Evolution of the trachydacite and pantellerite magmas of the bimodal volcanic association of Dzarta-Khuduk, Central Mongolia: Investigation of inclusions in minerals

Using various methods of melt inclusion investigation, including electron and ion microprobe techniques, we estimated the composition, evolution, and formation conditions of melts producing the trachydacites and pantellerites of the Late Paleozoic bimodal volcanic association of Dzarta-Khuduk, Central Mongolia. Primary crystalline and melt inclusions were detected in anorthoclase from trachydacites and quartz from pantellerites and pantelleritic tuffs. Among the crystalline inclusions, we identified hedenbergite, fluorapatite, and pyrrhotite in the trachydacites and F-arfvedsonite, fluorite, ilmenite, and the rare REE diorthosilicate chevkinite in the pantellerites. Melt inclusions in anorthoclase from the trachydacites are composed of glass, a gas phase, and daughter minerals (F-arfvedsonite, fluorite, villiaumite, and anorthoclase rim on the inclusion wall). Melt inclusions in quartz from the pantellerites are composed of glass, a gas phase, and a fine-grained salt aggregate consisting of Li, Na, and Ca fluorides (griceite, villiaumite, and fluorite). Melt inclusions in quartz crystalloclasts from the pantelleritic tuffs are composed of homogeneous silicate glasses. The phenocrysts of the trachydacites and pantellerites crystallized at temperatures of 1060–1000°C. During thermometric experiments with quartz-hosted melt inclusions from the pantellerites, the formation of immiscible silicate and salt (fluoride) melts was observed at a temperature of 800°C. Homogeneous melt inclusions in anorthoclase from the trachydacites have both trachydacite and rhyolite compositions (wt %): 68–70 SiO₂, 12–13 Al₂O₃, 0.34–0.74 TiO₂, 5–7 FeO, 0.4–0.9 CaO, and 9–12 Na₂O + K₂O. The agpaitic index ranges from 0.92 to 1.24. The glasses of homogenized melt inclusions in quartz from the pantellerites and pantelleritic tuffs have rhyolitic compositions. Compared with the homogeneous glasses trapped in anorthoclase of the trachydacites, quartz-hosted inclusions from the pantellerites show higher SiO₂ (72–78 wt %) and lower Al₂O₃ contents (7.8–10.0 wt %). They also contain 0.14–0.26 wt % TiO₂, 2.5–4.9 wt % FeO, 9–11 wt % Na₂O + K₂O, and 0.9–0.15 wt % CaO and show an agpaitic index of 1.2–2.05. Homogeneous melt inclusions in quartz from the pantelleritic tuffs contain 69–72 wt % SiO₂. The contents of other major components, including TiO₂, Al₂O₃, FeO, and CaO, are close to those in the homogeneous glasses of quartzhosted melt inclusions in the pantellerites. The contents of Na₂O + K₂O are 4–10 wt %, and the agpaitic index is 1.0–1.6. The glasses of melt inclusions from each rock group show distinctive volatile compositions. The H₂O content is up to 0.08 wt % in anorthoclase of the trachydacites, 0.4–1.4 wt % in quartz of the pantellerites, and up to 5 wt % in quartz of the pantelleritic tuffs. The content of F in the glasses of melt inclusions in the phenocrysts of the trachydacites is no higher than 0.67 wt %, and up to 1.4–2.8 wt % in quartz from the pantellerites. The Cl content is up to 0.2 wt % in the glasses of melt inclusions in the minerals of the trachydacites and up to 0.5 wt % in the glasses of quartz-hosted melt inclusions from the pantellerites. The investigation of trace elements in the homogenized glasses of melt inclusions in minerals showed that the trachydacites and pantellerites were formed from strongly evolved rare-metal alkaline silicate melts with high contents of Li, Zr, Rb, Y, Hf, Th, U, and REE. The analysis of the composition of homogeneous melt inclusions in the minerals of the above rocks allowed us to distinguish magmatic processes resulting in the enrichment of these rocks in trace and rare earth elements. The most important processes are the crystallization differentiation and immiscible separation of silicate and fluoride salt melts. It was also shown that all the melts studied evolved in spatially separated magma chambers. This caused the differences in the character of melt evolution between the trachydacites and pantellerites. During the final stages of differentiation, when the magmatic system was saturated with respect to ore elements, Na-Ca fluoride melts were separated and extracted considerable amounts of Li.     

Chemical composition,volatile components,and trace elements in melts of the Karymskii volcanic center,Kamchatka, and Golovnina volcano,Kunashir Island: Evidence from inclusions in minerals

Melt inclusions were examined in phenocrysts in basalt, andesite, dacite, and rhyodacite from the Karymskii volcanic center in Kamchatka and dacite form Golovnina volcano in Kunashir Island, Kuriles. The inclusions were examined by homogenization and by analyzing glasses in more than 80 inclusions on an electron microscope and ion microprobe. The SiO₂ concentrations in the melt inclusions in plagioclase phenocrysts from basalts from the Karymskii volcanic center vary from 47.4 to 57.1 wt %, these values for inclusions in plagioclase phenocrysts from andesites are 55.7–67.1 wt %, in plagioclase phenocrysts from the dacites and rhyodacites are 65.9–73.1 wt %, and those in quartz in the rhyodacites are 72.2–75.7 wt %. The SiO₂ concentrations in melt inclusions in quartz from dacites from Golovnina volcano range from 70.2 to 77.0 wt %. The basaltic melts are characterized by usual concentrations of major components (wt %): TiO₂ = 0.7–1.3, FeO = 6.8–11.4, MgO = 2.3–6.1, CaO = 6.7–10.8, and K₂O = 0.4–1.7; but these rocks are notably enriched in Na₂O (2.9–7.4 wt % at an average of 5.1 wt %, with the highest Na₂O concentration detected in the most basic melts: SiO₂ = 47.4–52.0 wt %. The concentrations of volatiles in the basic melts are 1.6 wt % for H₂O, 0.14 wt % for S, 0.09 wt % for Cl, and 50 ppm for F. The andesite melts are characterized by high concentrations (wt %) of FeO (6.5 on average), CaO (5.2), and Cl (0.26) at usual concentrations of Na₂O (4.5), K₂O (2.1), and S (0.07). High water concentrations were determined in the dacite and rhyodacite melts: from 0.9 to 7.3 wt % (average of 15 analyses equals 4.5 wt %). The Cl concentration in these melts is 0.15 wt %, and those of F and S are 0.06 and 0.01 wt %, respectively. Melt inclusions in quartz from the dacites of Golovnina volcano are also rich in water: they contain from 5.0 to 6.7 wt % (average 5.6 wt %). The comparison of melt compositions from the Karymskii volcanic center and previously studied melts from Bezymyannyi and Shiveluch volcanoes revealed their significant differences. The former are more basic, are enriched in Ti, Fe, Mg, Ca, Na, and P but significantly depleted in K. The melts of the Karymskii volcanic center are most probably less differentiated than the melts of Bezymyannyi and Shiveluch volcanoes. The concentrations of water and 20 trace elements were measured in the glasses of 22 melt inclusions in plagioclase and quartz from our samples. Unusually high values were obtained for Li concentrations (along with high Na concentrations) in the basaltic melts from the Karymskii volcanic center: from 118 to 1750 ppm, whereas the dacite and rhyolite melts contain 25 ppm Li on average. The rhyolite melts of Golovnina volcano are much poorer in Li: 1.4 ppm on average. The melts of the Karymskii volcanic center are characterized by relative minima at Nb and Ti and maxima at B and K, as is typical of arc magmas.     

Geochemistry of ultra-potassic rhyodacite magmas from the area of the Orlovka Massif of Li-F granites in Eastern Transbaikalia: Evidence from study of melt inclusions in quartz

Dikes, stocks and/or sheet flows of felsic volcanic and subvolcanic rocks are typically observed in the vicinity of rare-metal Li-F granite massifs. Their ubiquitous spatial association to rare-metal granites and, often, geochemical affinity to them suggest their certain petrological relation. Compositionally unique ultrapotassic trachydacites enriched in many rare elements were found among these rocks within the Khangilay complex of ore deposits in Eastern Transbaikalia. Melt inclusions in rock-forming quartz were studied to reconstruct the composition and evolution of parent melt. The obtained data demonstrated the existence of a super-potassic peraluminous melt (K₂O = 6.12 wt %, Na₂O = 1.08 wt %) having elevated contents of rare lithophile elements (730 ppm Rb₂O and 900 ppm BaO). The ion-microprobe content of Li is 354.23 ppm at a relatively low F content (up to 0.5 wt %). The residual melt is characterized by the most unusual composition: extremely low contents of mafic components and basicity (< 0.5 wt % femic oxides), a high Al index (A/CNK = 1.53) at comparatively low SiO₂ (60 wt %), and high total sodic alkalinity (more than 10 wt % K₂O + Na₂O; 6.11 wt % Na₂O). Such a composition corresponds to ongonite magma. However, the melt contains no F but has a high Cl content (0.34 wt %), which corresponds to the limit Cl saturation of haplogranite melt. SHRIMP-II U-Pb zircon dating showed significant difference between rare metal granites and trachyrhyodacites of the Khangilay complex of ore deposits: 139.9 ± 1.9 Ma and 253.4 ± 2.4 Ma, respectively. The geochemical similarity of these rocks, primarily in terms of abundance of refractory elements, REE distribution patterns, and initial Sr ratio, indicates their derivation from similar protolith.     

Silicate and salt melts in the genesis of the industrial’noe tin deposit: Evidence from inclusions in minerals

The data obtained on melt and fluid inclusions in minerals of granites, metasomatic rocks, and veins with tin ore mineralization at the Industrial’noe deposit in the southern part of the Omsukchan trough, northeastern Russia, indicate that the melt from which the quartz of the granites crystallized contained globules of salt melts. Silicate melt inclusions were used to determine the principal parameters of the magmatic melts that formed the granites, which had temperatures at 760–1020°C, were under pressures of 0.3–3.6 kbar, and had densities of 2.11–2.60 g/cm³ and water concentrations of 1.7–7.0 wt %. The results obtained on the fluid inclusions testify that the parameters of the mineral-forming fluids broadly varied and corresponded to temperatures at 920–275°C, pressures 0.1–3.1 kbar, densities of 0.70–1.90 g/cm³, and salinities of 4.0–75.0 wt % equiv. NaCl. Electron microprobe analyses of the glasses of twelve homogenized inclusions show concentrations of major components typical of an acid magmatic melt (wt %, average): 73.2% SiO₂, 15.3% Al₂O₃, 1.3% FeO, 0.6% CaO, 3.1% Na₂O, and 4.5% K₂O at elevated concentrations of Cl (up to 0.51 wt %, average 0.31 wt %). The concentrations and distribution of some elements (Cl, K, Ca, Mn, Fe, Cu, Zn, Pb, As, Br, Rb, Sr, and Sn) in polyphase salt globules in quartz from both the granites and a mineralized miarolitic cavity in granite were assayed by micro-PIXE (proton-induced X-ray emission). Analyses of eight salt globules in quartz from the granites point to high concentrations (average, wt %) of Cl (27.5), Fe (9.7), Cu (7.2), Mn (1.1), Zn (0.66), Pb (0.37) and (average, ppm) As (2020), Rb (1850), Sr (1090), and Br (990). The salt globules in the miarolitic quartz are rich in (average of 29 globules, wt %) Cl (25.0), Fe (5.4), Mn (1.0), Zn (0.50), Pb (0.24) and (ppm) Rb (810), Sn (540), and Br (470). The synthesis of all data obtained on melt and fluid inclusions in minerals from the Industrial’noe deposit suggest that the genesis of the tin ore mineralization was related to the crystallization of acid magmatic melts. Original Russian Text@ V.B. Naumov, V.S. Kamenetsky, 2006, published in Geokhimiya, 2006, No. 12, pp. 1279–1289.     

Compositions of magmas,formation conditions,and genesis of carbonate-bearing ijolites and carbonatites of the Belaya Zima alkaline carbonatite complex,eastern Sayan

Based on the investigation of melt inclusions using electron and ion microprobe analysis, we estimated the composition, evolution, and formation conditions of magmas responsible for the calcite-bearing ijolites and carbonatites of the Belaya Zima alkaline carbonatite complex (eastern Sayan, Russia). Primary melt and coexisting crystalline inclusions were found in the nepheline and calcite of these rocks. Diopside, amphibole (?), perovskite, potassium feldspar, apatite, calcite, pyrrhotite, and titanomagnetite were identified among the crystalline inclusions. The melt inclusions in nepheline from the ijolites are completely crystallized. The crystalline daughter phases of these inclusions are diopside, phlogopite, apatite, calcite, magnetite, and cuspidine. During thermometric experiments with melt inclusions in nepheline, the complete homogenization of the inclusions was attained through the dissolution of a gas bubble at temperatures of 1120–1130°C. The chemical analysis of glasses from the homogenized melt inclusions in nepheline of the ijolites revealed significant variations in the content of components: from 36 to 48 wt % SiO₂, from 9 to 21 wt % Al₂O₃, from 8 to 25 wt % CaO, and from 0.6 to 7 wt % MgO. All the melts show very high contents of alkalis, especially sodium. According to the results of ion microprobe analysis, the average content of water in the melts is no higher than a few tenths of a percent. The most salient feature of the melt inclusions is the extremely high content of Nb and Zr. The glasses of melt inclusions are also enriched in Ta, Th, and light rare earth elements but depleted in Ti and Hf. Primary melt inclusions in calcite from the carbonatites contain a colorless glass and daughter phlogopite, garnet, and diopside. The silicate glass from the melt inclusions in calcite of the carbonatite is chemically similar to the glasses of homogenized melt inclusions in nepheline from the ijolites. An important feature of melt inclusions in calcite of the carbonatites is the presence in the glass of carbonate globules corresponding to calcite in composition. The investigation of melt inclusions in minerals of the ijolites and carbonatites and the analysis of the alkaline and ore-bearing rocks of the Belaya Zima Massif provided evidence for the contribution of crystallization differentiation and silicate-carbonate liquid immiscibility to the formation of these rocks. Using the obtained trace-element compositions of glasses of homogenized melt inclusions and various alkaline rocks and carbonatites, we determined to a first approximation the compositions of mantle sources responsible for the formation of the rock association of the Belaya Zima alkaline-carbonatite complex. The alkaline rocks and carbonatites were derived from the depleted mantle affected by extensive metasomatism. It is supposed that carbonate melts enriched in sodium and calcium were the main agents of mantle metasomatism.     

Comendite Melts of the Early Mesozoic Bimodal Sant Association (Central Mongolia) and Mechanisms of Their Formation

Based on the investigation of melt inclusions using electron and ion microprobe analysis, we estimated the composition, evolution, and formation conditions of magmas producing the the comendites of the Sant bimodal volcanic association (Central Mongolia). The mechanisms of the formation of melts were determined. The primary melt and coexisting crystalline inclusions in quartz from three samples of comendites collected from different parts of the volcanic section were studied. Among the crystalline inclusions, sanidine, zircon, and the REE diortosilicate–chevkinite were identified. The phenocrysts of the comendites were determined to crystallize at temperatures of 880–960°C. The homogeneous glasses of melt inclusions have both trachydacite and rhyolite compositions. They are characterized by high concentrations of Zr, Nb, Rb, Y, Th and REE. Significant differences were determined in concentrations of Li and volatile component (H₂O and F) in the glasses: some of the melts are enriched in these components, whereas other are depleted in them.Analysis of the composition of the glasses of the homogenized melt inclusions in quartz of comendites from the Sant bimodal association allowed us to recognize magmatic processes responsible for formation of the comendite melts. The dominant role among them belongs to crystallization differentiation of the magma, accompanied by a process of liquid immiscibility with participation of fluoride melts.     

Unusual acid melts in the area of the unique Rosia Montana gold deposit, Apuseni Mountains, Romania: Evidence from inclusions in quartz

Crystalline and melt inclusions were studied in large (up to 2 cm across) dipyramidal quartz phenocrysts from Miocene dacites in the area of the Rosia Montana Au-Ag deposit in Romania. Data were obtained on the homogenization of fluid inclusions and the composition of crystalline inclusions and glasses in more than 40 melt inclusions, which were analyzed on a electron microprobe. The minerals identified in the crystalline inclusions are plagioclase (An 51–62), orthoclase, micas (biotite and phengite), zircon, magnetite (TiO₂ = 2.8 wt %), and Fe sulfide. Two types of the melts were distinguished when studying the glasses of the melt inclusions. Type 1 of the melts is unusual in composition. The average composition of 20 inclusions is as follows (wt %): 76.1 SiO₂, 0.39 TiO₂, 6.23 Al₂O₃, 4.61 FeO, 0.09 MnO, 1.64 MgO, 3.04 CaO, 2.79 Na₂O, 3.79 K₂O (Na₂O/K₂O = 0.74), 0.07 P₂O₅, 0.02 Cl. The composition of type 2 of the melts is typical of acid magmas. The average of 23 inclusion analyses is (wt %) 79.3 SiO₂, 0.16 TiO₂, 10.27 Al₂O₃, 0.63 FeO, 0.08 MnO, 0.29 MgO, 1.83 CaO, 3.56 Na₂O, 2.79 K₂O (Na₂O/K₂O = 1.28), 0.08 P₂O₅, 0.05 Cl. The compositions of these melts significantly differ in concentrations of Ti, Al, Fe, Mg, Ca, Na, and K. The high analytical totals of the analyses (close to 100 wt %, more specifically 98.9 and 99.0 wt %, respectively) testify that the melts were generally poor in water. Two inclusions of type 1 and two inclusions of type 2 were analyzed on an ion probe, and their analyses show remarkable differences in the concentrations of certain trace elements. These concentrations (in ppm) are for the melts of types 1 and 2, respectively, as follows: 10.0 and 0.69 for Be, 29.3 and 5.7 for B, 6.4 and 1.4 for Cr, 146 and 6.9 for V, 74 and 18 for Cu, 92 and 29 for Rb, 45 and 15 for Zr, 1.7 and 0.6 for Hf, 10.3 and 2.3 for Pb, and 52 and 1.3 for U. The Th/U ratio of these two melt types are also notably different: 0.04 and 0.19 for type 1 and 2.0 and 2.9 for type 2. These data led us to conclude that the magmatic melts were derived from two different sources. Our data on the melts of type 1 testify that the magmatic chamber was contaminated with compositionally unusual crustal rocks (perhaps, sedimentary, metamorphic, or hydrothermal rocks enriched in Si, Fe, Mg, U, and some other components). This can explain the ore-forming specifics of magmatic chambers in the area.     

Genesis of massive sulfide deposits in the Verkhneural’sk ore district, the South Urals, Russia: Evidence for magmatic contribution of metals and fluids

Melt inclusions and aqueous fluid inclusions in quartz phenocrysts from host felsic volcanics, as well as fluid inclusions in minerals of ores and wall rocks were studied at the Cu-Zn massive sulfide deposits in the Verkhneural’sk ore district, the South Urals. The high-temperature (850–1210°C) magmatic melts of volcanic rocks are normal in alkalinity and correspond to rhyolites of the tholeiitic series. The groups of predominant K-Na-type (K₂O/Na₂O = 0.3–1.0), less abundant Na-type (K₂O/Na₂O = 0.15–0.3), and K-type (K₂O/Na₂O = 1.9–9.3) rhyolites are distinguished. The average concentrations (wt %) of volatile components in the melts are as follows: 2.9 H₂O (up to 6.5), 0.13 Cl (up to 0.28), and 0.09 F (up to 0.42). When quartz was crystallizing, the melt was heterogeneous, contained magnetite crystals and sulfide globules (pyrrhotite, pentlandite, chalcopyrite, bornite). High-density aqueous fluid inclusions, which were identified for the first time in quartz phenocrysts from felsic volcanics of the South Urals, provide evidence for real participation of magmatic water in hydrothermal ore formation. The fluids were homogenized at 124–245°C in the liquid phase; the salinity of the aqueous solution is 1.2–6.2 wt % NaCl equiv. The calculated fluid pressure is very high: 7.0–8.7 kbar at 850°C and 5.1–6.8 kbar at 700°C. The LA-ICP-MS analysis of melt and aqueous fluid inclusions in quartz phenocrysts shows a high saturation of primary magmatic fluid and melt with metals. This indicates ore potential of island-arc volcanic complexes spatially associated with massive sulfide deposits. The systematic study of fluid inclusions in minerals of ores and wall rocks at five massive sulfide deposits of the Verkhneural’sk district furnished evidence that ore-forming fluids had temperature of 375–115°C, pressure up to 1.0–0.5 kbar, chloride composition, and salinity of 0.8–11.2 (occasionally up to 22.8) wt % NaCl equiv. The H and O isotopic compositions of sericite from host metasomatic rocks suggest a substantial contribution of seawater to the composition of mineral-forming fluids. The role of magmatic water increases in the central zones of the feeding conduit and with depth. The dual nature of fluids with the prevalence of their magmatic source is supported by S, C, O, and Sr isotopic compositions. The TC parameters of the formation of massive sulfide deposits are consistent with the data on fluid inclusions from contemporary sulfide mounds on the oceanic bottom.     

Mean concentrations of volatile components,major and trace elements in magmatic melts in major geodynamic environments on Earth. I. Mafic melts

Mean concentrations of major components, trace elements, and volatile components in magmatic melts from Earth’s major geodynamic environments are estimated using our database (which comprises more than 1200000 analyses for 75 chemical elements—state for the beginning of 2016) on melt inclusions and quench glasses of rocks). The geodynamic environments are classified into (I) environments of oceanic plate spreading (mid-oceanic ridges), (II) areas affected by mantle plumes in oceanic plates (oceanic islands and lava plateaus), (III and IV) subduction-related environments (III are magmatic zones in island arcs, and IV are magmatic zones in active continental margins, in which magma-generating processes involve the continental crust), (V) continental rifts in areas with continental hotspots, and (VI) backarc spreading zones. The distribution of SiO₂ concentrations (>71000 analyses) in natural magmatic melts in all geodynamic environments is obviously bimodal, with maxima at 50–52 and 72–76 wt % SiO₂. Herein we discuss only mafic melts (40–54 wt % SiO₂). Mean concentrations and confidence levels are calculated for each geodynamic environment for the first time in three variants: from melt inclusions in minerals, from quench glasses in rocks, and from all data. Systematic variations in the mean compositions of melt inclusions and glasses in rocks are detected for all geodynamic environments. Primitive mantle-normalized multielemental patterns for mean concentrations of elements are constructed for magmatic melts from all geodynamic environments, and the mean ratios and their variations are calculated for trace incompatible and volatile components (H₂O/Ce, K₂O/Cl, La/Y, Nb/U, Ba/Rb, Ce/Pb, etc.) in melts from all environments.     

Chemical composition,volatile components,and trace elements in the magmatic melt of the Kurama mining district,Middle Tien Shan: Evidence from the investigation of inclusions in quartz

Melt and fluid inclusions were investigated in six quartz phenocryst samples from the igneous rocks of the extrusive (ignimbrites and rhyolites) and subvolcanic (granite porphyries) facies of the Lashkerek Depression in the Kurama mining district, Middle Tien Shan. The method of inclusion homogenization was used, and glasses from more than 40 inclusions were analyzed on electron and ion microprobes. The chemical characteristics of these inclusions are typical of silicic magmatic melts. The average composition is the following (wt %): 72.4 SiO₂, 0.06 TiO₂, 13.3 Al₂O₃, 0.95 FeO, 0.03 MnO, 0.01 MgO, 0.46 CaO, 3.33 Na₂O, 5.16K₂O, 0.32 F, and 0.21 Cl. Potassium strongly prevails over sodium in all of the inclusions (K₂O/Na₂O averages 1.60). The average total of components in melt inclusions from five samples is 95.3 wt %, which indicates a possible average water content in the melt of no less than 3–4 wt %. Water contents of 2.0 wt % and 6.6 wt % were determined in melt inclusions from two samples using an ion microprobe. The analyses of ore elements in the melt inclusions revealed high contents of Sn (up to 970 ppm), Th (19–62 ppm, 47 ppm on average), and U (9–26 ppm, 18 ppm on average), but very low Eu contents (0.01 ppm). Melt inclusions of two different compositions were detected in quartz from a granite porphyry sample: silicate and chloride, the latter being more abundant. In addition to Na and K chlorides, the salt inclusions usually contain one or several anisotropic crystals and an opaque phase. The homogenization temperatures of the salt inclusions are rather high, from 680 to 820°C. In addition to silicate inclusions with homogenization temperatures of 820–850°C, a primary fluid inclusion of aqueous solution with a concentration of 3.7 wt % NaCl eq. and a very high density of 0.93 g/cm³ was found in quartz from the ignimbrite. High fluid pressure values of 6.5–8.3 kbar were calculated for the temperature of quartz formation. These estimates are comparable with values obtained by us previously for other regions of the world: 2.6–4.3 kbar for Italy, 3.7 kbar for Mongolia, 3.3–8.7 kbar for central Slovakia, and 3.3–9.6 kbar for eastern Slovakia. Unusual melt inclusions were investigated in quartz from another ignimbrite sample. In addition to a gas phase and transparent glass, they contain spherical Feoxide globules (81.2 wt % FeO) with high content of SiO₂ (9.9 wt %). The globules were dissolved in the silicate melt within a narrow temperature range of 1050–1100°C, and the complete homogenization of the inclusions was observed at temperatures of 1140°C or higher. The combined analysis of the results of the investigation of these inclusions allowed us to conclude that immiscible liquids were formed in the high-temperature silicic magma with the separation of iron oxide-dominated droplets.     

Melt inclusions in olivine from the boninites of New Caledonia: Postentrapment melt modification and estimation of primary magma compositions

Melt inclusions were investigated in olivine phenocrysts from the New Caledonia boninites depleted in CaO and TiO₂ and enriched in SiO₂ and MgO. The rocks are composed of olivine and pyroxene phenocrysts in a glassy groundmass. The olivine phenocrysts contain melt inclusions consisting of glass, a fluid vesicle, and daughter olivine and orthopyroxene crystals. The daughter minerals are completely resorbed in the melt at 1200?C1300°C, whereas the complete dissolution of the fluid phase was not attained in our heating experiments. The compositions of reheated and naturally quenched melt inclusions, as well as groundmass glasses were determined by electron microprobe analysis and secondary ion mass spectrometry. Partly homogenized melts (with gas) contain 12?C16 wt % MgO. The glasses of inclusions and groundmass are significantly different in H₂O content: up to 2 wt % in the glasses of reheated inclusions, up to 4 wt % in naturally quenched inclusions, and 6?C8 wt % in groundmass glasses. A detailed investigation revealed a peculiar zoning in olivine: its Mg/(Mg + Fe) ratio increased in a zone directly adjacent to the glass of inclusions. This effect is probably related to partial water (hydrogen) loss and Fe oxidation after inclusion entrapment. The numerical modeling of such a process showed that the water loss was no higher than a few tenths of percent and could not be responsible for the considerable difference between the compositions of inclusions and groundmass glasses. It is suggested that the latter were enriched in H₂O after the complete solidification of the rock owing to interaction with seawater. Based on the obtained data, the compositions of primary boninite magmas were estimated, and it was supposed that variations in melt composition were related not only to olivine and pyroxene fractionation from a single primary melt but also to different degrees and (or) depths of magma derivation.     

Compositions of magmatic melts and evolution of mineral-forming fluids in the banska Stiavnica epithermal Au-Ag-Pb-Zn deposit, Slovakia: A study of inclusions in minerals

Melt and fluid inclusions were investigated in minerals from igneous rocks and ore (Au-Ag-Pb-Zn) veins of the Stiavnica ore field in Central Slovakia. High H₂O (7.1–12.0 wt %) and Cl (0.32–0.46 wt %) contents were found in silicate melt inclusions (65–69 wt % SiO₂ and 5.2–5.6 wt % K₂O) in plagioclase phenocrysts (An 68–36) from biotite-homblende andesites of the eastern part of the caldera. Similar high water contents are characteristic of magmatic melts (71–76 wt % SiO₂ and 3.7–5.1 wt % K₂O) forming the sanidine rhyolites of the Vyhne extrusive dome in the northwestern part of the Stiavnica caldera (up to 7.1 wt %) and the rhyolites of the Klotilda dike in the eastern part of the ore field (up to 11.5 wt %). The examination of primary inclusions in quartz and sanidine from the Vyhne rhyolites revealed high concentrations of N₂ and CO₂ in magmatic fluid (8.6 g/kg H₂O and 59 g/kg H₂O, respectively). Fluid pressure was estimated as 5.0 kbar on the basis of primary CO₂ fluid inclusions in plagioclase phenocrysts from the Kalvari basanites. This value corresponds to a depth of 18 km and may be indicative of a deep CO₂ source. Quartz from the granodiorites of the central part of the Stiavnica-Hodrusa complex crystallized from a melt with 4.2–6.1 wt % H₂O and 0.24–0.80 wt % Cl. Magmatic fluid cogenetic with this silicate melt was represented by a chloride brine with a salinity of no less than 77–80 wt % NaCl equiv. Secondary inclusions in quartz of the igneous rocks recorded a continuous trend of temperature, pressure, and solution salinity, from the parameters of magmatic fluids to the conditions of formation of ore veins. The gold mineralization of the Svyatozar vein system was formed from boiling low-salinity fluids (0.3–8.0 wt % NaCl equv.) at temperatures of 365–160°C and pressures of 160–60 bar. The Terezia, Bieber, Viliam, Spitaler, and Rozalia epithermal gold-silver-base metal veins were also formed from heterogeneous low-salinity fluids (0.3–12.1 wt %) at temperatures of 380–58°C and pressures of 240–10 bar. It was found that the salt components of the solutions were dominated by chlorides (high content of fluorine, up to 0.45 mol/kg H₂O, was also detected), and sulfate solutions appeared in the upper levels. The dissolved gas of ore-forming solutions was dominated by CO₂ (0.1–8.4 mol %, averaging 1.3 wt %) and contained minor nitrogen (0.00–0.85 mol %, averaging 0.05 mol %) and negligible methane admixtures (0.00–0.05 mol %, averaging 0.004 mol %). These data allowed us to conclude that the magmatic melts could be sources of H₂O, Cl, CO₂, and N₂. The formation of the epithermal mineralization of the Stiavnica ore field was associated with the mixing of magmatic fluid with low-concentration meteoric waters, and the fluid was in a heterogeneous state.     

Composition of Li-F granite melt and its evolution during the formation of the ore-bearing Orlovka massif in Eastern Transbaikalia

By the example of the Orlovka massif of Li-F granites in Eastern Transbaikalia, the major- and trace-element (Li, Be, B, Ta, Nb, W, REE, Y, Zr, and Hf) compositions of the parental melt and the character of its variations during the formation of the differentiated rock series were quantitatively estimated for the first time on the basis of electron and ion microprobe analysis and Raman spectroscopy of rehomogenized glasses of melt inclusions in quartz. It was shown that the composition of the Orlovka melt corresponded to a strongly evolved alumina-saturated granitoid magma (A/CNK = 1.12–1.55) rich in normative albite, poor in normative quartz, and similar to ongonite melts. This magma was strongly enriched in water (up to 9.9 ± 1.1 wt %) and fluorine (up to 2.8 wt %). Most importantly, this massif provided the first evidence for high B₂O₃ contents in melts (up to 2.09 wt %). The highest contents of trace elements were observed in the melt from pegmatoid bodies in the amazonite granites of the border zone: up to 5077 ppm Li, 6397 ppm Rb, 313 ppm Cs, 62 ppm Ta, 116 ppm Nb, and 62 ppm W. Compared with the daughter rock, the Orlovka melt was depleted at all stages of formation in SiO₂ (by up to 6 wt %), Na₂O (by up to 2.5 wt %), and, to a smaller extent, in Ti, Fe, Mg, Sr, and Ba, but was enriched in Mn, Rb, F, B, and H₂O.     

Geochemistry and fluid evolution of the peralkaline rare-metal granite, Gabal Gharib, Eastern Desert of Egypt

The Neoproterozoic pluton of Gabal Gharib granite Eastern Desert of Egypt is intruded in subduction-related calc-alkaline granitic rocks of granodiorite to adamellite composition. A zone of metasomatized granite was developed along the contacts at the expense of the calc-alkaline granite. The granite of Gabal Gharib is hypersolvus, composed mainly of orthoclase-microperthite, quartz, and interstitial arfvedsonite. Fluorite, zircon, ilmenite, allanite, and astrophyllite are the main accessories. Pegmatite pods as well as miarolitic cavities (mineral-lined cavities) are common and ranging in size from a few millimeters to 50?cm. Rare-metal minerals such as columbite, cassiterite, and fluorite have been identified from the miarolitic cavities. Geochemical studies revealed that Gabal Gharib granite is a highly fractionated granite, homogeneous in composition, with high contents of SiO₂, and alkalis, high Ga/Al, and Fe/Mg ratios, and low concentrations of Al, Mg, and CaO relative to granodiorite?Cadamellite country rocks. Gabal Gharib granite is metaluminous to peralkaline with ASI (0.94?C1.07). Trace element characteristics of Gabal Gharib granite include abundances of Rb, Nb, Ta, Sn, Th, U, Y, Ga, Zn, rare earth elements (REEs, except Eu), and F, and depletion in Sr, and Ba relative to granodiorite?Cadamellite country rocks. It has the geochemical characteristic of anorogenic A-type granite. The uniform trends of differentiation, normal REE distribution patterns, and low calculated tetrad effects of REE (<0.2) indicate that the effect of post-magmatic subsolidus processes were minimal in the studied granite. Fluid inclusions were studied in quartz crystals from Gabal Gharib granite, quartz pods, and metasomatized granite. The study revealed the presence of high-temperature (480?C550°C), high-salinity (19.45?C39.13?wt.% NaCl eq.) primary inclusions in both metasomatized and rare-metal granites coexisting with melt inclusions and medium-temperature (350?C450°C), medium-salinity (10?C16?wt.% NaCl esq.) aqueous inclusions coexisting hydrocarbon-bearing inclusions. Hydrocarbon is represented by magmatic CH4 in Gabal Gharib granite, while heavier aliphatic compounds may be present in quartz pods. Melt inclusions with temperatures of homogenization >600°C were also reported. Petrographic, geochemical, and fluid inclusion studies constrain that the peralkaline anorogenic granite of Gabal Gharib was derived from highly evolved magma probably originated by fractional crystallization of mantle source.     

Leucocratic magmatic melts with the maximum fluorine concentrations: Experiment and relations in nature

Experimental data indicate that high F concentrations in leucocratic aluminosilicate melts (of granite and nepheline syenite composition) bring about the crystallization of F-rich minerals (topaz, villiaumite, and cryolite) on the liquidus. The crystallization of the minerals is controlled by the silicity, agpaitic coefficient, and proportions of alkalis in the system SiO₂-Al₂O₃-Na₂O-K₂O-F-H₂O. Our earlier experimental data on this system are compared with petrographic and petrochemical data on granites and nepheline syenites containing accessory topaz, cryolite, and villiaumite. The composition of topaz- and cryolite-bearing rocks is proved to correspond to the experimentally established equilibrium fields of F-rich aluminosilicate melt with these minerals. It is proved that the high-F minerals can crystallize from melt. The partial substitution of K and Na for Li modifies phase relations in the system, first of all, significantly expands the equilibrium field of aluminosilicate melt and alkaline aluminofluoride melts. The two melts are proved to be immiscible within broad compositional ranges in the SiO₂-Al₂O₃-Na₂O-Li₂O-F-H₂O system at 800–650°C and 1 kbar. Experimental data indicate that fluoride brine can coexist with aluminosilicate melts in nature. This finds support data on melt inclusions in granites and alkaline rocks whose contents of major components, water and fluorine are close to those in the experimental glasses. Our data lend support to the hypothesis that large cryolite bodies at the Ivigtut, Pitinga, Ulog-Tanzek, and other deposits were formed by fluoride salt melts that separated from F-rich aluminosilicate magmas late in the course of their differentiation. It is experimentally established that fluoride salt melts are able to concentrate valuable trace elements, such as Li, W, Nb, Hf, Sc, U, Th, and REE, which suggests that such melts can play an important role in the origin of rare-metal deposits genetically related to rocks that crystallize from magmas rich in F.     

Effect of Silicate Matter on Pyrochlore Solubility in Fluoride Solutions at <Emphasis Type="Italic">Т</Emphasis> = 550–850°C, <Emphasis Type="Italic">Р</Emphasis> = 50–100 MPa (Experimental Studies)

The experimental results of natural pyrochlore behavior in KF solutions in the presence of quartz at 550–850°C and 50–100 MPa are presented. It is shown that silicate matter (quartz) exerts a significant effect on pyrochlore solubility in aqueous solutions of fluorides of alkaline metals under hydrothermal conditions. This study of the fluid inclusions has revealed the occurrence of reactions of high-temperature hydrolysis of KF under the experimental conditions: KF + H₂O = KOH + HF; in which case, the interaction with quartz SiO₂ + 2KOH = K₂SiO₃ + H₂O is followed by the formation of a silicate glass phase (an aqueous solution–melt). This phase of alkaline glass is a Nb concentrator (Nb₂O₅ up to 16 wt %). The coefficient of Nb distribution between the glass and the fluid is ≈500 (in favor of the glass). It is determined that the phase of the silicate solution–melt can serve as an effective concentrator of the ore component (Nb) at the last lowtemperature stages of crystallization of rare-metal granites.     

The Zr/Hf ratio as a fractionation indicator of rare-metal granites

The Zr-Hf geochemical indicator, i.e., the Zr/Hf ratio (in wt %) in granitic rocks is proposed to be used as the most reliable indicator of the fractionation and ore potential of rare-metal granites. It was empirically determined that the fractional crystallization of granitic magma according to the scheme granodiorite → biotite granite → leucogranite → Li-F granite is associated with a decrease in the Zr/Hf ratio of the granites. The reason for this is the stronger affinity of Hf than Zr to granitic melt. This was confirmed by experiments on Zr and Hf distribution between granitic melt and crystals of Hf-bearing zircon (T = 800°C, P= 1 kbar). The application of the Zr/Hf indicator was tested at three classic territories of rare-metal granites: eastern Transbaikalia, central Kazakhstan, and the Erzgebirge in the Czech Republic and Germany. The reference Kukul’bei complex of rare-metal granites in eastern Transbaikalia (J₃) is characterized by a uniquely high degree of fractionation of the parental granitic melt, with the granites and their vein derivatives forming three intrusive phases. The biotite granites of phase 1 are barren, the leucogranites of phase 2 are accompanied by greisen Sn-W mineral deposits (Spokoininskoe and others), and the final dome-shaped stocks of amazonite Li-F granites of phase 3 host (in their upper parts) Ta deposits of the “apogranite” type: Orlovka, Etyka, and Achikan. The Kukul’bei Complex includes also dikes of ongonites, elvanes, amazonite granites, and miarolitic pegmatites. All granitic rocks of the complex are roughly coeval and have an age of 142±0.6 Ma. The Zr/Hf ratio of the rocks systematically decreases from intrusive phase 1 (40–25) to phases 2 (20–30) and 3 (10–2). Compared to other granite series, the granites of the Kukul’bei Complex are enriched in Rb, Li, Cs, Be, Sn, W, Mo, Ta, Nb, Bi, and F but are depleted in Mg, Ca, Fe, Ti, P, Sr, Ba, V, Co, Ni, Cr, Zr, REE, and Y. From earlier to later intrusive phases, the rocks become progressively more strongly enriched or depleted in these elements, and their Zr/Hf ratio systematically decreases from 40 to 2. This ratio serves as a reliable indicator of genetic links, degree of fractionation, and rare-metal potential of granites. Greisen Sn, W, Mo, and Be deposits are expected to accompany granites with Zr/Hf < 25, whereas granites related to Ta deposits should have Zr/Hf < 5.     

Experimental study of phase relations in a lithium-bearing fluorine-rich haplogranite and nepheline syenite system

Phase relations were investigated in the model water-saturated system Si-Al-Na-Li-F-O at high fluorine contents, a temperature of 800°C, and a pressure of 1 kbar. The obtained aluminosilicate melts are widely variable from quartz- to nepheline-normative compositions with agpaitic indexes both higher and lower than one. Various fluoride, aluminofluoride, and oxide phases were observed in the equilibrium assemblage depending on the melt composition: quartz and cryolite associate with the silica richest aluminosilicate melts, topaz and corundum coexist with peraluminous melts, and villiaumite was observed in highly peralkaline melts. Extensive immiscibility between aluminosilicate and aluminofluoride melts was observed in the system. Aluminofluoride melt coexists with quartz- and nepheline-normative aluminosilicate melts with agpaitic indexes (K _a) of 0.7–1.4. The composition of aluminosilicate melt in equilibrium with aluminofluoride melt ranges from 33 to 70 wt % SiO₂, from 12 to 24 wt % Al₂O₃, and from 5 to 16 wt % alkalis. The aluminofluoride melt is variable in composition, its Al/Na ratio ranges from 20/80 to 40/60 depending on the composition of the equilibrium aluminosilicate melt. The experimental aluminosilicate melts equilibrated with cryolite, topaz, and aluminofluoride melt coincide in major component proportions with the bulk compositions of cryolite- and topaz-bearing granites and melt inclusions in minerals.     

Physicochemical parameters of the melts participating in the formation of chromite ore hosted in the Klyuchevsky ultramafic massif,the Central Urals,Russia

The results of melt inclusion study are reported for chromites of the Klyuchevsky ultramafic massif, which is the most representative of all Ural ultramafic massifs localized beyond the Main Ural Fault Zone. The massif is composed of a dunite-harzburgite complex (tectonized mantle peridotite) and a dunite-wehrlite-clinopyroxenite-gabbro complex (layered portion of the ophiolitic section). The studied Kozlovsky chromite deposit is located in the southeastern part of the Klyuchevsky massif and hosted in serpentinized dunite as a series of lenticular bodies and layers up to 7–8 m thick largely composed of disseminated and locally developed massive ore. Melt inclusions have been detected in chromites of both ore types. The heated and then quenched into glass melt inclusions and host minerals were analyzed on a Camebax-Micro microprobe. The glasses of melt inclusions contain up to 1.06 wt % Na₂O + K₂O and correspond to melts of normal alkalinity. In SiO₂ content (49–56 wt %), they fit basalt and basaltic andesite. The melt inclusions are compared with those from chromites of the Nurali massif in the southern Urals and the Karashat massif in southern Tuva. The physicochemical parameters of magmatic systems related to the formation of disseminated and massive chromite ores of the Klyuchevsky massif are different. The former are characterized by a wider temperature interval (1185–1120°C) in comparison with massive chromite ore (1160–1140°C).     

Fluid+melt intrusions in lechatelierite from the Popigai suevites: A product of dynamic interaction melts and fluids during the shock melting of the target gneiss

The paper presents data on lechatelierite form suevites of the Daldyn Formation in the Popigai astrobleme. Some of the lechatelierite samples show a complicated structure and contain block of diaplectic quartz glass and dynamic “intrusions” of glasses of types I, II, and III. The glasses of types I and II abound in fluid inclusions and display evidence of partial homogenization with lechatelierite. The glasses of type III are clearly separated from all other glasses but show evidence of dynamic interaction with them in the molten state. Fluid inclusions in the glasses of types I and II are syngenetic but have notably different densities from those of completely liquid or gaseous inclusions at 20°C. As is indicated by cryometric data, the liquid phase of the inclusions is aqueous solution of low salinity (5–8 wt % NaCl_equiv). The bulk petrochemistry of the glasses of type I characterizes them as highly silicic (96.04 wt % SiO₂ on average), with elevated K and Na concentrations (Na₂O + K₂O = 0.72 wt % on average), with 0.73 wt % Al₂O₃ (on average) and analytical totals 1.97 wt % less than 100%. The glasses of type II are also rich in SiO₂ (91.51 wt % SiO₂ on average) but contain a broader spectrum of concentrations of major oxides (totaling 5.53 wt % on average) and deficient analytical totals (by 2.96 wt % on average). The glasses of type III are completely equal to impactites produced by melting gneisses of the Popigai astrobleme. The glasses of type I are interpreted to be the intrusion products of the “early” highly mobile and H₂O-rich fluid+melt mixtures, whose protolithic material was K-Na feldspars of the target rocks. The derivation of these melts was associated with the capturing of much silica and water at a highly mobile behavior of K and Na and an inert behavior of Al. The glasses of type II were produced by the extensive mixing of silica and water at the limited involvement of apogneiss melts, and these glasses are sometimes deficient in Al. The glasses of type III are usual mixed apogneiss melts. Excess silica in the glasses of types I and II and their richness in water and deficiency in Al suggest impact anatexis and the selective separation of components during their derivation; the parental fluid-melt mixtures of these glasses were derived from such “hydrous” varieties of the target gneisses as diaphthorized and fractured rocks. The evolution and partial vitrification of lechatelierite and the glasses of types I and II proceeded under residual shock pressures, as follows from data on the dense (from ∼0.5 to 1 g/cm³) aqueous inclusions in these glasses, which suggest that the inclusions were captured in the glasses under pressures from ∼0.8 to 3.3 GPa. It follows that our lechatelierite samples have a complex multistage genesis, and their quenching facilitated the preservation of “intrusions” of various stages of shock melting, including the products of the “early” impact anatexis of the gneisses with the selective separation of components at the active participation of water.