Melting of albite and dehydration of brucite in H2O–NaCl fluids to 9 kbars and 700–900°C: implications for partial melting and water activities during high pressure metamorphism

 The melting reaction: albite_(solid)+ H₂O_(fluid) =albite-H₂O_(melt) has been determined in the presence of H₂O–NaCl fluids at 5 and 9.2 kbar, and results compared with those obtained in presence of H₂O–CO₂ fluids. To a good approximation, albite melts congruently at 9 kbar, indicating that the melting temperature at constant pressure is principally determined by water activity. At 5 kbar, the temperature (T)- mole fraction (X _(H2O) ) melting relations in the two systems are almost coincident. By contrast, H₂O–NaCl mixing at 9 kbar is quite non-ideal; albite melts ∼70 ^°C higher in H₂O–NaCl brines than in H₂O–CO₂ fluids for X _(H2O) =0.8 and ∼100 ^°C higher for X _(H2O) =0.5. The melting temperature of albite in H₂O–NaCl fluids of X _(H2O)=0.8 is ∼100 ^°C higher than in pure water. The P–T curves for albite melting at constant H₂O–NaCl show a temperature minimum at about 5 kbar. Water activities in H₂O–NaCl fluids calculated from these results, from new experimental data on the dehydration of brucite in presence of H₂O–NaCl fluid at 9 kbar, and from previously published experimental data, indicate a large decrease with increasing fluid pressure at pressures up to 10 kbar. Aqueous brines with dissolved chloride salt contents comparable to those of real crustal fluids provide a mechanism for reducing water activities, buffering and limiting crustal melting, and generating anhydrous mineral assemblages during deep crustal metamorphism in the granulite facies and in subduction-related metamorphism. Low water activity in high pressure-temperature metamorphic mineral assemblages is not necessarily a criterion of fluid absence or melting, but may be due to the presence of low a _(H2O) brines. Received: 17 March 1995/Accepted: 9 April 1996     

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.     

Experimental study of eclogite melting with participation of the H<Subscript>2</Subscript>O-CO<Subscript>2</Subscript>-KCl fluid at 5 GPa

In order to model the processes of formation of the highly alkaline (potassic) melts during the partial melting of the eclogite nodules in kimberlites, experiments on the melting of the model and natural eclogites in presence of the H₂O-CO₂ and H₂O-CO₂-KCl fluids at 5 GPa and 1200 and 1300°C are performed. A comparative analysis of the phase relations in the systems with H₂O-CO₂ and H₂O-CO₂-KCl demonstrate that KCl in the fluid equilibrated with eclogites intensifies their melting. It is related to both high Cl concentration in the forming silicate melt (2.0–5.5 wt %) and its enrichment in K₂O owing to the K-Na exchange reactions with the immiscible chloride melt. Because of these reactions, the K₂O/Cl ratio in the melts increases with the KCl content in the system and reaches 2.5–3.5 in the silicate melts coexisting with the immiscible chloride liquid. However, the ratio KCl/(H₂O + CO₂ + KCl) in the fluid does not influence on the ratio K₂O/Cl in the melts. Thus, the solubility KCl in the melts, apparently, does not depend on presence of the H₂O-CO₂ fluid, at least, within the concentration range used in the experiments (up to 20 wt %). The experiments show that the deliberated chloride liquid is necessary to form the potassium-rich chlorine-bearing silicate melts during the eclogite melting. It corresponds to the KCl content in the system above 5 wt %.     

Solubility of carbon dioxide in melts of andesite,tholeiite, and olivine nephelinite composition to 30 kbar pressure

Carbon dioxide solubilities in H₂O-free hydrous silicate melts of natural andesite (CA), tholeiite (K 1921), and olivine nephelinite (OM1) compositions have been determined employing carbon-14 beta-track mapping techniques. The CO₂ solubility increases with increasing pressure, temperature, and degree of silica-undersaturation of the silicate melt. At 1650° C, CO₂ solubility in CA increases from 1.48±0.05 wt % at 15 kbar to 1.95±0.03 wt % at 30 kbar. The respective solubilities in OM1 are 3.41±0.08 wt % and 7.11±0.10 wt %. The CO₂ solubility in K1921 is intermediate between those of CA and OM1 compositions. At lower temperatures, the CO₂ contents of these silicate melts are lower, and the pressure dependence of the solubility is less pronounced. The presence of H₂O also affects the CO₂ solubility (20–30% more CO₂ dissolves in hydrous than in H₂O-free silicate melts); the solubility curves pass through an isothermal, isobaric maximum at an intermediate CO₂/(CO₂+H₂O) composition of the volatile phase. Under conditions within the upper mantle where carbonate minerals are not stable and CO₂ and H₂O are present a vapor phase must exist. Because the solubility of CO₂ in silicate melts is lower than that of H₂O, volatiles must fractionate between the melt and vapor during partial melting of peridotite. Initial low-temperature melts will be more H₂O-rich than later high-temperature melts, provided vapor is present during the melting. Published phase equilibrium data indicate that the compositional sequence of melts from peridotite +H₂O+CO₂ parent will be andesite-tholeiite-nephelinite with increasing temperature at a pressure of about 20 kbar. Examples of this sequence may be found in the Lesser Antilles and in the Indonesian Island Arcs.     

Melt–peridotite interaction in the shallow lithospheric mantle of the North China Craton: evidence from melt inclusions in the quartz-bearing orthopyroxene-rich websterite from Hannuoba

To better understand the origin, migration, and evolution of melts in the lithospheric mantle and their roles on the destruction of the North China Craton (NCC), we conducted a petrological and geochemical study on a quartz-bearing orthopyroxene-rich websterite xenolith from Hannuoba, the NCC, and its hosted melt and fluid inclusions. Both clinopyroxene and orthopyroxene in the xenolith contain lots of primary and secondary inclusions. High-temperature microthermometry of melt inclusions combined with Raman spectroscopy analyses of coexisting fluid inclusions shows that the entrapment temperature of the densest inclusions was ~1215°C and the pressure ~11.47 kbar, corresponding to a depth of ~38 km, i.e. within the stability of the spinel lherzolite. Intermediate pressure inclusions probably reflect progressive fluid entrapment over a range of depths during ascent, whereas the low-pressure inclusions (P < 2 kbar) may represent decrepitated primary inclusions. In situ laser-ablation ICP-MS analyses of major and trace elements on individual melt inclusions show that the compositions of these silicate melt inclusions in clinopyroxene and orthopyroxene are rich in SiO₂, Al₂O₃, and alkalis but poor in TiO₂ and strongly enriched in light rare earth elements (LREEs) and large ion lithophile elements (LILEs), with negative anomalies of high-field strength elements (HFSEs). These characteristics suggest that the silica-rich melts could be derived from the partial melting of subducted oceanic slab. Therefore, this kind of quartz-bearing orthopyroxene-rich websterite may be produced by interaction between the slab-derived melts with the mantle peridotite. This study provides direct evidence for the origin, migration, and evolution of melts in the lithospheric mantle, which may play an important role in the destruction of the NCC.     

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.     

Interaction of model peridotite with H2O-KCl fluid: Experiment at 1.9 GPa and its implications for upper mantle metasomatism

Mineralogical and geochemical data suggest that chloride components play an important role in the transformation and partial melting of upper mantle peridotites. The effect of KCl on the transformation of hydrous peridotite rich in Al₂O₃, CaO, and Na₂O was examined in experiments aimed at studying interaction between model NCMAS peridotite with H₂O-KCl fluid under a pressure of 1.9 GPa, temperatures of 900–1200°C, and various initial H₂O/KCl ratios. The experimental results indicate that KCl depresses the solidus temperature of the hydrous peridotite: this temperature is <900°C at 1.9 GPa, which is more than 100°C lower than the solidus temperature (1000–1025°C) of hydrous peridotite in equilibrium with KCl-free fluid. The reason for the decrease in the melting temperature is that the interaction of KCl with silicates prevails over the effect of chloride on the water activity in the fluid. Experimental data highlight the key role of Al₂O₃ as a component controlling the whole interaction process between peridotite and H₂O-KCl fluid. Garnet, spinel, and pargasite-edenite amphibole in association with aluminous orthopyroxene are unstable in the presence of H₂O-KCl fluid at a chloride concentration in the fluid as low as approximately 2 wt % and are replaced by Cl-bearing phlogopite (0.4–1.1 wt % Cl). Interaction with H₂O-KCl fluid does not, however, affect clinopyroxene and forsterite, which are the Al poorest phases of the system. Chlorine stabilizes phlogopite at relatively high temperatures in equilibrium with melt at temperatures much higher than the solidus (>1200°C). The compositional evolution of melt generated during the melting of model peridotite in the presence of H₂O-KCl fluid is controlled, on the one hand, by the solubility of the H₂O-KCl fluid in the melt and, on the other hand, by phlogopite stability above the solidus. At temperatures below 1050°C, at which phlogopite does not actively participate in melting reactions, fluid dissolution results in SiO₂-undersaturated (35–40 wt %) and MgO-enriched (up to 45 wt %) melts containing up to 4–5 wt % K₂O and 2–3 wt % Cl. At higher temperatures, active phlogopite dissolution and, perhaps, also the separation of immiscible aqueous chloride liquid give rise to melts containing >10 wt % K₂O and 0.3–0.5 wt % Cl. Our experimental results corroborate literature data on the transformation of upper mantle peridotites into phlogopite-bearing associations and the formation of ultrapotassic and highly magnesian melts.     

Melting of hydrous pyroxenites with alkali amphiboles in the continental mantle: 1. Melting relations and major element compositions of melts

Melting experiments on ultramafic rocks rich in the hydrous minerals phlogopite or phlogopite + K-richterite, some including 5% of accessory phases, have been conducted at 15 and 50 kbar. The assemblages represent probable source components that contribute to melts in cratonic regions, but whose melt compositions are poorly known. A main series of starting compositions based on MARID xenoliths consisted of a third each of clinopyroxene (CPX), phlogopite (PHL) and K-richterite (KR) with or without 5% ilmenite, rutile or apatite. Additional experiments were run without KR and with higher proportions of accessory phases. Melt traps were used at near-solidus temperatures to facilitate accurate analysis of well-quenched melts, for which reversal experiments demonstrate equilibrium.Results show that KR melts rapidly and completely within 50 °C of the solidus, so that melts reflect the composition of the amphibole and its melting reaction. Melts have high SiO₂ and especially K₂O but low CaO and Al₂O₃ relative to basaltic melts produced from peridotites at similar pressures. They have no counterparts amongst natural rocks, but most closely resemble leucite lamproites at 15 kbar. KR and PHL melt incongruently to form olivine (OL) and CPX at 15 kbar, promoting SiO₂ contents of the melt, whereas orthopyroxene OPX is increasingly stable at lower lithosphere pressures, leading to an increase in MgO and decrease in SiO₂ in melts, which resemble olivine lamproites. Melts of mica pyroxenites without KR are richer in CaO and Al₂O₃ and do not resemble lamproites. These experiments show that low CaO and Al₂O₃ in igneous rocks is not necessarily a sign of a depleted peridotite source. Accessory phases produce melts exceptionally rich in P₂O₅ or TiO₂ depending on the phases present and are unlike any melts seen at the Earth’s surface, but may be important agents of metasomatism seen in xenoliths. The addition of the 5% accessory phases ilmenite, rutile or apatite result in melting temperatures a few ten of degrees lower; at least two of these appear essential to explain the compositions of many alkaline igneous rocks on cratons.Melting temperatures for CPX + PHL + KR mixtures are close to cratonic geotherms at depths > 130 km: minor perturbations of the stable geotherm at >150 km will rapidly lead to 20% melting. Melts of hydrous pyroxenites with a variety of accessory phases will be common initial melts at depth, but will change if reaction with wall-rocks occurs, leading to volcanism that contains chemical components of peridotite even though the temperature in the source region remains well below the melting point of peridotite. At higher temperatures, extensive melting of peridotite will dilute the initial alkaline melts: this is recognizable as alkaline components in basalts and, in extreme cases, alkali picrites. Hydrous pyroxenites are, therefore, components of most mantle-derived igneous rocks: basaltic rocks should not be oversimplified as being purely melts of peridotite or of mixtures of peridotite and dry pyroxenite without hydrous phases.     

Low melting temperature for calcite at 1000 bars on the join CaCO3‐H2O – some geological implications

Melting experiments of calcite were performed on the join CaCO₃‐H₂O at a pressure of 1000 bars. The system evolves to the ternary CaO‐H₂O‐CO₂ system during melting experiments. Our experiments show that partial melting of calcite begins at a low temperature, below 650 °C. Such a low partial melting temperature for carbonates revives the debate about the presence of carbonate melts in the upper crust. More specifically, the conditions for carbonate partial melting are present in carbonate host rocks undergoing contact metamorphism at high temperatures in the presence of water‐rich fluid. The presence of carbonate melts influences physical parameters such as viscosity and permeability in contact aureoles, and, furthermore, decarbonation reactions release massive amounts of CO₂.     

High-grade metamorphism, dehydration and crustal melting: a reinvestigation based on new experiments in the silica-saturated portion of the system KAlO2–MgO–SiO2–H2O–CO2 at P≤ 1.5 GPa

The system KAlO₂–MgO–SiO₂–H₂O–CO₂ has long been used as a model for the processes of granulite-facies metamorphism and the development of orthopyroxene-bearing mineral assemblages through the breakdown of biotite-bearing assemblages. There has been considerable controversy regarding the role of carbon dioxide in metamorphism and partial melting. We performed new experiments in this system (at pressures of 342 to 1500 MPa with T between 710 and 1045 °C and X ^Fl _H2O between 0.05 and 1.00), accurately locating most of the dehydration and melting equilibria in P-T-X ^Fl _H2O space. The most important primary result is that the univariant reaction Phl + Qtz + Fl = En + Sa + melt must be almost coincident with the fluid-absent reaction (Phl + Qtz = En + Sa + melt) in the CO₂-free subsystem. In conjunction with the results of previous measurements of CO₂ solubility in silicate melts and phase equilibrium experiments, our theoretical analysis and experiments suggest that CO₂ cannot act as a flux for partial melting. Crustal melting in the presence of H₂O–CO₂ mixed fluids will always occur at temperatures higher than with pure H₂O fluid present. Magmas produced by such melting will be granitic (s.l.) in composition, with relatively high SiO₂ and low MgO contents, irrespective of the H₂O–CO₂ ratio in any coexisting fluid phase. We find no evidence that lamprophyric magmas could be generated by partial fusion of quartz-saturated crustal rocks. The granitic melts formed will not contain appreciable dissolved CO₂. The channelled passage of hot CO₂-rich fluids can cause local dehydration of the rocks through which they pass. In rock-dominated (as opposed to fluid-dominated) systems, minor partial melting can also occur in veins initially filled with CO₂-rich fluid, as dehydration and local disequilibrium drive the fluid towards H₂O-rich compositions. However, CO₂ is unlikely to be a significant agent in promoting regional granulite-grade metamorphism, melting, magma generation, metasomatism or long-range silicate mass transfer in Earth's crust. The most viable model for the development of granulite-facies rocks involves the processes of fluid-absent partial melting and withdrawal of the melt phase to higher crustal levels. Received: 28 November 1996 / Accepted: 25 June 1997     

Cordierite as a sensor of fluid conditions in high-grade metamorphism and crustal anatexis

Cordierite H₂O and CO₂ volatile saturation surfaces derived from recent experimental studies are presented for P–T conditions relevant to high‐grade metamorphism and used to evaluate fluid conditions attending partial melting and granulite formation. The volatile saturation surfaces and saturation isopleths for both H₂O and CO₂ in cordierite are strongly pressure dependent. In contrast, the uptake of H₂O by cordierite in equilibrium with melts formed through biotite dehydration melting, controlled by the distribution of H₂O between granitic melt and cordierite, D_w[D_w = wt% H₂O (melt)/wt% H₂O(Crd)], is mainly temperature dependent. D_w = 2.5–6.0 for the H₂O contents (0.4–1.6 wt percentage) typical of cordierite formed through biotite dehydration melting at 3–7 kbar and 725–900 °C. This range in D_w causes a 15–30% relative decrease in the total wt% of melt produced from pelites. Cordierite in S‐type granites are H₂O‐rich (1.3–1.9 wt%) and close to or saturated in total volatiles, signifying equilibration with crystallizing melts that achieved saturation in H₂O. In contrast, the lower H₂O contents (0.6–1.2 wt percentage) preserved in cordierite from many granulite and contact migmatite terranes are consistent with fluid‐absent conditions during anatexis. In several cases, including the Cooma migmatites and Broken Hill granulites, the cordierite volatile compositions yield a_H2O values (0.15–0.4) and melt H₂O contents (2.2–4.4 wt%) compatible with model dehydration melting reactions. In contrast, H₂O leakage is indicated for cordierite from Prydz Bay, Antarctica that preserve H₂O contents (0.5–0.3 wt%) which are significantly less than those required (1.0–0.8 wt%) for equilibrium with melt at conditions of 6 kbar and 860 °C. The CO₂ contents of cordierite in migmatites range from negligible (< 0.1 wt%) to high (0.5–1.0 wt%), and bear no simple relationship to preserved cordierite H₂O contents and a_H2O. In most cases the cordierite volatile contents yield total calculated fluid activities (a_H2O + a_CO2) that are significantly less than those required for fluid saturation at the P–T conditions of their formation. Whether this reflects fluid absence, dilution of H₂O and CO₂ by other components, or leakage of H₂O from cordierite is an issue that must be evaluated on a case‐by‐case basis.     

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.     

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.     

Fluid-Absent Melting Behavior of an F-Rich Tonalitic Gneiss at Mid-Crustal Pressures: Implications for the Generation of Anorogenic Granites

Fluid-absent melting experiments on a biotite (20 wt.%) andhornblende (2 wt.%) bearing tonalitic gneiss were conductedat 6 kbar (900–975C), 10 kbar (875–1075C), and14 kbar (950–975C) to study melt productivity from weaklyperaluminous quartzofeldspathic metamorphic rocks. At 6 kbar,biotite dehydration–melting is completed at 975C viaincongruent melting reactions that produce orthopyroxene, twooxides, and {small tilde}25 wt.% granitic melt. At 6 kbar, hornblendedisappears at 900C, probably in reaction with biotite. At 10kbar, biotite dehydration–melting produces <10 wt.%melt up to 950C via incongruent melting reactions that produceorthopyroxene, garnet, and granitic melt. Hornblende disappearsin the satne temperature interval either by resorption or byreaction with biotite. Widespread biotite dehydration–meltingoccurs between 950 and 975C and produces orthopyroxene, twooxides, and {small tilde}20 wt.% fluorine-rich (up to 0•31wt.%) granitic melt. At 14 kbar only a trace of melt is presentat 950C, and the amounts of hornblende and biotite are virtuallythe same as in the starting material. At 975C, hornblende isgone and {small tilde}10 wt.% granitic melt is produced by meltingof both biotite and hornblende. Our results show that hornblende-bearing assemblages cannotgo through dehydration–melting on their own (althoughthey can in combination with biotite) if the Ca content in thesource rock is too low to stabilize clinopyroxene. In such rocks,hornblende will either resorb or melt by reaction with biotite.Under fluid-absent conditions, intrusion of hot, mantle-derivedmagmas into the lower crust is necessary to initiate widespreaddehydration–melting in rocks with compositions similarto those discussed here. We argue that the high thermal stabilityof biotite in our starting material is caused mainly by theincorporation of fluorine. The relatively high F content inbiotite in the starting material (0•47 wt.%) suggests thatthe rock has experienced dehydroxylation in its past. F enrichmentby a previous fluid-absent partial melting event is excludedbecause of the lack of phases such as orthopyroxene and garnetwhich would have been produced. Our experiments show that thedehydration–melting of such F-enriched biotite producesF-rich granitic liquids, with compositions within the rangeof A-types granites, and leaves behind a granulitic residuedominated by orthopyroxene, quartz, and plagioclase. This studytherefore supports the notion that A-type granites can be generatedby H₂O-undersaturated melting of rocks of tonalitic composition(Creaser et al., 1991), but does not require that these sourcerocks should be residual after a previous melting event.     

Internal Differentiation of the Archean Continental Crust: Fluid-Controlled Partial Melting of Granulites and TTG-Amphibolite Associations in Central Finland

Fault bound blocks of granulite and enderbite occur within upperamphibolite-facies migmatitic tonalitic–trondhjemitic–granodioritic(TTG) gneisses of the Iisalmi block of Central Finland. Theseunits record reworking and partial melting of different levelsof the Archean crust during a major tectonothermal event at2·6–2·7 Ga. Anhydrous mineral assemblagesand tonalitic melts in the granulites formed as a result ofhydrous phase breakdown melting reactions involving amphiboleat peak metamorphic conditions of 8–11 kbar and 750–900°C.A nominally fluid-absent melting regime in the granulites issupported by the presence of carbonic fluid inclusions. Thegeochemical signature of light rare earth element (LREE)-depletedmafic granulites can be modelled by 10–30 wt % partialmelting of an amphibolite source rock leaving a garnet-bearingresidue. The degree of melting in intermediate granulites isinferred to be less than 10 wt % and was restricted by the availabilityof quartz. Pressure–temperature estimates for the TTGgneisses are significantly lower than for the granulites at660–770°C and 5–6 kbar. Based on the P–Tconditions, melting of the TTG gneisses is inferred to haveoccurred at the wet solidus in the presence of an H₂O-rich fluid.A hydrous mineralogy, abundant aqueous fluid inclusions andthe absence of carbonic inclusions in the gneisses are in accordancewith a water-fluxed melting regime. Low REE contents and strongpositive Eu anomalies in most leucosomes irrespective of thehost rock composition suggest that the leucosomes are not meltcompositions, but represent plagioclase–quartz assemblagesthat crystallized early from felsic melts. Furthermore, similarplagioclase compositions in leucosomes and adjacent mesosomesare not a ‘migmatite paradox’, as both record equilibrationwith the same melt phase percolating along grain boundaries. KEY WORDS: Archean continental crust; fluid inclusion; granulite; migmatite; partial melting     

Genesis and mechanisms of formation of rare-metal peralkaline granites of the Khaldzan Buregtey massif,Mongolia: Evidence from melt inclusions

Melt inclusions were studied by various methods, including electron and ion microprobe analysis, to determine the compositions of melts and mechanisms of formation of rare-metal peralkaline granites of the Khaldzan Buregtey massif in Mongolia. Primary crystalline and coexisting melt inclusions were found in quartz from the rare-metal granites of intrusive phase V. Among the crystalline inclusions, we identified potassium feldspar, albite, tuhualite, titanite, fluorite, and diverse rare-metal phases, including minerals of zirconium (zircon and gittinsite), niobium (pyrochlore), and rare earth elements (parisite). The observed crystalline inclusions reproduce almost the whole suite of major and accessory minerals of the rare-metal granites, which supports the possibility of their crystallization from a magmatic melt. Melt inclusions in quartz from these rocks are completely crystallized. Their daughter mineral assemblage includes quartz, microcline, aegirine, arfvedsonite, polylithionite, a zirconosilicate, pyrochlore, and a rare-earth fluorocarbonate. The melt inclusions were homogenized in an internally heated gas vessel at a temperature of 850°C and a pressure of 3 kbar. After the experiments, many inclusions were homogeneous and consisted of silicate glass. In addition to silicate glass, some inclusions contained tiny quench zircon crystals confined to the boundary of inclusions, which indicates that the melts were saturated in zircon. In a few inclusions, glass coexisted with a CO₂ phase. This allowed us to estimate the content of CO₂ in the inclusion as 1.5 wt %. The composition of glasses from the homogeneous melt inclusions is similar to the composition of the rare-metal granites, in particular, with respect to SiO₂ (68–74 wt %), TiO₂ (0.5–0.9 wt %), FeO (2.2–4.6 wt %), MgO (0.02 wt %), and Na₂O + K₂O (up to 8.5 wt %). On the other hand, the glasses of melt inclusions appeared to be strongly depleted compared with the rocks in CaO (0.22 and 4 wt %, respectively) and Al₂O₃ (5.5–7.0 and 9.6 wt %, respectively). The agpaitic index is 1.1–1.7. The melts contain up to 3 wt % H₂O and 2–4 wt % F. The trace element analysis of glasses from homogenized melt inclusions in quartz showed that the rare-metal granites were formed from extensively evolved rare-metal alkaline melts with high contents of Zr, Nb, Th, U, Ta, Hf, Rb, Pb, Y, and REE, which reflects the metallogenic signature of the Khaldzan Buregtey deposit. The development of unique rare metal Zr–Nb–REE mineralization in these rocks is related to the prolonged crystallization differentiation of melts and assimilation of enclosing carbonate rocks.     

Dehydration melting of tonalites. Part II. Composition of melts and solids

 Dehydration melting of tonalitic compositions (phlogopite or biotite-plagioclase-quartz assemblages) is investigated within a temperature range of 700–1000°C and pressure range of 2–15 kbar. The solid reaction products in the case of the phlogopite-plagioclase(An₄₅)-quartz starting material are enstatite, clinopyroxene and potassium feldspar, with amphiboles occurring occasionally. At 12 kbar, zoisite is observed below 800°C, and garnet at 900°C. The reaction products of dehydration melting of the biotite (Ann₅₀)-plagioclase (An₄₅)-quartz assemblage are melt, orthopyroxene, clinopyroxene, amphibole and potassium feldspar. At pressures > 8 kbar and temperatures below 800°C, epidote is also formed. Almandine-rich garnet appears above 10 kbar at temperatures ≥ 750°C. The composition of melts is granitic to granodioritic, hence showing the importance of dehydration melting of tonalites for the formation of granitic melts and granulitic restites at pressure-temperature conditions within the continental crust. The melt compositions plot close to the cotectic line dividing the liquidus surfaces between quartz and potassium feldspar in the haplogranite system at 5 kbar and a _{H 2O} = 1. The composition of the melts changes with the composition of the starting material, temperature and pressure. With increasing temperature, the melt becomes enriched in Al₂O₃ and FeO+MgO. Potash in the melt is highest just when biotite disappears. The amount of CaO decreases up to 900°C at 5 kbar whereas at higher temperatures it increases as amphibole, clinopyroxene and more An-component dissolve in the melt. The Na₂O content of the melt increases slightly with increase in temperature. The composition of the melt at temperatures > 900°C approaches that of the starting assemblage. The melt fraction varies with composition and proportion of hydrous phases in the starting composition as well as temperature and pressure. With increasing modal biotite from 20 to 30 wt%, the melt proportion increases from 19.8 to 22.3 vol.% (850°C and 5 kbar). With increasing temperature from 800 to 950°C (at 5 kbar), the increase in melt fraction is from 11 to 25.8 vol.%. The effect of pressure on the melt fraction is observed to be relatively small and the melt proportion in the same assemblage decreases at 850°C from 19.8 vol.% at 5 kbar to 15.3 vol.% at 15 kbar. Selected experiments were reversed at 2 and 5 kbar to demonstrate that near equilibrium compositions were obtained in runs of longer duration. Received: 27 December 1995 / Accepted: 7 May 1996     

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.     

Partial melting in the Inzie Head gneisses: the role of water and a petrogenetic grid in KFMASH applicable to anatectic pelitic migmatites

A sequence of prograde isograds is recognized within the Dalradian Inzie Head gneisses where pelitic compositions have undergone variable degrees of partial melting via incongruent melting reactions consuming biotite. Three leucosome types are identified. At the lowest grades, granitic leucosomes containing porphyroblasts of cordierite (CRD‐melt) are abundant. At intermediate grades, CRD‐melt mingles with garnetiferous leucosomes (GT‐melt). At the highest grades, CRD‐melt coexists with orthopyroxene‐bearing leucosomes (OPX‐melt), while garnet is conspicuously absent. The prograde metamorphic field gradient is constrained to pressures of 2–3 kbar below the CRD‐melt isograd, and no greater than 4.5 kbar at the highest grade around Inzie Head. A petrogenetic grid, calculated using thermocalc , is presented for the K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (KFMASH) system for the phases orthopyroxene, garnet, cordierite, biotite, sillimanite, H₂O and melt with quartz and K‐feldspar in excess. For the implied field gradient, the reaction sequence predicted by the grid is consistent with the successive prograde development of each leucosome type. Compatibility diagrams suggest that, as anatexis proceeded, bulk compositions may have been displaced towards higher MgO content by the removal of (relatively) ferroan granitic leucosome. An isobaric (P = 4 kbar) T–a_H2O diagram shows that premigmatization fluids must have been water‐rich (a_H2O > 0.85) and suggests that, following the formation of small volumes of CRD‐melt, the system became fluid‐absent and melting reactions buffered a_H2O to lower values as temperatures rose. GT‐ and OPX‐melt formed by fluid‐absent melting reactions, but a maximum of 7–11% CRD‐melt fraction can be generated under fluid‐absent conditions, much less than the large volumes observed in the field. There is strong evidence that the CRD‐melt leucosomes could not have been derived by buoyantly aided upwards migration from levels beneath the migmatites. Their formation therefore required a significant influx of H₂O‐rich fluid, but in a quantity insufficient to have exhausted the buffering capacity of the solid assemblage plus melt. Fluid : rock ratios cannot have exceeded 1 : 30. The fluid was channelled through a regionally extensive shear zone network following melt‐induced failure. Such an influx of fluid at such depths has obvious consequences for localized crustal magma production and possibly for cordierite‐bearing granitoids in general.     

The petrogenesis of basic and ultrabasic alkaline rocks of western Makhtesh Ramon,Israel: geochemistry,melt and fluid inclusion study

The basic and ultrabasic alkaline rocks of western Makhtesh Ramon, Israel crop out in numerous lava flows and subvolcanic bodies. The rock suite is composed of tephrite, basanite, basanitic nephelinite, analcimite, olivine nephelinite, and melilite-olivine nephelinite and in many outcrops is represented by glass-bearing varieties. Melt and fluid inclusions have been studied in olivine, clinopyroxene, and plagioclase phenocrysts. The EP, SIMS and microthermometry methods were used for inclusion study. The geochemical data obtained on glasses of melt inclusions (major, REE, trace elements, volatiles) are compared with the data on whole-rock and groundmass glass compositions. The compositions of melt inclusions reflect the different stages of rock crystallization: the initial products of crystallization are similar to whole-rock compositions whereas final portions of melts are usually enriched in SiO₂, Al₂O₃, and alkalis, and depleted in mafic components. The data on contemporaneous melt and CO₂ inclusions were used for the evaluation of the P–T conditions of rock generation. The following parameters were obtained: tephrite: P = 6.3–7.7 kbar and T = 1,150–1,250°C; basanite: P = 6.6–9.2 kbar and T = 1,150–1,250°C; olivine and analcime-olivine nephelinite: P = 5.6–8.2 kbar and T = 1,150–1,250°C; melilite-olivine nephelinite: 4.0–5.4 kbar and T mainly between 1,150 and 1,200°C. Magma genesis was restricted to P–T conditions of spinel- and plagioclase-lherzolite fields. These data suggest the shallowest depth of magma genesis occurred in Makhtesh Ramon compared to other occurrences of Early Cretaceous magmatism at the Middle East. Differences in the degree of batch partial melting of the same source rocks best explain the diversity of the igneous suite in western Makhtesh Ramon.