U-Pb SHRIMP-II ages of titanite and timing constraints on apatite-nepheline mineralization in the Khibiny and Lovozero alkaline massifs (Kola Peninsula)

Results of this study of titanite samples collected from silicate rocks and apatite-nepheline-(sphene) ores from Paleozoic polyphase alkaline nepheline syenite complexes of the Khibiny and Lovozero massifs revealed the possibility of their in-situ U-Pb dating using sensitive high-resolution ion microprobe SHRIMP-II with an accuracy of 1.0-1.5%, which is comparable with that of U-Pb zircon analysis. Employing different approaches to age determination of the formation of the U-Pb system of titanites, the combined isochrons and mixing lines were plotted from the data obtained from the differentiated complex samples (121 analyses of five Khibiny samples and 52 analyses of one Lovozero sample) and apatite-nepheline ores (120 analyses of five Khibiny samples and 88 analyses of three Lovozero samples). They indicate synchronous crystallization of titanite in silicate rocks throughout the complexes: 374.1 ± 3.7 Ma for the Khibiny massif and 380.9 ± 4.5 Ma for the Lovozero massif, and attest to the later formation of phosphate-rare-metal ores: 371.0 ± 4.2 and 361.4 ± 3.2 Ma, respectively. The relatively delayed ore mineralization specific to the Lovozero massif can be accounted for the significantly lower volumes of magmatic melt and ore fluid involved, different thermal conditions, and the pattern of the investigated mineralization. As such, the obtained U-Pb data from titanite make it possible to limit significantly the time interval (most likely, not exceeding 15-20 Ma) comprising the evolution and activity of the ore-magmatic system of major agpaitic complexes, which is probably associated with plume magmatism.     

A review of the occurrence, form and origin of C-bearing species in the Khibiny Alkaline Igneous Complex, Kola Peninsula, NW Russia

The Khibiny Complex hosts a wide variety of carbon-bearing species that include both oxidized and reduced varieties. Oxidised varieties include carbonate minerals, especially in the carbonatite complex at the eastern end of the pluton, and Na-carbonate phases. Reduced varieties include abiogenic hydrocarbon gases, particularly methane and ethane, dispersed bitumens, solid organic substances and graphite. The majority of the carbon in the Khibiny Complex is hosted in either the carbonatite complex or within the so-called “Central Arch”. The Central Arch is a ring-shaped structure which separates khibinites (coarse-grained eudialite-bearing nepheline-syenites) in the outer part of the complex from lyavochorrites (medium-grained nepheline-syenites) and foyaites in the inner part. The Central Arch is petrologically diverse and hosts the major REE-enriched apatite–nepheline deposits for which the complex is best known. It also hosts zones with elevated hydrocarbon (dominantly methane) gas content and zones of hydrothermally deposited Na-carbonate mineralisation. The hydrocarbon gases are most likely the product of a series of post-magmatic abiogenic reactions. It is likely that the concentration of apatite-nepheline deposits, hydrocarbon gases and Na-carbonate mineralisation, is a function of long lived fluid percolation through the Central Arch. Fluid migration was facilitated by stress release during cooling and uplift of the Khibiny Complex. As a result, carbon with a mantle signature was concentrated into a narrow ring-shaped zone.     

Typochemistry of rinkite and products of its alteration in the Khibiny Alkaline pluton,Kola Peninsula

The occurrence, morphology, and composition of rinkite are considered against the background of zoning in the Khibiny pluton. Accessory rinkite is mostly characteristic of foyaite in the outer part of pluton, occurs somewhat less frequently in foyaite and rischorrite in the central part of pluton, even more sparsely in foidolites and apatite–nepheline rocks, and sporadically in fenitized xenoliths of the Lovozero Formation. The largest, up to economic, accumulations of rinkite are related to the pegmatite and hydrothermal veins, which occur in nepheline syenite on both sides of the Main foidolite ring. The composition of rinkite varies throughout the pluton. The Ca, Na, and F contents in accessory rinkite and amorphous products of its alteration progressively increase from foyaite and fenitized basalt of the Lovozero Formation to foidolite, rischorrite, apatite–nepheline rocks, and pegmatite–hydrothermal veins.     

Trap formation of the Kola peninsula

The nepheline syenites and foidolites of the world’s largest Lovozero and Khibiny allkaline massifs contain numerous xenoliths of intercalating olivine basalts, their tuffs, tuffites, and quartzitosandstones that experienced more (in the Khibiny Massif) or less (in the Lovozero Massif) intense thermal-metasomatic transformation. In terms of geological, petrographical, and petrochemical features, the unaltered rocks of the Lovozero Formation can be ascribed to the rocks of the trap formation, while all wealth of the rocks formed during their contact-metasomatic alteration (sekaninaite-anorthoclase, annite-anorthoclase, fayalite-anorthoclase, rutile-freudenbergite-anorthoclase, topaz-andalusite-anorthoclase, and others) was formed due to alkaline metasomatism. The Fourier analysis of the color variation curves for the volcanogenic-sedimentary rocks revealed the identity between bedding of initial tuffs (tuffites) and banding of their fenitized analogues.     

Helium and argon isotopes in rocks and minerals of the Lovozero Alkaline Massif

The contents and ratios of helium and argon isotopes were studied in rocks of the Lovozero Massif and related rare-metal (loparite) deposits. The gases were extracted by melting (from whole-rock and mineral samples) and crushing (mainly from fluid inclusions) methods. The wide variations in the He and Ar isotopic compositions can be explained by the fact that the trapped fluid represents a mixture of variable proportions of mantle, crustal, and atmogenic components and radiogenic in situ produced gas. The obtained gas-geochemical data reflect the complex evolution of the considered ore-magmatic system and the similar trends of melt evolution and complementary fluid phase in the magmatic chamber, in general, in three-rock (urtite-foyaite-lujavrite) units and, in each individual layers, the relative closeness of the system during magmatic crystallization and initial epimagmatic processes. It was also found that the earliest magmatic mineral was loparite and that ore units and mineralization could be partially transformed during a comparatively late postmagmatic stage. An important role of paleometeoric waters in the low-temperature mineral formation was shown.     

Spinel-group minerals in rocks of the Khibiny alkaline pluton,Kola Peninsula

Seven spinel-group minerals in various geological settings have been revealed in the rocks of the Khibiny pluton. Hercynite, gahnite, and vuorelainenite occur only in xenoliths of hornfels after volcanic and sedimentary rocks, whereas spinel and magnesiochromite occur in alkaline ultramafic rocks of dike series. Franklinite has been discovered in a low-temperature hydrothermal vein. Ubiquitous magnetite is abundant in foyaite, foidolites, alkaline ultrabasic rocks, and pegmatite and hydrothermal veins and may even be the main mineral in some foidolite varieties. The spinel-group minerals are characterized by various chemical compositions due to the fractionation of nepheline syenites resulting in formation of the Main ring of foidolites and apatite-nepheline ore. Like most other minerals found throughout the pluton, magnetite is characterized by variation in the chemical composition along the radial line from the contact with country Proterozoic volcanic rocks to the geometric center of the pluton. Toward the center, the total Ti and Mn contents in magnetite increase from 5–15 up to 40 at %.     

Origin and evolution of skarn fluids,Empire zinc skarns,Central Mining District,New Mexico,U.S.A.

Garnet-pyroxene-sphalerite skarns in the Empire Mine replace Paleozoic carbonates adjacent to the Tertiary Hanover-Fierro granodiorite. Skarn geometry suggests that fluids migrated up pre-ore dikes, faults and the igneous contact, and were deflected laterally into the permeable Tierra Blanca Limestone beneath the relatively impermeable Parting Shale.Silicates associated with propylitically altered pre-ore dikes are enriched in deuterium (D), and depleted in¹⁸O relative to the Hanover-Fierro pluton and post-ore igneous rocks. Early skarn silicates are also depleted in¹⁸O with respect to the pluton, while later skarn minerals are depleted in both D and¹⁸O. Variations in isotope composition of alteration and skarn minerals indicate isotope heterogeneities in mineralizing fluids, even at the small scale of centimeters. Isotope thermometry indicates that there is some degree of subsolidus re-equilibration of igneous and alteration minerals.Several possible fluid flow regimes may have operated to produce the fluids calculated to be in exchange equilibrium with the various rocks and minerals of the Empire skarn system, and mixing of end-member meteoric, formation and magmatic fluids in different proportions can produce observed δDδ¹⁸O trends. An end-member magmatic fluid could produce the D-enrichment observed for early skarn fluids, but this would require isolating magmatic fluids from external fluid sources during cooling of the system from magmatic temperatures of 700°C to skarn temperatures of the order of ≤ 400°C. The D-enrichment may also be explained by the mixing of magmatic and formation waters. Lower δD values, however, require that a large proportion of late-stage skarn fluids must be a D-depleted Tertiary meteoric water, and magmatic water is restricted to a relatively minor component.The end-member mixing approach indicates significant changes in fluid flow systematics over a relatively narrow range in temperature. Alternatively, observed trends in both δD and δ¹⁸O for skarn fluids can also be reproduced by interacting a D-depleted meteoric water with the Hanover-Fierro pluton at low and variable system water-rock ratios, and temperatures between 250 and 400°C. During migration along the long fluid flow paths implied by the low system water-rock ratios (≤0.1), the salinity of dilute meteoric waters could increase through interaction with minerals or leaking fluid inclusions in the country rock. Correlation of isotope depletions of the carbonate wallrocks with inferred fluid flow conduits, suggests significant amounts of fluid-rock exchange at relatively high local water-rock ratios during focusing of flow by critical structures. Although different C sources might require smaller values, it is clear that large (>1) local water-rock ratios are required to produce depletions observed in both¹⁸O and¹³C in hydrothermal calcites. Stable isotope evidence does not require the presence of a significant magmatic fluid component, and suggests that the bulk of the skarn fluids could instead be derived predominantly from a D-depleted meteoric water.     

Formation of Pt-bearing Western Pana pluton on the Kola Peninsula: Fluid regime as deduced from helium and argon isotopic compositions

The distribution of He and Ar isotopes has been studied in 41 rock samples and seven monomineralic fractions from ore-bearing layered units and poorly differentiated host gabbronorite of the Western Pana mafic–ultramafic pluton on the Kola Peninsula. The gases assigned for mass-spectrometric analysis were released by means of whole-rock sample melting and by comminution mainly from fluid microinclusions. The data show that the present-day isotopic composition of noble gases in rocks from the pluton is caused by many factors: the degree of melt degassing, various concentrations and retention of the trapped isotopes, the contents of radioactive elements, and the generation and loss of radiogenic gases. The hypabyssal conditions of pluton formation facilitate the loss of primary mantle-derived volatile components and the dilution of magmatic fluid with near-surface paleometeoric waters containing air dissolved therein. The correlation of noble gas isotopes and ore-forming chemical elements does not suggest derivation of the latter from crustal material and evidences their mantle origin. Variations in the geochemical indices of the gas corroborate previously established or proposed multistage formation of the pluton, mainly, the autometamorphic character of postmagmatic processes and the participation of fluids in ore formation.     

Topography formation as an element of lithospheric self-organization

In geologic objects of different characters and extents, the fractal properties of topography are related to the intensity of endogenic energy flows and the composition of geologic complexes. A good correlation between the topographic differentiation of the Khibiny pluton and the variables of different levels of its structural and compositional organization (mineral and chemical compositions of the rocks and minerals, rock texture, etc.) suggests that topography formation is an element of the self-organization of the Khibiny pluton. Analysis of the fractal dimension of topography in the Khibiny pluton, Primorye, and detailed areas in Transbaikalia revealed a coincidence of its maxima with the position of ore clusters, fields, and deposits, i.e., areas with the contents of elements significantly higher than their clarkes. All the above data suggest that the fractal properties of topography can be used as a prospecting criterio.     

Alteration, HFSE mineralisation and hydrocarbon formation in peralkaline igneous systems: Insights from the Strange Lake Pluton, Canada

Two characteristics of peralkaline igneous rocks that are poorly understood are the extreme enrichment in HFSE, notably Zr, Nb, Y and REE, and the occurrence of fluid inclusions dominated by methane and higher hydrocarbons. Although much of the HFSE enrichment can be explained by magmatic processes, the common intense alteration of the parts of the peralkaline intrusions most enriched in these elements suggests that hydrothermal processes also play an important role in HFSE enrichment. Likewise, although the origin of the higher order hydrocarbons that occur as inclusions in these rocks is still debated, there is strong evidence that at least in some cases their formation involved hydrothermal processes. The issues of HFSE enrichment and hydrocarbon formation in peralkaline intrusions are examined using data from the Strange Lake pluton, a small, middle-Proterozoic intrusion of peralkaline granite in northeast Canada. This pluton contains some of the highest concentrations of Zr, REE and Y ever reported in an igneous body, and is characterised by abundant hydrocarbon-dominated fluid inclusions in rocks that have been hydrothermally altered, including those that form a potential HFSE ore zone. We show that HFSE at Strange Lake were partly concentrated to near exploitable levels as a result of their transport in a high salinity magmatic aqueous liquid, and that this fluid coexisted immiscibly with a carbonic phase which reacted with hydrogen and iron oxides generated during the associated hydrothermal alteration to produce hydrocarbons via a Fischer–Tropsch synthesis. As a result, hydrocarbons and HFSE mineralization are intimately associated. We then go on to show that hydrothermal alteration, HFSE mineralisation and hydrocarbons are also spatially associated in other peralkaline complexes, and present a model to explain this association, which we believe may be applicable to any peralkaline intrusion where HFSE enrichment was accompanied by calcium metasomatism, hematisation and hydrothermal fluorite. We also suggest that, even where these criteria are not satisfied, hydrothermally enriched HFSE and hydrocarbons will be intimately associated simply because they are products of the same initial magmatic fluid. Finally, we speculate that the association of HFSE and hydrocarbons may in some cases actually be genetic, if, as seems possible, unmixing or effervescence of a reduced carbonic fluid from the original magmatic fluid caused changes in temperature, pH, fO₂ or the activity of volatile ligands sufficient to induce the deposition of HFSE minerals.     

U-Pb geochronology and Sr-Nd isotopic systematics of minerals from the ultrabasic-alkaline massifs of the Kola province

This paper reports the results of U-Pb geochronological and Sr-Nd isotopic geochemical investigations (LA-ICP-MS) for perovskite, apatite, titanite, and calcite from the ultrabasic-alkaline rocks of the Paleozoic Kola alkaline province of the Fennoscandian Shield. Based on the obtained data, two main stages were distinguished in the history of Paleozoic intrusions in this province: (1) formation of ultrabasic-alkaline series of the Kovdor, Afrikanda, Turiy Mys, Ozernaya Varaka, Lesnaya Varaka, and other massifs, as well as the ultrabasic-alkaline series of the Khibiny and Lovozero massifs (385–375 Ma) and (2) formation of agpaitic syenites in the Khibiny and Lovozero calderas (375–360 Ma) and related apatite-nepheline deposits (370 Ma). The Sr-Nd isotopic geochemical investigations of perovskite, apatite, and titanite, which are the main hosts for the rare earth elements and Sr in ultrabasic-alkaline rocks, showed that variations in the Sr and Nd isotopic characteristics of these rocks are related to a large extent to crustal contamination during the ascent of their parental melts toward the surface and crystallization in magma chambers. As a result, the Sr and Nd isotopic characteristics of late minerals (apatite and titanite) do not reflect the initial Sr and Nd isotopic ratios of the primary magma. Initial ratios in the primary mantle melts are most closely approximated by the isotopic characteristics of phases crystallizing during early stages (e.g., perovskite).     

On the problem of the formation and geochemical role of bituminous matter in pegmatites of the Khibiny and Lovozero alkaline massifs, Kola Peninsula, Russia

Solid bituminous matter (SBM) typically occurs in the late hydrothermal assemblages of pegmatites of the Khibiny and Lovozero massifs, being confined to a microporous framework Ti-, Nb-, and Zr-silicates, which are sorbents of small molecules and efficient catalysts of the polymerization, reforming, and selective oxidation of organic matter. Bituminous matter from the pegmatites of the Lovozero Massif typically have elevated contents of aliphatic hydrocarbons, sulfur, and sodium, but are depleted in oxygen and trace elements. SBM from the pegmatites of the Khibiny Massif are depleted in sulfur and enriched in oxygen-bearing derivatives of polycyclic aromatic hydrocarbons. Being complexing agents for Th, REE, Ba, Sr, and Ca, they play a key role in the transfer and accumulation of Th and in the accumulation of alkali earth and rare earth elements during the hydrothermal stage of mineral formation. Oxidized SBM bearing rare and alkali earth elements are complex microheterogenous systems, which contain mineral (Th silicates, calcite, etc.), metalorganic (with REE, Ca, Sr, Ba), and predominantly organic phases formed by the exsolution of initial metalorganic material with decreasing temperature.     

Redox potential of the Khibiny magmatic system and genesis of abiogenic hydrocarbons in alkaline plutons

The temperature and redox conditions of the crystallization of rocks from the Khibiny alkaline pluton have been estimated based on an analysis of coexisting magnetite, ilmenite, titanite, and pyroxene. Under redox conditions characteristic of the Khibiny Complex, CO₂ is contained in fluid and carbonate anions are contained in melt at high temperature; then graphite is released and an appreciable amount of hydrocarbons appear at a lower temperature as products of reaction of graphite with fluid. Abiogenic hydrocarbons can arise in igneous complexes owing to a processes distinct from Fischer-Tropsch synthesis.     

Corundum-group minerals in rocks of the Khibiny alkaline pluton,Kola Peninsula

Five minerals of the corundum group have been identified in the Khibiny pluton with certainty. Corundum proper and karelianite occur only in hornfels after volcanic and sedimentary rocks. Xenoliths of hornfels mark the ring faults that bound foidalite within the field of foyaite. Hematite occurs in hydrothermally altered nepheline syenite and crosscutting hydrothermal veins related to the ring faults. Minerals of the ilmenite-pyrophanite series are present in all rocks of the pluton, including veins. Accessory ilmenite in foyaite varies from the manganese variety and pyrophanite in the inner and outer parts of the pluton to manganese-free ilmenite in zone of the Main Ring Fault. In xenoliths of volcanic rocks and alkaline ultramafic rocks, ilmenite is enriched in magnesium. The zoning in distribution of the above-mentioned minerals and the character of variation in their compositions from margins of the pluton to its center are consistent with the petrochemical zoning formed as a result of foyaite alteration of near ring faults.     

铜官山岩体矿物学-矿物化学特征：岩浆结晶动力学意义

本文对皖南官山岩体开展详细地显微镜观察鉴定,利用电子探针和LA-ICP-MS技术对岩浆岩典型矿物斜长石、角闪石和榍石进行了主量和微量元素测定。显微镜鉴定表明,铜官山岩体中存在着大量的岩浆不平衡结构：如斜长石和角闪石嵌晶结构以及针状磷灰石等。这些现象的存在表明铜官山岩体在形成过程中曾发生过一次或多次岩浆混合作用。电子探针分析结果显示,斜长石的成分环带是震荡环带,而大尺度的震荡环带可能代表了大规模的岩浆混合作用;角闪石成分TiO2-Al2O3图解、CaO/NaO2-Al2O3/TiO2图解和Mg-(Fe2++Fe3+)- LiNaKCa角闪石成因矿物族三角图解指示铜官山岩体中角闪石很可能为壳-幔混合成因。LA-ICP-MS技术对主要造岩矿物的微量和稀土元素分析表明,角闪石很可能为幔源或壳幔混合源,斜长石可能为不同分异程度岩浆的混合形成。本研究比较明确地反映了铜官山岩体的形成过程中岩浆来源和结晶动力学过程,即壳幔源区的混合交代作用,与前人通过元素-同位素手段获得的信息比较吻合。     

Minerals of zirconolite group from fenitized xenoliths in nepheline syenites of Khibiny and Lovozero plutons,Kola Peninsula

Zirconolite, its Ce-, Nd-, and Y-analogs, and laachite, another member of the zirconolite group, are typomorphic minerals of the fenitized xenoliths in nepheline syenite and foidolite of the Khibiny–Lovozero Complex, Kola Peninsula, Russia. All these minerals are formed at the late stage of fenitization as products of ilmentie alteration under the effect of Zr-bearing fluids. The diversity of these minerals is caused by the chemical substitutions of Na and Ca for REE, Th, and U compensated by substitution of Ti and Zr for Nb, Fe and Ta, as well as by the redistribution of REE between varieties enriched in Ti (HREE) or Nb (LREE). The results obtained can be used in the synthesis of Synroc-type titanate ceramics assigned for the immobilization of actinides.     

The Donoso copper-rich,tourmaline-bearing breccia pipe in central Chile: petrologic,fluid inclusion and stable isotope evidence for an origin from magmatic fluids

The copper-rich, tourmaline-bearing Donoso breccia pipe is one among more than 15 different mineralized breccias in the giant (>50 million metric tonnes of copper) Miocene and Pliocene Río Blanco-Los Bronces copper deposit in the high Andes of central Chile. This breccia pipe, bracketed in age between 5.2 and 4.9 Ma, has dimensions of 500 by 700 m at the current surface 3,670 m above sea level. Its roots have yet to be encountered, and it is >300 m in diameter at the depth of the deepest drill holes. The Donoso breccia is, for the most part, monolithic, containing clasts of the equigranular quartz monzonite pluton which hosts the pipe. It is matrix supported, with between 5 and 25% of the total rock volume consisting of breccia-matrix minerals, which include tourmaline, quartz, chalcopyrite, pyrite, specularite, and lesser amounts of bornite and anhydrite. An open pit mine, centered on this breccia pipe, has a current production of 50,000 tonnes of ore per day at an average grade of 1.2% copper, and copper grade in the breccia matrix is significantly higher. Measured '¹⁸O for tourmaline and quartz from the matrix of the Donoso breccia at different levels of the pipe range from +6.9 to +12.0‰, and measured 'D in tourmaline ranges from -73 to -95‰. Temperatures of crystallization of these minerals, as determined by the highest homogenization temperatures of highly saline fluid inclusions, range from 400 to >690°C. When corrected for these temperatures, the stable isotope data indicate that fluids from which these breccia-matrix minerals precipitated were magmatic, with '¹⁸O between +5.6 to +9.1‰ and 'D between -51 to -80‰. These isotopic data preclude participation of a significant amount of meteoric water in the formation of the Donoso breccia. They support a model in which brecciation is caused by expansion of magmatic fluids exsolved from a cooling pluton, and breccia-matrix minerals, including copper sulfides, precipitated from the same magmatic fluids responsible for brecciation. Sericitic alteration of clasts in the breccia was also caused by these magmatic fluids. Different types of fluid inclusions imply that several different magmatic fluids were involved in formation of the Donoso breccia. These include high-temperature, highly saline, non-boiling fluids, trapped in inclusions that homogenize by halite dissolution, which probably exsolved from a magma cooling under relatively high (>1 kbar) lithostatic pressure conditions, consistent with geologic constraints. Other high-temperature, highly saline fluids are trapped in inclusions that homogenize by vapor-bubble disappearance and are spatially associated with vapor-rich inclusions, suggesting either phase separation (boiling) or simultaneous separation of immiscible brine and vapor from a magma cooling at lower hydrostatic pressure conditions. Both types of high-temperature, highly saline fluids circulated intermittently, as pressure fluctuated between lithostatic and hydrostatic conditions because of episodes of sealing and rebrecciation.     

新疆准噶尔地区金矿床成矿流体稀土元素地球化学特征

新疆准噶尔地区出现大量不同类型金矿床，为了探讨它们的成因，为金矿床的找矿勘探提供依据。笔者进行了哈图、包谷图、阔尔真阔腊、科克萨依等金矿床包裹体流体中稀土元素及同位素等研究。结果表明，尽管它们成矿形式不同，规模不等，但它们的金均主要来自深源，并有地层物质参与。其中哈图金矿石英脉型矿体与蚀变岩型矿体是两种不同来源的流体叠加成矿，石英脉型矿体主要与哈图岩体岩浆流体关系密切，蚀变岩型矿体与深源流体有关。包谷图、阔尔真阔腊金矿矿、科克萨依金矿成矿流体主要来源于深源，成矿过程中受到浅成流体的综合影响。矿物包裹体流体的稀土元素特征主要反映了原始成矿流体来源，矿物的稀土元素特征可能较多地体现了矿床特有的后期地质作用，这在今后研究中将进一步探讨。     

The Cretaceous Ofuku Pluton and Its Relation to Mineralization in the Western Akiyoshi Plateau,Yamaguchi Prefecture,Japan

The relationship between the magmatism of the Cretaceous Ofuku pluton and mineralization in and around the Akiyoshi Plateau, Yamaguchi Prefecture, Japan was investigated using a combination of field observation, petrographic and geochemical analyses, K–Ar geochronology, and fluid inclusion data. The Ofuku pluton has a surface area of 1.5 × 1.0 km, and was intruded into the Paleozoic accretionary complexes of the Akiyoshi Limestone, Ota Group and Tsunemori Formation in the western part of the Akiyoshi Plateau. The pluton belongs to the ilmenite‐series and is zoned, consisting mainly of early tonalite and granodiorite that share a gradational contact, and later granite and aplite that intruded the tonalite and granodiorite. Harker diagrams show that the Ofuku pluton has intermediate to silicic compositions ranging from 60.4 to 77.9 wt.% SiO₂, but a compositional gap exists between 70.5 to 73.4 wt.% SiO₂ (anhydrous basis). Modal and chemical variations indicate that the assumed parental magma is tonalitic. Quantitative models of fractional crystallization based on mass balance calculations and the Rayleigh fractionation model using major and trace element data for all crystalline phases indicate that magmatic fractionation was controlled mainly by crystal fractionation of plagioclase, hornblende, clinopyroxene and orthopyroxene at the early stage, and quartz, plagioclase, biotite, hornblende, apatite, ilmenite and zircon at the later stage. The residual melt extracted from the granodiorite mush was subsequently intruded into the northern and western parts of the Ofuku pluton as melt lens to form the granite and aplite. The age of the pluton was estimated at 99–97 Ma and 101–98 Ma based on K–Ar dating of hornblende and biotite, respectively. Both ages are consistent within analytical error, indicating that the Ofuku pluton and the associated Yamato mine belong to the Tungsten Province of the San‐yo Belt, which is genetically related to the ilmenite‐series granitoids of the Kanmon to Shunan stages. The aplite contains Cl‐rich apatite and REE‐rich monazite‐(Ce), allanite‐(Ce), xenotime and bastnäsite‐(Ce), indicating that the residual melt was rich in halogens and REEs. The tonalite–granodiorite of the Ofuku pluton contains many three‐phase fluid inclusions, along with daughter minerals such as NaCl and KCl, and vapor/liquid (V/L) volume ratios range from 0.2 to 0.9, suggesting that the fluid was boiling. In contrast, the granite and aplite contain low salinity two‐phase inclusions with low V/L ratios. The granodiorite occupies a large part of the pluton, and the inclusions with various V/L ratios with chloride daughter minerals suggest the boiling fluids might be related to the mineralization. This fluid could have carried base metals such as Cu and Zn, forming Cu ore deposits in and around the Ofuku pluton. The occurrence and composition of fluid inclusions in the igneous rocks from the Akiyoshi Plateau are directly linked to Cu mineralization in the area, demonstrating that fluid inclusions are useful indicators of mineralization.     

Immiscible phases of magmatic fluid and their relation to Be and Mo mineralization at the Yermakovka F–Be deposit, Transbaikalia, Russia

Melt and fluid inclusions in minerals from the peralkaline granite intrusion and associated mineralized country rocks from the Yermakovka F–Be deposit were studied to characterize the behaviour of trace elements and exsolved fluids in the transition from magmatic to hydrothermal processes. Ore mineralization was mostly due to volatile release from a deep-seated pluton for which crystallization history and fluid exsolution can be tracked by three batches of magma (Gr1→Gr3) intruded at the level of the ore deposition to form the Yermakovka stock. Each batch of the sequential granite group is found to intrude at decreasing temperature (from 840 to 730 °C) and progressively increasing extent of crystallization of magma in the parental pluton. This resulted in the enrichment of the ascending melts in H₂O (3.9 to 6.1 wt.%), F (2.6 to 4.1 wt.%) and some incompatible elements (Zr, Nb, Th, Rb, Pb). Although the earliest evidence for the exsolution of homogeneous fluoride–sulphate brine correlates with the final stage of the Gr2 ascent, the most intensive volatile(s) release from the emplaced magmas is shown to occur during their in situ crystallization, which was associated with the separation of exsolved fluid into immiscible phases, brine and low-salinity solution. Compositions of these fluid phases are determined using atomic emission spectroscopy of the appropriate fluid inclusions opened by a laser microprobe and EMPA and SEM–EDS analyses of daughter crystals. The brine phase is enriched in Mo, Mn, Be (up to 17, 8, and 0.3 g/kg, respectively) and contains perceptible abundances of Ce, La, Pb, Zn, whereas the low-salinity phase is enriched only in Be (up to 0.6 g/kg). The selective mobilization of the metals from the melt into fluids is considered to result from the oxidized state of the melt and fluids, peralkalinity of the melt during crystallization, and high F content of the melt. The immiscible fluid phases are shown to migrate together through the solidifying stock giving rise to the albitized granite that is enriched in molybdenite but devoid of Be minerals. In the country rocks, solutions similar to the brine and low-salinity phases of the magmatic fluid made up separate fluid flows, which produced Be and Mo mineralization and were issued predominantly from the parental pluton. Both types of mineralization are nearly monometallic which suggests that of the metals, jointly transported by the brine, only Mo and, in part, Ce and La precipitated separately at the level where the low-salinity solutions deposited Be ores.