proposed that continental subduction is an efficient pathway for transporting crustal carbon into an orogenic subcontinental lithospheric mantle wedge, where the recycled carbon can be stored for &amp;gt;100 m.y. and eventually released to the surface during postcollisional magmatism.

Thermal Expansion of Metal Oxides in Silicate Melts: A Simple Theoretical Analysis

The isobaric, isochemical coefficient of thermal expansion ( α) is the proportionality constant relating ∂V/V and ∂T. Noting that ∂V/V equals ∂lnV at constant pressure and composition (i.e., P and X): α=(∂VV∂T)P,X=(∂lnV∂T)P,X A polynomial expression for the temperature dependence of lnV yields direct and accurate calculation of α of melts and glasses. Using the approach, αG of Na-silicate glasses is shown to be constant between 300 and ∼650 K (P and X constant), but it increases linearly with Na2O content, indicating that α is controlled mostly by Na behaviour. Values of α for a melt or glass are necessarily (thermodynamically) related to the coefficients of thermal expansion of its ‘N’ melt components ( αN) by: α=α1θ1+α2θ2+α3θ3+⋯+αNθN where θ represents volume fraction of a component. Calculated αNa2O and αSiO2 values compare satisfactorily with reported values for melts containing ∼40–60 mole% Na2O but are less satisfactory for highly siliceous melts, implying need for refinement of α values. The Coulombic force of attraction between cation and anion is the primary determinant of the magnitude of α values of alkali and alkaline earths oxides. Their values represent a lower bound on α of 3d and 4f modifier oxides. Values larger than this lower bound likely result from a change in coordination number (CN) from higher to lower CN values of modifier cations. Experimental and molecular dynamics studies indicate that partial charges on NBO (O of Si-O-M moieties) and BO (O of Si-O-Si moieties) are about −0.96 and −0.64 respectively, thus NBOs should be incorporated into the first coordination spheres of modifier cations in preference to BOs. A simple mechanism is proposed whereby NBO-BO exchange occurs and CN of the modifier cation decreases with minimal topological adjustment or energetic cost to the melt.

Trace element partitioning in the lunar magma ocean: an experimental study

Modeling the behavior of trace elements during lunar magma ocean solidification is important to further our understanding of the chemical evolution of the Moon. Lunar magma ocean evolution models rely on consistent datasets on how trace elements partition between a lunar silicate melt and coexisting minerals at different pressures, temperatures, and redox conditions. Here we report new experimental trace element partition coefficients (D) between clinopyroxene (cpx), pigeonite, orthopyroxene, plagioclase, olivine (ol), and silicate melt at conditions relevant for the lunar magma ocean. The data include Dcpx−melt at ambient and high pressures (1.5 GPa and 1310 °C), and partition coefficients at ambient pressure for pig, opx, ol, and pl. Overall, clinopyroxene is a phase that may control the fractionation of key geochemical trace element ratios, such as Lu/Hf and Sm/Nd, during the evolution of the lunar magma ocean. We explore the impact of the new silicate Dmineral−melt on the trace element evolution of the lunar magma ocean and we find that accessory phosphate minerals, such as apatite or whitlockite are of critical importance to explain the observed trace element and isotopic signature of the KREEP reservoir on the Moon. The new partition coefficients were applied to calculate the trace element evolution of the residual melts of the crystallizing lunar magma ocean and we propose a new trace element composition for the urKREEP reservoir. The new data will be useful for future thermo-chemical models in order to adequately predict the duration of the lunar magma ocean and the age of the Moon.

Redox control of the partitioning of platinum and palladium into magmatic sulfide liquids

The partitioning behavior of platinum group elements in magmas is critical for their use as tracers of planetary accretion and in understanding magmatic sulfide deposits. Here we use laboratory experiments to determine sulfide liquid–silicate melt partition coefficients for platinum and palladium at 1.5 GPa, 1400 °C, and oxygen fugacity 1.5–2 log units above the fayalite–magnetite–quartz buffer. We find that the partitioning coefficients of these elements are 2.3 × 105 to 1.1 × 106 and are independent of the platinum and palladium concentration in the system. Combined with previous data obtained at oxygen fugacity below the fayalite–magnetite–quartz buffer, this indicates redox-controlled partitioning behavior whereby at oxidizing conditions platinum- and palladium-enrichments are achieved through their dissolution in sulfide liquids, while at reducing conditions the entrapment of platinum- and palladium-rich clusters in sulfide liquids is more critical. This redox-controlled partitioning behavior should be considered when studying crust–mantle differentiation and the formation of magmatic sulfide deposits.

Metasomatic ijolite, glimmerite, silicocarbonatite, and antiskarn formation: carbonatite and silicate phase equilibria in the system Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O–O2–CO2

AbstractSilicocarbonatites are carbonatite rocks containing &gt; 20% silicate minerals. Their formation is not well understood due to low silica solubility in carbonatite melts and negligible amounts of silicate minerals on carbonatite melt cotectics at upper crustal conditions. We explore whether silicocarbonatites can be thought of as antiskarns: rocks formed by leaching of SiO2 from siliceous wall rocks by carbonatite melts, and its deposition as solid silicate minerals by reaction with chemical components already present in the carbonatite melt. Solid state thermodynamic modelling at 1–5 kbar and 500–800 °C predicts that calcite–dolomite–magnetite assemblages will transform to dolomite-free silicocarbonatites with an increase in silica contents. In sodic systems, the formation of aegirine and alkali amphiboles suppresses silica activity despite elevated silica contents. Therefore, dolomite remains stable, but Fe3+ is consumed, firstly from magnetite breakdown, and secondly by coupled Fe oxidation and reduction of CO2 to CO, CH4, and graphite, particularly at higher pressures. Despite a net increase in Fe3+/Fe2+, the system evolves to increasingly lower oxygen fugacity. In aluminous systems, nepheline indicates high temperatures whereas alkali feldspars form at lower temperatures. Modelling of potassic systems demonstrates stability of mostly phlogopite-rich biotites, leading to Fe2+ increase in all other carbonate and silicate phases. We find that perthites are expected in high pressures whereas two feldspars are more likely in lower pressures.Aspects of the clinopyroxene natural compositional trend (diopside to hedenbergite to aegirine) of carbonatite systems can be explained by silica contamination. Ferrous clinopyroxenes typically require low alumina and are predicted in potassic or low temperature sodic systems, primarily at mid to high pressures. Silica contamination permits the formation of silicocarbonatite-like assemblages in a way that is not limited by SiO2 solubility in carbonatite melts. Glimmerites and clinopyroxene-rich rocks (such as the ijolite series) that often occur around carbonatite rocks at the contact with silica-oversaturated wall rocks can be explained as the extreme end of silica contamination of carbonatite melts. Therefore, these clinopyroxenites and glimmerites can form solely via metasomatic processes without the presence of a silicate melt.

An experimental study on the role of F−, PO43−, Cl− and SO42− ligands in the natrocarbonatite-nephelinite system at 850 °C and 0.1 GPa

Carbonatites and their comagmatic silicate rocks related deposit provide significant resources of rare earth elements (REEs), niobium (Nb) and other elements such as U, Th, Mo, V, Ba, Sr, etc. However, the genesis of mineralization, especially for REEs and Nb, in carbonatite remains enigmatic. Previous liquid immiscibility experiments have demonstrated that both REEs and Nb are preferentially enriched in the silicate conjugate instead of carbonate melts under anhydrous conditions. Nevertheless, ligands other than carbonate ion appear to be abundant due to ubiquity of apatite, baryte, celestine, fluorite and sodalite in carbonate–silicate magmatic systems. Here, we experimentally investigate the trace element partitioning between natrocarbonate and silicate (nephelinite) melts in systems doped with varying amounts of additional F−, PO43−, Cl−, and SO42− ligands (0, 2, 4 and 6 wt%) to understand and constrain the role of ligands.The experiments were conducted at 850 °C and 0.1 GPa using rapid quench cold-seal pressure vessels (CSPVs). A comparison of experimental partition coefficients in this study reveals that the significant amounts F− and PO43− incorporated in the silicate melts can increase the D values for REE by influencing melt structure (DLaCM/SM = 0.85–7.42). In contrast, irrespective of the amount of added Cl− and SO42−, DCM/SM is not affected significantly by these species and the DREECM/SM values remain always lower than 1 (DLaCM/SM = 0.12–0.40). Notably, the DNbCM/SM values are all <1, with only one exception containing 6 wt% F. Besides, in all the investigated systems, Ba, Sr, Mo, V, Cs, Rb and Li preferentially partition into the conjugate carbonate melt. All the high field strength elements (Pb, Th, U, Zr, Hf, Nb, Ta), transition metals (Mn, Co, Cu, Zn) and common network formers (Ga, Ge) essentially partition into the silicate melt.

Silicate melt immiscibility as the cause of large-scale rare-metal mineralization in a peralkaline granite system: The case of the Baerzhe deposit in NE China

The Early Cretaceous peralkaline Baerzhe pluton hosts a potentially large REE-Nb-Zr-Be deposit in inner Mongolia, northeastern China. The mechanism responsible for the extreme enrichment of rare metals and rare earth elements in the pluton is still ambiguous. This study presents new evidence for silicate melt immiscibility as the key mechanism at Baerzhe using amphibole-group minerals from spherulite granite, which contains spherulites with abundant REE- and HFSE-bearing minerals. The spherulite from the transsolvus granite is composed of two distinct zones, i.e., a dark-colored core consisting of arfvedsonite aggregates and a light-colored rim consisting mostly of quartz and feldspar, rare amphibole, and abundant HFSE- and REE-bearing minerals. Four types of amphibole (AmpI, Amp-IIa, Amp-IIb and Amp-III) from the transsolvus granite and one type (Amp-IV) from the subsolvus granite are recognized, and all of them are magmatic fluoro-arfvedsonite. The earliest phase consists of euhedral inclusions of Amp-I within quartz or feldspar. They show an enrichment in HREEs relative to LREEs and a depletion in medium REEs, consistent with the REE pattern controlled by the mineral lattice. This implies that Amp-I likely formed in an initial homogeneous mel relatively depleted in REEs; thus, the mineral structure played a dominant role in REE partitioning. Compared with other types of amphiboles, Amp-IIa and Amp-IIb from the spherulite phase display the highest REE contents, with flat LREEs and MREEs and a slight upward HREE pattern. Combined with the significant accumulation of REE- and HFSE-bearing minerals in the rim zone, differences in REE patterns among different amphibole types imply that the spherulite crystallized in a volatile-rich silicate melt and was probably the product of silicate melt immiscibility. Interstitial Amp-III with lower REE contents from the matrix phase crystallized in the separate volatile-poor silicate melt. The Amp-IV from the subsolvus granite has the lowest CaO content, with strong depletion in LREEs relative to HREEs, suggesting a more evolved melt composition. It is concluded that silicate melt immiscibility may serve as an important key mechanism that occurred in the early stage of magmatic evolution, resulting in the enrichment of REEs and HFSEs, which played a critical role in the formation of large to giant ore deposits such as the Baerzhe deposit.

Decoding degassing modes of magma chamber of arc volcanoes: Insights from CO2/Cl and Cl/H2O ratios of magmatic fluids in groundwater

The H2O-CO2-Cl composition of the fluids released from the magma chambers for arc volcanoes was calculated based on the solubilities of H2O and CO2 in the silicate melt and the partition coefficient of Cl between the aqueous fluid and melt for the stages defined by a simple evolution model of the magma chamber. The degassing modes consisted of mafic bubbling (MB: first boiling) and felsic bubbling (FB: second boiling) releasing fluids as separate bubbles due to the mafic magma supply and felsic magma formation by differentiation, respectively, and felsic solidification (FS) releasing fluid due to felsic pluton formation. The variations in the CO2/Cl and Cl/H2O ratios of the fluids were examined for each degassing mode at pressures ranging from 150 to 400 MPa and were found to have very large variations at 0.00024–845 for CO2/Cl and 0.00043–0.041 for Cl/H2O. The CO2/Cl is concluded to be a good indicator of magma chamber conditions because each mode has a specific ratio distinguished from that of the other modes; i.e., CO2/Cl > 43 for MB, 0.027–23 for FB, and < 0.62 for FS.The alteration of magmatic composition of fluid during ascent was discussed considering the phase separation of fluid, CO2 bubbling in groundwater, dissolution, and deposition of minerals; furthermore, the limitation of the method when applied to natural groundwater systems were outlined. This method was tested for a natural volcanic system, the Kuju volcano in central Kyusyu, Japan, which is an active volcano complex composed of various magma types from rhyolitic to basaltic, replacing the eruption centers from west to east. Groundwater samples from springs and boreholes were collected and analyzed for chemical and isotopic compositions to determine the magmatic H2O, dissolved inorganic carbon (DIC), and Cl concentrations. The new approach to determine the magmatic CO2 concentration in groundwater using 3He concentration proposed herein cancelled the effect of carbonate deposition/dissolution, addition of DIC from organic matter, and bubbling of CO2. The estimated magmatic CO2/Cl ratios were 0.0009–14, which overlapped consistently with the modeled variation in the CO2/Cl ratio. The spatial variation of magmatic CO2/Cl in groundwater showed that higher-CO2/Cl are found near the central part of the volcanic complex which composed of felsic to mafic volcanoes, and low-CO2/Cl are only found around old felsic volcanoes. The CO2 bubbling springs were found to be associated with younger mafic volcanoes. The condition of the magma chambers, as shown by the spatial variation in CO2/Cl, were consistent with the record of the eruptive activities of the Kuju volcano. The CO2/Cl method proposed in this study using groundwater is useful for estimating magmatic conditions in chambers.

Iron‐Rich Grain‐Decorated Depressions on Surfaces of Lunar Impact Glasses

AbstractIron‐rich particles are widespread on the surfaces and interiors of lunar impact glasses, and they record delicate physicochemical processes during space weathering and regolith gardening on the Moon. Different from nanophase iron in amorphous rims of regolith minerals, iron‐rich particles in lunar impact glasses are mostly larger than 10 nm and are spherical and semi‐hemispherical in shape. In regolith samples returned by Luna, Apollo and Chang'E‐5 missions, a special form of microscopic iron‐rich structure commonly exists on surfaces of impact glasses, which appear as rimless depressions that are filled with nano‐sized grains. Termed grain‐decorated iron‐rich depressions, their possible origin is elusive. Here we perform detailed observations of the morphology, composition and crystallography of these microstructures, showing that they are not degassing pits that were later filled with nano‐sized grains as has been previously considered. They are hemispherical integrated compounds of α‐Fe and troilite that have variable area proportion. The surface grains are dominated by α‐Fe, which mainly develop on top of vesiculated surfaces of the underlying troilite. The α‐Fe grains are mainly formed by desulphurization of troilite due to radiation and heating. While iron‐rich grain‐decorated depressions have larger diameters and different surface morphologies compared to other iron‐rich microstructures in lunar impact glasses, their identical occurrences and phase components (α‐Fe and troilite) suggest a common origin caused by liquid immiscibility between Fe‐S melt and silicate melt. Their diverse surface morphology is mainly caused by heterogeneous S contents and local ratios of Fe and S in silicate impact melt.

Sulfide saturation and resorption modulates sulfur and metal availability during the 2014–15 Holuhraun eruption, Iceland

Mafic magmas may experience multiple stages of sulfide saturation and resorption during ascent and differentiation. Quenched tephra erupted during the 2014–15 Holuhraun eruption preserve abundant evidence for sulfide resorption, offering a rare opportunity to explore the sulfide life cycle from nucleation to resorption. Specifically, we combine detailed textural and chemical analyses of sulfides and silicate melts with geochemical models of sulfide saturation and degassing. This integrative approach demonstrates that sulfides began nucleating in melts with ~8 wt% MgO, persisted during fractionation to 6.5 wt% MgO, before resorbing heterogeneously in response to sulfur degassing. Sulfides are preserved preferentially in confined geometries within and between crystals, suggesting that kinetic effects impeded sulfur loss from the melt and maintained local sulfide saturation on eruption. The proportion of sulfides exhibiting breakdown textures increases throughout the eruption, coincident with decreasing magma discharge, indicating that sulfide resorption and degassing are kinetically limited. Sulfides likely modulate the emission of sulfur and chalcophile elements to the atmosphere and surface environment, with implications for assessing the environmental impacts and societal hazards of basaltic fissure eruptions.

Element partitioning and stabilization for impurities removal between liquid silicon and silicate melts: Ab initio insights into electronic structure

The partitioning and stabilization of common impurity elements challenge the impurity removal process during slag refining for developing high-purity metals. The role of electronic properties remains indistinct in the stability of non-metallic, alkaline earth metal, and transition metal impurity clusters in silicon and silicate melts, impeding the advancement of separation medium and purification process. Herein, local structures of impurity atoms are explored through ab initio molecular dynamics, and notable configurations are [PSi4], [TiSi10], [MgSi12] in silicon melts and [PO4], [TiO5], [MgO5] in silicate melts. A novel partition model based on impurity coordination predicted the impurity atoms’ distribution behavior consistent with industrial experiments. Furthermore, this model proposes a critical parameter k that evaluates impurity oxidation levels in coexisting systems and establishes a quantitative link between melt structures and distribution ratio, enabling precise predictions from two-phase ab initio calculations. Innovatively, the electronic structure analysis assessed element partitioning through bonding characteristics and interactions within impurity clusters via parameters: electron density distribution, partial density of states, electron localization function, and Mayer bond order. This yields a distinctive mapping relationship between impurity distribution ratio and stability, evidenced by quantitative associations with 12 key ab initio-derived descriptors through Pearson correlation analysis. This work unveils the electronic properties governing partitioning and endows modeling approach for distribution, driven by cluster structure analysis and ab initio calculations.