Evidence of magmatic CO2-rich fluids in peraluminous graphite-bearing leucogranites from Deep Freeze Range (northern Victoria Land,Antarctica)

Fine-grained peraluminous synkinematic leuco-monzogranites (SKG), of Cambro-Ordovician age, occur as veins and sills (up to 20–30 m thick) in the Deep Freeze Range, within the medium to high-grade metamorphics of the Wilson Terrane. Secondary fibrolite + graphite intergrowths occur in feldspars and subordinately in quartz. Four main solid and fluid inclusion populations are observed: primary mixed CO₂+H₂O inclusions + Al₂SiO₅ ± brines in garnet (type 1); early CO₂-rich inclusions (± brines) in quartz (type 2); early CO₂+CH₄ (up to 4 mol%)±H₂O inclusions + graphite + fibrolite in quartz (type 3); late CH₄+CO₂+N₂ inclusions and H₂O inclusions in quartz (type 4). Densities of type 1 inclusions are consistent with the crystallization conditions of SKG (750°C and 3 kbar). The other types are post-magmatic: densities of type 2 and 3 inclusions suggest isobaric cooling at high temperature (700–550°C). Type 4 inclusions were trapped below 500°C. The SKG crystallized from a magma that was at some stage vapour-saturated; fluids were CO₂-rich, possibly with immiscible brines. CO₂-rich fluids (±brines) characterize the transition from magmatic to post-magmatic stages; progressive isobaric cooling (T<670°C) led to a continuous decrease off _{O 2} can entering in the graphite stability field; at the same time, the feldspars reacted with CO₂-rich fluids to give secondary fibrolite + graphite. Decrease ofT andf _{O 2} can explain the progressive variation in the fluid composition from CO₂-rich to CH₄ and water dominated in a closed system (in situ evolution). The presence of N₂ the late stages indicates interaction with external metamorphic fluids.Contribution within the network Hydrothermal/metamorphic water-rock interactions in crystalline rocks: a multidisciplinary approach on paleofluid analysis. CEC program: Human Capital and Mobility     

Post-metamorphic CO2-rich fluid inclusions in granulites

In granulite-facies samples from the Adirondack Mountains, NY, estimates of peak-metamorphic CO₂ fugacities based on mineral equilibria are not consistent with estimates based on data for high-density, CO₂-rich fluid inclusions. Of the 21 Adirondack samples investigated for this study, all contain CO₂-rich inclusions. Inclusions occur in quartz, apatite, and garnet. They range in size from 3 to 50 m and are without visible H₂O. In a few of the inclusions, freezing point determinations and preliminary Laser Raman spectroscopy show the presence of small amounts (<3%) of other fluids (N₂ and H₂S). CO₂ liquid-vapor homogenization temperatures are between –46 and +31° C, corresponding to densities between 1.14 and 0.5 gm/cc. Some of these densities are consistent with peak-metamorphic entrapment (1.06 to 1.1 gm/cc).Peak metamorphic fluid compositions in these samples are inferred from fluid-buffering equilibria that restrict the fugacity of CO₂ (f CO₂) directly (i.e., calcite+quartz+wollastonite) or buffer the fugacity of oxygen (f O₂). Assemblages that bufferf O₂ are important because knowledge off O₂ places an upper limit onf CO₂. In 13 of the 21 samples, estimates of peak-metamorphic fluid compositions based on these equilibria show that the mole fraction of CO₂ (XCO₂) in equilibrium with the rock was low, in some cases less than 0.2.The contradiction of mineral equilibria and fluid inclusion data shows that the inclusions record post-metamorphic conditions. At present, there are no criteria to distinguish these primary appearing CO₂-rich inclusions from those found in other granulite-facies terranes. Therefore, inferences of pressure-temperature conditions and peakmetamorphic fluid compositions based on fluid inclusions must be viewed with caution.     

Experiments on the phase transition calcite+wollastonite+ +epidote=grossular-andraditess+CO2+H2O

The reaction 2 epidote+2 calcite+3 wollastonite3 grossular-andradite_ss+ 2 CO₂+1 H₂O has been explored by hydrothermal experiments at a total fluid pressure of 1000 bars. For a grossular-andradite_ss of andradite ₂₅ composition, the isobaric univariant curve passes through the points 458°C: X_CO2=0.00; 521°C: X_CO2=0.026; 523°C: X_CO2=0.052; 526°C: 0.088; 528°C: X_CO2=0.104. This curve intersects the isobaric univariant curve of the reaction calcite+quartz+[H₂O] wollastonite+CO₂+[H₂O] at the isobaric invariant point around 528°C and X_CO2=0.12. At higher values of X_CO2, this reaction is replaced by another one, namely: 2 epidote+5 calcite+3 quartz3 grossular-andradite_ss+5 CO₂+ 1 H₂O. It is demonstrated that both the reactions do actually take place during the metamorphism of calcareous rocks. The petrologic significance of contrasted sequence of reactions within this system observed by various workers is also discussed.     

High-density CO2 inclusions in the Colorado Front Range

A fluid density in an inclusion is commonly observed to be too low for the P-T estimates for the postulated time of trapping, and is generally attributed to a fluid loss during the uplift process. It is more difficult to explain a fluid density which is too high. In the 1700 m.y. Front Range migmatites, such high densities occur in some of CO₂ inclusions which were deduced to have formed during the migmatization episode. The peak P-T estimates for migmatization in the Front Range are 4–6 kb and 650°–700° C (in sillimanite field) but pressures required to form the most dense inclusions are >7.6 kb (in kyanite field). The high density is not likely to be a relic of a higher pressure condition earlier than the main migmatization episode for the following reasons: (a) no kyanite (or any other relic high pressure phase) has been found in the Precambrian Front Range; (b) the high density inclusions are rare in zones with least signs of deformation and melting (paleosomes and quartz inclusions within feldspar grains) which instead contain relatively undisturbed early inclusions; (c) high density inclusions with Th <–30° C are associated with heavily altered plagioclase caused by hydrothermal activity which was a late event in leucosome formation. Further, there is evidence for post-entrapment change(s) in density: an intragranular trail in quartz contains CO₂ inclusions that exhibit almost the whole range in Th (–40 to +24° C) as displayed by the entire population of the early CO₂ inclusions (–66 to +30° C). The density of an inclusion in the trail is not related to inclusion size but to the position of the inclusion relative to apparent micro-shear zones crossing the CO₂ trail. A change to a higher density (=a smaller volume) could have resulted from an initially isobaric cooling path which intersects CO₂ isochores with increasingly higher densities. Additional excess pressure may have resulted from overthrusting. However, because high density inclusions occur selectively in the zones in which plagioclase shows alteration indicating a high and because there is a correlation between shear zones and high density inclusions, it is postulated that local hydrolytic weakening of quartz was necessary for the decrease of inclusion volume which occurred during deformation. The localized deformation may also result in an excess pressure. However, the introduction of a small amount of H₂O into these inclusions as a possible cause of high density inclusions cannot be ruled out.     

Geological,fluid inclusion and stable isotope studies of Mo mineralization,Galway Granite,Ireland

Mo mineralization within the Galway Granite at Mace Head and Murvey, Connemara, western Ireland, has many features of classic porphyry Mo deposits including a chemically evolved I-type granite host, associated K- and Si-rich alteration, quartz vein(Mace Head) and granite-hosted (Murvey) molybdenite, chalcopyrite, pyrite and magnetite mineralization and a gangue assemblage which includes quartz, muscovite and K-feldspar. Most fluid inclusions in quartz veins homogenize in the range 100–350°C and have a salinity of 1–13 eq. wt.% NaCl. They display Th-salinity covariation consistent with a hypothesis of dilution of magmatic water by influx of meteoric water. CO₂-bearing inclusions in an intensely mineralized vein at Mace Head provide an estimated minimum trapping temperature and pressure for the mineralizing fluid of 355°C and 1.2 kb and are interpreted to represent a H₂O-CO₂ fluid, weakly enriched in Mo, produced in a magma chamber by decompression-activated unmixing from a dense Mo-bearing NaCl-H₂O-CO₂ fluid. ³⁴S values of most sulphides range from c. 0 at Murvey to 3–4 at Mace Head and are consistent with a magmatic origin. Most quartz vein samples have ¹⁸O of 9–10.3 and were precipitated from a hydrothermal fluid with ¹⁸O of 4.6–6.7. Some have ¹⁸O of 6–7 and reflect introduction of meteoric water along vein margins. Quartz-muscovite oxygen isotope geothermometry combined with fluid inclusion data indicate precipitation of mineralized veins in the temperature range 360–450°C and between 1 and 2 kb. Whole rock granite samples display a clear ¹⁸O-D trend towards the composition of Connemara meteoric waters. The mineralization is interpreted as having been produced by highlyfractionated granite magma; meteoric water interaction postdates the main mineralizing event. The differences between the Mace Head and Murvey mineralizations reflect trapping of migrating mineralizing fluid in structural traps at Mace Head and precipitation of mineralization in the granite itself at Murvey.     

Magmatic CO2 and saline melts from the Sybille Monzosyenite,Laramie Anorthosite Complex,Wyoming

There are three populations of fluid inclusions in quartz from the Sybille Monzosyenite: early CO₂, secondary CO₂, and rare secondary brines. The oldest consist of low density CO₂ (0.70) inclusions that appear to be co-magmatic. The densities of these inclusions are consistent with the inferred crystallization conditions of the Sybille Monzosyenite, namely 3 kilobars and 950–1000° C. The other types of inclusions are secondary; they contain CO₂ (0.50) and secondary brine inclusions that form trains radiating out from a decrepitated inclusion. The sites of these decrepitated inclusions are now marked by irregularly shaped fluid inclusions and solid inclusions of salt and carbonate. Rather than fluid inclusions, feldspar contain abundant solid inclusions. These consist of magmatic minerals, hedenbergite, hornblende, ilmenite, apatite, and graphite, intimately associated with K, Na chlorides. We interpret these relations as follows: The Sybille Monzosyenite formed from a magma that contained immiscible droplets of a halide-rich melt along with a CO₂ vapor phase. The salt was trapped along with the other obvious magmatic minerals during growth of the feldspars. CO₂ may have also been included in the feldspars but it probably leaked later during exsolution of the feldspars and was not preserved. Both the saline melt and the CO₂ vapor were trapped in the quartz. The melt inclusions in the quartz later decrepitated, perhaps due to progressive exsolution of fluids, to produce the secondary H₂O and CO₂ inclusions. These observations indicate that the Sybille Monzosyenite, which is a markedly anhydrous rock, was actually vapor-saturated. Rather than being H₂O, however, the vapor was CO₂-rich and possibly related to an immiscible chloride-rich melt.     

Stable isotope and fluid inclusion studies of gem-bearing granitic pegmatite-aplite dikes,San Diego Co., California

Late Cretaceous, granitic pegmatite-aplite dikes in southern California have been known for gem-quality minerals and as a commercial source of lithium. Minerals, whole-rock samples, and inclusion fluids from nine of these dikes and from associated wall rocks have been analyzed for their oxygen, hydrogen, and carbon isotope compositions to ascertain the origins and thermal histories of the dikes. Oxygen isotope geothermometry used in combination with thermometric data from primary fluid inclusions enabled the determination of the pressure regime during crystallization.Two groups of dikes are evident from their oxygen isotope compositions (¹⁸O_qtz+10.5 in Group A, and +8.5 in Group B). Prior to the end of crystallization, Group A pegmatites had already extensively exchanged oxygen with their wall rocks, while Group B dikes may represent a closer approximation to the original isotopic composition of the pegmatite melts. Oxygen isotope fractionations between minerals are similar in all dikes and indicate that the pegmatites were emplaced at temperatures of about 730 ° to 700 ° C. Supersolidus crystallization began with the basal aplite zone and ended with formation of quench aplite in the pocket zone, nearly to 565 ° C. Subsolidus formation of gem-bearing pockets took place over a relatively narrow temperature range of about 40 ° C (approximately 565–525 ° C). Nearly closed-system crystallization is indicated.Hornblende in gabbroic and noritic wall rocks (D_w.r. = –90 to –130) in the Mesa Grande district crystallized in the presence of, or exchanged hydrogen with, meteoric water (D –90) prior to the emplacement of the pegmatite dikes. Magmatic water was subsequently added to the wall rocks adjacent to the pegmatites.Groups A and B pegmatites cannot be distinguished on the basis of their hydrogen isotope compositions. A decrease in D of muscovite inward from the walls of the dikes reflects a decrease in temperature. D values of H₂O from fluid inclusions are: –50 to –73 (aplite and pegmatite zones); –62 to –75 (pocket quartz: Tourmaline Queen and Stewart dikes); and –50 ± 4 (pocket quartz from many dikes). The average ¹³C of juvenile CO₂ in fluid inclusions in Group B pegmatites is –7.9. In Group A pegmatities, ¹³C of CO₂ is more negative (–10 to –15.6), due to exchange of C with wall rocks and/or loss of ¹³C-enriched CO₂ to an exsolving vapor phase.Pressures during crystallization of the pockets were on the order of 2,100 bars, and may have increased slightly during pocket growth. A depth of formation of at least 6.8 km (sp. gr. of over burden = 3.0, and P _fiuid=P _load) is indicated, and a rate of uplift of 0.07 cm/yr. follows from available geochronologic data.     

Fluid inclusions in charnockites from the Bjerkreim-Sokndal massif (Rogaland,southwestern Norway): fluid origin and in situ evolution

Fluid inclusions and mineral associations were studied in late-stage charnockitic granites from the Bjerkreim-Sokndal lopolith (Rogaland anorthosite province). Because the magmatic and tectonic evolutions of this complex appear to be relatively simple, these rocks are a suitable case for investigation of the origin and evolution of granulitic fluids. Fluid inclusions, primarily contained in quartz, can be divided into four types: carbonic (type I), N₂-bearing (type II), CO₂+H₂O (type III) and aqueous inclusions (type IV). For each type, the role of leakage and fluid mixing are discussed from microthermometric and Raman spectrometric data. The most striking features of CO₂-rich inclusions (the predominant fluid) is the presence of graphite in numerous, trail-bound inclusions (Ib) and its absence in a few isolated, very dense (d=1.16), pure CO₂ inclusions (Ia) and in the late carbonic inclusions (Ic). Fluid chronology and mineral assemblages suggest that carbonic Ia inclusions represent the first fluid (pure CO₂) trapped at or close to magmatic conditions (T=780–830° C, fO₂=10^-15 atm and P=7.4±1 kb), outside the graphite stability field. In contrast, type Ib inclusions enclosed graphite particles from a channelized fluid during retrograde rock evolution (P=3–4 kb and T=600° C). Decreases in T-fO₂ could explain a progressive evolution from a CO₂-rich fluid to an H₂O-rich fluid in a closed C–O–H system. However, graphite destabilization observed in type Ic inclusions implies some late introduction of external water during the last stage of retrogression. The main results of this study are the following: (1) a carbonic fluid was present in an early stage of rock evolution (probably in the charnockitic magma) and (2) this granulite occurrence offers good evidence of crossing the graphite stability field during post-magmatic evolution.     

Granulite facies amphibole and biotite equilibria,and calculated peak-metamorphic water activities

Samples located near the Oregon Dome anorthosite massif in the south-central Adirondack Mountains, New York contain the fluid-buffering mineral assemblages: amphibole + clinopyroxene + orthopyroxene + quartz or biotite + quartz + orthopyroxene + K-feldspar. These rocks were metamorphosed under granulite-facies conditions (T=725°–750°C, P=7.5 kbar) during the Grenville orogeny. The Mg-rich nature of amphiboles, micas, and pyroxenes allow accurate calculation of water activities because corrections for the effects of solid solution are relatively small. The activity of water was low during the peak of granulite-facies metamorphism, with H₂O0.15±0.14. Wollastonite occurrences indicate that the CO₂ was low (<0.3) in nearby rocks, demonstrating that large quantities of CO₂ did not infiltrate in a pervasive manner. The combination of low H₂O with low CO₂ is consistent with the hypothesis that magmatic processes were dominant, generating dry, fluid-absent conditions.Abbreviations fi Fugacity of species i in a fluid - Xi mole fraction of component i in a phase - T temperature - P lithostatic pressure - P _F fluid pressure - _i ^x activity of component i phase X     

Synthesis and stability relations of wairakite,CaAl2 Si4 O12·2H2O

Hydrothermal investigation of the bulk composition CaO·Al₂O₃·4SiO₂ + excess H₂O has been conducted using conventional techniques over the temperature range 200–500° C and 500–5,000 bars P _fluid. The fully ordered wairakite was synthesized unequivocally in the laboratory, probably for the first time.The gradual, sluggish and continuous transformation from disordered to ordered wairakite evidently accounts for failure by previous investigators to synthesize ordered wairakite in runs of week-long duration. The dehydration of metastable disordered wairakite to metastable hexagonal anorthite, quartz and H₂O has been determined; this reaction takes place at temperatures exceeding 400° C, even at fluid pressures of 500 bars or less. The upper P _fluid-T boundary of the disordered phase is equivalent to the maximum temperature curve of synthetic wairakite presented by previous investigators. The hydrothermal breakdown of natural wairakite above its stability limit appears to be a very slow process.The equilibrium dehydration of wairakite to anorthite, quartz and H₂O occurs at 330±5° C at 500 bars, 348±5° C at 1,000 bars, 372±5° C at 2,000 bars and 385±5° C at 3,000 bars. Where fluid pressure equals total pressure, the thermal stability range of wairakite is about 100° C wide. At lower temperatures wairakite reacts with H₂O to form laumontite. Reconnaissance experiments dealing with the effect of CO₂ on stabilities of calcium zeolites suggest that wairakite or laumontite may be replaced by the assemblage calcite + montmorillonite in the presence of a CO₂-bearing fluid phase.The determined P _fluid -T field of wairakite is compatible with field observations in some metamorphic terrains where it is related to the shallow emplacement of granitic magma and with direct pressure-temperature measurements in certain active geothermal areas. Under inferred conditions of higher _CO2/_H2O ratios, essentially unmetamorphosed rocks grade directly into those characteristic of the greenschist facies; moderately high values of _CO2 in carbonate-bearing rocks result in the downgrade extension of the greenschist facies at the expense of zeolite-bearing assemblages.     

The Rosita Hills epithermal Ag-Base metal deposits, Colorado, USA A stable isotope and fluid inclusion study

The Rosita Hills volcanic centre is an alkalicalcic, mid-Tertiary complex overlying orthoand paragneissic basement, on the eastern margin of the Rio Grande Rift in south central Colorado, USA. The centre contains vein-hosted, adularia-sericite type, epithermal Ag and base-metal mineralisation with minor Au. Stable isotope studies (O and H) of whole rock and mineral separate (quartz and sericite) samples from veins and hydrothermal eruption breccias show that the hydrothermal fluid had both magmatic and meteoric components. The D and ¹⁸O values of the hydrothermal fluid, calculated from mineral values, range from -22 to -103 and 0.5 to 5.9 respectively. Fluid inclusion data from vein minerals (quartz, baryte and sphalerite) and from an advanced argillic lithocap overlying the veins again show that the hydrothermal system had more than one component fluid. Fluid inclusions have salinities which range from 1.7 to 25.1 wt% NaCl equivalent and show evidence of boiling in the advanced argillic lithocap. Homogenisation temperatures range from 135°C to 298°C. Liquid CO₂ is present in some inclusions. These data indicate that a saline, isotopically heavy fluid mixed with a dilute, isotopically light fluid to precipitate the ore. We argue that the saline, isotopically heavy fluid is magmatic and derived from a resurgent rhyolitic magma below the mineralisation.     

La rétromorphose du talc dans les dolomies métallifères de Boukdema (Algérie); discussion du rôle des fluides

Résumé Les échantillons étudiés proviennent du gîte stratiforme de Boukdema (Algérie), où l'on observe notamment l'association dolomite-quartz-talcsphalérite. L'étude des inclusions fluides primaires des quartz contemporains, selon toute vraisemblance, de la dissolution partielle du talc, montre que ceux-ci se sont développés dans des solutions de salinités très variables (entre 4 et 28% en équivalent pondéral NaCl). L'hypothèse d'une ébullition des solutions (par suite d'une chute brutale de pression) rend compte de ce fait inhabituel. Dans le cadre d'un tel modèle, les corrections dues à la pression sont nulles et l'on peut en déduire à partir des mesures de températures d'homogénéïsation que la croissance du quartz s'est amorcée vers 250 °C. Compte tenu de cette indication thermométrique, on discute enfin du rôle relatif des facteurs physiques et chimiques (T, f_{CO 2}, a_Mg/a_Ca) sur la stabilité du talc dans le contexte minéralogique du gîte de Boukdema.

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The samples studied were collected in the Boukdema stratabound deposit (Algeria), where the association dolomite-quartz-talc-sphalerite occurs. Cryoscopic investigations of fluid inclusions in quartz indicate a wide salinity range in mineral forming fluids (4 to 28 weight % NaCl eq). Boiling of hydrothermal fluids possibly explains this unusual characteristic. In this hypothesis thermometric data need no pressure corrections and one may conclude that quartz growth (and simultaneously talc dissolution) occurred in the 250°–200 °C range. On the basis of this last indication, the relative role of T, f_{CO 2}, a_Mg/a_Ca, on talc stability is discussed in the mineralogical environment of Boukdema.

     

Retrograde evolution of quartz segregations from the Dos Picos shear zone in the Nevado-Filabride Complex (Betic chains,Spain). Evidence from fluid inclusions and quartz c-axis fabrics

Synkinematic quartz veins are ubiquitous in the shear zone separating the Veleta unit from the Calar Alto unit in the internal part of the Betic Cordilleras. They have been studied with respect to quartz c-axis fabrics, microstructures and fluid inclusions. Veins were probably generated during syn-metamorphic stacking of the units at P = 500 – 600 MPa and T = 400 – 500°C. Quartz displays two groups of microstructures in the shear zone: (1) older coarse-grained mosaics (CGM) resulting from exaggerated grain growth; and (2) younger fine-grained mosaics (FGM) developed at the expense of the former. The fine-grained mosaics show polygonal granoblastic and elongate mosaic microstructures in general, with ribbon microstructures often found near the boundary of the units. Fluids contained in secondary inclusions vary from high salinity brines to different types of CO₂—brine mixtures and low density CO₂ fluids. Differences in composition and P-T trapping conditions are indicated for the different types of inclusions. Some fluid inclusions are older than the FGM, whereas others are younger, thus constraining the P- T conditions at which the two microstructural events took place. Fluid inclusion evidence suggests conditions of P_fluid > 170 MPa and T 370–430°C for the CGM and P_fluid 20–80 MPa and T > 340°C for the FGM.The quartz c-axis fabrics dealt with here correspond to the second recrystallization event, as little evidence of older fabrics is preserved in the shear zone. C-axis patterns vary across the shear zone from slightly asymmetrical type I crossed girdles in the hanging wall and footwall to more asymmetrical crossed girdles at the boundary of the units. This indicates a correlative increase in the magnitude of the heterogeneous shear strain in the same direction. Most of the deformation is concentrated at the top of the Veleta unit. The sense of movement is top to the west, in agreement with other kinematic markers.The quartz c-axis fabrics resulted from dynamic recrystallization during simple shear. The retrograde P-T path inferred from fluid inclusion analysis, along with other geological and geochronological evidence, indicates that this deformation is coeval with a reduction in the crustal overburden.Geochronological and stratigraphic data show that the proposed Dos Picos extensional detachment, separating the Calar Alto and Veleta units, took place during the early Miocene, synchronous with the intense thinning of the Nevado-Filábride Complex and of the whole continental crust underlying the Alborán Basin.     

High-density CO2−N2 inclusions in eclogite-facies metasediments of the Münchberg gneiss complex,SE Germany

The eclogite-facies metasedimentary rocks in the Münchberg gneiss complex (T=630±30° C/P17–24 kbar) locally contain CO₂–N₂-rich fluid inclusions of extremely low molar volumes (32 cm³/mol) in quartz. These fluid compositions are mainly found in rocks intercalated with calcsilicate bands. Densities were determined from low-temperature phase transitions like stable or metastable homogenization (L+VL), partial homogenization (S+L+VS+L) and the transition S+LL (L = liquid, V = vapour, S = solid). The high fluid densities are in agreement with eclogite-facies pressure and temperature and subsequent amphibolite facies. CO₂–N₂ inclusions were not observed in adjacent eclogites nor in non-calcareous metasediments. These rock types contain predominantly H₂O-rich inclusions correlating with amphibolite-facies conditions. The variation of fluid composition with lithological differences indicates local fluid gradients and speaks against a pervasive fluid flow during eclogite-facies metamorphism.     

Fluid inclusions in granulite-facies metapelites of the Hercynian ancient lower crust of the Serre,Calabria, Southern Italy

Investigations of fluid inclusions in granulitefacies metapelites of southern Calabria enable characterization of the fluid composition of these lower crustal rocks, and constrain the petrologically deduced retrograde P-T path characterized by isothermal uplift prior to isobaric cooling in middle crustal levels. Fluid inclusions in cordierite, garnet and sillimanite have a CO₂-rich composition. Inclusions in cordierite rarely contain minor amounts of N₂ and H₂O, and in garnets some CO₂–CH₄–N₂ inclusions have been analyzed by Raman microprobe. Quartz reveals the most complex fluid melusion compositions (1) CO₂-rich, (2) CO₂–CH₄–N₂, (3) CH₄–N₂, (4) H₂O–MgCl₂–CaCl₂–NaCl, (5) H₂O–NaCl and (6) H₂O–CO₂. The earliest fluid inclusions after peak metamorphism are rich in CO₂ with minor amounts of N₂ and H₂O. An early CO₂–(H₂O–N₂) fluid composition has been confirmed by detection of CO₂, H₂O and N₂ in the channels of the cordierite structure. Most of the early CO₂-rich fluid inclusions were modified during the uplift from the lower to the middle crustal level, resulting in a density decrease with CO₂ still dominant. The subsequent isobaric cooling led to further modifications of the fluid inclusions. High-density inclusions around implosion textures or scattered amongst lower-density ones must have formed during this cooling episode. Aqueous inclusions in quartz are mostly formed late and are consistent with trapping during retrograde rehydration.This project has been supported by the DFG as contribution to the special program Continental Lower Crust     

Genesis of the Sb-W-Au deposits at Ixtahuacan,Guatemala: evidence from fluid inclusions and stable isotopes

The Ixtahuacan Sb-W deposits are hosted by upper Pennsylvanian to Permian metasedimentary rocks of the central Cordillera of Guatemala. The deposits consist of gold-bearing arsenopyrite, stibnite and scheelite. Arsenopyrite and scheelite are early in the paragenesis, occurring as disseminations in pyritiferous black shale/sandstone and in argillaceous limestone, respectively. Some stibnite is disseminated, but the bulk of the stibnite occurs as massive stratabound lenses in black shales and in quartz-ankerite veins and breccias, locally containing scheelite.Microthermometric measurements on fluid inclusions in quartz and scheelite point to a low temperature (160–190°C) and low to moderate salinity (5–15 wt% NaCl eq.) aqueous ore fluid. Abundant vapour-rich inclusions suggest that the fluid boiled. Carbon dioxide was produced locally as a result of interaction of the aqueous fluid with the argillaceous limestone. Bulk leaching experiments and SEM-EDS analyses of decrepitated fluid inclusion residues indicate that the ore-bearing solution was NaCl-dominated. The ¹⁸O values of quartz, ankerite and scheelite from mineralized veins range from 19.7 to 20.5, 18.1 to 20.0 and 7.0 to 8.4 respectively. The average temperature calculated from quartz-scheelite oxygen isotopic fractionation is 170°C. The oxygen isotopic composition of the fluid, interpreted to have been in equilibrium with these minerals, ranged from 5.7 to 7.6, and is considered to represent an evolved meteoric water. Diagenetic or syngenetic pyrite has a sulphur isotopic composition of 0.5±0.3 which is consistent with bacterial reduction of sulphate. The ³⁴S values of arsenopyrite and stibnite range from –2.8 to 2.0 and –2.7 to –2.3 respectively, and are though to reflect sulphur derived from pyrite.The Ixtahuacan deposits are interpreted to have formed at low temperature (<200°C) and a depth of a few hundred metres from a low fO₂ (10^–49–10^–57), high pH (7–8) fluid. Arsenic was probably transported as arsenious acid, antimony and gold as thio-complexes and tungsten as the complex HWO ₄ ^– .A model is proposed in which a meteoric fluid, heated by a felsic intrusion at depth, was focused to shallow levels along faults. The interaction of the fluid with pyritiferous beds caused the deposition of arsenopyrite as a result of sulphidation and/or decreasing fO₂; gold probably co-precipitated with As or was adsorbed onto the arsenopyrite. The precipitation of stibnite was caused by boiling. Scheelite deposited in response to the increase in Ca²⁺ activity which accompanied interaction of the ore fluid with the argillaceous limestones.     

Ore-forming fluids associated with granite-hosted gold mineralization at the Sanshandao deposit, Jiaodong gold province, China

The Sanshandao gold deposit, with total resources of more than 60 t of gold, is located in the Jiaodong gold province, the most important gold province of China. The deposit is a typical highly fractured and altered, disseminated gold system, with high-grade, quartz-sulphide vein/veinlet stockworks that cut Mesozoic granodiorite. There are four stages of veins that developed in the following sequence: (1) quartz-K-feldspar-sericite; (2) quartz-pyrite±arsenopyrite; (3) quartz-base metal sulfide; and (4) quartz-carbonate. Fluid inclusions in quartz and calcite in vein/veinlet stockworks contain C-O-H fluids of three main types. The first type consists of dilute CO₂–H₂O fluids coeval with the early vein stage. Molar volumes of these CO₂–H₂O fluid inclusions, ranging from 50–60 cm³/mol, yield estimated minimum trapping pressures of 3 kbar. Homogenization temperatures, obtained mainly from CO₂–H₂O inclusions with lower CO₂ concentration, range from 267–375 °C. The second inclusion type, with a CO₂–H₂O±CH₄ composition, was trapped during the main mineralizing stages. These fluids may reflect the CO₂–H₂O fluids that were modified by fluid/rock reactions with altered wallrocks. Isochores for CO₂-H₂O±CH₄ inclusions, with homogenization temperatures ranging from 204–325 °C and molar volumes from 55 to 70 cm³/mol, provide an estimated minimum trapping pressure of 1.2 kbar. The third inclusion type, aqueous inclusions, trapped in cross-cutting microfractures in quartz and randomly in calcite, are post-mineralization, and have homogenization temperatures between 143–228 °C and salinities from 0.71–7.86 wt% NaCl equiv. Stable isotope data show that the metamorphic fluid contribution is minimal and that ore fluids are of magmatic origin, most likely sourced from 120–126 Ma mafic to intermediate dikes. This is consistent with the carbonic nature of the fluid, and the cross-cutting nature of those deposits relative to the host Mesozoic granitoid.Editorial handling: R.J. Goldfarb     

Mobility of metamorphic fluids inferred from infrared microspectroscopy on natural fluid inclusions: the example of Tinos Island,Greece

OH structure of metamorphic fluids has been studied by high temperature infrared (IR) microspectroscopy on natural fluid inclusions contained in quartz veins, over the temperature range 25–370 °C. Blueschist-facies veins from Tinos island core complex (Cyclades, Greece) display H₂O–NaCl–CaCl₂–CO₂ inclusions whereas greenschist-facies veins contain H₂O–NaCl ± CO₂ inclusions. From 25 to 370 °C, peak positions of OH stretching IR absorption bands increase quasi-linearly with slopes of 0.25 and 0.50 cm^–1 °C^–1 for inclusions trapped under blueschist and greenschist conditions, respectively. Extrapolation to 400 °C yield peak positions of 3,475 cm^–1 for blueschist inclusions and 3,585 cm^–1 for greenschist inclusions. Because the smaller wave number indicates the shorter hydrogen-bond distance between water molecules, fluids involved in the greenschist event have a loose structure compared with blueschist fluids. We suggest that these properties might correspond to a low wetting angle of fluids. This would explain the high mobility of aqueous fluids suggested by structural observation and stable isotope analysis.Editorial responsibility: J. Hoefs     

Wetting behavior of partial melts during crustal anatexis: the distribution of hydrous silicic melts in polycrystalline aggregates of quartz

The equilibrium distribution of hydrous silicic melts in polycrystalline aggregates of quartz was characterized in a series of partial melting and melt distribution experiments in the systems quartz-albite-orthoclase-H₂O and quartz-anorthite-H₂O, at 650 to 1000 MPa and 800 to 900° C. Near-equilibrium textures in these experiments are characterized by very low quartz-quartz-melt wetting angles, and by a substantial number of thin melt films along grain boundaries. Wetting angles in the H₂O-saturated experiments are as follows: 18° at 800° C-1000 MPa, and 12° at 900° C-1000 MPa in the granitic system; 18° at 850° C-650 MPa, 15° at 900° C-650 MPa, and 15° at 900° C-1000 MPa in the quartzanorthite system. In the granitic system at 900° C-1000 MPa, a decrease of H₂O content in melt from 17 wt% (at saturation) to 6 wt%, results in a slight increase of wetting angle from 12° to 16°. These low wetting angles — and the observation that many grain boundaries are wetted by melt films-indicate that the ratio of quartz-quartz to quartz-melt interfacial energies (_ss/_s1) is high: 2. Secondary electron imaging of fracture surfaces of melt-poor samples provided a three-dimensional insight into the geometry of melt; at low melt fraction, melt forms an interconnected network of channels along grain edges, as predicted for isotropic systems with wetting angles below 60°. This high-permeability geometry suggests that the segregation of granitic melts is not as sluggish as previously anticipated; simple compaction calculations for a permeability range of 10^-12 to 10^-9 m² indicate that segregation may operate at low to moderate melt fractions (below 30 vol. %), within relatively short time-scales, i.e., 10⁵ to 10⁶ years. Quartzmelt textures show significant deviations from the equilibrium geometries predicted for isotropic partially molten systems. The most consistent deviation is the pervasive development of crystallographically-controlled, planar faces of quartz; these faces provide definitive evidence for non-isotropic quartz-melt surface energy. For most silicates other than quartz, the grain-scale distribution of partial melts deviates even more significantly from equilibrium distributions in isotropic systems; accordingly, in order to describe adequately melt distributions in most natural source regions, the equilibrium model should be modified to account for anisotropy of solid-liquid interfacial energy.Contribution CNRS-INSU-DBT n^o 651     

Experimental study of the stability of cordierite and garnet in pelitic compositions at high pressures and temperatures

In pelitic rocks, under conditions of low f _{O 2} and low f _{H 2 O}, the stability of the mineral pair cordierite-garnet is limited by five univariant reactions. In sequence from high pressure and low temperature to high temperature and low pressure these are: cordierite+garnet hypersthene+sillimanite+quartz, cordierite+garnet hypersthene+sapphirine+quartz, cordierite+garnet hypersthene+spinel+quartz and cordierite+garnet olivine+spinel +quartz. In this sequence of reactions the Mg/Mg+Fe²⁺ ratio of all ferro-magnesian minerals involved decreases continuously from the first reaction to the fifth. The five univariant boundaries delimit a wide P-T range over which cordierite and garnet may coexist.Two divariant equilibria in which the Mg/Mg+ Fe²⁺ ratio of the coexisting phases are uniquely determined by pressure and temperature have been studied in detail. P-T-X grids for the reactions cordierite garnet+sillimanite+quartz and cordierite+hypersthene garnet+quartz are used to obtain pressure-temperature estimates for several high grade metamorphic areas. The results suggest temperatures of formation of 700–850° C and load pressures of 5–10 kb. In rare occasions temperatures of 950–1000° C appear to have been reached during granulite metamorphism.On the basis of melting experiments in pelitic compositions it is suggested that Ca-poor garnet xenocrysts found in calc-alkaline magmas derive from admixed pelitic rocks and did not equilibrate with the calc-alkaline magma.