Synthetic fluid inclusions - VII. Re-equilibration of fluid inclusions in quartz during laboratory-simulated metamorphic burial and uplift

ABSTRACT P-T conditions inferred from fluid inclusions in metamorphic rocks often disagree with the values predicted from mineral equilibria calculations. These observations suggest that inclusions formed during early stages of regional metamorphism continue to re-equilibrate during burial and subsequent uplift in response to differential pressure. P-T conditions accompanying burial and uplift were experimentally simulated by initially forming pure H₂O inclusions in quartz at elevated temperatures and pressures, and then re-equilibrating the inclusions in the presence of a 20 wt% NaCl solution such that final confining pressures ranged from 5 kbar above to 4 kbar below the initial internal pressure of the inclusions at the temperature of re-equilibration. In all samples re-equilibrated at confining pressures below the internal pressure, some inclusions were formed that had compositions of 20 wt% NaCl and densities in accord with the final P-T conditions. Additionally, some inclusions were observed to contain fluids of intermediate salinities (between 0 and 20 wt% NaCl). Densities of these inclusions were also consistent with formation at the re-equilibration P-T conditions. The remainder of the fluid inclusions observed in these samples contained pure H₂O and their homogenization temperatures corresponded to densities intermediate between the initial and final P-T conditions. In short-term experiments (7 days) where the initial internal overpressure exceeded 1 kbar, no inclusions were found that contained the original density and none were found to have totally re-equilibrated. Instead, most H₂O inclusions re-equilibrated until their internal pressures were between ∼750 and 1500 bars above the confining pressure, regardless of the initial pressure differential. In a long-term experiment (52 days), inclusions re-equilibrated at a lower confining pressure than the initial internal pressure displayed homogenization temperatures corresponding to a range in final internal pressures between 0 kbar (i.e. total re-equilibration) and 1.2 kbar above the confining pressure. In experiments where the confining pressure during re-equilibration exceeded the initial internal pressure, densities of pure H₂O inclusions increased to values intermediate between the initial and final P-T conditions. Additionally, these inclusions were generally surrounded by a three-dimensional halo of smaller inclusions, also of intermediate density, resulting in a texture similar to that previously ascribed to decrepitation from internal overpressure. In extreme cases where confining pressures were 4–5 kbar above the initial pressure, the parent inclusion almost completely closed leaving only the three-dimensional array of small (5 μm) inclusions, the outline of which may be several times the volume of the original inclusion. Groups of such inclusions closely resemble textures commonly observed in medium- to high-grade metamorphic rocks. Inclusions containing 10 and 42 wt% NaCl solutions trapped at 600 °c and 3 kbar were re-equilibrated at 600 °c and 1 kbar for 5 days in dry argon to evaluate the importance of H₂O diffusion as a mechanism of lowering the inclusion bulk density. Salinities of re-equilibrated inclusions obtained from freezing point depressions and halite dissolution temperatures indicate that original compositions were preserved. Density changes similar to those previously described were noted in these experiments, in inclusions showing no visible microfractures. Therefore, density variations observed in inclusions in this study, re-equilibrated under rapid deformation conditions, are considered to result from a change in the inclusion volume, without significant loss of contents by diffusion or leakage.     

Decrepitometry of fluid inclusions in quartz from the guadalcazar granite of Mexico; principles and application to mineral exploration

A simple acoustic decrepitometric method, with which samples of granite quartz are heated to about 600°C while the number of decrepitations are counted, has been developed to study rock samples derived from the mineralized guadalcazar granite in Mexico. Decrepitation temperatures for individual inclusions have also been determined by observing the point at which they rupture upon heating using a microscope heating stage. Decrepitation temperatures of individual fluid inclusions in granite quartz are influenced by a variety of factors notably size, shape, composition, homogenization temperature and proximity to the surface. There is a positive correlation between total decrepitation activity and fluid inclusion abundances (determined optically using point counting methods). Decrepitographs show a period of low intensity decrepitation activity below 390°C followed by a period of intensive decrepitation up to 570°C. The onset of massive decrepitation at around 390°C is constant for all samples, but variations in decrepitation activity often occur between mineralized and barren samples. These variations reflect complex differences in the fluid inclusion populations, but illustrate the potential for applying simple audio-decrepitometry as an aid to mineral exploration in granite terrains.     

Synthetic fluid inclusions. XV. TEM investigation of plastic flow associated with reequilibration of fluid inclusions in natural quartz

The nature and abundance of dislocations in quartz surrounding fluid inclusions were studied to obtain a better understanding of processes associated with fluid inclusion reequilibration. Synthetic fluid inclusions containing 10 wt% NaCl aqueous solution were formed in three samples at 700 °C and 5 kbar. One of the samples was quenched along an isochore to serve as a reference sample. The other two samples were quenched along a P-T path that generated internal pressures in excess of the confining pressure. The two samples were held at the final reequilibration P-T conditions of 625 °C and 2 kbar for 30 and 180 days, respectively. Following the experiments, microstructures associated with fluid inclusions were examined with the TEM. Quartz in healed fractures in the reference sample that was quenched isochorically shows a moderate dislocation activity. Quartz adjacent to reequilibrated fluid inclusions in the other two samples, however, showed a marked increase in dislocation activity compared to the un-reequilibrated sample. Deformation of the inclusion walls occurred anisotropically by expansion of mobile dislocations in their slip systems. Dislocation expansion was controlled by glide in the rhombohedral planes {1 0 1 1} that was restricted to narrow zones (≤3 μm) in the immediate vicinity of the fluid inclusion walls outside of the healed fracture plane. These plastic zones were observed after both short term (30 days) and long term (180 days) experiments and are attributed to hydrolytic weakening of quartz around fluid inclusions owing to diffusion of water into the quartz matrix during the experiment. The close spatial association of submicroscopic water bubbles with dislocations, and the rarity of water bubbles in the reference sample, show clearly that in both the 30 and 180 day experiments reequilibration involves water loss from the fluid inclusions. Our results indicate that synthetic fluid inclusions in this study recover (chemically and volumetrically), even at relatively fast experimental loading rates, such that internal stresses never reach the point of brittle failure. The driving force for fluid inclusion deformation involves two related mechanisms: plastic deformation of hydrolytically weakened wet quartz in the healed fracture, and water leakage associated with preexisting and strain-induced dislocations. Received: 5 May 1998 / Accepted: 10 February 2000     

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.     

Statistical microthermometry of synthetic fluid inclusions in quartz during decompression reequilibration

Fluid inclusion microthermometric data are often reported as homogenization temperature frequency histograms. Interpretation of such histograms for a single fluid inclusion assemblage (FIA) of non-reequilibrated fluid inclusions is usually straightforward and provides an accurate determination of the original density (Th) of that FIA. However, interpretation of such histograms for reequilibrated inclusions is more problematic. Decompression experiments using synthetic inclusions in natural quartz and conducted at 2–5 kbar and 600–700 °C with a maximum internal overpressure of 2 kbar indicate that histogram shape reflects the sample's P-T history. Our results further indicate that the mean, mode, range, standard deviation, extreme values, etc., all have a significance with respect to the P-T history of the sample. Thus, a mound-shaped, unimodal histogram with low range is indicative of a nearly isochoric cooling P-T path. A unimodal histogram that is slightly skewed to the right, and with a low standard deviation but high range, results from inclusion deformation in the plastic regime (high temperature/low strain rates). Fluid inclusions deformed plastically show no correlation between size and density. Histogram outliers should not be ignored and may be used to determine an isochore that passes close to the conditions of entrapment (minimum Th) or close to the final reequilibration conditions (maximum Th). The histogram mean Th value corresponds to an isochore that represents the internal overpressure (about 1 kbar) that can be maintained over geologic time by a majority of reequilibrated fluid inclusions. A multimodal histogram with high range and high standard deviation indicates inclusion brittle deformation (low temperature/high strain environments). Fluid inclusions deformed in a brittle manner show strong positive correlation between size and density. Histograms produced in the laboratory show many similarities to histograms for natural samples, offering the hope that laboratory results may be used to interpret P-T histories of natural samples. Received: 20 May 1997 / Accepted: 3 April 1998     

The use of fluid inclusion decrepitometry to distinguish mineralized and barren quartz veins in the aberfoyle tin-tungsten mine area, Tasmania

In the Aberfoyle Sn/W district of N.E. Tasmania, mineralization is in quartz veins associated with Devonian granite. The host rocks to the mineralization are folded Silurian quartzites, greywackes and shales and these also contain abundant pre-mineralization quartz veins which can be difficult to distinguish from irregularly mineralized ore veins on geological criteria, especially in drill core. It was found that the decrepitation characteristics of the quartz, chiefly the intensity ratio of high and low temperature peaks, which are developed in all decrepigrams, enable a distinction between the two generations of veins to be readily made. The differences between the fluid inclusions in the two generations of veins are relatively subtle, however it seems clear that “CO₂-rich” inclusions having a wide range of composition and density are the main source of decrepitation events and that the major differences in decrepitation behaviour can be correlated with differences in average homogenization temperature of these inclusions. Even those ore veins which have undergone moderate ductile deformation have the typical signature of their origin. The decrepitation results are supported by analyses of inclusion gases by Raman microprobe. These analyses differentiate a third group of veins which are possibly unmineralized veins belonging to a separate hydrothermal system.     

A boundary layer-induced immiscibility in naturally re-equilibrated H2O-CO2-NaCl inclusions from metamorphic quartz (Western Carpathians,Czechoslovakia)

Naturally re-equilibrated fluid inclusions have been found in quartz crystals from alpine fissures of the Western Carpathians. Re-equilibration textures, such as planar arrangement of the decrepitation clusters as well as the quartz c- and a-axis oriented fracturing indicate explosion of fluid inclusions. The extent of fracturing, which is dependent on inclusion diameters, suggests inclusion fluid overpressures between 0.6–1.9 kb. Microthermometry data are controversial with the textures because of indicating roughly fixed initial fluid composition and density during re-equilibration, although inclusion volumes have been sometimes substantially reduced by crystallization of newly-formed quartz. It is concluded that fluid loss from re-equilibrated inclusions must have been compensated for by replacing equivalent quartz volume from cracks into parent inclusion. Such a mechanism has operated in a closed system and the re-equilibration related cracks have not been connected with mineral surface. The compositional and density differences between aqueous inclusions in decrepitation clusters and CO₂-rich parent inclusions cannot be interpreted in terms of classical fluid immiscibility. Moreover, monophase liquid-filled aqueous inclusions and coexisting monophase CO₂ vapour-filled inclusions in the decrepitation clusters are thermodynamically unacceptable under equilibrium metamorphic conditions. The effect of disjoining pressure resulting from structural and electrostatic forces in very thin fractures is suspected to have caused density and compositional inconsistencies between parent and cluster inclusions, as well as the unusual appearance of cluster inclusions. In high-grade metamorphic conditions, the re-equilibration probably leads to boundary layer-induced immiscibility of homogeneous H₂O–CO₂–NaCl fluids and to formation of compositionally contrasting CO₂-rich and aqueous inclusions.     

Decrepitated UHP fluid inclusions: about diverse phase assemblages and extreme decompression rates (Erzgebirge, Germany)

Minute polyphase inclusions in garnet of quartzofeldspathic rocks (saidenbachite) from the Saxonian Erzgebirge, Germany, contain microdiamond or graphite, phlogopite, quartz, paragonite, phengite and other minerals in minor amounts. These inclusions are interpreted to represent an original dense COH + silicate fluid, trapped in crystallizing garnet at depths of >150 km. Inspection of the inclusion population in a single garnet by SEM reveals two characteristic features: (i) The shape of most inclusions indicates healed radial cracks in the host garnet, and, thus, the buildup of a significant differential pressure ΔP, i.e. a contrast in pressure between the inclusion (P_i) and the host mineral (P_e). The mineral assemblages sealing the cracks and showing an equilibrated microstructure indicate temperatures of ～750 ± 50 °C and pressures below 2.5 GPa. (ii) The diverse types of inclusions appear to be randomly distributed in the garnet host. Thus, the variable phase assemblages do not reflect a compositional evolution of the fluid trapped in the garnet. Combining observations (i) and (ii), we propose that the diversity of the phase assemblage in the inclusions is the result of decrepitation at different times, and thus, of distinct histories of P_i, as ΔP at decrepitation is primarily controlled by inclusion size and shape. Applying a flow law for dislocation creep of garnet, a low strength of garnet at 750 ± 50 °C for low geological strain rates is predicted. Thus, differential pressure should have been kept low (i.e. P_i≈ P_e) by continuous stretching of the inclusion for typical exhumation rates of metamorphic rocks. To attain the differential pressure (P_i >> P_e) required for catastrophic brittle failure of the garnet host, the decompression rate must have been extremely high. As a robust lower bound, a minimum exhumation rate on the order of 100 m year^?1 is suggested, which corresponds to ascent rates of magma.     

Compositional re-equilibration of fluid inclusions in quartz

Compositional modifications to salt-water fluid inclusions in quartz were observed following exposure to disequilibrium conditions in a series of laboratory experiments in which samples containing inclusions of known composition were annealed at 3 kbar and 600≤T≤825°C in the presence of fluids having different compositions for time intervals ranging from a few days to one month. Changes in inclusion compositions following re-equilibration were monitored using salt crystal dissolution temperatures and/or IR (infra red) spectroscopy. The behaviors of both synthetic and natural fluid inclusions were studied. The synthetic samples were re-equilibrated under P _int=P _conf conditions to minimize stress in the crystal surrounding the inclusions, and were subjected to both f _H2O ^int f _H2O ^conf and f _H2O ^int f _H2O ^conf . After re-equilibration for four days at T≥600°C, most inclusions displayed significant compositional changes Without decrepitation. Salinity variations as large as ≈ 25 wt% were inferred for brine inclusions exposed to f _H2O ^int ≠f _H2O ^conf for 16 days at 825°C. The majority of our observations are consistent with the net diffusion of water toward the reservior having the lowest μH₂O; i.e., synthetic NaCl−H₂O fluid inclusions exhibited increased Tm(NaCl)s (implying lower relative H₂O contents) when re-equilibrated in the presence of fluids having lower μH₂O, whereas, similar (and, in some cases, the same) inclusions exhibited decreased Tm(NaCl)s (implying higher H₂O contents) after exposure to fluids having higher μH₂O. The behavior of natural salt-water fluid inclusions during re-equilibration was generally consistent with corresponding observations on synthetic samples verifying that compositional changes are not restricted to synthetic inclusions. Our results clearly show that there was chemical communication between fluids trapped as inclusions in quartz and the external fluid reservoir. Additionally, it is evident that although applied stress can significantly enhance the re-equilibration rate, strain in the crystal host around the inclusions resulting from large pressure differentials between the internal and confining fluids is not a necessary prerequisite for compositional change. Finally, because significant compositional changes can be induced in brine inclusions in quartz during shortterm exposure to non-equilibrium conditions at 600≤T≤825°C in the laboratory, it is likely that similar changes may result at much lower temperatures during exposure of natural rocks to non-equilibrium conditions over geologic time.     

Fluid inclusions in high-pressure granulites of the Pan-African belt in Tanzania (Uluguru Mts): a record of prograde to retrograde fluid evolution

The high-pressure granulites of the Uluguru Mountains are part of the Pan-African belt of Tanzania, the metamorphic evolution of which is characterized by an anticlockwise P-T path. Mineral assemblages that represent distinct metamorphic stages are selected for fluid inclusion studies in order to deduce the fluid evolution in metapelites and pyroxene granulites from the prograde to the retrograde stage. Fluid inclusion data improve the petrologically derived P-T path and confirm the anticlockwise evolution. Fluid inclusions in quartz enclosed in garnet porphyroblasts in metapelites preserve prograde fluids of CO₂–N₂ composition and later-trapped pure CO₂. During isochoric heating at temperatures near the peak of metamorphism, deformation and recrystallization led to fluid homogenization yielding N₂-poor CO₂ composition in the metapelites. Near-peak CO₂–N₂ fluid inclusions in quartz of metapelites and CO₂ inclusions in garnet-pyroxene granulites are characterized by perfect negative crystal shape. Garnet formed in veins and as coronas around orthopyroxene represent the near-isochoric/isobaric cooling stage which is characterized by high-density CO₂-rich fluid inclusions. Up to 15 mol% N₂ in some primary CO₂ inclusions in corona garnet indicate small-scale fluid heterogeneity during the static garnet growth. The fact that high-density fluid inclusions are preserved, suggests a shallow dP/dT slope of the uplift path. Nevertheless, some fluid inclusions decrepitated or re-equilibrated and low-density CO₂ inclusions were trapped in the garnet-pyroxene granulite while N₂–CH₄ inclusions formed in the metapelites. Different fluid compositions in metapelite and metabasite argue for an internal control of the fluid composition by phase equilibria. In shear zones where the pyroxene granulite was transformed into scapolite-biotite schist, CO₂–N₂ and low-density N₂–CH₄ fluid inclusions indicate several stages of tectonic activity and suggest fluid influx from the nearby metapelites. High- and low-salinity aqueous inclusions observed beside CO₂ inclusions in garnet-pyroxene granulites, in vein quartz and shear zones could be of high-grade origin but are mainly re-equilibrated or re-trapped along healed microfractures during lower-grade stages. Received: 21 May 1997 / Accepted: 6 October 1997     

Preferential water loss from synthetic fluid inclusions

A fundamental question in most fluid inclusion studies is whether inclusions behave as compositionally closed systems after trapping, and, thus, represent samples of the fluid phase(s) present in the system at the time of their formation. This question was addressed in high-temperature laboratory experiments with synthetic fluid inclusions in quartz and it was found that at 825°C the inclusions exhibited open-system behavior with respect to water. Synthetic salt-water fluid inclusions in quartz were reequilibrated for 12 hours to 35 days at 825° C in a dry argon atmosphere under 1.5 kbar confining pressure. These conditions created initial internal overpressures (P _int> P _conf) of 1.5–4 kbar in the inclusions and differential water fugacities in the same sense i.e., fH₂OfH₂O. After 108 hours of reequilibration, preferential water loss had resulted in salinity increases as large as 22 wt% salt (e.g., from 57 to 79 wt% NaCl, as determined from measured temperatures of salt dissolution). Also, following reequilibration, a strong inverse correlation between salinity and inclusion volume was observed, and this trend became more pronounced with increasing reequilibration time. These observations, together with a lack of evidence for selective H₂O removal via hydration reactions, suggest that water loss occurred by a diffusion-related mechanism. Fluxes of 4x10^-11 g/cm²-s and diffusion coefficients on the order of 10^-9 cm²/s are calculated for water loss from the inclusions. The calculated H₂O diffusion coefficient is consistent with the determination of Blacic (1981) derived from hydrolytic weakening experiments, but is much larger than the value obtained by Giletti and Yund (1984) for volume diffusion of oxygen in isotope exchange experiments. These observations suggest that the mechanism of water loss from our synthetic fluid inclusions may have been pipe diffusion along dislocations, subgrain boundaries or other structural defects rather than bulk volume diffusion.The results of this study are relevant to the interpretation of fluid inclusions in quartz from several natural high-temperature environments where water fugacities of included and ambient fluids are known to have evolved along separate paths over geologic time.     

Fluid inclusion geochemistry in minerals obtained from Zhao-Ye gold metallogenetic belt, Shandong Province

A large number of fluid inclusions are observed in quartz contained in Au ores. A study of the geochemistry of inclusions from the Linglong Au deposit in Shandong Province shows that ore-forming temperature and pressure, frequency of appearance for critical inclusion, and saline halo of the main Au-bearing veins 108 and 51 increase in the direction of Linglong Fault. We concluded accordingly, that: (1) the Linglong Fault was a conduit structure for mineralization and will form a favourable place for prospecting where the fault intersects a host structure trending east-northeast; (2) distinct differences in geochemical characteristics are present in relation to the fluid inclusions contained in Au-bearing quartz veins and barren quartz veins, with the former having higher homogenization temperatures, appearing frequency for critical inclusion, content of CO₂, H₂ and CH₄, and molar concentration ratio of (H₂ + CH₄) to CO₂, than those of the latter; (3) decrepitation curves for the two sorts of quartz veins have obviously different characteristics; and (4) geochemical characteristics of fluid inclusions present in the quartz of quartz-vein-type Au ore deposits demonstrate that its metallogenetic pressure, salinity, and decrepitation temperature all increased progressively towards the deeper part of the quartz vein, approximating those of altered-rock-type Au ore deposits. We already know of some Au mines where quartz-vein-type Au ore deposits are turned at depth into altered-rock-type Au ore deposits. Therefore, attention should be paid to prospecting for altered-rock-type Au ore deposits below the quartz-vein-type. From this study, we believe that the geochemical study of fluid inclusions in minerals is a new and useful exploration approach, which should be further explored and used.     

Fluid inclusions in high pressure/low temperature rocks from the Calabrian Arc (Southern Italy): the burial and exhumation history of the subduction-related Diamante-Terranova unit

The Diamante-Terranova Unit (DIATU), in the Calabrian Arc of southern Italy, is part of an ophiolitic sequence involved in a high pressure/low temperature event (P=8 kbar; T =400 °C) followed by re-equilibration at greenschist facies conditions (P=3 kbar; T =300 °C). The rocks contain two types of quartz–calcite veins – an earlier generation of deformed, folded and faulted veins formed during or before subduction, and a later set of planar, undeformed veins formed during exhumation of the DIATU. The earlier folded quartz–calcite veins contain regularly shaped aqueous inclusions as well as inclusions with a highly irregular dendritic texture. The later planar veins contain only regularly shaped aqueous inclusions similar to those in the earlier veins. In both vein types, all inclusions are demonstrably secondary in origin. Regularly shaped inclusions from both vein types are low salinity (0–5 wt% NaCl). Most contain liquid and vapour and homogenize to the liquid (Th 135–180 °C), whereas others contain only liquid at room temperature. Both the two-phase and monophase inclusions occur in the same fractures and are thought to record the same trapping event, with the monophase inclusions remaining metastable liquid at room temperature. No microthermometric data could be obtained from the dendritic inclusions in the earlier folded veins. Inclusions with the highly irregular dendritic texture found in the earlier veins are similar to those produced experimentally during laboratory-induced deformation of synthetic inclusions in quartz under conditions of internal underpressure, simulating either isobaric cooling or isothermal compression. The occurrence of inclusions with the dendritic texture in the earlier folded veins, and their absence from the later planar veins, suggests that the earlier veins formed before or during subduction and were folded and faulted in a compressional environment and their contained fluid inclusions were modified to produce the dendritic texture. During later uplift of the DIATU, planar veins containing regularly shaped aqueous inclusions formed and some of the fluids forming these veins were also trapped as secondary inclusions in the earlier folded veins. The results of this study provide convincing evidence that inclusions with a highly irregular dendritic morphology represent early inclusions that have survived prograde conditions in a high pressure/low temperature metamorphic environment (but have been texturally modified). The high pressure/low temperature ‘implosion’ texture is preserved over geological time, even after being overprinted by internal overpressure conditions generated during retrograde decompression. We suggest that inclusions that have survived prograde metamorphism are common in high pressure/low temperature rocks, but are often not identified as such due to their morphology which makes their recognition difficult.     

Modification of fluid inclusions in quartz by deviatoric stress. III: Influence of principal stresses on inclusion density and orientation

Extraction of useful geochemical, petrologic and structural information from deformed fluid inclusions is still a challenge in rocks displaying moderate plastic strain. In order to better understand the inclusion modifications induced by deviatoric stresses, six deformation experiments were performed with a Griggs piston-cylinder apparatus. Natural NaCl–H₂O inclusions in an oriented quartz crystal were subjected to differential stresses of 250–470 MPa at 700–900 °C and at 700–1,000 MPa confining pressure. Independently of the strain rate and of the crystallographic orientation of the quartz, the inclusions became dismembered and flattened within a crystallographic cleavage plane subperpendicular to σ ₁. The neonate (newly formed) inclusions that result from dismemberment have densities that tend towards equilibrium with P _fluid = σ ₁ at T _shearing. These results permit ambiguities in earlier deformation experiments on CO₂–H₂O–NaCl to be resolved. The results of the two studies converge, indicating that density changes in neonate inclusions are promoted by high differential stresses, long periods at high P and high T, and fluid compositions that maximize quartz solubility. Neonates spawned from large precursor inclusions show greater changes in density that those spawned from small precursors. These findings support the proposal that deformed fluid inclusions can serve as monitors of both the orientation and magnitude of deviatoric stresses during low-strain, ductile deformation of quartz-bearing rocks.     

Modification of fluid inclusions in quartz by deviatoric stress I: experimentally induced changes in inclusion shapes and microstructures

Fluid inclusions in quartz are known to modify their shapes and microstructures (textures) during weak plastic deformation. However, such changes have not been experimentally demonstrated and criteria are not available to relate them to paleostress conditions. To address these issues, quartz crystals containing natural CO₂–H₂O–NaCl fluid inclusions have been experimentally subjected to compressive deviatoric stresses of 90–250 MPa at 700°C and ~600 MPa confining pressure. Strains of up to 1% cause the inclusions to develop irregular shapes and to generate microcracks in crystallographic planes oriented subperpendicular to the major compression axis, σ ₁. The uniform alignment of the microcracks imparts a planar fabric to the samples. The microcracks heal and form swarms of tiny satellite inclusions. These new inclusions lose H₂O by diffusion, thereby triggering plastic deformation of the surrounding quartz via H₂O-weakening. Consequently, the quartz samples deform plastically only in domains originally rich in inclusions. This study shows that fluid inclusions deformed by deviatoric stresses may indeed record information on paleostress orientations and that they play a key role in facilitating crystal-plastic deformation of quartz.     

A mechanism for preferential H2O leakage from fluid inclusions in quartz,based on TEM observations

Preferential leakage of H₂O from fluid inclusions containing multiple gas components has been suspected in natural metamorphic rocks and has been demonstrated experimentally for synthetic H₂O-CO₂-rich inclusions in natural quartz. Knowledge of the physical and chemical characteristics of the leakage mechanism, which may be very complex, increases the value of natural fluid inclusions to metamorphic geology. It is proposed that crystal defects play a major role in nondecrepitative preferential H₂O leakage through quartz, and remain effective during metamorphism. Inclusions with either an internal overpressure or underpressure produce strain in the adjacent quartz crystal via the nucleation of many dislocations and planar defects (like Dauphiné twin boundaries). These defects allow preferential loss of H₂O from H₂O-CO₂-rich inclusions at supercritical conditions. The transport capacity of this leakage mechanism is enhanced by nucleation of small bubbles on defect structures. The nucleation of these bubbles seems to be a recovery process in strained crystals. Solubility gradients of quartz in water in a crystal with internally underpressurized inclusions may result in optical visible implosion halos in a three dimensional spatial arrangement, caused by the growth of small bubbles at the expense of the larger original fluid inclusion. Natural fluid inclusions from Naxos (Greece) are always associated with numerous interlinked dislocations. These dislocations may have been produced by plastic derormation or by crystal growth related processes (e.g. crack healing). The presence of small bubbles on these dislocations indicates that a similar leakage mechanism for H₂O must have occurred in these rocks.     

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.     

Fluid inclusion modification by H2O and D2O diffusion: the influence of inclusion depth, size, and shape in re-equilibration experiments

The mobility of H₂O and D₂O by diffusion through quartz is illustrated with H₂O-rich fluid inclusions synthesized at 600 °C and 337 MPa, within the α-quartz stability field. Inclusions are re-equilibrated at the same experimental conditions within a pure D₂O fluid environment. Consequently, a gradient in volatile fugacities is the only driving force for diffusion, in the absence of pressure gradients and deformation processes. Up to 100 individual inclusions are analyzed in each experiment before and after re-equilibration by microscopic investigation, microthermometry, and Raman spectroscopy. Changes in fluid inclusion composition are obtained from the ice-melting temperatures, and density changes are obtained from total homogenization temperatures. After 1-day re-equilibration, inclusions already contain up to 11 mol % D₂O. A maximum concentration of 63 mol % D₂O is obtained after 40-day re-equilibration. D₂O concentration profiles in quartz are determined from the concentration in inclusions as a function of their distance to the quartz surface. These profiles illustrate that deep inclusions contain less D₂O than shallow inclusions. At equal depths, a variety of D₂O concentration is observed as a function of fluid inclusion size: Small inclusions are stronger effected compared with large inclusions. A series of 19-day re-equilibration experiments are performed at 300, 400, 500, and 600 °C (at 337 MPa), at the same conditions as the original synthesis. The threshold temperature of diffusion is estimated around 450 °C at 337 MPa, because D₂O is not detected in inclusions from re-equilibration experiments at 300 and 400 °C, whereas maximally 26 mol % D₂O is detected at 500 °C. Our study indicates that the isotopic composition of natural fluid inclusions may be easily modified by re-equilibration processes, according to the experimental conditions at 600 °C and 337 MPa.     

Easily altered minerals and reequilibrated fluid inclusions provide extensive records of fluid and thermal history: gypsum pseudomorphs of the Tera Group, Tithonian-Berriasian, Cameros Basin

This study reports a complex fluid and thermal history using petrography, electron microprobe, isotopic analysis and fluid inclusions in replacement minerals within gypsum pseudomorphs in Tithonian-Berriasian lacustrine deposits in Northern Spain. Limestones and dolostones, formed in the alkaline lakes, contain lenticularly shaped gypsum pseudomorphs, considered to form in an evaporative lake. The gypsum was replaced by quartz and non-ferroan calcite (Ca-2), which partially replaces the quartz. Quartz contains solid inclusions of a preexisting non-ferroan calcite (Ca-1), anhydrite and celestine. High homogenization temperatures (T _h ) values and inconsistent thermometric behaviour within secondary fluid inclusion assemblages in quartz (147?C351°C) and calcite (108?C352°C) indicate high temperatures after precipitation and entrapment of lower temperature FIAs. Th are in the same range as other reequilibrated fluid inclusions from quartz veins in the same area that are related to Cretaceous hydrothermalism. Gypsum was replaced by anhydrite, likely during early burial. Later, anhydrite was partially replaced by Ca-1 associated with intermediate burial temperatures. Afterward, both anhydrite and Ca-1 were partially replaced by quartz and this by Ca-2. All were affected during higher temperature hydrothermalism and a CO₂-H₂O fluid. Progressive heating and hydrothermal pulses, involving a CO₂-H₂O fluid, produce the reequilibration of the FIAs, which was followed by uplift and cooling.     

Post-entrapment modification of fluid inclusions due to overpressure: evidence from natural samples

Abstract Effects of post-entrapment fluid-inclusion modification are examined with reference to retrogression-related quartz veins from the Caledonian, Øse Thrust, northern Norway. The inclusions occur in secondary trails, and contain high-density hypersaline aqueous fluids. On morphological characteristics, they are subdivided into, Type A: elongate, ellipsoidal and/or irregular inclusions, and Type B: more equant, regular, and/or negative crystal form. With reference to previous research on post-entrapment modification of inclusions in quartz it is proposed that Type A inclusions experienced little or no post-entrapment modification, whereas Type B inclusions show features characteristic of post-entrapment permanent inelastic stretching and/or leakage. This produces increased homogenization temperatures ( T _h), associated with increased inclusion volume and lowering of density, whilst maintaining constant salinity. The similarity of data for degree of fill and salinity between Type A and Type B inclusions indicates that Type B inclusions have primarily modified by stretch rather than leakage. However, the spread towards slightly larger volume of vapour in Type B inclusions suggests that some leakage has also occurred. Because stretched and/or partially leaked inclusions have increased T _h, isochore projections significantly underestimate trapping pressure ( P _t) relative to unmodified inclusions. Therefore, recognition of post-entrapment inclusion modification due to overpressure is crucial to avoid misinterpretation of data, but has considerable potential for constraining the detail of P-T trajectories of individual rocks. On this basis, rocks from the Øse Thrust zone, north Norway, are shown to have experienced rapid uplift on a 'clockwise' P-T-t path during the final stages of Caledonian (Scandian) orogenesis.