Mobility of components in metasomatic transformation and partial melting of gneisses: an example from Sri Lanka

Reaction textures, fluid inclusions, and metasomatic zoning coupled with thermodynamic calculations have allowed us to estimate the conditions under which a biotite–hornblende gneiss from the Kurunegala district, Sri Lanka [hornblende (N_Mg=38–42) + biotite (N_Mg=42–44) + plagioclase + quartz + K-feldspar + ilmenite + magnetite] was transformed into patches of charnockite along shear zones and foliation planes. Primary fluid inclusion data suggest that two immiscible fluids, an alkalic supercritical brine and almost pure CO₂, coexisted during the charnockitisation event and subsequent post-peak metamorphic evolution of the charnockite. These metasomatic fluids migrated through the amphibolite gneiss along shear zones and into the wallrock under peak metamorphic conditions of 700–750 °C, 5–6 kbar, and a^fl _H2O=0.52–0.59. This resulted in the formation of charnockite patches containing the assemblage orthopyroxene (N_Mg=45–48) + K-feldspar (Or_70–80) + quartz + plagioclase (An₂₈) in addition to K-feldspar microveins along quartz and plagioclase grain boundaries. Remnants of the CO₂-rich fluid were trapped as separate fluid inclusions. The charnockite patches show the following metasomatic zonation patterns: – a transition zone with the assemblage biotite (N_Mg= 49–51) + hornblende (N_Mg = 47–50) + plagioclase + quartz + K-feldspar + ilmenite + magnetite; – a KPQ (K-feldspar–plagioclase–quartz) zone with the assemblage K-feldspar + plagioclase + orthopyroxene (N_Mg=45–48) + quartz + ilmenite + magnetite; – a charnockite core with the assemblage K-feldspar + plagioclase + orthopyroxene (N_Mg = 39–41) + biotite (N_Mg=48–52) + quartz + ilmenite + magnetite. Systematic changes in the bulk chemistry and mineralogy across the four zones suggest that along with metasomatic transformation, this process may have been complicated by partial melting in the charnockite core. This melting would have been coeval with metasomatic processes on the periphery of the charnockite patch. There is also good evidence in the charnockitic core that a second mineral assemblage, consisting of orthopyroxene (N_Mg= 36–42) + biotite (N_Mg=50–51) + K-feldspar (Or_70–80) + quartz + plagioclase (An_28–26), could have crystallised from a partial melt during cooling from 720 to 660 °C at decreasing a^fl _H2O from 0.67 to 0.5. Post-magmatic evolution of charnockite at T < 700 °C resulted in fluids being released during the crystallisation of the charnockitic core. These gave rise to the formation of late stage rim myrmekites along K-feldspar grain boundaries as well as late stage biotite, cummingtonite, and carbonates. Received: 15 September 1999 / Accepted: 8 June 2000     

Genesis of the Proterozoic Mangabeira tin–indium mineralization,Central Brazil: Evidence from geology,petrology, fluid inclusion and stable isotope data

The Mangabeira deposit is the only known Brazilian tin mineralization with indium. It is hosted in the Paleo- to Mesoproterozoic Mangabeira within-plate granitic massif, which has geochemical characteristics of NYF fertile granites. The granitic massif is hosted in Archean to Paleoproterozoic metasedimentary rocks (Ticunzal formation), Paleoproterozoic peraluminous granites (Aurumina suite) and a granite–gneiss complex. The mineralized area comprises evolved Li-siderophyllite granite, topaz–albite granite, Li–F-rich mica greisens and a quartz–topaz rock, similar to topazite. Two types of greisens are recognized in the mineralized area: zinnwaldite greisen and Li-rich muscovite greisen, formed by metasomatism of topaz–albite granite and Li-siderophyllite granite, respectively. Cassiterite occurs in the quartz–topaz rock and in the greisens. Indium minerals, such as roquesite (CuInS₂), yanomamite (InAsO₄·2H₂O) and dzhalindite (In(OH₃)), and In-rich cassiterite, sphalerite, stannite group minerals and scorodite are more abundant in the quartz–topaz rock, and are also recognized in albitized biotite granite and in Li-rich muscovite greisen. The host rocks and mineralized zones were subsequently overprinted by the Brasiliano orogenic event.Primary widespread two-phase aqueous and rare coeval aqueous-carbonic fluid inclusions are preserved in quartz from the topaz–albite granite, in quartz and topaz from the quartz–topaz rock and in cassiterite from the Li-rich muscovite greisen. Eutectic temperatures are − 25 °C to − 23 °C, allowing modeling of the aqueous fluids in the system H₂O–NaCl(–KCl). Rare three-phase H₂O–NaCl fluid inclusions (45–50 wt.% NaCl equiv.) are restricted to the topaz–albite granite. Salinities and homogenization temperatures of the aqueous and aqueous-carbonic fluid inclusions decrease from the topaz–albite granite (15–20 wt.% NaCl equiv.; 400 °C–450 °C), to the quartz–topaz rock (10–15 wt.% NaCl equiv.; 250 °C–350 °C) and to the greisen (0–5 wt.% NaCl equiv.; 200 °C–250 °C). Secondary fluid inclusions have the same range of salinities as the primary fluid inclusions, and homogenize between 150 and 210 °C.The estimated equilibrium temperatures based on δ¹⁸O of quartz–mica pairs are 610–680 °C for the topaz–albite granite and 285–370 °C for the Li-rich muscovite greisens. These data are coherent with measured fluid inclusion homogenization temperatures. Temperatures estimated using arsenopyrite geothermometry yield crystallization temperatures of 490–530 °C for the quartz–topaz rock and 415–505 °C for the zinnwaldite greisens. The fluids in equilibrium with the topaz–albite granite have calculated δ¹⁸O and δD values of 5.6–7.5‰ and − 67 to − 58‰, respectively. Estimated δ¹⁸O and δD values are mainly 4.8–7.9‰ and − 60 to − 30‰, respectively, for the fluids in equilibrium with the quartz–topaz rock and zinnwaldite greisen; and 3.4–3.9‰ and − 25 to − 17‰, respectively, for the Li-rich muscovite greisen fluid. δ³⁴S data on arsenopyrite from the quartz–topaz rock vary from − 1.74 to − 0.74‰, consistent with a magmatic origin for the sulfur. The integration of fluid inclusion with oxygen isotopic data allows for estimation of the minimum crystallization pressure at ca. 770 bar for the host topaz–albite granite, which is consistent with its evolved signature.Based on petrological, fluid inclusion and isotope data it is proposed that the greisens and related Mangabeira Sn–In mineralization had a similar hydrothermal genesis, which involved exsolution of F-rich, Sn–In-bearing magmatic fluids from the topaz–albite granite, early formation of the quartz–topaz rock and zinnwaldite greisen, progressive cooling and Li-rich muscovite greisen formation due to interaction with meteoric water. The quartz–topaz rock is considered to have formed in the magmatic-hydrothermal transition. The mineralizing saline and CO₂-bearing fluids are interpreted to be of magmatic origin, based on the isotopic data and paragenesis, which has been documented as characteristic of the tin mineralization genetically related to Proterozoic within-plate granitic magmatism in the Goias Tin Province, Central Brazil.     

The nature, origin and physicochemical controls of hydrothermal Mo-Bi mineralization in the Cadillac deposit, Quebec, Canada

Mo-Bi mineralization occurs in subvertical and subhorizontal quartz-muscovite-± K-feldspar veins surrounded by early albitic and later K-feldspathic alteration halos in monzogranite of the Archean Preissac pluton, Abitibi region, Québec, Canada. Molybdenite is intergrown with muscovite in the veins or associated with K-feldspar in the alteration halos. Mineralized veins contain five main types of fluid inclusions: aqueous liquid and liquid-vapor inclusions, aqueous carbonic liquid-liquid-vapor inclusions, carbonic liquid and vapor inclusions, halite-bearing aqueous liquid and liquid-vapor inclusions, trapped mineral-bearing aqueous liquid and liquid-vapor inclusions. The carbonic solid in frozen carbonic and aqueous-carbonic inclusions melts in most cases at −56.7 ± 0.1 °C indicating that the carbonic fluid consists largely of CO₂. All aqueous inclusion types and the aqueous phase in carbonic inclusions have low initial melting temperatures (≥70 °C), requiring the presence of salts other than NaCl. Leachate analyses show that the bulk fluid contains variable proportions of Na, K, Ca, Cl, and traces of Mg and Li. The following solids were identified in the fluid inclusions by SEM-EDS analysis: halite, calcite, muscovite, millerite (NiS), barite and antarcticite (CaCl₂ · 6H₂O). All are interpreted to be trapped phases except halite which is a daughter mineral, and antarcticite which formed during sample preparation (freezing). Aqueous inclusions homogenize to liquid at temperatures between 75 °C and 400 °C; the mode is 375 °C. Aqueous-carbonic inclusions homogenize to liquid or vapor between 210 °C and 400 °C. Halite-bearing aqueous inclusions homogenize by halite dissolution at approximately 170 °C. Aqueous inclusions containing trapped solids exhibit liquid-vapor homogenization at temperatures similar to those of halite-bearing aqueous inclusions. Temperatures of vein formation, based on oxygen isotopic fractionation between quartz and muscovite, range from 342 °C to 584 °C. The corresponding oxygen isotope composition of the aqueous fluid in equilibrium with these minerals ranges from 1.2 to 5.5 per mil with a mean of 3.9 per mil, suggesting that the liquid had a significant meteoric component. Isochores for aqueous fluid inclusions intersect the modal isotopic isotherm of 425 °C at pressures between 590 and 1900 bar. A model is proposed in which molybdenite was deposited owing to decreasing temperature and/or pressure from CO₂-bearing, moderate to high salinity fluids of mixed magmatic-meteoric origin that were in equilibrium with K-feldspar and muscovite. These fluids resulted from the degassing of a monzogranitic magma and evolved through interaction with volcanic (komatiitic) and sedimentary country rocks. Received: 6 February 1997 / Accepted: 28 January 1998     

Stability of phlogopite in granitic melts, an experimental investigation

Water-saturated and water-undersaturated experiments (a _{H2 O} = 1.0 and 0.5) were performed in the temperature range 780–1040°C at 2 and 5 kbar in order to determine the upper thermal stability of phlogopite in granitic melts. Starting compositions were: (A) subaluminous mixtures of 20 wt % synthetic phlogopite and 80 wt % synthetic anhydrous haplogranitic glass; (B) peraluminous mixtures (normative corundum  = 4 %) of 20 wt % synthetic phlogopite and 80 wt % synthetic anhydrous peraluminous haplogranitic glass. The molar quartz: albite: orthoclase ratio of the glasses of the 2␣kbar runs was 35:39:26 and that of the 5 kbar runs 30:42:28. In the subaluminous system, phlogopite is stable up to 820°C at a _{H2 O} = 1.0 and up to 780°C at a _{H2 O} = 0.5. At higher temperatures, it is replaced by enstatite. In the peraluminous system phlogopite has a remarkably higher thermal stability (up to 1000°C at 5 kbar and a _{H2 O} = 1.0) and there is a temperature interval of 80°C at a _{H2 O} = 1.0, and 90–100°C at a _{H2 O} = 0.5 between the first appearance of enstatite and the disappearance of phlogopite. In the peraluminous system, phlogopite is a solid solution (ss) of phlogopite, muscovite, talc and eastonite components. The crystalline product of the phlogopite_ss breakdown reaction is an aluminous enstatite. The MgO-content of the melt depends on the normative corundum content of the starting material and the run temperature. It is independent of pressure. In the subaluminous system, the MgO-content ranges between 0.05 and 0.3 wt % in the temperature interval 780–880°C at both investigated water activities. The MgO-content of the peraluminous melts at a _{H2 O} = 1.0 ranges between 0.4 and 1.7 wt % and at a _{H2 O} = 0.5 between 0.2 and 1.4 wt % in the temperature range 780–980°C. Received: 28 August 1995 / Accepted: 6 August 1996     

K-feldspar–quartz and K-feldspar–plagioclase phase boundary interactions in garnet–orthopyroxene gneiss's from the Val Strona di Omegna, Ivrea–Verbano Zone, northern Italy

A detailed study based on textural observations combined with microanalysis [back scattered electron imaging (BSE) and electron microprobe analysis (EMPA)] and microstructural data transmission electron microscopy (TEM) has been made of K-feldspar micro-veins along quartz–plagioclase phase and plagioclase–plagioclase grain boundaries in granulite facies, orthopyroxene–garnet-bearing gneiss's (700–825 °C, 6–8 kbar) from the Val Strona di Omegna, Ivrea–Verbano Zone, northern Italy. The K-feldspar micro-veins are commonly associated with quartz and plagioclase and are not found in quartz absent regions of the thin section. This association appears to represent a localised reaction texture resulting from a common high grade dehydration reaction, namely: amphibole + quartz = orthopyroxene + clinopyroxene + plagioclase + K-feldspar + H₂O, which occurred during the granulite facies metamorphism of these rocks. There are a number of lines of evidence for this. These include abundant Ti-rich biotite, which was apparently stable during granulite facies metamorphism, and total lack of amphibole, which apparently was not. Disorder between Al and Si in the K-feldspar indicates crystallisation at temperatures >500 °C. Myrmekite and albitic rim intergrowths in the K-feldspar along the K-feldspar–plagioclase interface could only have formed at temperatures >500–600 °C. Symplectic intergrowths of albite and Ca-rich plagioclase between these albitic rim intergrowths and plagioclase suggest a high temperature grain boundary reaction, which most likely occurred at the start of decompression in conjunction with a fluid phase. Relatively high dislocation densities (>2 × 10⁹ to 3 × 10⁹/cm²) in the K-feldspar suggest plastic deformation at temperatures >500 °C. We propose that this plastic deformation is linked with the extensional tectonic environment present during the mafic underplating event responsible for the granulite facies metamorphism in these rocks. Lastly, apparently active garnet grain rims associated with side inclusions of K-feldspar and quartz and an exterior K-feldspar micro-vein indicate equilibrium temperatures within 20–30 °C of the peak metamorphic temperatures estimated for the sample (770 °C). Contact between these K-feldspar micro-veins and Fe-Mg silicate minerals, such as garnet, orthopyroxene, clinopyroxene or biotite along the interface, is observed to be very clean with no signs of melt textures or alteration to sheet silicates. This lends support to the idea that these micro-veins did not originate from a melt and, if fluid induced, that the water activity of these fluids must have been relatively low. All of these lines of evidence point to a high grade origin for the K-feldspar micro-veins and support the hypothesis that they formed during the granulite facies metamorphism of the metabasite layers in an extensional tectonic environment as the consequence of localised dehydration reactions involving the breakdown of amphibole in the presence of quartz to orthopyroxene, clinopyroxene, plagioclase, K-feldspar and H₂O. It is proposed that the dehydration of the metabasite layers to an orthopyroxene–garnet-bearing gneiss over a 4-km traverse in the upper Val Strona during granulite facies metamorphism was a metasomatic event initiated by the presence of a high-grade, low H₂O activity fluid (most likely a NaCl–KCl supercritical brine), related to the magmatic underplating event responsible for the Mafic Formation; and that this dehydration event did not involve partial melting. Received: 15 February 2000 / Accepted: 26 June 2000     

An experimental investigation on diffusion of water in haplogranitic melts

  The diffusivity of water has been investigated for a haplogranitic melt of anhydrous composition Qz₂₈Ab₃₈Or₃₄ (in wt %) at temperatures of 800–1200°C and at pressures of 0.5–5.0 kbar using the diffusion couple technique. Water contents of the starting glass pairs varied between 0 and 9 wt %. Concentration-distance profiles for the different water species (molecular water and hydroxyl groups) were determined by near-infrared microspectroscopy. Because the water speciation of the melt is not quenchable (Nowak 1995; Nowak and Behrens 1995; Shen and Keppler 1995), the diffusivities of the individual species can not be evaluated directly from these profiles. Therefore, apparent chemical diffusion coefficients of water (D _water) were determined from the total water profiles using a modified Boltzmann-Matano analysis. The diffusivity of water increases linearly with water content <3 wt % but exponentially at higher water contents. The activation energy decreases from 64 ± 10 kJ/mole for 0.5 wt % water to 46 ± 5 kJ/mole for 4 wt % water but remains constant at higher water contents. A small but systematic decrease of D _water with pressure indicates an average activation volume of about 9 cm³/mole. The diffusivity (in cm²/s) can be calculated for given water content (in wt %), T (in K) and P (in kbar) by

Fluid inclusion microthermometry and the P-T evolution of gold-bearing hydrothermal fluids in the Niuxinshan gold deposit, eastern Hebei province, NE China

Niuxinshan is a typical example of the numerous mesothermal gold deposits formed during Mesozoic tectono-magmatic reactivation of the Archean North China Craton in eastern Hebei province. Gold occurs in quartz-sulfide lodes in Archean amphibolites and also in greisen zones in the Mesozoic Niuxinshan granite stock. Four mineralization stages can be recognized from early to late: (1) quartz-K-feldspar, (2) quartz-pyrite, (3) quartz-polysulfide, and (4) quartz-carbonate. Gold mineralization mainly occurs in stages 2 and 3. Fluid inclusions in quartz and fluorite from greisen zones in the Niuxinshan granite, and inclusions in vein quartz and sphalerite from stages 1 to 3 in the amphibolites, have been studied by microthermometry. Three compositional types of inclusions are recognized: type 1 (Tp1) are H₂O-CO₂-bearing inclusions and include primary (Tp1-P) and secondary (Tp1-S) inclusions. These are found in quartz and fluorite from the greisen zones as well as in vein quartz and sphalerite from stages 1 to 3. The Tp1-P inclusions are considered to represent the gold-bearing hydrothermal fluids. Type 2 (Tp2-S) are secondary H₂O-CO₂ + solid phase inclusions in fluorite from the greisen zones. Type 3 (Tp3-S) are secondary aqueous inclusions with a solid phase which coexist with the Tp2-S in fluorite from the greisen zones. The Tp1-P inclusions show variable V_CO2 (commonly 0.3 to 0.6) and X_CO2 values (mainly 0.1 to 0.4). The salinities of inclusions cluster around 3 to 11 wt.% NaCl equivalent and their homogenization temperatures to the liquid phase (Th(L)) fall dominantly in the range of 260 to 360 °C. The compositional variations of inclusions in stage 1 probably result from exsolution of magmatic fluids at various stages; immiscibility or boiling of the fluids can be ruled out. The compositional variations of inclusions in the greisen zones and in vein stages 2 and 3 are attributed to cooling, mixing (dilution), and necking-down of the fluids. The Tp1-S and Tp2-S inclusions show salinities of 3 to 6 wt.% NaCl equivalent and X_CO2 values of 0.04 to 0.17. Th(L) clusters at 240 to 260 °C. The Tp3-S inclusions have salinities of 3 to 6 wt.% NaCl equivalent and Th(L) of 170 to 240 °C. Isochoric reconstructions, combined with oxygen and sulfur isotope geothermometry of mineral pairs, give trapping P-T conditions for the gold-bearing fluids. The greisen zones formed at 310 to 460 °C and 1.3 to 3.7 kbar; stage 1 veins at 300 to 430 °C and 1.2 to 3.7 kbar; stage 2 veins at 290 to 380 °C and 1 to 3 kbar; stage 3 veins at 250 to 350 °C and 1 to 3 kbar. H₂O-CO₂ fluids with low to moderate salinities and moderate to high densities (0.66 to 1.01 g/cm³) dominated at early mineralization stages, and evolved towards H₂O-richer and CO₂- and less saline fluids through time. The retrograde P-T evolution probably resulted from regional uplift and cooling of gold-bearing hydrothermal fluids. The gold bisulfide complex was dominant in the fluids during mineralization and gold deposition was mainly induced by decreases of temperature and pressure, as well as destabilization of the bisulfide complex during sulfidization of wall rocks. Received: 16 March 1998 / Accepted: 11 January 1999     

High CO2 content of fluid inclusions in gold mineralisations in the Ashanti Belt, Ghana: a new category of ore forming fluids?

Fluid inclusions were studied in samples from the Ashanti, Konongo-Southern Cross, Prestea, Abosso/Damang and Ayanfuri gold deposits in the Ashanti Belt, Ghana. Primary fluid inclusions in quartz from mineralised veins of the Ashanti, Prestea, Konongo-Southern Cross, and Abosso/Damang deposits contain almost exclusively volatile species. The primary setting of the gaseous (i.e. the fluid components CO₂, CH₄ and N₂) fluid inclusions in clusters and intragranular trails suggests that they represent the mineralising fluids. Microthermometric and Raman spectroscopic analyses of the inclusions revealed a CO₂ dominated fluid with variable contents of N₂ and traces of CH₄. Water content of most inclusions is below the detection limits of the respective methods used. Aqueous inclusions are rare in all samples with the exception of those from the granite-hosted Ayanfuri mineralisation. Here inclusions associated with the gold mineralisation contain a low salinity (<6 eq.wt.% NaCl) aqueous solution with variable quantities of CO₂. Microthermometric investigations revealed densities of the gaseous inclusions of 0.65 to 1.06 g/cm³ at Ashanti, 0.85 to 0.98 g/cm³ at Prestea, up to 1.02 g/cm³ at Konongo-Southern Cross, and 0.8 to 1.0 g/cm³ at Abosso/Damang. The fluid inclusion data are used to outline the PT ranges of gold mineralisation of the respective gold deposits. The high density gaseous inclusions found in the auriferous quartz at Ashanti and Prestea imply rather high pressure trapping conditions of up to 5.4 kbar. In contrast, mineralisation at Ayanfuri and Abosso/Damang is inferred to have occurred at lower pressures of only up to 2.2 kbar. Mesothermal gold mineralisation is generally regarded to have formed from fluids characterized by H₂O > CO₂ and low salinity ( ±  6 eq.wt.%NaCl). However, fluid inclusions in quartz from the gold mineralisations in the Ashanti belt point to distinctly different fluid compositions. Specifically, the predominance of CO₂ and CO₂ >> H₂O have to be emphasized. Fluid systems with this unique bulk composition were apparently active over more than 200␣km along strike of the Ashanti belt. Fluids rich in CO₂ may present a hitherto unrecognised new category of ore-forming fluids. Received: 30 May 1996 / Accepted: 8 October 1996     

Fluid inclusion study of the Ballinglen W-Sn-sulphide mineralization, SE Ireland

Scheelite-mineralized microtonalite sheets occur on the SE margin of the end-Caledonian Leinster Granite in SE Ireland. Scheelite, polymetallic sulphides and minor cassiterite occur in veins in the microtonalites, disseminated throughout the greisened microtonalite sheets and in the adjacent wallrocks. Two major mineralized vein types occur in the microtonalite sheets: (1) Scheelite ± arsenopyrite ± pyrrhotite occur in quartz-fluorite veins, generally without a muscovite selvage; (2) Sphalerite ± chalcopyrite ± pyrite ± galena ± cassiterite ± stannite occur in quartz + fluorite veins with a coarse muscovite selvage and are often intergrown with the muscovite. Quartz-hosted fluid inclusions were examined from representative samples of both vein types using petrographic, microthermometric and laser Raman spectroscopic techniques. Three distinct types of fluid inclusions have been recognized. Primary, vapour rich Type 1 inclusions in quartz from the scheelite-mineralized veins are of H₂O-CO₂-CH₄-N₂ ± H₂S ± NaCl composition and formed between 360–530 °C. Primary and secondary, liquid-rich Type 2 fluid inclusions in the base metal sulphide-mineralized veins are of H₂O-CH₄-N₂ ± H₂S-NaCl composition and formed between 340–480 °C. They also occur as pseudosecondary and secondary inclusions in scheelite-mineralized veins. Late dilute, low temperature H₂O-NaCl + KCl fluid inclusions may be related to late-Caledonian convection of meteoric waters around the cooling Leinster Granite batholith. Received: 4 September 1996 / Accepted: 23 May 1997     

Retrograde fluids in the Archean Shawmere anorthosite, Kapuskasing Structural Zone, Ontario, Canada

The Archean Shawmere anorthosite lies within the granulite facies portion of the Kapuskasing Structural Zone (KSZ), Ontario, and is crosscut by numerous linear alteration veins containing calcite + quartz ± dolomite ± zoisite ± clinozoisite ± margarite ±paragonite ± chlorite. These veins roughly parallel the trend of the Ivanhoe Lake Cataclastic Zone. Equilibria involving clinozoisite + margarite + quartz ± calcite ± plagioclase show that the vein minerals were stable at T < 600 °C, XCO₂ < 0.4 at P ≈ 6 kbar. The stabilities of margarite and paragonite in equilibrium with quartz are also consistent with T < 600 °C and XCO₂ < 0.4 at 6 kbar. Additional assemblages consisting of calcite + clinochlore + quartz + talc + margarite indicate T < 500 °C with XCO₂ > 0.9. Thus, vein formation, while clearly retrograde, spanned a range of temperatures, and fluid compositions evolved from H₂O-rich to CO₂-rich. The calcite in the retrograde veins has δ¹⁸O values that range from 8.4 to 11.2‰ (average = +9.7 ± 0.9‰) and δ¹³C values that range from −3.9 to −1.6‰ (average = −3.1 ± 0.6‰). These values indicate that the fluids from which calcite precipitated underwent extensive exchange with the anorthosite and other crustal lithologies. The fluids may have been initially derived either from devolatilization of metamorphic rocks or crystallization of igneous rocks in the adjacent Abitibi subprovince. Vein quartz contains CO₂-rich fluid inclusions (final melting T = −57.0 to −58.7 °C) that range in size from 5 to 17 μm. Measured homogenization temperatures (T h) range from −44.0 to 14.5 °C, however for most inclusions (46 of S1), T h = −44.0 to −21.1 °C (ρCO₂ ≈ 1.13 to 1.05 g/cm³). At 400 to 600 °C, these densities correspond to pressures of 3.5 to 7 kbar, which is the best estimate of pressures of vein formation. It has been argued that some high density CO₂-rich fluid inclusions found in the KSZ were formed during peak metamorphism and thus document the presence of a CO₂-rich fluid during peak granulite facies metamorphism (Rudnick et al. 1984). The association of high density CO₂-rich fluid inclusions with clearly retrograde veins documents the formation of similar composition and density inclusions after the peak of metamorphism. Thus, the coincidence of entrapment pressures calculated from fluid inclusion density measurements with peak metamorphic pressures alone should not be considered strong evidence for peak metamorphic inclusion entrapment. All fluid inclusion results are consistent with an initially semi-isobaric retrograde P–T path. Received: 2 April 1996 / Accepted: 15 November 1996     

Fluid inclusion characteristics of mesothermal gold deposits in the Xiaoqinling district, Shaanxi and Henan Provinces, People's Republic of China

Fluid inclusions were studied in quartz samples from early (stage I) gold-poor quartz veins and later (stage II) gold- and sulphide-rich quartz veins from the Wenyu, Dongchuang, Qiangma, and Guijiayu mesothermal gold deposits in the Xiaoqinling district, China. Fluid inclusion petrography, microthermometry, and bulk gas analyses show remarkably consistent fluid composition in all studied deposits. Primary inclusions in quartz samples are dominated by mixed CO₂-H₂O inclusions, which have a wide range in CO₂ content and coexist with lesser primary CO₂-rich and aqueous inclusions. In addition, a few secondary aqueous inclusions are found along late-healed fractures. Microthermometry and bulk gas analyses suggest hydrothermal fluids with typically 15–30 mol% CO₂ in stage I inclusions and 10–20 mol% CO₂ in stage II inclusions. Estimates of fluid salinity decrease from 7.4–9.2 equivalent wt.% NaCl to 5.7–7.4 equivalent wt.% NaCl between stage I and II. Primary aqueous inclusions in both stages show consistent salinity with, but slightly lower Th _total than, their coexistent CO₂-H₂O inclusions. The coexisting CO₂-rich, CO₂-H₂O, and primary aqueous inclusions in both stage I and II quartz are interpreted to have been trapped during unmixing of a homogeneous CO₂-H₂O parent fluid. The homogenisation temperatures of the primary aqueous inclusions give an estimate of trapping temperature of the fluids. Trapping conditions are typically 300–370 °C and 2.2 kbar for stage I fluids and 250–320 °C and 1.6 kbar for stage II fluids. The CO₂-H₂O stage I and II fluids are probably from a magmatic source, most likely devolatilizing Cretaceous Yanshanian granitoids. The study demonstrates that gold is largely deposited as pressures and temperatures fall accompanying fluid immiscibility in stage II veins. Received: 15 May 1997 / Accepted: 10 June 1998     

The Malanjkhand copper ( + molybdenum) deposit, India: mineralization from a low-temperature ore-fluid of granitoid affiliation

  Copper and subordinate molybdenum mineralization at Malanjkhand occurs within a fracture-controlled quartz-reef enclosed in a pink granitoid body surrounded by grey-granitoids constituting the regional matrix. Sulfide-bearing stringers, pegmatites with only quartz + microcline and sulfide disseminations, all within the pink-granitoid, represent other minor modes of occurrences. Despite this diversity in mode of occurrence, the mineralogy of ores is quite consistent and conform to a common paragenetic sequence comprising an early `ferrous' stage of precipitation of magnetite (I) and pyrite (I) and, the main-stage chalcopyrite mineralization with minor sphalerite, pyrite (II), magnetite (II), molybdenite and hematite. Both stages witnessed continuous precipitation of quartz ± microcline ± (chlorite, biotite and epidote). The enclosing pink-granitoid and the regional grey-granitoids display alteration features such as saussuritization of plagioclase, breakdown of hornblende and chloritization of biotite on a regional scale, indicating interaction with a pervasive fluid. Quartz and microcline precipitation mostly restricted within the pink granitoid, postdates this alteration. Four types of primary inclusions were encountered in quartz from ore samples: (1) type-I – aqueous-biphase(L + V) inclusions, the commonest variety in all ore types; (2) type-II – aqueous-carbonic(L_aq + L_carb ± V_carb); (3) type-III – pure-carbonic(L_carb ± V_carb) – type-II and III being restricted to stringer and pegmatitic ores, and (4) rare polyphase (L_aq + V_aq + calcite/gypsum) inclusions. Quartz in granitoids contain primary type-I inclusions only. Type-I inclusions from ore samples furnish a temperature range (after a rough pressure correction to the T _H  -maxima of 140–180 °C) of 150–275 °C and a moderately low salinity of 4–12 wt.% NaCl equivalent. This is inferred to represent the signature of the major component (F2) of the ore fluid. A few type-I inclusions of higher T _M (up to 380 °C) and low salinity and density represent the other (F1) identifiable component of the ore fluid present in low proportion. The T _H  -maxima and the total range in salinity of type-I inclusions in quartz from granitoids are strikingly similar to those from the ore samples. Composition of syn-ore chlorites furnished a temperature range of 185–327 °C, which conforms to the fluid inclusion microthermometric data. Pressure estimates using standard fluid inclusion geobarometric methods, vary from 550 to 1790 bar in the stringer ores. Observed temperature-salinity/density relationships are best explained by a two-stage evolution model of the ore fluid: the first stage witnessed mixing of the two components, F1 and F2 in unequal proportion, bringing about mineralization. The second stage of evolution was marked by the separation of a carbonic component on continued sulfide precipitation and attendant increase in salinity of the fluid. The F1 component emerged as a distinct, heated and (CO₂ + S)-charged entity due to steam-heating and contamination of the early-ingressed F2 fluid at the fracture zone. The pervasive fluid phase in the surrounding granitoids contributed the F2 component. Received: (10 August 1994), 15 August 1995 / Accepted: 12 January 1996     

Fluid chemistry and processes at the Porgera gold deposit, Papua New Guinea

The Porgera gold deposit in Papua New Guinea is a world-class example of an alkalic-type epithermal gold system (stage II), which overprints a precursor stage of magmatic-hydrothermal gold mineralization (stage I). Gas and ion chromatographic analyses of fluid inclusions contained in vein minerals from both mineralization stages have been carried out in order to constrain the compositions of the fluids involved in, and the processes attending, ore deposition. These data indicate the presence of three end-member liquids, the most dilute of which was present throughout the mineralization history and is interpreted to represent evolved groundwater of meteoric origin. Its composition is estimated to have been approximately 500 mM Na⁺, 10 mM K⁺, 5 mM Li⁺, 250 mM Cl⁻, 0.15 mM Br⁻, and 0.01 mM I⁻, plus significant concentrations of dissolved gases. More saline liquids were also present during the two main stages of ore formation, and although their compositions differ, both are interpreted to have been derived at least in part from magmatic fluids, and to have been the media by which gold was introduced into the system. Stage I minerals contain fluid inclusions which decrease in salinity towards this dilute end-member composition through the vein paragenesis, reflecting progressive dilution at depth of the magmatic fluid source by groundwaters. Ore deposition is thought to have been caused largely by simple cooling and/or wallrock reactions, although limited in situ fluid mixing may also have occurred. The most saline fluids, present in early quartz and pyrite, contain at least 810 mM Na⁺, 530 mM Ca²⁺, 130 mM K⁺, 12 mM Li⁺, 87 mM SO₄ ²⁻, 960 mM Cl⁻, 1.1 mM Br⁻, and 0.05 mM I⁻, plus significant but variable concentrations of dissolved gases. Fluid inclusions from stage II hydraulic breccia veins reveal the presence of two distinct liquids with contrasting salinities, which were present at different times during vein formation. A higher salinity liquid appears to have predominated during mineralization, whereas lower salinity groundwaters filled the structures during intervening periods. The ore-forming fluid may have been forcibly injected into the veins from depth during fracturing and depressurization events, displacing the resident groundwaters in the process. The original composition of this fluid is estimated to have been at least 1770 mM Na⁺, 59 mM K⁺, 180 mM Li⁺, 210 mM SO₄ ²⁻, 680 mM Cl⁻, 1.4 mM Br⁻, and 0.09 mM I⁻, plus 1.5 mol% CO₂, 0.19 mol% CH₄, and 0.04 mol% N₂. Gas chromatographic analyses of fluid inclusions from stage II samples show a decrease in total gas content between early unmineralized veins and post-mineralization vuggy quartz (suitable samples could not be obtained from the ore stage itself). Post-mineralization samples plot along an experimental gas-saturation curve in the CO₂-CH₄-H₂O-NaCl system, obtained at conditions similar to those attending stage II ore deposition at Porgera (200–300 bar, ˜165 °C). These results are interpreted to indicate a period of depressurization-induced phase separation during hydraulic fracturing, which resulted in rich ore deposition. Volatile gases such as CH₄ and N₂, in addition to CO₂ in solution, are shown to have a significant negative effect on total gas solubility. This effect may be of critical importance in lowering the temperature and increasing the depth (pressure) at which phase separation can occur in epithermal systems. Received: 28 November 1995 / Accepted: 17 July 1996     

Evolution of metamorphic volatiles during exhumation of microdiamond-bearing granulites in the Western Gneiss Region, Norway

Fluid inclusions in garnet, kyanite and quartz from microdiamond-bearing granulites in the Western Gneiss Region, Norway, document a conspicuous fluid evolution as the rocks were exhumed following Caledonian high- and ultrahigh-pressure (HP–UHP) metamorphism. The most important of the various fluid mixtures and daughter minerals in these rocks are: (N₂ + CO₂ + magnesian calcite), (N₂ + CO₂ + CH₄ + graphite + magnesian calcite), (N₂ + CH₄), (N₂ + CH₄ + H₂O), (CO₂) and (H₂O + NaCl + CaCl₂ + nahcolite). Rutile also occurs in the N₂ + CO₂ inclusions as a product of titanium diffusion from the garnet host into the fluid inclusions. Volatiles composed of N₂ + CO₂ + magnesian calcite characterise the ambient metamorphic environment between HP–UHP (peak) and early retrograde metamorphism. During progressive decompression, the mole fraction of N₂ increased in the fluid mixtures; as amphibolite-facies conditions were reached, CH₄ and later, H₂O, appeared in the fluids, concomitant with the disappearance of CO₂ and magnesian calcite. Graphite is ubiquitous in the host lithologies and fluid inclusions. Thermodynamic modelling of the metamorphic volatiles in a graphite-buffered C-O-H system demonstrates that the observed metamorphic volatile evolution was attainable only if the f _O2 increased from c. −3.5 (±0.3) to −0.8 (±0.3) log units relative to the FMQ oxygen buffer. External introduction of oxidising aqueous solutions along a system of interconnected ductile shear zones adequately explains the dramatic increase in the f _O2. The oxidising fluids introduced during exhumation were likely derived from dehydration of oceanic crust and continental sediments previously subducted during an extended period of continental collision in conjunction with the Caledonian orogeny. Received: 15 December 1997 / Accepted: 25 May 1998     

Fluid inclusion and stable isotope evidence for the genesis of quartz-scheelite veins, Metaggitsi area, central Chalkidiki Peninsula, N. Greece

Scheelite mineralization accompanied by muscovite and albite, and traces of Mo-stolzite and stolzite occurs in epigenetic quartz vein systems hosted by two-mica gneissic schists, and locally amphibolites, of the Paleozoic or older Vertiskos Formation, in the Metaggitsi area, central Chalkidiki, N Greece. Three types of primary fluid inclusions coexist in quartz and scheelite: type 1, the most abundant, consists of mixed H₂O-CO₂ inclusions with highly variable (20–90 vol.%) CO₂ contents and salinities between 0.2 and 8.3 equivalent weight % NaCl. Densities range from 0.79 to 0.99 g/cc; type 1 inclusions contain also traces (<2 mol%) of CH₄. Type 2 inclusions are nearly 100 vol.% liquid CO_2, with traces of CH₄, and densities between 0.75 and 0.88 g/cc. Type 3 inclusions, the least abundant, contain an aqueous liquid of low salinity (0.5 to 8.5 equivalent weight% NaCl) with 10–30 vol.% H₂O gas infrequently containing also small amounts of CO₂ (<2 mol%); densities range from 0.72 to 0.99 g/cc. The wide range of coexisting fluid inclusion compositions is interpreted as a result of fluid immiscibility during entrapment. Immiscibility is documented by the partitioning of CH₄ and CO₂, into gas-rich (CO₂-rich) type 1 inclusions, and the conformity of end-member compositions trapped in type 1 inclusions to chemical equilibrium fractionation at the minimum measured homogenization temperatures, and calculated homogenization pressures. Minimum measured homogenization temperatures of aqueous and gas-rich type 1 inclusions of 220°–250 °C, either to the H₂O, or to the CO₂ phase, is considered the best estimate of temperature of formation of the veins, and temperature of scheelite deposition. Corresponding fluid pressures were between 1.2 and 2.6 kbar. Oxygen fugacities during mineralization varied from 10⁻³⁵ to 10⁻³¹ bar and were slightly above the synthetic Ni-NiO buffer values. The fluid inclusion data combined with δ¹⁸O water values of 3 to 6 per mil (SMOW) and δ¹³C CO₂₋ fluid of −1.2 to +4.3 per mil (PDB), together with geologic data, indicate generation of mineralizing fluids primarily by late- to post-metamorphic devolatilization reactions. Received: 8 April 1997 / Accepted: 8 July 1997     

Contrasting evolution of low-P rare metal granites from two different terranes in the Hoggar area, Algeria

Two mineralogically different rare metal granites located in two distinct terranes from the Tuareg area are compared: the Tin-Amzi granite in the north of the Laouni Terrane and the Ebelekan granite in the Assodé–Issalane Terrane.The Tin-Amzi granite is enclosed within Eburnean granulitic gneisses, and consists of albite, quartz, protolithionite, K-feldspar and topaz granite (PG). The accessory minerals include columbite tantalite, U- and Hf-rich zircon, Th-uraninite, wolframoixiolite and wolframite. This facies is characterised by a mineralogical evolution from the bottom to the top underlined by a strong resorption of K-feldspar and albite and the crystalliK-feldspar of more abundant topaz and protolithionite II which is further altered in muscovite and Mn-siderite. It is underlain by an albite, K-feldspar, F-rich topaz, quartz and muscovite granite (MG), with W–Nb–Ta oxides, wolframite, Nb-rutile, zircon and scarce uranothorite as accessories.The Ebelekan granite intrudes into a coarse-grained biotite granite enclosed within upper amphibolite-facies metasediments. It comprises a zinnwaldite, albite, topaz porphyritic granite (ZG) with “snow ball” quartz and K-feldspar. The accessories are zircon, monazite, uranothorite, Ta bearing cassiterite, columbite tantalite and wodginite. It is capped by a banded aplite-pegmatite (AP).The geochemistry of Tin-Amzi and Ebelekan granites is nearly comparable. Both are peraluminous (A/CNK=1.10–1.29; ASI=1.17–1.31), sodolithic and fluorine rich with high SiO₂, Al₂O₃, Na₂O+K₂O, Rb, Ga, Li, Ta, Nb, Sn and low FeO, MgO, TiO₂, Ba, Sr, Y, Zr and REE contents. These rare metal Ta bearing granites belong to the P-poor subclass, relating to their P₂O₅ content ( 0.03–0.15 wt.%). Nevertheless, they are distinguished by their concentration of W, Sn and Ta. The Tin-Amzi granite is W–Ta bearing with high W/Sn ratio whereas the Ebelekan granite is Ta–Sn bearing with insignificant W content.At Tin-Amzi the W–Nb–Ta minerals define a sequence formed by W-columbite tantalite followed by wolframoixiolite and finally wolframite showing the effect of hydrothermal overprinting with an extreme W enrichment of the fluids. At Ebelekan, the Sn–Nb–Ta oxides follow a Mn sequence: manganocolumbite→manganotantalite→wodginite+titanowodginite→cassiterite that represents a trend of primary crystallisation resulting from progressive substitution Fe→Mn and Nb→Ta during the magmatic fractionation.     

A fluid inclusion and stable isotope study of 200 Ma of fluid evolution in the Galway Granite, Connemara, Ireland

Fluid inclusions in granite quartz and three generations of veins indicate that three fluids have affected the Caledonian Galway Granite. These fluids were examined by petrography, microthermometry, chlorite thermometry, fluid chemistry and stable isotope studies. The earliest fluid was a H₂O-CO₂-NaCl fluid of moderate salinity (4–10 wt% NaCl eq.) that deposited late-magmatic molybdenite mineralised quartz veins (V₁) and formed the earliest secondary inclusions in granite quartz. This fluid is more abundant in the west of the batholith, corresponding to a decrease in emplacement depth. Within veins, and to the east, this fluid was trapped homogeneously, but in granite quartz in the west it unmixed at 305–390 °C and 0.7–1.8 kbar. Homogeneous quartz δ¹⁸O across the batholith (9.5 ± 0.4‰n = 12) suggests V₁ precipitation at high temperatures (perhaps 600 °C) and pressures (1–3 kbar) from magmatic fluids. Microthermometric data for V₁ indicate lower temperatures, suggesting inclusion volumes re-equilibrated during cooling. The second fluid was a H₂O-NaCl-KCl, low-moderate salinity (0–10 wt% NaCl eq.), moderate temperature (270–340 °C), high δD (−18 ± 2‰), low δ¹⁸O (0.5–2.0‰) fluid of meteoric origin. This fluid penetrated the batholith via quartz veins (V₂) which infill faults active during post-consolidation uplift of the batholith. It forms the most common inclusion type in granite quartz throughout the batholith and is responsible for widespread retrograde alteration involving chloritization of biotite and hornblende, sericitization and saussuritization of plagioclase, and reddening of K-feldspar. The salinity was generated by fluid-rock interactions within the granite. Within granite quartz this fluid was trapped at 0.5–2.3 kbar, having become overpressured. This fluid probably infiltrated the Granite in a meteoric-convection system during cooling after intrusion, but a later age cannot be ruled out. The final fluid to enter the Granite and its host rocks was a H₂O-NaCl-CaCl₂-KCl fluid with variable salinity (8–28 wt% NaCl eq.), temperature (125–205 °C), δD (−17 to −45‰), δ¹⁸O (−3 to + 1.2‰), δ¹³C_CO2 (−19 to 0‰) and δ³⁴S_sulphate (13–23‰) that deposited veins containing quartz, fluorite, calcite, barite, galena, chalcopyrite sphalerite and pyrite (V₃). Correlations of salinity, temperature, δD and δ¹⁸O are interpreted as the result of mixing of two fluid end-members, one a high-δD (−17 to −8‰), moderate-δ¹⁸O (1.2–2.5‰), high-δ¹³C_CO2 (> −4‰), low-δ³⁴S_sulphate (13‰), high-temperature (205–230 °C), moderate-salinity (8–12 wt% NaCl eq.) fluid, the other a low-δD (−61 to −45‰), low-δ¹⁸O (−5.4 to −3‰), low-δ¹³C (<−10‰), high-δ³⁴S_sulphate (20–23‰) low-temperature (80–125 °C), high-salinity (21–28 wt% NaCl eq.) fluid. Geochronological evidence suggests V₃ veins are late Triassic; the high-δD end-member is interpreted as a contemporaneous surface fluid, probably mixed meteoric water and evaporated seawater and/or dissolved evaporites, whereas the low-δD end-member is interpreted as a basinal brine derived from the adjacent Carboniferous sequence. This study demonstrates that the Galway Granite was a locus for repeated fluid events for a variety of reasons; from expulsion of magmatic fluids during the final stages of crystallisation, through a meteoric convection system, probably driven by waning magmatic heat, to much later mineralisation, concentrated in its vicinity due to thermal, tectonic and compositional properties of granite batholiths which encourage mineralisation long after magmatic heat has abated. Received: 3 April 1996 / Accepted: 5 May 1997     

Kinetic Modeling of Diagenesis of Eogene Lacustrine Sandstone Reservoirs in the Jianghan Basin,Southeastern China

In the Tuoshi oilfield,located in the Cenozoic Jianghan Basin of southeastern China ,there have been found hydrocarbon reservoirs hosted in lacustrine sandstones of the Eogene Xingouzui Formation.The main diagenetic features identified in these sandstones include the dissolution of detrital K-feldspar and albite grains,the precipitation of quartz as overgrowths and /or cements ,and the precipitation and /or transformation of clay minerals.These diagenetic features were interpreted to have occurred in early,intermediate and late stages,based on the burial depth.The kinetics of fluid-mineral reactions and the concentrations of aqueous species au each stage of diagenesis were simulated numerically for these lacustrine sandstones,using a quasi-sta-tionary state approximation that incorporates simultaneous chemical reactions in a time-space continuum.During the early diagenetic stage,pore fluid was weakly acidic,which resulted in dissolution of K-feldspar and albite and,therefore,led to the release of K^ ,Na^ ,Al^3 and SiO2(aq) into the diagenetic fluid.The increased K^ ,Na^ ,Al^3 and SiO2(aq) concentrations in the diagenetic fluid caused the precipitation of quartz,kaolinite and illite.At the beginning of the intermediate diagenetic stage the concentration of H^ was built up due to the decomposition of organic matter,which was responsible for further dissolution of K-feldspar and albite and pre-cipitation of quartz,kaolinite,and illite.During the late diagenetic stage,the pore fluid was weakly alkaline,K-feldspar became stable and was precipitated with quartz and clay minerals.When the burial depth was greater than 3000 m,the pore fluids became supersaturated with respect to allbite,but undersaturated with respect to quartz,resulting in the precipitation of albite and the dissolution of quartz.The diagenetic reactions forecasted in the numerical modeling closely matched the diagenet-ic features identified by petrographic examination, and therefore,can help us to gain a better understanding of the diagenetic processes and associated porosity evolution in sandstone reservoirs.     

Geochemistry and mineralization age of magnesian skarn-type iron deposits of the Janggun mine, Republic of Korea

The Janggun iron deposits, Republic of␣Korea, occur as lens-shaped magnesian skarn, magnetite and base-metal sulfide orebodies developed in the Cambrian Janggun Limestone Formation. Mineralization stage of the deposits can be divided into two separate events. The skarn stage (107 Ma) consists of magnetite, pyrrhotite, base-metal sulfides, carbonates and magnesian skarn minerals. The hydrothermal stage (70 Ma) consists of base-metal sulfides, native bismuth, bismuthinite, tetrahedrite, boulangerite, bournonite and stannite. Mineral assemblages, chemical compositions and thermodynamic considerations indicate that formation temperatures, −log fs₂ and −log fo₂ values of ore fluids from the skarn stage were 433 to 345 °C, 8.1 to 9.7 bar and 29.4 to 31.6 bar, and the hydrothermal stage was 245 to 315 °C, 10.4 to 13.2 bar and 33.6 to 35.4 bar, respectively. Thermochemical considerations indicate that the XCO₂ during magnesian skarnization ranged from 0.06 to 0.09, and the activity of H⁺ presumably decreased when the fluids equilibrated with host dolomitic limestone which resulted in a pH change from about 6.1 to 7.8, and decreases in fo₂ and fs₂. The δ³⁴S values of ore sulfides have a wide range from 3.2 to 11.6 ‰ (CDT). Calculated ³⁴SH_{2 S} values of ore fluids are 2.9 to 5.4 ‰ (skarn stage) and 8.7 to 13.5 ‰ (hydrothermal stage). These are interpreted to represent an initial deep-seated, igneous source of sulfur which gave way to influence of oxidized sedimentary sulfur to hydrothermal stage. The δ¹³C values of carbonates in ores range from −4.6 to −2.5 ‰ (PDB). It is likely that carbon in the ore fluids was a mixture of deep-seated magmatic carbon and dissolved carbon of dolomitic limestone. The δ¹⁸OH_{2 O} and δD values (SMOW) of water in the ore fluids were 14.7 to 1.8 and −85 to −73 ‰ during the skarn stage and 11.1 to −0.2 and −87 to −80 ‰ in the hydrothermal stage. Received: 5 March 1997 / Accepted: 28 August 1997     

Experimental investigation of H2O and Cl− solubilities in F-enriched silicate liquids; implications for volatile saturation of topaz rhyolite magmas

To interpret the degassing of F-bearing felsic magmas, the solubilities of H₂O, NaCl, and KCl in topaz rhyolite liquids have been investigated experimentally at 2000, 500, and ≈1 bar and 700° to 975 °C. Chloride solubility in these liquids increases with decreasing H₂O activity, increasing pressure, increasing F content of the liquid from 0.2 to 1.2 wt% F, and increasing the molar ratio of ((Al + Na + Ca + Mg)/Si). Small quantities of Cl⁻ exert a strong influence on the exsolution of magmatic volatile phases (MVPs) from F-bearing topaz rhyolite melts at shallow crustal pressures. Water- and chloride-bearing volatile phases, such as vapor, brine, or fluid, exsolve from F-enriched silicate liquids containing as little as 1 wt% H₂O and 0.2 to 0.6 wt% Cl at 2000 bar compared with 5 to 6 wt% H₂O required for volatile phase exsolution in chloride-free liquids. The maximum solubility of Cl⁻ in H₂O-poor silicate liquids at 500 and 2000 bar is not related to the maximum solubility of H₂O in chloride-poor liquids by simple linear and negative relationships; there are strong positive deviations from ideality in the activities of each volatile in both the silicate liquid and the MVP(s). Plots of H₂O versus Cl⁻ in rhyolite liquids, for experiments conducted at 500 bar and 910°–930 °C, show a distinct 90° break-in-slope pattern that is indicative of coexisting vapor and brine under closed-system conditions. The presence of two MVPs buffers the H₂O and Cl⁻ concentrations of the silicate liquids. Comparison of these experimentally-determined volatile solubilities with the pre-eruptive H₂O and Cl⁻ concentrations of five North American topaz and tin rhyolite melts, determined from melt inclusion compositions, provides evidence for the exsolution of MVPs from felsic magmas. One of these, the Cerro el Lobo magma, appears to have exsolved alkali chloride-bearing vapor plus brine or a single supercritical fluid phase prior to entrapment of the melt inclusions and prior to eruption. Received: 6 November 1995 / Accepted: 29 January 1998