Mass Transfer, Oxygen Isotopic Variation and Gold Precipitation in Epithermal System: A Case Study of the Hishikari Deposit, Southern Kyushu, Japan

Abstract: Transportation of various kinds of elements occurred in wall rocks (Quaternary andesites) during the hydrothermal alteration accompanied by the Hishikari epithermal gold mineralization. For example, K₂O and MgO contents of wall rocks decrease away from the gold-quartz veins, while (CaO+Na₂O) content increases, and SiO₂ content is variable near the veins. Hydrothermal alteration zoning and bulk compositional variations in wall rocks suggest that the mixing of hydrothermal solution and acidic groundwater took place an important role as the cause for the hydrothermal alteration and bulk compositional variations. The relationship between dissolved silica concentration and temperature of hydrothermal solution mixed with groundwater is obtained based on precipitation kinetics-fluid flow–mixing model, and the computed results are compared with the distribution of SiO₂ minerals (quartz and cristobalite) in the hydrothermal alteration zones. This comparison suggests that the most reasonable flow rate of fluids migrating through hydrothermal alteration zones, and A/M (A: surface area of rocks interacting with fluid, M: mass of fluid) are estimated to be ca. 10^-4.2 m/sec, and ca. 0.10 m²/kg, respectively. The mixing of two fluids (hydrothermal solution and acidic groundwater) can also explain δ¹⁸O zoning in the altered country rocks, hydrothermal alteration zoning from K-feldspar through K-mica to kaolinite from the center (veins) to margin, and deposition of gold.     

Grain boundary migration of water and carbon dioxide during uplift of garnet-zone Alpine Schist, New Zealand

Abstract Deformed quartz veins in garnet-zone schist adjacent to the active Alpine Fault, New Zealand, have fluid inclusions trapped along quartz grain boundaries. Textures suggest that the inclusions formed in their present shapes during annealing of the deformed veins. Many of the inclusions are empty, but some contain carbon dioxide with densities that range from 0.16 to 0.80 g cm⁻³. No water, nitrogen or methane was detected. The inclusions are considerably more CO₂-rich than either the primary metamorphic fluid (<5% CO₂) or fluids trapped in fracture-related situations in the same, or related, rocks (<50% CO₂). Enrichment of CO₂ is inferred to have resulted from selective migration (wicking) of saline water from the inclusions along water-wet grain boundaries after cooling-induced immiscibility of a water-CO₂ mixture. Inclusion volumes changed after loss of water. Non-wetting CO₂ remained trapped in the inclusions until further percolation progressively removed CO₂ in solution. This mechanism of fluid migration dominated in ductile quartz-rich rocks near, but below, the brittle-ductile transition. At deeper levels, hydraulic fracturing is also an important mechanism for fluid migration, whereas at shallower levels advection through open fractures dominates the fluid flow regime.     

Synmetamorphic veining: origin of andalusite-bearing veins in the Vedrette di Ries contact aureole, Eastern Alps, Italy

Discordant andalusite-biotite-quartz-bearing veins occur in the contact aureole of the Vedrette di Ries pluton (Italian Eastern Alps), never outside the area of contact metamorphic andalusite development. Andalusite veins are found only within andalusite-bearing hornfelses, and vein biotite occurs wherever host-rock garnet is partially replaced by biotite. Veins formed during contact metamorphism, synchronously with the crystallization of andalusite and biotite within host rocks. Their pegmatitic structure and their orientation suggest that vein parageneses crystallized within fluid-filled cavities that opened by hydraulic fracturing. A mechanism of synmetamorphic veining is proposed to explain rock failure and subsequent mineral deposition within veins. During hydrofracturing induced by dehydration reactions in response to heating in the aureole, fissures were immediately filled with locally derived fluids. The lack of large-scale flux, together with high fluid pressures required by hydrofracturing, suggest fluid in the cavities was a virtually stagnant, passive medium, and that mass-transport toward fractures was driven by intergranular diffusion. Because temperature and P_f values within veins are similar to those in the host rock, vein assemblages are interpreted as the stable, high-T side of reactions taking place within pelitic schists, at the time when fractures opened. Once nucleation of product phases occurred, chemical components released by dissolution of reactant minerals were driven to precipitation sites by chemical potential gradients. Since nucleation was favoured at the strained grains of vein walls, andalusite and biotite simultaneously grew in vein and host rock. The proposed genetic model contrasts with generally adopted metasomatic mechanisms for the genesis of Al₂SiO₅-bearing veins, in not requiring large fluid/rock ratios or a highly ‘aggressive’ fluid composition. The mechanism of synmetamorphic veining may be particularly useful in the interpretation of vein occurrences in medium- and deep-crustal rocks which have undergone extensive devolatilization.     

Stable isotopic and fluid inclusion evidence for meteoric fluid penetration into an active mountain belt; Alpine Schist, New Zealand

Calcite and quartz veins have formed, and are forming, in steeply dipping fissures in the actively rising Alpine Schist metamorphic belt of New Zealand. The fluids that deposited these minerals were mostly under hydrostatic pressure almost down to the brittle-ductile transition, which has been raised to 5-6 km depth by rapid uplift. Some fluids were trapped under lithostatic pressures. Fluids in the fissure veins were immiscible H₂O + NaCl-CO₂ mixtures at 200-350 C. Bulk fluid composition is 15-20 mol% CO₂ and <4.3 total mol CH₄+ N₂+ Ar/100mol H₂O. Water hydrogen isotopic ratio δD_H2O in the fissure veins spans -29 to -68‰, δ¹⁸O_H2O -0.7 to 8.5‰, and bulk carbon isotopic ratio δ¹³C ranges from -3.7 to -11.7‰. The oxygen and hydrogen isotopic data suggest that the water has a predominantly meteoric source, and has undergone an oxygen isotope shift as a result of interaction with the host metamorphic rock. Similar fluids were present during cooling and uplift. Dissolved carbon is not wholly derived from residual metamorphic fluids; part may be generated by oxidation of graphite.     

Active skarn formation beneath Lascar Volcano, northern Chile: a petrographic and geochemical study of xenoliths in eruption products

Calcsilicate xenoliths occur in large numbers in some lavas and pyroclastic flows of Lascar Volcano. Their whole-rock major element and REE compositions indicate that the protolith was the Upper Cretaceous Yacoraite Formation, which crops out extensively in NW Argentina. The whole-rock major element compositions of the xenoliths fall into specific groups suggesting a strong geochemical zonation in the skarn zone. Three geochemical zones have been identified; (1) an outer metamorphic zone rich in wollastonite; (2) a middle zone rich in pyroxene and garnet; (3) an inner zone rich in pyroxene and magnetite. The two innermost zones have developed from the wollastonite zone by infiltration of metasomatic fluids rich in Fe, Mn, Mg, Ti and Al. Whole-rock REE patterns have not changed significantly during prograde metamorphism and metasomatism, indicating REE immobility in the altering fluids. Retrograde alteration by acid-sulphate fluids produced anhydrite skarns and secondary calcite and wilkeite veins in the wollastonite zone. The carbon and oxygen isotopic compositions of this calcite indicate that it formed by Rayleigh crystallization from a low-temperature (<200 °C) fluid containing dissolved H₂CO₃. The calculated δ¹⁸O of the water in this fluid suggests a magmatic origin whereas the calculated δ¹³C of the dissolved carbonate is consistent with derivation from rocks of the Yacoraite Formation at 350 °C. It is suggested that the magmatic acid-sulphate fluid was responsible for leaching carbonate from the surrounding carbonate rocks and redepositing it in the skarn zone. REEs were mobilized during the retrograde acid-sulphate and acid-carbonate alteration. A negative Ce anomaly associated with this carbonate and sulphate indicates high oxygen fugacities in the mineralizing fluids.     

Constraints from high-pressure veins in eclogites on the composition of hydrous fluids in subduction zones

Hydrous high-pressure veins formed during dehydration of eclogites in two paleo-subduction zones (Trescolmen locality in the Adula nappe, central Alps and Münchberg Gneiss Massif, Variscan fold belt, Germany) constrain the major and trace element composition of solutes in fluids liberated during dehydration of eclogites. Similar initial isotopic compositions of veins and host eclogites at the time of metamorphism indicate that the fluids were derived predominantly from the host rocks. Quartz, kyanite, paragonite, phengite, zoisite and omphacite are the dominant minerals in the veins. The major element compositions of the veins are in agreement with experimental evidence indicating that the composition of solutes in such fluids is dominated by SiO₂ and Al₂O₃. Relative to N-MORB, the veins show enrichments of Cs, Rb, Ba, Pb, and K, comparable or slightly lower abundances of Sr, U, and Th, and very low abundances of Nd, Sm, Zr, Nb, Ti and Y. The differential fractionation of highly incompatible elements such as K, U and Th in the veins, as well as the presence of hydrous minerals in the eclogites rule out partial melting as a cause for vein formation. These results confirm previous suggestions that fluids derived from subducted basalt may have low abundances of high field strength elements, rare earth elements and Y. Variable vein-eclogite enrichment factors of incompatible alkalis and to a lesser extent Pb appear to reflect mineralogical controls (phengite, epidote-group minerals) on partitioning of these elements during dehydration of eclogite in subduction zones. However, abundance variations of incompatible elements in minerals from eclogites suggest that the composition of fluids released from eclogites at temperatures <700°C may not reflect true equilibrium partitioning during dehydration. Simple models for the trace elements U and Th indicate the relative importance of the basaltic and sedimentary portions of subducted oceanic crust in producing the characteristic chemical signatures of these elements in convergent plate margin volcanism.     

Stable isotope geochemistry of Alpine ophiolites: a window to ocean-floor hydrothermal alteration and constraints on fluid–rock interaction during high-pressure metamorphism

 The subduction of hydrated oceanic lithosphere potentially transports large volumes of water into the upper mantle; however, despite its potential importance, fluid–rock interaction during high-pressure metamorphism is relatively poorly understood. The stable isotope and major element geochemistry of Pennine ophiolite rocks from Italy and Switzerland that were metamorphosed at high pressures are similar to that of unmetamorphosed ophiolites, suggesting that they interacted with little pervasive fluid during high-pressure metamorphism. Cover sediments also have oxygen isotope ratios within the expected range of their protoliths. In the rocks that escaped late greenschist-facies retrogression, different styles of sub-ocean-floor alteration may be identified using oxygen isotopes, petrology, and major or trace element geochemistry. Within the basalts, zones that have undergone high- and low-temperature sub-ocean-floor alteration as well as relatively unaltered rocks can be distinguished. Serpentinites have δ¹⁸O and δ²H values that suggest that they were formed by hydration on or below the ocean floor. The development of high-pressure metamorphic mineralogies in metagabbros occurred preferentially in zones that underwent sub-ocean-floor alteration and which contained hydrated, fine-grained, reactive assemblages. Given that the transformation of blueschist-facies metabasic rocks to eclogite-facies assemblages involves the breakdown of hydrous minerals (e.g. lawsonite, zoisite, and glaucophane), and will thus liberate considerable volumes of fluids, metamorphic fluid flow must have been strongly channelled. High-pressure (quartz+calcite±omphacite±glaucophane±titanoclinohumite) veins that cut the ophiolite rocks represent one possible channel; however, stable isotope and major element data suggest that they were not formed from large volumes of exotic fluids. Fluids were more likely channelled along faults and shear zones that were active during high-pressure metamorphism. Such strong fluid channelling may cause fluids to migrate toward the accretionary wedge, especially along the slab–mantle interface, which is probably a major shear zone. This may preclude all but a small fraction of the fluids entering the mantle wedge to flux melting. Additionally, because fluids probably interact with relatively small volumes of rock in the channels, they cannot "scavenge" elements from the subducting slab efficiently. Received: 28 January 1999 / Accepted: 2 February 1999     

Shallow-level metamorphic fluids in a high uplift rat metamorphic belt; Alpine Schist, New Zealand

Abstract Fluids, some of which are CO₂-rich (up to 40 mol.% CO₂) and some of which are highly saline (up to 18 wt% NaCl equivalent), are trapped as fluid inclusions in quartz-calcite (∼ metallic minerals) veins which cross-cut the pumpellyite-actinolite to amphibolite facies rocks of the Alpine Schist. Fluids were commonly trapped as immiscible liquid-vapour mixes in quartz and calcite showing open-space growth textures. Fluid entrapment occurred at fluid pressures near 500 bars (possibly as low as 150 bars) at temperatures ranging from 260 to 330° C. Saline fluids may have formed by partitioning of dissolved salts into an aqueous phase on segregation of immiscible fluids from a low-density CO₂-rich fluid. Calcite deposited by these fluids has δ¹³C ranging from – 8.4 to – 11.5 and δ¹⁸O from + 4 to + 13. Isotopic data, fluid compositions and mode of occurrence suggest that the fluids are derived from high-grade metamorphic rocks. Fluid interaction with wall-rock has caused biotite crystallization and/or recrystallization in some rocks and retrogression of biotite to chlorite in other rocks.
Fluid penetration through the rock is almost pervasive in many areas where permeability, probably related to Alpine Fault activity, has focussed fluids on a regional scale into fractured rocks. The fluid flow process is made possible by high uplift-rates (in excess of 10 mm/year) bringing hot rocks near to the surface.     

http://www.sciencedirect.com/science/article/pii/S1674987111000764

The Jinding Zn-Pb deposit has been generally considered to have formed from circulating basinal fluids in a relatively passive way,with fluid flow being controlled by structures and sedimentary facies,similar to many other sediments-hosted base metal deposits.However,several recent studies have revealed the presence of sand injection structures,intrusive breccias,and hydraulic fractures in the open pit of the Jinding deposit and suggested that the deposit was formed from explosive release of overpres-sured fluids.This study reports new observations of fluid overpressure-related structures from underground workings(Paomaping and Fengzishan).which show clearer crosscutting relationships than in the open pit.The observed structures include:I) sand(±rock fragment) dikes injecting into fractures in solidified rocks:2) sand(±rock fragment) bodies intruding into unconsolidated or semi-consolidated sediments;3) disintegrated semi-consolidated sand bodies;and 4) veins and breccias formed from hydraulic fracturing of solidified rocks followed by cementation of hydrothermal minerals.The development of ore minerals(sphalerite) in the cement of the various clastic injection and hydraulic fractures indicate that these structures were formed at the same time as mineralization.The development of hydraulic fractures and breccias with random orientation indicates small differential stress during mineralization,which is different from the stress field with strong horizontal shortening prior to mineralization. Fluid flow velocity may have been up to more than 11 m/s based on calculations from the size of the fragments in the clastic dikes.The clastic injection and hydraulic fracturing structures are interpreted to have formed from explosive release of overpressured fluids,which may have been related to either magmatic intrusions at depth or seismic activities that episodically tapped an overpressured fluid reservoir.Because the clastic injection and hydraulic structures are genetically linked with the mineralizing fluid source,they can be used as a guide for mineral exploration.     

Andalusite-bearing veins at Vedrette di Ries (eastern Alps, Italy): fluid phase composition based on fluid inclusions

Abstract Andalusite-bearing veins formed during contact metamorphism in the aureole of the Vedrette di Ries tonalite. In the veins, quartz crystals that are completely armoured by andalusite or that occur in strain shadow areas contain three generations of fluid inclusions: low-salinity H₂O-CO₂-CH₄ mixtures with CH₄/(CO₂+ CH₄) ± 0.35 (type A); low-salinity aqueous fluids (type B); H₂O-free, CO₂-CH₄ fluids with the same carbonic speciation as A (type C). Carbonic types A and C typically have a dark appearance, which is attributed to graphite coatings on inclusion walls. Microstructural analysis of the host quartz and calculated densities indicate that type A inclusions were likely trapped during vein formation. These inclusions underwent strain-assisted re-equilibration during cooling that resulted in density increases without change of composition. After the rocks had cooled below about 350 ° C, type C inclusions appear to have formed from one of the immiscible fractions after unmixing of the H₂O-CO₂-CH₄ fluid mixtures. Aqueous type B inclusions, apparently trapped between 225 and 350 ° C, could represent an independent fluid, or could be the H₂O-rich fraction of unmixed type A fluids. Taking account of the uncertainties, the composition and density of the complex type A inclusion fluids are in good agreement with the properties of primary fluids calculated from the petrological data. The fluid inclusion data support the model of vein formation by hydrofracturing as a result of dehydration of graphitic metapelites. These new results also demonstrate the importance of considering strain in the interpretation of metamorphic fluid inclusions.     

Fluid generation, vein formation and the degree of fluid–rock interaction during decompression of high-pressure terranes: the Schistes Lustrés, Alpine Corsica, France

Centimetre‐ to decimetre‐wide quartz+calcite veins in schistes lustrés from Alpine Corsica were formed during exhumation at 30–40 Ma following blueschist facies metamorphism. The δ¹⁸O and δ¹³C values of the veins overlap those of the host schistes lustrés, and the δ¹⁸O values of the veins are much higher than those of other rocks on Corsica. These data suggest that the vein‐forming fluids were derived from the schistes lustrés. Fluids were probably generated by reactions that broke down carpholite, lawsonite, chlorite and white mica at 300–350 °C during decompression between c. 1400 and 800 MPa. However, the δ¹⁸O values of the veins are locally several per mil higher than expected given those of their host rocks. The magnitude of oxygen isotope disequilibrium between the veins and the host rock is inversely proportional to the δ¹⁸O value of the host rock. Additionally, calcite in some schists is in isotopic equilibrium with calcite in adjacent veins, but not with the silicate fraction of the schists. Locally, the schists are calcite bearing only within 1–20 cm of the veins. The vein‐forming fluids may have been preferentially derived from calcite‐bearing, high‐δ¹⁸O rocks that are common within the schistes lustrés and that locally contain abundant (>15%) veins. If the fluids were unable to completely isotopically equilibrate with the rocks, due to relatively rapid flow at moderate temperatures or being confined to fractures, they could form veins with higher δ¹⁸O values than those of the surrounding rocks. Alteration of the host rocks was probably inhibited by isolation of the fluid in ‘quartz‐armoured’ veins. Overall, the veins represent a metre‐ to hectometre‐scale fluid‐flow system confined to within the schistes lustrés unit, with little input from external sources. This fluid‐flow system is one of several that operated in the western Alps during exhumation following high‐pressure metamorphism.     

Structurally controlled fluid flow associated with breccia vein formation

A breccia vein sampled from a shear zone in greenschist facies metapelites at Mount Isa, Queensland, Australia, shows a systematic variation in vein geometry that is related to the geometry of folding and faulting within the sample. Calcite vein-fill is coarse grained and equigranular, suggesting precipitation in a fluid-filled space. Partially folded veins suggest that veining occurred during folding and faulting. The breccia vein contains a central zone in which dilation has occurred simultaneously in all directions in the plane of section, implying that this was a zone of high fluid pressure and nearly isostatic differential stress during folding and faulting. From these observations, it can be inferred that the breccia vein was a zone of high permeability and a likely fluid channel during deformation. This hypothesis was tested by stable isotope analysis of veins and host rocks. The calcite veins have δ¹³C values of -11.1 ± 0.1% and δ¹⁸O values of 6-10%_o, whereas the host metapelite has δ¹³C values of -10.62 and -10.11% and δ¹⁸O values of 14-15%_o. These values are consistent with an igneous-derived, H₂O-dominated fluid that exchanged little oxygen with the host rocks, but derived much of its carbon from the wall rock. The isotopic disequilibrium between the veins and the wall rock confirms that the fluid was externally derived, and that the breccia vein acted as a channel for large-volume fluid flow within the shear zone.     

Oxygen, carbon, and strontium isotope geochemistry of diamond-bearing carbonate rocks from Kumdy-Kol, Kokchetav Massif, Kazakhstan

Diamond-bearing carbonate rocks from Kumdy-Kol, Kokchetav massif, Kazakhstan, were strongly altered by fluids flowing through fractures and infiltrating along grain boundaries during exhumation. Alteration includes retrogradation of high-grade silicate assemblages by hydrous minerals, replacement of diamond by graphite and of dolomite by calcite. Diamond-bearing carbonate rocks are among the most intensely altered isotopically with δ¹⁸O_VSMOW values as low as +9‰, δ¹³C_VPDB=−9‰, and ⁸⁷Sr/⁸⁶Sr as high as 0.8050. Evidence of isotopic equilibration between coexisting dolomite and high-Mg calcite during ultrahigh-pressure metamorphism (UHPM) is preserved only rarely in samples isolated from infiltrating fluids by distance from fractures. Isotopic heterogeneity and isotopic disequilibrium are widespread on a hand-specimen scale. Because of this lack of homogeneity, bulk analyses cannot provide definitive measurements of ¹³C/¹²C fractionation between coexisting diamond and carbonate. Our study adequately documents alteration on a scale commensurate with observed vein structures. But, testing the hypothesis of metamorphic origin of microdiamonds has not fully succeeded because our analytical spatial resolution, limited to 0.5 mm, is not small enough to measure individual dolomite inclusions or individual diamond crystals.     

Hydrothermal alterations in the Echassières granitic cupola (Massif central,france)

Detailed petrographic and mineralogic investigations of an albite-lepidolite granite at Echassières (Massif Central, France; scientific deep drill program) shows the existence of hydrothermal stages which are closely related to the magmatic and structural history. According to fluid inclusion data, K-Ar datations and ¹⁸O/¹⁶O-D/H compositions of secondary minerals, two successive hydrothermal periods have been recognized. The early one (273–268 million years) produced a series of aluminous phyllosilicates: muscovite, pyrophyllite, donbassite, tosudite, kaolinite which are observed as vein deposits (<10 mm wide) and alteration products of primary minerals in wall-rocks. The vein system was sealed by monomineralic assemblages during a cooling period (400–150°C). This early hydrothermal alteration stage was controlled by interactions of rock with low salinity (1–10 wt% NaCl equivalent) fluids expelled from the granitic body during the cooling processes. The chemical properties of these fluids were the following: low pH, very low Mg and Fe and high Li, Na and K contents. Thermodynamic calculations show that the sequence pyrophyllite, Li-bearing donbassite, tosudite is mostly temperature dependent. From the chemical composition of secondary minerals and isotopic data it can be deduced that these fluids, which have a meteoric origin, have been expelled from the granite body during its cooling period and after interaction with it at high temperature. The late hydrothermal stage corresponds to deposits of fluorite and Fe-Mg rich illite (151 million years) in subvertical fractures. Temperature conditions did not exceed 250° C and fluids came through the surrounding metamorphic rocks into the granitic body. IIlite/smectite mixed-layer minerals have been identified in subvertical fractures which were opened during Tertiary periods. In the host micaschists, successive hydrothermal alterations took place during the cooling of the Beauvoir granite. Early magmatic fluids interacted with these micaschists. Locally, the metamorphic assemblage is replaced by a metasomatic one. Secondary topaz and (F, Li)-rich mica crystals were formed over a range of 450 of 150°C. Later hydrothermal fluids reacted with the country rocks to form phengite-biotite, chlorite-illite and kaolinite over a range of 300 to 150°C. Illite/smectite mixed-layer minerals crystallized in the roof micaschists and within the Beauvoir granite during the Tertiary alteration period. Meteoric water invaded open fractures producing supergene alteration mineral assemblages.     

Evolution of gas and aqueous fluid in low-permeability argillaceous rocks during uplift and exhumation of the central Swiss Alps

Fluid chemistry and the hydraulic regime in a marl formation of the Swiss Alps were studied by a number of techniques. Fluid inclusions record the conditions of maximum burial and regional low-temperature metamorphism, whereas fluid samples and hydraulic tests derived from deep boreholes reflect present-day, near-surface conditions. The characterization of the different types of fluids places constraints on the geochemical and hydraulic evolution of low-permeability argillaceous rocks during uplift and exhumation.Fluid inclusions were studied by microthermometry and sampled directly by decrepitation techniques. They contain a two-phase system consisting of an aqueous fluid and a coexisting CH₄-rich gas (T=190–250°C, P_lith≈2500 bar). Bulk and isotopic compositions of aqueous fluid inclusions are consistent with a mixture of connate seawater and water derived from the dehydration of clay minerals. Methane was generated in situ by thermal cracking of kerogen. Textural evidence and stable isotopic signatures of carbonates in veins and in the rock matrix indicate local buffering of fluid compositions and very low water/rock ratios. Free fluids residing in the present-day fracture and matrix porosity consist of CH₄-saturated Na–Cl groundwater with minute amounts of free CH₄ gas which occurs in druses. Their chemical and isotopic compositions are very similar to those of the fluid inclusions, suggesting a common origin. Post-metamorphic admixtures of externally derived waters cannot be identified, and it is suggested that present-day Na–Cl groundwaters that occur in the central parts of the marl have resided in the formation since the time of metamorphism some 20 Ma b.p. The only major change in the fluid composition has been the outgassing of CH₄ from the formation, most probably by diffusion.The hydraulic regime during metamorphism was characterized by localized fluid underpressures in open veins because widely scattered, sub-hydrostatic pressures were often identified in fluid inclusions. The central part of the argillaceous rock body, approximately coinciding with the region where Na–Cl groundwaters occur, has sub-hydrostatic pressures today, as indicated by hydraulic tests in deep boreholes.Both the closed-system behavior derived from the chemical and isotopic characteristics of the fluids and the (recurrent or continuous) existence of hydraulic underpressures suggest very low permeabilities of argillaceous rocks during metamorphism and throughout subsequent uplift and exhumation. All fluids present in the central parts of the formation are either connate or produced in situ. Even though major events of brittle faulting and unloading due to uplift occurred since the peak of metamorphism, fluid flow through the formation has been negligible.     

Relationship between CO2-dominated fluids,hydrothermal alterations and gold mineralization in the Red Lake greenstone belt,Canada

The Red Lake greenstone belt is one of the foremost Au mining camps in Canada and hosts the world-class Campbell-Red Lake Au deposit. Belt-scale hydrothermal alteration is characterized by proximal ferroan dolomite zones associated with Au mineralization surrounded by distal calcite zones, both being accompanied by potassic alterations (sericite, muscovite, and biotite). At the Campbell-Red Lake and Cochenour deposits Au mineralization (in particular high-grade ore) is associated with silica and sulfides (especially arsenopyrite) that replace carbonate ± quartz veins and the host rocks. The prevalence of carbonic fluid inclusions and rare occurrence of aqueous-bearing inclusions in carbonate–quartz–Au veins in the Campbell-Red Lake deposit, and the consistency of homogenization temperatures of carbonic inclusions within individual fluid inclusion assemblages (FIA), have been interpreted to indicate that H₂O-poor, CO₂-dominated fluids were responsible for the carbonate veining and Au mineralization. Further studies of fluid inclusions in carbonate–quartz veins within and outside the deformation zone hosting the Campbell-Red Lake deposit (the Red Lake Mine trend) including the Cochenour Au deposit, the Redcon Au prospect, and outcrops in the distal calcite zone also reveal the dominance of carbonic fluid inclusions in vein minerals. These studies indicate that CO₂-dominated fluids were flowing through fractures during carbonate vein formation and Au mineralization both within and outside major structures. The carbonic fluid may have been initially undersaturated with water, or it may have resulted from phase separation of an H₂O–CO₂–NaCl fluid. In the latter case, phase separation modeling indicates that the initial fluid likely had XCO₂${\text{X}}_{{\text{CO}}_2}$ values larger than 0.8. Calculations based on hydrothermal mineral assemblages indicate XCO₂${\text{X}}_{{\text{CO}}_2}$ values in the host rocks from 0.025 to 0.85, reflecting a change from CO₂-dominated fluids in the fractures (veins) to H₂O-dominated fluids in the host rocks away from the fractures. The CO₂-dominated fluids were likely advected from granulite facies in the deeper crust, whereas the H₂O-dominated fluids were derived from the ambient host rocks of amphibole to greenschist facies. Calculations based on CO₂ requirements and source constraints indicate that the mineralizing fluids were likely two orders of magnitude more enriched in Au than the commonly assumed values of a few μg/L, which may explain why the Campbell-Red Lake deposit has a very high-grade of Au (average 21 g/t for the whole deposit and 81 g/t for the Goldcorp High-Grade zone). Fluid inclusion data suggest that the carbonate veining and Au mineralization likely took place at depths from 7 to 14 km. The development of crustiform–colloform structures in the carbonate ± quartz veins, which was previously interpreted to indicate relatively shallow environments, may alternatively have been related to extremely high fluid pressures and the CO₂-dominated nature of the fluids, which could have enhanced the brittle properties of the rocks due to their high wetting angles.     

The nature and distribution of fluids during amphibolite facies metamorphism, Naxos (Greece)

On the basis of fluid inclusion evidence, pervasive influx of deep-seated CO₂-rich fluids has been invoked to account for mid- to upper amphibolite facies (M2_B) metamorphism on the island of Naxos (Cyclades, Greece). In this paper, mineral devolatilization and melt equilibria are used to constrain the composition of both syn- and post-peak-M2_B fluids in the deepest exposed levels of the metamorphic complex. The results indicate that peak-M2_B fluids were spatially and compositionally heterogeneous throughout the high-grade core of the complex, whereas post-peak-M2_B fluids were generally water-rich. The observed heterogeneities in syn-M2_B fluid composition are inconsistent with pervasive CO₂-flushing models invoked by previous workers on the basis of fluid inclusion evidence. It is likely that few CO₂-rich fluid inclusions on Naxos preserve fluids trapped under peak metamorphic conditions. It is suggested that many of these inclusions have behaved as chemically open systems during the intense deformation that accompanied the uplift of the metamorphic complex. A similar process may explain the occurrence of some CO₂-rich fluid inclusions in granulite facies rocks.     

Gold mineralization in the West Hoggar shear zone,Algeria

The Amesmessa gold prospect is located along a vertical N-S-trending crustal-scale ductile shear zone; stretching lineations are subhorizontal. This major shear zone is a Late Pan African dextral strike-slip fault of the Pharusian Belt of the Tuareg Shield (Algeria). The Amesmessa shear zone is asymmetric: strong thermal and deformational gradients are present along its western border where biotitic ultramylonites are in contact with a rigid Archean complex (In Ouzzal block), whereas there is a progressive gradation, through mylonite then protomylonite, to the Proterozoic gneiss of the Eastern block which displays co-axial Pan African structures. The Amesmessa shear zone is characterized by the presence of a felsic dike complex emplaced during shearing, and forming the most important parent material for ultramylonites. Basic magmas and carbonatites also intruded within the shear zone. The gold-rich quartz veins are located within the ultramylonitic western part of the shear zone. These N-S-trending laminated quartz veins formed during the late increments of shearing (plastic/brittle transition), by repeated syntectonic hydraulic fracturing along zones of rheological contrast parallel to foliation. The ore mineral association (pyrite, galena, native gold, sphalerite) crystallized in the deformed quartz matrix along late shear planes. Undeformed E-W trending banded quartz veins are present in the mylonitic eastern part of the shear zone; their gold content is low and no native gold has been observed. A strong hydrothermal alteration resulted in the development (along the walls of the N-S gold-bearing quartz veins) of a 5-m-wide carbonate-sericite-albite-pyrite secondary mineral association which implies an important CO₂ supply and moderate temperature conditions. There is no alteration halo around the E-W quartz veins. Ultramylonites, hydrothermally altered rocks and quartz veins display similar REE patterns characterized by strong LREE enrichments. Shear-related fluids could be likely parental fluids for the Amesmessa gold mineralization and the associated hydrothermal alteration. Hydrothermal fluids were drawn into dilation zones and filled opening fractures along the main planar discontinuity of the most deformed rocks. The supply of CO₂ may come from a deep-seated source as suggested by the presence of carbonatite dikes in the shear zones and the existence of CO₂-H₂O-rich fluid inclusions in quartz. The location of the gold-bearing quartz veins in the western part of the shear zone can be explained by the presence of strong thermal and rheological gradients.     

Infiltration-driven dehydration and anatexis in granulite facies metagabbro, Grenville Province, Ontario, Canada

Dark hornblende + garnet-rich, quartz-absent metagabbro boudins from the Seguin subdomain, Ontario Grenville Province, are transected by anastomosing light-coloured veins rich in orthopyroxene, clinopyroxene, plagioclase and sometimes quartz. The veins vary in texture from fine-grained diffuse veins and patches that overprint the metagabbro, to coarse tonalitic leucosomes with sharp borders. The diffuse veins and patches are suggestive of channellized subsolidus dehydration of the metagabbro, while the tonalitic leucosomes are suggestive of local internally-derived anatexis. All vein types grade smoothly into each other, with the tonalitic leucosomes being the latest.
Relative to the host metagabbro, the veins have higher Si, Na, Ba & Sr, lower Fe, Mg, Ca & Ti, and similar Al. The coarser veins are enriched in K. Plagioclase becomes steadily enriched in Na in the transition from host metagabbro (An₄₇) to the veins (An₃₅), and in the coarsest veins it is antiperthitic. Differences in composition of the other minerals between host metagabbro and vein are minor. Pressure–temperature estimates are scattered, but indicate a minimum temperature during vein formation of 700°C at about 8 kbar.
Mass balance constraints indicate that the veins formed from the metagabbro in an open system. The transecting veins are interpreted to represent pathways of Si + Na + Ba + Sr ± K ± Al-enriched, low a _H2O fluids that metasomatized the host metagabbro to form the anhydrous veins. An initial period of localized solid-state dehydration of the metagabbro, represented by the diffuse veins, was followed by a transition to localized anatexis, represented by the tonalitic leucosomes. The change to anatexis may have been due to the addition of K to the infiltrating fluid. The source and delivery mechanism of the fluids is unknown.     

P-T-X (CO2) conditions in mafic and calc-silicate hornfelses from Oberon, New South Wales, Australia

Abstract The Rockley Volcanics from near Oberon, New South Wales occur within the aureole of the Carboniferous Bathurst Batholith and have been contact metamorphosed at P ∼ 100 ± 50MPa (10.5kbar) and a maximum T ∼ 565°C in the presence of a C–O–H fluid. Prior to contact metamorphism the volcanics were regionally metamorphosed and altered with the extensive development of actinolite, chlorite, plagioclase, quartz and calcite. The contact metamorphosed equivalents of these rocks have been subdivided into: Ca-poor (cordierite + gedrite), Mg-rich (amphibole + olivine + spinel), mafic (amphibole + plagioclase) and Ca-rich (amphibole + garnet + diopside; diopside + plagioclase; garnet + diopside + wollastonite) rocks.
The chemistry of the minerals in the hornfelses was controlled by the bulk rock chemistry and fluid composition. Pargasites and hastingsites as well as an unusual phlogopite with blue green pleochroism, are found in Ca-rich hornfelses. A comparison of the assemblages with experimentally derived equilibria suggests that the fluid phase associated with the Ca-rich hornfelses was water-rich (X_co2= 0.1 to 0.3) while that associated with the Mg-rich hornfelses was enriched in CO₂ (X_co2 > 0.7). The different hornfels types have reacted to contact metamorphism independently in both their solid and fluid chemistries.