Compositional zoning of calcite in a high-pressure metamorphic calc-schist: clues to heterogeneous grain-scale fluid distribution during exhumation

Calcite in former aragonite–dolomite-bearing calc-schists from the ultrahigh-pressure metamorphic (UHPM) oceanic complex at Lago di Cignana, Valtournanche, Italy, preserved different kinds of zoning patterns at calcite grain and phase boundaries. These patterns are interpreted in terms of lattice diffusion and interfacial mass transport linked with a heterogeneous distribution of fluid and its response to a changing state of stress. The succession of events that occurred during exhumation is as follows: As the rocks entered the calcite stability field at T=530–550 °C, P ca. 1.2 GPa, aragonite occurring in the matrix and as inclusions in poikilitic garnet was completely transformed to calcite. Combined evidence from microstructures and digital element distribution maps (Mn-, Mg-, Fe- and Ca–Kα radiation intensity patterns) indicates that transformation rates have been much higher than rates of compositional equilibration of calcite (involving resorption of dolomite and grain boundary transport of Mg, Fe and Ca). This rendered the phase transformation an isochemical process. During subsequent cooling to T ca. 490 °C (where lattice diffusion effectively closed), grains of matrix calcite have developed diffusion-zoned rims, a few hundred micrometres thick, with Mg and Fe increasing and Ca decreasing towards the phase boundary. Composition profiles across concentrically zoned, large grains in geometrically simple surroundings can be successfully modelled with an error function describing diffusion into a semi-infinite medium from a source of constant composition. The diffusion rims in matrix calcite are continuous with quartz, phengite, paragonite and dolomite in the matrix. This points to an effective mass transport on phase boundaries over a distance of several hundred micrometres, if matrix dolomite has supplied the Mg and Fe needed for incorporation in calcite. In contrast, diffusion rims are lacking at calcite–calcite and most calcite–garnet boundaries, implying that only very minor mass transport has occurred on these interfaces over the same T–t interval. From available grain boundary diffusion data and experimentally determined fluid–solid grain boundary structures, inferred large differences in transport rates can be best explained by the discontinuous distribution of aqueous fluid along grain/phase boundaries. Observed patterns of diffusion zoning indicate that fluid was distributed not only along grain-edge channels, but spread out along most calcite–white mica and calcite–quartz two-grain junctions. On the other hand, the inferred non-wetting of calcite grain boundaries in carbonate-rich domains is compatible with fluid–calcite–calcite dihedral angles >60° determined by Holness and Graham (1995) for a wide range of fluid compositions under the P–T conditions of interest. Whereas differential stress has been very low at the stage of diffusion zoning (T > 490 °C), it increased as the rocks were cooling below 440 °C (at 0.3–0.5 GPa). Dislocation creep and the concomitant increase of strain energy in matrix calcite induced migration recrystallisation of high-angle grain boundaries. For that stage, the compositional microstructure of recrystallised calcite grain boundary domains indicates significant mass transport along calcite two-grain junctions, which at the established low temperatures is likely to have been accomplished by ionic diffusion within a hydrous grain boundary fluid film (“dynamic wetting” of migrating grain boundaries). Received: 10 January 2000 / Accepted: 10 April 2000     

Distribution of brine in grain boundaries during static recrystallization in wet, synthetic halite: insight from broad ion beam sectioning and SEM observation at cryogenic temperature

We report observations from room temperature static recrystallization experiments (annealing times from minutes to year) of cold-pressed, synthetic, coarse-grained, wet sodium chloride, prepared by broad ion beam polishing and SEM observations at cryogenic temperature to observe directly the brine in grain boundaries. At all stages of annealing, the majority of the brine in the samples is connected in 2D sections along grain boundaries. Another part of the brine is in isolated brine inclusion arrays along grain boundaries and in brine inclusions left behind by migrating brine-filled grain boundaries. Most of these boundaries are mobile because the aggregate is coarsening. We interpret that the boundaries without observable brine films (<15 nm) and brine inclusion arrays are healed and immobile. Evolution of grain boundary structure involves three major processes. First, dissolution on one side of the grain boundary and precipitation on the other side, resulting in grain boundary migration. Second, the development of facets formed by low-index crystallographic planes of the grains bounding the grain boundary brine. When both sides of a grain boundary are able to develop low-index facets in a thick brine film, the resulting impingement boundary is interpreted to be immobile and may prevent the new grain from migrating into a deformed neighbor. When one side of a faceted boundary consists of low-index crystallographic planes and the other side passively follows this faceted shape along irrational surfaces, the boundary is mobile. Third, the healing of grain boundary brine films, producing solid–solid grain boundaries without resolvable brine films.     

Timescales and mechanisms of fluid infiltration in a marble: an ion microprobe study

Using a recently developed ion microprobe technique, a detailed oxygen isotope map of calcite grains in a coarse-grained marble has been constructed, supported by trace element (Mn, Sr, Fe) analysis and cathodoluminescence (CL) imaging, in order to constrain scales of oxygen isotope equilibrium, timescales and mechanisms of metamorphic fluid infiltration, and fluid sources and pathways. Results are compared with a previous study of this sample (Wada 1988) carried out using a cryo-microtome technique and conventional oxygen isotope analysis. The marble, from the high temperature/low pressure Hida metamorphic belt in north-central Japan, underwent granulite facies followed by amphibolite facies metamorphic events, the latter associated with regional granite intrusion. The CL imaging indicates two types of calcite, a yellow luminescing (YLC) and a purple luminescing (PLC) variety. The YLC, which occupies grain boundaries, fractures, replacement patches, and most of the abundant deformation twin lamellae, post-dates the dominant PLC calcite and maps out fluid pathways. Systematic relationships were established between oxygen isotope and trace element composition, calcite type and texture, based on 74 ¹⁸O/¹⁶O and 17 trace element analyses with 20–30 μ m spatial resolution. The YLC is enriched in Mn and Fe, and depleted in ¹⁸O and Sr compared to PLC, and is much more ¹⁸O depleted than is indicated from conventional analyses. Results are interpreted to indicate infiltration of ¹⁸O-depleted (metamorphic or magmatic) fluid (initial δ¹⁸O = 9‰–10.5‰) along grain boundaries, fractures and deformation twin lamellae, depleting calcite grains in Sr and enriching them in Mn and Fe. The sample is characterised by gross isotopic and elemental disequilibrium, with important implications for the application of chromatographic theory to constrain fluid fluxes in metacarbonate rocks. Areas of PLC unaffected by “short-circuiting” fluid pathways contain oxygen diffusion profiles of ∼10‰/∼200 μm in grain boundary regions or adjacent to fractures/patches. When correction is made for estimated grain boundary/fracture and profile orientation in 3D, profiles are indistinguishable within error. Modelling of these profiles gives consistent estimates of Dt (where D is the diffusion coefficient and t is time) of ∼0.8 × 10⁻⁸ m², from which, using experimental data for oxygen diffusion in calcite, timescales of fluid transport along grain boundaries at amphibolite facies temperatures of ∼10³ to ∼10⁴ years are obtained. These short timescales, which are much shorter than plausible durations of metamorphism, imply that rock permeabilities may be transiently much higher during fluid flow than those calculated from time integrated fluid fluxes or predicted from laboratory measurements. The preservation of ¹⁸O/¹⁶O profiles requires either rapid cooling rates (∼100–600 °C/million years), or, more plausibly, loss of grain boundary fluid such that a dry cooling history followed the transient passage of fluid. The δ¹⁸O/trace element correlations are also consistent with volume diffusion-controlled transport in the PLC. Fluid transport and element exchange occurred by two inter-related mechanisms on short timescales and on different lengthscales – long-distance flow along cracks, grain boundaries and twin lamellae coupled to ∼200 μm-scale volume diffusion of oxygen. Received: 8 December 1997 / Accepted: 18 May 1998     

Formation of kyanite–quartz veins of the Alpe Sponda,Central Alps,Switzerland: implications for Al transport during regional metamorphism

In this study, we have investigated the formation of quartz–kyanite veins of the Alpe Sponda, Central Alps, Switzerland. We have integrated field observations, fluid inclusion and stable isotope data and combined this with numerical geochemical modeling to constrain the chemical processes of aluminum transport and deposition. The estimated P–T conditions of the quartz–kyanite veins, based on conventional geothermometry (garnet–biotite, white mica solvus and quartz–kyanite oxygen isotope thermometry) and fluid inclusion data, are 550 ± 30°C at 5.0 ± 0.5 kbar. Geochemical modeling involved construction of aqueous species predominance diagrams, calculation of kyanite and quartz solubility, and reaction–path simulations. The results of the modeling demonstrate that (1) for the given chemical composition of the vein-forming fluids mixed Al–Si aqueous species are dominant in transporting Al, and that (2) fluid cooling along a small temperature gradient coupled with a pH decrease is able to explain the precipitation of the quartz–kyanite assemblages in the proportions that are observed in the Alpe Sponda veins. We conclude that sufficient amounts of Al can be transported in typical medium- to high-grade regional metamorphic fluids and that immobile behavior of Al is not very likely in advection–dominanted fluid–rock systems in the upper and middle crust.     

New constraints on fluid sources in orogenic gold deposits,Victoria, Australia

Fluid inclusion microthermometry, Raman spectroscopy and noble gas plus halogen geochemistry, complemented by published stable isotope data, have been used to assess the origin of gold-rich fluids in the Lachlan Fold Belt of central Victoria, south-eastern Australia. Victorian gold deposits vary from large turbidite-hosted ‘orogenic’ lode and disseminated-stockwork gold-only deposits, formed close to the metamorphic peak, to smaller polymetallic gold deposits, temporally associated with later post-orogenic granite intrusions. Despite the differences in relative timing, metal association and the size of these deposits, fluid inclusion microthermometry indicates that all deposits are genetically associated with similar low-salinity aqueous, CO₂-bearing fluids. The majority of these fluid inclusions also have similar ⁴⁰Ar/³⁶Ar values of less than 1500 and ³⁶Ar concentrations of 2.6–58 ppb (by mass) that are equal to or much greater than air-saturation levels (1.3–2.7 ppb). Limited amounts of nitrogen-rich fluids are present at a local scale and have the highest measured ⁴⁰Ar/³⁶Ar values of up to 5,700, suggesting an external or distinct source compared to the aqueous fluids. The predominance of low-salinity aqueous–carbonic fluids with low ⁴⁰Ar/³⁶Ar values, in both ‘orogenic’ and ‘intrusion-related’ gold deposits, is attributed to fluid production from common basement volcano-sedimentary sequences and fluid interaction with sedimentary cover rocks (turbidites). Aqueous fluid inclusions in the Stawell–Magdala deposit of western Victoria (including those associated with N₂) preserve mantle-like Br/Cl and I/Cl values. In contrast, fluid inclusions in deposits in the eastern structural zones, which contain more abundant shales, have elevated molar I/Cl ratios with maximum values of 5,170 × 10⁻⁶ in the Melbourne Zone. Br/I ratios in this zone range from 0.5 to 3.0 that are characteristic of fluid interaction with organic-rich sediments. The maximum I/Cl and characteristic Br/I ratios provide evidence for organic Br and I released during metamorphism of the shales. Therefore, the regional data provide strong evidence for the involvement of sedimentary components in gold mineralisation, but are consistent with deeper metamorphic fluid sources from basement volcano-sedimentary rocks. The overlying sediments are probably involved in gold mineralisation via fluid–rock interaction.     

Ion probe and fluid inclusion evidence for co-seismic fluid infiltration in a crustal detachment

We have investigated the geochemical pattern of fluid infiltration in the extensional detachment of Tinos Island (Cyclades, Greece). Ion microprobe O-isotope analyses and fluid inclusion studies have been conducted in strain fringes developing around pyrite blasts in the mylonite of the shear zone. Micro-scale traverses in quartz and calcite fibres show that δ¹⁸O increases from 17–18 to 20–21‰ in 1 mm towards the blast, drops of 3‰ in ∼200 μm, then rises again in the direction of growth. δ¹⁸O variations are interpreted as transient influxes of exotic fluids into the shear zone between periods of closed system buffering by the host rock. Fluid inclusions trapped in the fibres show fluctuating salinities (0–4 wt% NaCl eq.) and densities that reflect drops of the pore pressure from lithostatic (λ=1) to hydrostatic (λ=0.4) values during fringe growth. Isotopic and microthermometric data are consistent with models of seismic pumping developed for compressive shear zones. We therefore suggest that co-seismic pore pressure variations developed suction forces sufficient to drive large-scale fluid migration in the Tinos detachment, as in convergent tectonic settings.     

Fluid Assisted Recrystallization in Upper Mantle Peridotite Xenoliths from Kimberlites

The development of recrystallization microstructures has beenstudied in some ‘hot deformed’ peridotite xenolithsfrom the Thaba Putsoa Kimberlite pipe in S. Africa. The xenolithswere deformed to high strains by dislocation creep in the uppermantle and then annealed as they were uplifted by the kimberlitefluid. Static recrystallization occurs during annealing producingeuhedral shaped ‘tablet’ grains. Tablet grain boundariesare sub-parallel to crystal growth habits in olivine and orthopyroxene.This microstructure is characteristic of recrystallization byfluid-assisted grain boundary migration, where a thin fluidfilm is present along the boundary. There is microstructural evidence for a complex fluid infiltrationhistory involving an early Fe-Ti rich metasomatic silicate fluidand later kimberlite fluids. Minor partial melting of clinopyroxenecan also be inferred, which, is consistent with infiltrationof a kimberlite-derived C-H-O rich fluid into the xenoliths.Any of these fluids could have been present along the tabletgrain boundaries during static recrystallization. The occurrenceof tablet grains in ‘cold deformed’ xenoliths, whichhave a simple infiitration history, suggests that a C-H-O richfluid derived from kimberlite is the most probable boundaryfluid in both the hot and cold deformed xenoliths. The occurrence of dynamically stable semi-continuous grain boundaryfluid films during re crystallization indicates that mechanismsof fluid segregation and transport in the upper mantle are likelyto be dependent upon the type of deformation and recrystallizationmechanisms operating. In addition the destabilization of thestatic fluid distribution by grain boundary migration and deformationwill also influence the rheology of the upper mantle where fluidsare present. ^*Present address: Mineralogy Research Centre, Research School of Chemistry, Australian National University Canberra ACT 2601, Australia.     

Geological and fluid inclusion studies of the Dongpo tungsten skarn ore deposit,China

The Dongpo tungsten ore deposit, the largest scheelite skarn deposit in China, is located at the contact of a 172-m. y. biotite granite with a Devonian marble. The mineralization associated with the granite includes W, Bi-Mo, Cu-Sn and Pb-Zn ores. Several W mineralization stages are shown by the occurrence of ore in massive skarn deposits and in later cross-cutting veins. The high garnet/pyroxene ratio, the hedenbergite and diopside-rich pyroxene and the andradite-rich garnet show the deposit belongs to the oxidized skarn type. Detailed fluid inclusion studies of granite, greisen, skarn and vein samples reveal three types of fluid inclusion: (1) liquid-rich, (2) gas-rich and (3) inclusions with several daughter minerals. Type (3) is by far the most common in both skarn and vein samples. The dominant daughter mineral in fluid inclusions is rhembic, highly birefringent, and does not dissolve on heating even at 530°C. We assume that this mineral is calcite. The liquid phase in most of the fluid inclusions has low to moderate salinities: 0–15 wt. %; in a few has higher salinities (30–40 wt. % NaCl equivalent). The homogenization temperatures of inclusions in the skarn stage range from 350°C to 530°C, later tungsten mineralization-stage inclusions homogenize between 200°C and 300°C, as do inclusions in veins. Fluid inclusions in granite and greisen resemble those of the late tungsten mineralization stage, with low salinity and homogenization temperatures of 200°–360°C. The tungsten-forming fluids are probably a mixture that came from biotite granite and the surrounding country rocks.     

Source and evolution of ore-forming hydrothermal fluids in the northern Iberian Pyrite Belt massive sulphide deposits (SW Spain): evidence from fluid inclusions and stable isotopes

A fluid inclusion and stable isotopic study has been undertaken on some massive sulphide deposits (Aguas Teñidas Este, Concepción, San Miguel, San Telmo and Cueva de la Mora) located in the northern Iberian Pyrite Belt. The isotopic analyses were mainly performed on quartz, chlorite, carbonate and whole rock samples from the stockworks and altered footwall zones of the deposits, and also on some fluid inclusion waters. Homogenization temperatures of fluid inclusions in quartz mostly range from 120 to 280 °C. Salinity of most fluid inclusions ranges from 2 to 14 wt% NaCl equiv. A few cases with T _h=80–110 °C and salinity of 16–24 wt% NaCl equiv., have been also recognized. In addition, fluid inclusions from the Soloviejo Mn–Fe-jaspers (160–190 °C and ˜6 wt% NaCl equiv.) and some Late to Post-Hercynian quartz veins (130–270 °C and ˜4 wt% NaCl equiv.) were also studied. Isotopic results indicate that fluids in equilibrium with measured quartz (d ¹⁸O _fluid ˜–2 to 4‰), chlorites (d ¹⁸O _fluid ˜8–14‰, dD _fluid ˜–45 to –27‰), whole rocks (d ¹⁸O _fluid ˜4–7‰, dD _fluid ˜–15 to –10‰), and carbonates (d ¹⁸O _ankerite ˜14.5–16‰, d ¹³C _fluid =–11 to –5‰) evolved isotopically during the lifetime of the hydrothermal systems, following a waxing/waning cycle at different temperatures and water/rock ratios. The results (fluid inclusions, d ¹⁸O, dD and d ¹³C values) point to a highly evolved seawater, along with a variable (but significant) contribution of other fluid reservoirs such as magmatic and/or deep metamorphic waters, as the most probable sources for the ore-forming fluids. These fluids interacted with the underlying volcanic and sedimentary rocks during convective circulation through the upper crust.     

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     

流体包裹体研究对成矿流体动力学模式的制约

热液矿床的形成既包括地球化学过程也包括流体动力学过程,后者主要研究成矿流体的驱动力、流动方向、速度及持续时间。流体及金属的来源,金属在热液中的溶解度及溶解机制,以及矿石的沉淀机制等可以通过多种地球化学手段来研究,而流体动力学过程的确定相对比较困难。流体包裹体分析不仅可以为成矿地球化学过程,而且可为流体动力学过程提供制约,因为流体包裹体研究所得到的流体P-V-T-X性质与流体流动、热传导及质量迁移等控制方程直接相关。本文阐述流体包裹体与流体动力学研究的理论关系,流体包裹体研究对已有成矿流体动力学模式的贡献,以及未来的研究方向。从流体包裹体研究得出的流体压力状态为岩浆热液及造山型成矿系统的超压驱动模式提供了关键的证据。流体包裹体均一温度及其分布为沉积盆地成矿流体动力学模式提供了重要的制约。流体包裹体研究在揭示流体混合及流体相分离等重要成矿过程方面提到了至关重要的作用,但它们在研究流体混合及多相流体流动的物理过程方面的潜力有待进一步开发。精心设计的流体包裹体研究有可能应用于古流体流动数值模型的调试。     

Metamorphic reactions between fluid inclusions and mineral hosts. I. Progress of the reaction calcite+quartz=wollastonite+CO2 in natural wollastonite-hosted fluid inclusions

 At the Bufa del Diente contact-metamorphic aureole, brine infiltration through metachert layers embedded in limestones produced thick wollastonite rims, according to Cc+Qz=Wo+CO₂. Fluid inclusions trapped in recrystallized quartz hosts include: (1) high salinity four phase inclusions [Th(V-L)=460–573° C; Td(salts)=350–400° C; (Na+K)_Cleq=64–73 wt%; X _{CO 2}≤0.02]; (2) low density vapour-rich CO₂-bearing inclusions [Th(L-V)≈500±100° C; X _{CO 2}=0.22–0.44; X _NaCl≤0.01], corresponding to densities of 0.27± 0.05 gcm⁻³. Petrographical observations, phase compositions and densities show that the two fluids were simultaneously trapped in the solvus of the H₂O-CO₂-salts system at 500–600° C and 700±200 bars. The low density fluid was generated during brine infiltration at the solvus via the wollastonite producing reaction. Identical fluid types were also trapped as inclusion populations in wollastonite hosts 3 cm adjacent to quartz crystals. At room temperature, both fluid types additionally contain one quartz and one calcite crystal, generated by the back-reaction Wo+CO₂=Cc+Qz of the host with the CO₂-proportion of the fluid during retrogression. All of the CO₂ was removed from the fluid. On heating in the microstage, the reaction progress of the prograde reaction was estimated via volume loss of the calcites. In vapour-rich fluids, 50% progress is reached at 490–530° C; 80% at 520–560° C; and 100% at 540–590° C, the latter representing the trapping temperatures of the original fluid at the two fluid solvus. The progress is volume controlled. With knowledge of compositions and densities from unmodified inclusions in quartz and using the equation of state of Duan et al. (1995) for H₂O-CO₂-NaCl, along with f _{CO 2}-values extracted from it, the reaction progress curve was recalculated in the P-T-X-space. The calculated progress curve passes through the two fluid solvus up to 380° C/210 bars, continues in the one fluid field and meets the solvus again at trapping conditions. The P-T slope is steep, most of the reaction occurs above 450° C and there is high correspondence between calculated and measured reaction progress. We emphasize that with the exception of quartz, back-reactions between inclusion fluids and mineral hosts is a common process. For almost any prograde metamorphic mineral that was formed by a devolatilization reaction and that trapped the equilibrium fluid or any peak metamorphic fluid as an inclusion, a fluid-host back-reaction exists which must occur somewhere along the retrograde path. Such retrograde reactions may cause drastic changes in density and composition of the fluid. In most cases, however, evidence of the evolving mineral assemblages is not given for they might form submicroscopical layers at the inclusion walls. Received: 15 March 1995 / Accepted: 1 June 1995     

Carbonic fluid inclusions in South Indian granulites: evidence for entrapment during charnockite formation

Field evidence and fluid inclusion studies on South Indian incipient charnockites suggest that charnockite formation occurred during a decompressional brittle regime following the ‘peak’ of metamorphism and regional deformation. The most abundant type of inclusions in quartz and garnet grains in these charnockites contain high-density carbonic fluids, although lower-density fluids occur in younger arrays of inclusions. Discrete fluid inclusion generations optically are observed to decrepitate over well-defined temperature intervals, and quantitative measurements of CO₂ abundance released from these inclusions by stepped thermal decrepitation show up to a four-fold increase (by volume) in the incipient charnockites relative to the adjacent gneisses from which they are derived. Studies based on optical thermometry, visual decrepitation and stepped-heating inclusion release together indicate that entrapment of carbonic fluids coincided with charnockite formation. We confirm that an influx of carbon dioxide-rich fluids is associated with the amphibolite-granulite transition, as recorded by the incipient charnockites, the remnants of which are commonly preserved as the earliest generation of high-density fluid inclusions.     

A geochemical study of the Sweet Home Mine,Colorado Mineral Belt,USA: hydrothermal fluid evolution above a hypothesized granite cupola

Deposition of quartz–molybdenite–pyrite–topaz–muscovite–fluorite and subsequent hübnerite and sulfide–fluorite–rhodochrosite mineralization at the Sweet Home Mine occurred coeval with the final stage of magmatic activity and ore formation at the nearby world-class Climax molybdenum deposit about 26 to 25 m.y. ago. The mineralization occurred at depths of about 3,000 m and is related to at least two major fluid systems: (1) one dominated by magmatic fluids, and (2) another dominated by meteoric water. The sulfur isotopic composition of pyrite, strontium isotopes and REY distribution in fluorite suggest that the early-stage quartz–molybdenite–pyrite–topaz–muscovite–fluorite mineral assemblage was deposited from magmatic fluids under a fluctuating pressure regime at temperatures of about 400°C as indicated by CO₂-bearing, moderately saline (7.5–12.5 wt.% NaCl equiv.) fluid inclusions. LA-ICPMS analyses of fluid inclusions in quartz demonstrate that fluids from the Sweet Home Mine are enriched in incompatible elements but have considerably lower metal contents than those reported from porphyry–Cu–Au–Mo or Climax-type deposits. The ore-forming fluid exsolved from a highly differentiated magma possibly related to the deep-seated Alma Batholith or distal porphyry stock(s). Sulfide mineralization, marking the periphery of Climax-type porphyry systems, with fluorite and rhodochrosite as gangue minerals was deposited under a hydrostatic pressure regime from low-salinity ± CO₂-bearing fluids with low metal content at temperatures below 400°C. The sulfide mineralization is characterized by mostly negative δ³⁴S values for sphalerite, galena, chalcopyrite, and tetrahedrite, highly variable δ¹⁸O values for rhodochrosite, and low REE contents in fluorite. The Pb isotopic composition of galena as well as the highly variable ⁸⁷Sr/⁸⁶Sr ratios of fluorite, rhodochrosite, and apatite indicates that at least part of the Pb and Sr originated from a much more radiogenic source than Climax-type granites. It is suggested that the sulfide mineralization at the Sweet Home Mine formed from magmatic fluids that mixed with variable amounts of externally derived fluids. The migration of the latter fluids, that were major components during late-stage mineralization at the Sweet Home Mine, was probably driven by a buried magmatic intrusion.     

Patterns of fluid flow in the contact aureole of the Late Miocene Monte Capanne pluton (Elba Island,Italy): the role of structures and rheology

Fluid–rock interaction was investigated in the inner aureole of the Late Miocene Monte Capanne pluton on Elba Island (Tuscany, central Italy) by integrating structural, petrological, fluid inclusion, and stable isotope analyses. In the north-western sector of the aureole (Procchio–Spartaia area), calc–silicates alternate with nearly pure carbonate layers at the metre scale. Close to the pluton, the prograde metamorphic sequence includes calc–silicates that transition within a few metres to overlying nearly pure calcite marbles. The calc–silicates are extensively metasomatised to form massive wollastonite-grossular-bearing exoskarn. The mineralogical assemblage found in the marbles and the unshifted carbon and oxygen isotopic ratios in calcite attest that the fluid phase was internally buffered. On the other hand, the calc–silicates constituted channels for infiltration of disequilibrium fluids of magmatic origin. Fluid infiltration was enhanced by hydrofracturing and structurally-controlled by existing planar anisotropies in calc–silicates (layering and lithological boundaries). At the metamorphic peak (∼600°C and 1.5–2 kbar), the marble–calc–silicate interface acted as a barrier to fluids exsolved from the crystallising intrusions, separating two different flow patterns in the inner aureole: a high fluid–flux region on its higher grade side (Wol-zone) and a low fluid–flux region on the lower-grade side (Cpx zone). Results of this study: (1) documented that fluid pathways in the aureole rocks at the top of the pluton were largely horizontal, controlled by the lithological layering and the pluton–host rock contact; and (2) elucidated the primary control exerted by the structural and rheological properties of the host rocks on the geometry of fluid flow during pluton emplacement.     

The migration of fluid-filled grain boundaries in recrystallizing synthetic bischofite: first results of in-situ high-pressure, high-temperature deformation experiments in transmitted light

The effect of fluids on recrystallization behaviour is well known; however, the detailed microscale distribution of fluid in grain boundaries and the influence of fluid on grain boundary migration are still unresolved. In this study, in‐situ deformation experiments in transmitted light microscopy were undertaken, as this allows continuous and direct observation of the whole range of processes involved in fluid‐assisted grain boundary migration. A new see‐through deformation apparatus was developed to enable the control of fluid pressure. Bischofite containing small amounts of aqueous fluid was deformed at temperatures between 50 and 90 °C, over a range of fluid pressure from 0.5 to 1 MPa, and strain rates of 5 × 10^?6 to 1 × 10^?4 s^?1. The rates of grain boundary migration were measured at different temperatures and strain rates. Detailed observations during and after the deformation illustrate the evolution of migrating fluid‐filled grain boundaries and show that the incorporation of fluids from inclusions as well as their pinch‐off is dependent on the grain boundary velocity, the thickness of the grain boundary and the size and shape of the inclusions. Direct evidence is presented for the contraction of the grain boundary fluids into isolated inclusions after equilibrium conditions are attained.     

Criteria for recognition of localization and timing of multiple events of hydrothermal alteration in sandstones illustrated by petrographic,fluid inclusion,and isotopic analysis of the Tera Group,Northern Spain

Stratigraphic relations, detailed petrography, microthermometry of fluid inclusions, and fine-scale isotopic analysis of diagenetic phases indicate a complex thermal history in Tithonian fluvial sandstones and lacustrine limestones of the Tera Group (North Spain). Two different thermal events have been recognized and characterized, which are likely associated with hydrothermal events that affected the Cameros Basin during the mid-Cretaceous and the Eocene. Multiple stages of quartz cementation were identified using scanning electron microscope cathodoluminescence on sandstones and fracture fills. Primary fluid inclusions reveal homogenization temperatures (Th) from 195 to 350°C in the quartz cements of extensional fracture fillings. The high variability of Th data in each particular fluid inclusion assemblage is related to natural reequilibration of the fluid inclusions, probably due to Cretaceous hydrothermal metamorphism. Some secondary fluid inclusion assemblages show very consistent data (Th = 281–305°C) and are considered not to have reequilibrated. They are likely related to an Eocene hydrothermal event or to a retrograde stage of the Cretaceous hydrothermalism. This approach shows how multiple thermal events can be discriminated. A very steep thermal gradient of 97–214°C/km can be deduced from δ¹⁸O values of ferroan calcites (δ¹⁸O −14.2/−11.8‰ V-PDB) that postdate quartz cements in fracture fillings. Furthermore, illite crystallinity data (anchizone–epizone boundary) are out of equilibrium with high fluid inclusion Th. These observations are consistent with heat-flux related to short-lived events of hydrothermal alteration focused by permeability contrasts, rather than to regional heat-flux associated with dynamo-thermal metamorphism. These results illustrate how thermal data from fracture systems can yield thermal histories markedly different from host-rock values, a finding indicative of hydrothermal fluid flow.     

Characteristics of pore migration controlled by diffusion through the pore-filling fluid

We analyze drag and drop of pores filled with a fluid phase, e.g., water or melt, in which the constituting elements of the solid matrix are dissolved. Assuming that the diffusion through the fluid-phase dominates bulk transport kinetics, we address the problem of pore motion and calculate the pore mobility and the critical velocity of elongated and lenticular pores on a grain boundary for arbitrary dihedral angle. The found variations in critical velocity and mobility with dihedral angle are modest for given volume of pores with the two considered geometries. For given pore size, however, the dependence on dihedral angle accounts for several orders of magnitude in pore mobility and critical velocity.     

Thermodynamic modelling of a cooling C–O–H fluid–graphite system: implications for hydrothermal graphite precipitation

Carbon-saturated crustal fluids in the C–O–H system comprise H₂O, CO₂ and CH₄ as the most important fluid species. Graphite precipitation from a cooling C–O–H is discussed for two different systems, namely for a fluid–rock system in which no transfer of atomic oxygen and hydrogen between the fluid and the rock is possible (closed fluid system), and for an open fluid system. Thermodynamic model calculations show that the graphite-forming reactions and the graphite precipitation potential are different for these two systems. Furthermore, the calculations demonstrate that for both systems, the following factors play a role in determining the graphite precipitation potential, i.e. (1) the redox state of the fluid, (2) the initial pressure and temperature conditions and (3) whether cooling is combined with decompression. Open and closed fluid system graphite precipitation can be distinguished from each other using fluid inclusion and stable carbon isotope studies. The results of this study provide insight in the formation of hydrothermal graphite deposits.