Mineralization in the andesitic lava from Kildyam volcanic complex, central Yakutia, Russia

This contribution presents the first detailed analysis of a new volcanic succession of olivine-pyroxenites, andesite, and dacite discovered in the Kildyam Late Jurassic complex in Central Yakutia. Petrographic and microprobe studies confirmed the liquid immiscibility in silicate melts during crystallization. Immiscible liquids are preserved as globules of one glass in another in andesites and as melted inclusions of native iron in matrix, clinopyroxene and plagioclase phenocrysts. Our analyses reveal the complex textural relationships between silicates and Fe-oxides, native iron and (Cu, Pb, Ag and Au)-rich phases, and provide unequivocal textural evidences, not observed previously. Purpose of this research is to preserve a very important data on IO (Iron Oxide) or IOCG (Iron Oxide Copper Gold) mineralization. Obtained results support occurrence and diverse of gold, silver, copper and lead minerals in magnetite lavas. During the early stage of fine-grained subvolcanic olivine-clinopyroxenite end pyrrhotite, globular igneous sulfides is a first proposed style of economic deposit formation. The second proposed style of economic mineralization in Kildyam is to be a magnetite-bearing lava; iron enrichment of the melilitic melt phase, followed by iron depletion and silica enrichment. The vesicle-hosted alloys and sulfides provide significant new data on metal transport and precipitation from high-temperature magmatic vapors. During syneruptive vapor phase exsolution, volatile metals (Cu-Zn, Fe-Al-Cu, Ni-Fe-Cu-Sn) and Ag-Cu-sulfides contribute to the formation of economic concentrations. Major conclusions contribute to 3-step genetic model. (1) Early-formed magmatic minerals led to partial dissolution of olivine-clinopyroxenite and their enrichment in Cu, Co and Ni relative to other metals, while troilite globules droplets grew.(2) First stage of division into two immiscible silicate and sulfide melt liquids (a) K-rich dacitic and rhyolithic glass, and (b) vesicles of heavy sulfide minerals with a large segregations and drops of native iron. (3) Lava of fused magnetite crystals and voids enriched in silver and gold, and (b) globular disseminated chalcopyrite in mineralized melilitic rocks.

Immiscible silicate liquids: K and Fe distribution as a test for chemical equilibrium and insight into the kinetics of magma unmixing

Silicate liquid immiscibility leading to formation of mixtures of distinct iron-rich and silica-rich liquids is common in basaltic and andesitic magmas at advanced stages of magma evolution. Experimental modeling of the immiscibility has been hampered by kinetic problems and attainment of chemical equilibrium between immiscible liquids in some experimental studies has been questioned. On the basis of symmetric regular solutions model and regression analysis of experimental data on compositions of immiscible liquid pairs, we show that liquid–liquid distribution of network-modifying elements K and Fe is linked to the distribution of network-forming oxides SiO2, Al2O3 and P2O5 by equation: $$\log K_{{\text{d}}}^{{\text{K/Fe}}} = \, 3.796\Delta X_{{{\text{SiO}}_{2} }}^{{{\text{sf}}}} + \, 4.85\Delta X_{{{\text{Al}}_{2} {\text{O}}_{3} }}^{{{\text{sf}}}} + \, 7.235\Delta X_{{{\text{P}}_{2} {\text{O}}_{5} }}^{{{\text{sf}}}} - \, 0.108,$$ log K d K/Fe = 3.796 Δ X SiO 2 sf + 4.85 Δ X Al 2 O 3 sf + 7.235 Δ X P 2 O 5 sf - 0.108 , where $$K_{{\text{d}}}^{{\text{K/Fe}}}$$ K d K/Fe is a ratio of K and Fe mole fractions in the silica-rich (s) and Fe-rich (f) immiscible liquids: $$K_{d}^{{\text{K/Fe}}} = \, \left( {X_{{\text{K}}}^{s} /X_{{\text{K}}}^{f} } \right)/ \, \left( {X_{{{\text{Fe}}}}^{s} /X_{{{\text{Fe}}}}^{f} } \right)$$ K d K/Fe = X K s / X K f / X Fe s / X Fe f and $$\Delta X_{{\text{i}}}^{sf}$$ Δ X i sf is a difference in mole fractions of a network-forming oxide i between the liquids (s) and (f): $$\Delta X_{i}^{sf} = X_{i}^{s} - X_{i}^{f}$$ Δ X i sf = X i s - X i f . We use the equation for testing chemical equilibrium in experiments not included in the regression analysis and compositions of natural immiscible melts found as glasses in volcanic rocks. Departures from equilibrium that the test revealed in crystal-rich multiphase experimental products and in natural volcanic rocks imply kinetic competition between liquid–liquid and crystal–liquid element partitioning. Immiscible liquid droplets in volcanic rocks appear to evolve along a metastable trend due to rapid crystallization. Immiscible liquids may be closer to chemical equilibrium in large intrusions where cooling rates are lower and crystals may be spatially separated from liquids.

Thermodynamic assessment of the Sb–S and In–S binary systems

The Sb–S and In–S binary systems were assessed thermodynamically using the CALculation of PHase Diagrams (CAL-PHAD) approach based on the experiment data in the literature. Both phase diagrams revealed a congruent melting compound and liquid immiscibility. Therefore, associate species, Sb2S3 and In2S3, were introduced into the associate model to describe the liquid phase during optimization. The binary intermediate compounds, Sb2S3, InS(α, β), and In6S7, were treated as stoichiometric phases. Considering the wide composition range, In2S3(α, β, γ), were modeled using the sublattice model. A set of self-consistent thermodynamic parameters representing most of the reliable thermodynamic properties and phase diagram information were derived.

Solubility of Monazite-Cheralite and Xenotime in Granitic Melts, and Experimental Evidence of Liquid-Liquid Immiscibility in Concentrating REE

We provide new experimental data of monazite, xenotime and U-Th-bearing cheralite solubility in slightly peralkaline to peraluminous granitic melts using dissolution and reverse (i.e., recrystallisation after dissolution) experiments in water-saturated and flux-bearing (P+F+Li) granitic melts, at 800 °C and 200 MPa. Although a positive correlation between REE solubility and melt peralkalinity is confirmed, monazite solubilities reported here are much lower than the values previously published. We suggest that the presence of elevated phosphorus concentrations in our melts depresses monazite solubility, principally because phosphorus complexes with Al and alkali which normally depolymerise the melt through the formation of non-bridging oxygens. The new solubility data provide an explanation for the very low REE concentrations generally encountered in phosphorus-bearing peraluminous granites and pegmatites. This accounts for the compatibility of REE in peraluminous systems, as the early crystallisation of REE-bearing minerals (mainly monazite and zircon) leads to progressive REE depletion during liquid differentiation. In addition, dissolution and reverse experiments of U-Th-bearing cheralite-monazite display liquid-liquid immiscibility processes in our slightly peralkaline glass. The immiscible liquid forms droplets up to 10 µm in diameter and hosts in average 35 wt.% P2O5, 25-30 wt.% F, 22 wt.% Al2O3, 4 wt.% CaO, 5 wt.% Na2O, 2 wt.% La2O3, and 12 wt.% ThO2+UO2. We believe that the droplets formed during the runs and may have coalesced to larger droplets during quenching. We suggest that liquid-liquid immiscibility is a possible mechanism of REE concentration in highly-fluxed melts and should be considered in natural systems where REE are extremely concentrated (up to thousands of µg/g) in magmatic rocks.

IODP Hole 1473A (Atlantis Bank, SWIR) - Formation of felsic veins in gabbros: reactions at the contact between felsic melt and host rock

<p>Hole U1473 (32° 42.3622’ S; 57° 16.6880’ E), located on the summit of Atlantis Bank at the ultra-slow spreading Southwest Indian Ridge was drilled to 789.7 m below seafloor (mbsf) during IODP Expedition 360. It consists of massive gabbros cut by nearly 400 felsic veins, which are evolved, SiO<sub>2</sub>- enriched lithologies comprising ~1.5 vol% of the drill core. They vary in composition from diorite to trondhjemite. For their formation, 3 endmember models are discussed: (1) fractional crystallization; (2) hydrous anatexis of mafic rocks; (3) liquid immiscibility in an evolved MORB system.</p><p>Mineral assemblages in the felsic veins include mainly plagioclase, amphibole, Fe-Ti oxides ± quartz and minor zircon, apatite, ± titanite, ± biotite, ± K-feldspar.</p><p>Vein minerals often show strong zoning, which is especially expressed in amphiboles clearly visible by their variation in color ranging from brown to green corresponding to compositions from pargasite via pargasitic amphiboles, magnesiohornblendes to tremolite/actinolite. Moreover, zoning patterns can be observed in plagioclases from the veins, in which their An contents vary from An<sub>34</sub> down to An<sub>5</sub>. This is distinctly lower than in the plagioclases of the host gabbros, which are virtually unzoned.</p><p>Clinopyroxenes at the contact between felsic vein and host gabbro show reactions either towards orthopyroxene or amphibole. TiO<sub>2</sub> in brown pargasites in the host rock at the contact is enriched (up to ~4.6 wt%), whereas counterparts of the same crystals in the felsic veins are distinctly lower in TiO<sub>2</sub> varying from ~2.5 wt% down to 0.1 wt% TiO<sub>2</sub>, associated with variation in color from brown to green. Calculated equilibrium temperatures based on Ti-content in amphibole (Ernst & Liu, 1998), consequently lead to higher formation temperatures for amphiboles in the host gabbro (up to ~1000 °C) compared to their counterparts in the veins, ranging from ~890 °C to ~500 °C.</p><p>Amphiboles contain ~0.2 wt% F and distinctively lower contents in Cl (with one exception found). Most amphiboles at the contact show a core-rim evolution trend with decreasing F and increasing Cl content, implying a magmatic formation with increasing influence of processes involving a hydrothermal fluid. Only one out of twenty-two investigated samples shows a trend vice versa.</p><p>The record of eutectic crystallization expressed by granophyric structures of quartz and plagioclase indicates that the felsic veins crystallized from a melt.</p><p><em>Ernst, W. G., & Liu, J. (1998). Experimental phase-equilibrium study of Al-and Ti-contents of calcic amphibole in MORB—A semiquantitative thermobarometer. American mineralogist, 83(9-10), 952-969.</em></p>

Magmatic diversification of dykes is controlled by adjacent alkaline carbonatitic massifs

<p>The study reports petrography, bulk major and trace element compositions of lamprophyric Devonian dykes in three areas of the Kola Alkaline Carbonatite Province (N Europe). Dykes in one of these areas, Kandalaksha, are not associated with a massif, while dykes in Kandaguba and Turij Mys occur adjacent (< 5 km) to coeval central multiphase ultramafic alkaline-carbonatitic massifs. Kandalaksha dyke series consists of aillikites - phlogopite carbonatites and monchiquites. Kandaguba dykes range from monchiquites to nephelinites and phonolites; Turij Mys dykes represent alnoites, monchiquites, foidites, turjaites and carbonatites. Some dykes show extreme mineralogical and textural heterogeneity and layering we ascribe to fluid separation. The crystallization and melt evolution of the dykes were modelled with Rhyolite-MELTS and compared with the observed order and products of crystallization. Our results suggest that the studied rocks were related by fractional crystallization and liquid immiscibility. Primitive melts of alkaline picrites or olivine melanephelinites initially evolved at P=1.5-0.8 GPa without a SiO<sub>2</sub> increase due to abundant clinopyroxene crystallization controlled by the CO<sub>2</sub>-rich fluid. At 1-1.1 GPa the Turij Mys melts separated immiscible carbonate melt, which subsequently exsolved carbothermal melts extremely rich in trace elements. Kandaguba and Turij Mys melts continued to fractionate at lower pressures in the presence of hydrous fluid to the more evolved nephelinite and phonolite melts. The studied dykes highlight the critical role of the parent magma chamber in crystal fractionation and magma diversification. The Kandalaksha dykes may represent a carbonatite - ultramafic lamprophyres association, which fractionated at 45- 20 km in narrow dykes on ascent to the surface and could not get more evolved than monchiquite. In contrast, connections of Kandaguba and Turij Mys dykes to their massif magma chambers ensured the sufficient time for fractionation, ascent and a polybaric evolution. This longevity generated more evolved rock types with the higher alkalinity and an immiscible separation of carbonatites.</p>

Gold in Mineralized Volcanic Systems from the Lesser Khingan Range (Russian Far East): Textural Types, Composition and Possible Origins

While gold partitioning into hydrothermal fluids responsible for the formation of porphyry and epithermal deposits is currently well understood, its behavior during the differentiation of metal-rich silicate melts is still subject of an intense scientific debate. Typically, gold is scavenged into sulfides during crustal fractionation of sulfur-rich mafic to intermediate magmas and development of native forms and alloys of this important precious metal in igneous rocks and associated ores are still poorly documented. We present new data on gold (Cu-Ag-Au, Ni-Cu-Zn-Ag-Au, Ti-Cu-Ag-Au, Ag-Au) alloys from iron oxide deposits in the Lesser Khingan Range (LKR) of the Russian Far East. Gold alloy particles are from 10 to 100 µm in size and irregular to spherical in shape. Gold spherules were formed through silicate-metal liquid immiscibility and then injected into fissures surrounding the ascending melt column, or emplaced through a volcanic eruption. Presence of globular (occasionally with meniscus-like textures) Cu-O micro-inclusions in Cu-Ag-Au spherules confirms their crystallization from a metal melt via extremely fast cooling. Irregularly shaped Cu-Ag-Au particles were formed through hydrothermal alteration of gold-bearing volcanic rocks and ores. Association of primarily liquid Cu-Ag-Au spherules with iron-oxide mineralization in the LKR indicates possible involvement of silicate-metallic immiscibility and explosive volcanism in the formation of the Andean-type iron oxide gold-copper (IOCG) and related copper-gold porphyry deposits in the deeper parts of sub-volcanic epithermal systems. Thus, formation of gold alloys in deep roots of arc volcanoes may serve as a precursor and an exploration guide for high-grade epithermal gold mineralization at shallow structural levels of hydrothermal-volcanic environments in subduction zones.

Textural and Geochemical Evidence for Multiple, Sheet-Like Magma Pulses in the Limeira Intrusion - Paraná Magmatic Province, Brazil

Quantitative petrographic, structural, and textural parameters are integrated with geological, geochemical, and Sr-isotope data to examine the emplacement, growth processes, and the magmatic evolution of the high-Ti tholeiitic Limeira Intrusion, in the Paraná Magmatic Province - Southeastern Brazil. Our data strongly support a multiple-stage evolution, due to the nested emplacement of distinct crystal-bearing magma pulses that probably evolved independently, except at their boundaries. A stage of cooling and crystallization between magma injections originates a stepwise T-t path, leading to variations in the plagioclase residence times and effective growth rates inwards, also occasioning sudden changes in crystal shape and size at the boundaries of each magma pulse. The time delay between pulses allows preserving internal “chilled margins” and the development of near-rigid surfaces at their contacts, increasing the alignment and clustering of crystals during magma replenishment. Isotopic and textural data demonstrate a complex assembly history, in which the appearance of mixed plagioclase populations in between magma pulses coincides with the onset of initial Sr isotope ratio increase, which can be attributed to a locally enhanced cooling-rate, and the extraction of residual melts from the previous crystallizing batches and mixing with the younger pulses. Typical C- and S-shaped MgO (wt.%) compositional profiles within individual pulses indicate that the first pulse probably evolved by in situ fractional crystallization followed by melt migration inward, while the younger ones have contributions from both compaction of the lowermost crystallization front and compositional convection. Mafic globular structures are found at the boundaries of magma pulses and constituting the mafic-rich layers in layered rocks. They are interpreted as evidence for chemical disequilibrium, arguably associated with the trigger of silicate liquid immiscibility. The upwards compositional convection of the silica-rich residual liquid and the accumulation of the Fe-Ti-P-rich crystal-bearing end member in the bottom of the latest magma pulses might represent the most significant mechanism of differentiation in the Limeira Intrusion.