Gas Measurement of Fluid Inclusions from the Hishikari Epithermal Gold Deposit, Southern Kyushu, Japan, Using Laser Raman Microprobe

Abstract. Laser Raman microprobe analysis was performed on the fluid inclusions from the Honko-Sanjin zone in the Hishikari epithermal gold deposit, southern Kyushu, Japan. Gas concentrations of fluid inclusions through the zone were below detection limits (e.g., 5 mmole/kg H₂O for CO₂), with an exception at shallow portion in which the CO₂/N₂ mole ratio was determined to be 5.3. Boiling of hydrothermal solutions probably separated gases from ore fluids at the deep portion of the deposit, and migration of gases to shallow portion resulted in CO₂-rich steam-heated water and related acid alteration.     

Ionic association in H2O–CO2 fluids at mid-crustal conditions

The equilibrium constant, K _a, of the association reaction to form ion pairs from charged solute species in supercritical solutions can be calculated from a model based on published equations. Log K _a at constant pressure is a linear function of the inverse in the dielectric constant of the fluid times temperature. The dielectric properties of H₂O and CO₂ at supercritical pressures and temperatures can also be evaluated using the Kirkwood equation. Using Looyenga mixing rules, the dielectric constant of H₂O–CO₂ mixtures can be obtained and the change in log K _a with addition of CO₂ in aqueous solutions evaluated. These changes in log K _a with addition of CO₂ are consistent with measured changes of log K _a with addition of Ar in supercritical H₂O–Ar solutions.
Log K _a of KCl and NaCl increase to an increasing extent as the mole fraction of CO₂ increases in H₂O–CO₂ solutions. For instance, at 2 kbar and constant temperature between 400 and 600° C, log K _a of KCl increases by about two orders of magnitude whilst that of NaCl increases by over four orders of magnitude as the CO₂ mole fraction increases from 0.0 to 0.35. Such changes in log K _a will have dramatic effects on the solubility of minerals in CO₂-rich environments.     

Magmatic and hydrothermal processes in the Bouvet Triple Junction Region (South Atlantic)

Results of electron microprobe and microthermometric studies of samples collected from the Bouvet Triple Junction Region (BTJR) during a joint Russian-Italian geological expedition on the R/V Academician Nikolaj Strakhov (1994) have revealed new data on the composition of basaltic magmas and oceanic hydrothermal fluids connected with magmatic processes. Detailed analysis of basaltic glasses shows that the modem Mid-Atlantic Ridge (MAR) rift valley is composed of normal mid-ocean ridge basalts with low concentrations of K₂ O and TiO_z (N-MORB), while its flanks are more enriched with these components approaching E-MORB. A marked influence of the Bouvet hot spot volcanism on magma generation on the South-West Indian Ridge (SWIR) near Bouvet Island is observed. Basaltic melts in this area belong to alkalic and transitional series and have maximum contents of K₂O, TiO₂, H₂O.
Microthermometric analyses of fluid inclusions in the samples from the BTJR have revealed major differences in the oceanic hydrothermal fluid systems on the MAR and near SWIR, which depends on the peculiarities of magma. In the area of the MAR (with dry melts) only H₂O solution inclusions in quartz were found; thus, seawater is probably the only primary source of hydrothermal fluids (NaCl + MgCl₂+ H₂O; T = 170–200°C). In the SWIR area (with the high content of water in melts) syngenetic liquid CO₂ and H₂O solution inclusions in quartz indicate the influence of the magmatic fluid component on the ore-forming water/carbon dioxide solutions (NaCl + CaC1₂+ H₂O + CO₂; T = 200–310 °C; P = 900–1700 bar).     

On the origin of CO2-rich fluid inclusions in migmatites

Abstract Nearly pure CO₂ fluid inclusions are abundant in migmatites although H₂O-rich fluids are predicted from the phase equilibria. Processes which may play a role in this observation include (1) the effects of decompression on melt, (2) generation of a CO₂-bearing volatile phase by the reaction graphite + quartz + biotite + plagioclase = melt + orthopyroxene + CO₂-rich vapour, (3) selective leakage of H₂O from CO₂+ H₂O inclusions when the pressure in the inclusion exceeds the confining pressure during decompression, and (4) enrichment of grain-boundary vapour in CO₂ by subsolidus retrograde hydration reactions.     

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.     

Reaction textures in calc-silicate granulites from the Bolingen Islands, Prydz Bay, East Antarctica: implications for the retrograde P–T path

Calc-silicate granulites from the Bolingen Islands, Prydz Bay, East Antarctica, exhibit a sequence of reaction textures that have been used to elucidate their retrograde P–T path. The highest temperature recorded in the calc-silicates is represented by the wollastonite- and scapolite-bearing assemblages which yield at least 760°C at 6 kbar based on experimental results. The calc-silicates have partially re-equilibrated at lower temperatures (down to 450°C) as evidenced by the successive reactions: (1) wollastonite + scapolite + calcite = garnet + CO₂, (2) wollastonite + CO₂= calcite + quartz, (3) wollastonite + plagioclase = garnet + quartz, (4) scapolite = plagioclase + calcite + quartz, (5) garnet + CO₂+ H₂O = epidote + calcite + quartz, and (6) clinopyroxene + CO₂+ H₂O = tremolite + calcite + quartz.
The reaction sequence observed indicates that a CO₂ was relatively low in the wollastonite-bearing rocks during peak metamorphic conditions, and may have been further lowered by local infiltration of H₂O from the surrounding migmatitic gneisses on cooling. Fluid activities in the Bolingen calc-silicates were probably locally variable during the granulite facies metamorphism, and large-scale CO₂ advection did not occur.
A retrograde P–T path, from the sillimanite stability field ( c. 760°C at 6 kbar) into the andalusite stability field ( c. 450°C at <3 kbar), is suggested by the occurrence of secondary andalusite in an adjacent cordierite–sillimanite gneiss in which sillimanite occurs as inclusions in cordierite.     

Genesis of Kanggur Gold Deposit in Eastern Tianshan Orogenic Belt, NW China: Fluid Inclusion and Oxygen and Hydrogen Isotope Constraints

Abstract. Primary fluid inclusions in quartz and carbonates from the Kanggur gold deposit are dominated by aqueous inclusions, with subsidiary CO₂-H₂O inclusions that have a constant range in CO₂ content (10–20 vol %). Microthermometric results indicate that total homogenization temperatures have a wide but similar range for both aqueous inclusions (120 to 310C) and CO₂-H₂O inclusions (140 to 340C). Estimates of fluid salinity for CO₂-H₂O inclusions are quite restricted (5.9∼10.3 equiv. wt% NaCl), whereas aqueous inclusions show much wider salinity ranging from 2.2 to 15.6 equivalent wt %NaCl.
The 6D values of fluid inclusions in carbonates vary from -45 to -61 %, in well accord with the published δD values of fluid inclusions in quartz (-46 to -66 %). Most of the δ¹⁸O and δD values of the ore-forming fluids can be achieved by exchanged meteoric water after isotopic equilibration with wall rock by fluid/rock interaction at a low water/rock ratio. However, the exchanged meteoric water alone cannot explain the full range of δ¹⁸O and δD values, magmatic and/or meta-morphic water should also be involved. The wide salinity in aqueous inclusions may also result from mixing of meteoric water and magmatic and/or metamorphic water.     

Fluid Evolution and Metallogenic Dynamics during Tectonic Regime Transition: Example from the Jiapigou Gold Belt in Northeast China

The Jiapigou gold belt, one of the most important gold-producing districts in China, is located in the northern margin of the North China Craton (NCC). The tectonic evolution of the gold belt is closely related to the Siberian Plate (SP) in the north, Yangtze Craton (YC) in the south and Pacific Plate in the east. In order to investigate the nature of the tectono-fluid-metallogenic system, the authors investigated the relationships among the tectonic regimes, fluid evolution and metallogenesis. This paper examined the corresponding spatial–temporal relationship between the ore-controlling tectonic regime and hydrothermal fluid evolution in the Jiapigou gold belt. There are two types of gold mineralization: disseminated ores that are distributed within the NW-trending main ductile shear zone and gold-bearing quartz veins and minor disseminated ores that are distant to the ductile shear zone. The fluid inclusions in quartz contain a large amount of CO₂. Metamorphic fluids of middle to high temperatures and pressures and meteoric waters of low temperatures and pressures mixed together during mineralization. A proposed ore-forming model is as follows: in the pre-ore phase, the collision of SP and NCC resulted in the NS-trending compression of the ore belt. This formed the NE-trending and NW-trending shear faults and EW-trending folds. During the ore-forming phase, the collision of YC and NCC resulted in dextral shearing of the NW-trending Jiapigou fault and the NE-trending Green faults. High-pressure fluids caused by the compression flowed into the dilatant zone. This may have caused both phase separation of CO₂-bearing fluids and the mixing of meteoric waters, metamorphic waters and magmatic source fluids and finally resulted in the disequilibrium of the ore fluids and precipitation of ore minerals.     

Plio–Pleistocene Hydrothermal Activity Related to Gold Mineralization in the Seta Area, Northeastern Hokkaido, Japan

Abstract: Plio–Pleistocene hydrothermal activity resulted in high grade low sulfidation epithermal gold mineralization in the Seta area, the southern end of the Monbetsu-Kamishihoro Graben of northeastern Hokkaido, Japan. Hydrothermal activity and accompanying hydrothermal eruptions began at approximately 2 Ma along NNW-SSE trending faults, the Tohbu-ko fault I and II. This activity resulted in two main zones of gold mineralization, the west quartz-adularia veins(QAV) and east stock-work zone(STZ), formed between 1. 8 and 1. 2 Ma. A smectite-chlorite alteration zone is observed at deeper levels, while kaolinite and kaolinite-smectite zones occur at shallower levels with an acid-leached zone present near the surface. The kaoli-nite and kaolinite-smectite zones are also distributed along faults and the STZ, to depths of several hundred meters. δ³⁴S values of pyrite and alunite from the kaolinite and silicified zones indicate alunite formed by the oxidation of sulfide, either H₂S(vapor) or mineral.
Formation of the STZ and the southern part of the QAV took place during lacustrine sedimentation, while formation of the northern part of the QAV took place after eruption of andesitic lava; the latter being associated with widespread alteration formed under neutral-pH conditions. δ¹⁸O values of quartz veins and silicified rocks indicate that the paleo-hydrothermal waters have a large meteoric component, increasing with decreasing depth in the STZ. Acid hydrothermal waters, resulting from near surface oxidation of H₂S were responsible for acid-leaching and kaolinization of surrounding rocks. Between 1. 4 and 0. 3 Ma, the acid hot waters drained back along the STZ to depths of at least 500m, as a result of a fall in the paleo-water table level.     

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.     

Metamorphic evolution of calcsilicate granulites near Battye Glacier, northern Prince Charles Mountains, East Antarctica

Calcsilicate granulites of probable Middle Proterozoic age ( c .1000–1100  Ma) in the vicinity of Battye Glacier, northern Prince Charles Mountains, East Antarctica, contain prograde metamorphic assemblages comprising various combinations of wollastonite, scapolite, clinopyroxene, An-rich plagioclase, calcite, quartz, titanite and, rarely, orthoclase, ilmenite, phlogopite and graphite. Comparison of the prograde assemblages with calculated and experimentally determined phase relations in the simple CaO–Al₂O₃–SiO₂–CO₂–H₂O system suggests peak metamorphism at ≥835 °C in the presence (in wollastonite-bearing assemblages at least) of a CO₂-bearing fluid ( X _CO≥0.3) at a probable pressure of 6–7  kbar.
Well-preserved retrograde reaction textures represent: (1) breakdown of scapolite to anorthite+calcite±quartz; (2) formation of grossular–andradite garnet and, locally, (3) epidote, both principally by reactions involving scapolite breakdown products and clinopyroxene; (4) local coupled replacement of clinopyroxene and ilmenite by hornblende and titanite, respectively; and finally (5) local sericitization of prograde and retrograde plagioclase. These retrograde reactions are interpreted to be the result of cooling and variable infiltration by H₂O-rich fluids, possibly derived from crystallizing pegmatitic intrusions and segregations that may be partial melts, which are common throughout the area.     

Carbonate Minerals in the Warrawoona Group, Pilbara Craton: Implications for Continental Crust, Life, and Global Carbon Cycle in the Early Archean

Abstract: The occurrences of the Early Archean carbonate minerals are compiled and their precipitation processes are investigated for the Warrawoona Group, Pilbara Craton. Sedimentary carbonate rocks such as limestone and dolostone are very rare, and only a small amount of sedimentary carbonate minerals are sometimes contained in the hydrothermal bedded chert, implying that a sink of CO₂ was minor in the Early Archean sediments. Moreover, it is very likely that the activity of cyanobacteria forming stromatolites was considerably low in the Early Archean. Microfossils and carbonaceous matter in the hydrothermal cherts are probably derived from a non-photosynthetic microorganisms related to the seafloor hydrothermal activity. Their preservation in sediments may play a very minor role in carbon sink of the Earth's surface.
On the other hand, carbonatized volcanic rocks subjected to seafloor hydrothermal alteration occur ubiquitously in the Early Archean greenstone belts such as the Warrawoona Group, suggesting that the hydrothermally altered oceanic crust had large amounts of CO₂ as carbonate minerals. Global carbon cycle in the Early Archean is considered to have been controlled by the intense seafloor hydrothermal alteration. Large amounts of CO₂ were sunk into the oceanic crust by the alteration. The carbonatized oceanic crust was partly accreted to the continents and/or island–arcs, and partly subducted into the mantle without decomposition. Significant amounts of carbonate minerals in the carbonatized oceanic crust were very likely to store in the accretionary prisms and mantle, consequently giving rise to a decrease of atmospheric and oceanic CO₂.     

A Possible Role of Boiling in Ore Deposition: A Numerical Approach

Abstract. A possible role of boiling of the H₂O-NaCl-CO₂(-H₂S) fluid in ore deposition has been examined numerically by using the equations of state (EOS) of Duan et al. (1995, 1996), a modified EOS of Bowers and Helgeson (1983) and the water-rock interaction simulator MIX99 (Hoshino et al., 2000).
The following three models are examined to evaluate an efficiency of boiling on mineral precipitation: (1) hypothetical non-boiling process, (2) hypothetical boiling process with sulfur partitioned only in liquid phases and (3) boiling process in which partition ratios of H₂S between liquid and vapor phases are assumed to be the same as those of CO₂. The processes are simulated from 450C and 900 bar to 310C and 620 bar with an analytical step of 10C / 20 bar. Boiling occurs below 400C in the latter two processes when the initial composition (in mole fraction) of the fluid is: X_H2o = 0.84, X_NaC1 = 0.10 and X_Co2 = 0.06.
Ore deposition occurs abruptly at a boiling point when the partition ratios of total sulfur (X_s^vap/X_s^liq) are as high as those of total carbon during boiling. A decrease of concentration of sulfur in the liquid phase during boiling leads to an increase of pH of the solution, resulting in propelling mineral precipitation. It has been made clear that a possible role of boiling in ore formation mainly depends on the partition ratios of sulfur between the liquid and vapor phases, although they cannot be estimated accurately by the currently available EOS.     

Fluid-mineral equilibria in prehnite-pumpellyite to greenschist facies metabasites near Flin Flon, Manitoba, Canada: implications for petrogenetic grids

A sequence of regional metamorphic isograds indicating a range from prehnite-pumpellyite to lower amphibolite facies was mapped in metabasites near Flin Flon, Manitoba. The lowest grade rocks contain prehnite + pumpellyite and are cut by younger brittle faults containing epidote + chlorite + calcite. Isobaric temperature- X _CO2 and pressure-temperature (constant X _CO2) diagrams were calculated to quantify the effects of CO₂ in the metamorphic fluid on the stability of prehnite-pumpellyite facies minerals in metabasites containing excess quartz and chlorite. Prehnite and, to a lesser extent, pumpellyite are stable only in fluids with X _co2 <0.002. For X _co2>0.002, epidote + chlorite + calcite assemblages are stable. Our calculated phase relations are consistent with regional metamorphism in the Flin Flon area in the presence of an H₂O-rich fluid and a more CO₂-rich fluid in the later fault zones. We believe that the potential effects of small amounts of CO₂ in the metamorphic fluid should be assessed when considering the pressure-temperature implications of mineral assemblages in low-grade metabasites.     

Temperatures and Oxygen Isotopic Compositions of Hydrothermal Fluids for the Takatori Tungsten-copper Deposit, Japan

Abstract. Fluid inclusion and oxygen isotope studies are performed to obtain temperatures and oxygen isotopic compositions of hydrothermal fluids for the vein-type tungsten-copper deposit at Takatori in Ibaraki Prefecture, Japan. Temperatures of the hydrothermal fluids are calculated from fluid inclusion data. The calculation incorporates the effects of the salinity, gas concentration, and fluid pressure. The fluid temperatures range from 370 to 460C. For these calculations, this study obtains a density equation for H₂O-NaCl-CO₂ solution at the vapor-liquid two-phase boundary. Then the present study combines the obtained equation with the equation of state by Bowers and Helgeson (1983).
The fluid temperatures determined in this study are applied to the calculation of oxygen isotopic compositions of the hydrothermal fluids. The calculation of the oxygen isotopic compositions is based on the oxygen isotope analyses of vein quartz. The oxygen isotopic compositions of vein quartz range from +13.5 to +14.4 % relative to SMOW. Then, the oxygen isotopic compositions of the hydrothermal fluids in equilibrium with the vein quartz are calculated to be from +9.7 to +10.5 %. These δ¹⁸O_fluid values agree with those of magmatic fluids derived from the ilmenite-series granitic rock, which is related to the mineralization. Keywords: Takatori tungsten-copper deposit, fluid inclusion, oxygen isotope, vein quartz, H₂O-NaCl-CO₂ solution, density     

Wollastonite and scapolite in Precambrian calc-silicate granulites from Australia and Antarctica

Abstract Scapolite, wollastonite, calcite, diopside, grossular-andradite garnet and sphene occur in calc-silicate rocks in the granulite terrain of the Arunta Block, central Australia. This assemblage buffers the CO₂ activity at a low value, so that any coexisting fluid phase must be H₂O rich and CO₂ poor ( X _co2 = 0.2-0.3). In contrast, the H₂O activity in the surrounding felsic and mafic granulites was low. Thus fluid activities during granulite facies metamorphism were locally buffered in various rock units and fluid flow appears to have been restricted or fluid may have been absent. Late retrograde rims of garnet and garnet-quartz separate phases formed in the high-grade stage. Formation of these rims would have required either an influx of water-rich fluid or a decrease in pressure. Evidence from the surrounding granulites shows that in one locality, the calc-silicate rocks had undergone late isobaric hydration; in another locality, minor uplift had occurred soon after peak P-T conditions. In both, scapolite had partly broken down to plagioclase-calite. A calc silicate rock from the granulite terrain of Enderby Land, Antarctica, contains scapolite, wollastonite, calcite, diopside, quartz and sphene; this assemblage also indicates low CO₂ activities. In this rock, wollastonite has broken down to calcite-quartz, to indicate isobaric cooling without influx of hydrous fluid.     

Two-stage corona growth during Precambrian granulite facies metamorphism of Smitbson Bjerge, north-west Greenland

Abstract Late Archaean orthogneisses and aluminous and iron-rich metasedimentary rocks intruded by anorthosite and a ferrodiorite-granite suite were completely recrystallized during Proterozoic granulite facies metamorphism. Geobarometry and geothermometry indicate P-T conditions of around 7.5kbar. 700°C, with a CO₂-rich fluid phase and logfO₂ at or below -16. A two-stage high-grade history of near isochemical corona growth is preserved in metasediments with the reaction cycle opx + plag + H₂O → hbl+gar+SiO₂→ opx+plag+H₂O. End product compositions resemble those of the initial phases, and the only mobile components were SiO₂ and/or H₂O. The coronas reflect shortlived fluctuations in chemical activity at essentially constant P and T, contrary to simple progressive change in equilibrium parameters recorded by most corona-bearing textures.     

Synthetic Fluid Inclusions in the Systems NaCl-H2O and NaCl-CO2-H2O: Dissolution Temperatures of Halite

Abstract. This study examined the effect of CO₂ on NaCl solubility in hydrothermal fluid, with the synthetic fluid inclusion technique. Fluid inclusions of 30–40 wt% NaCl and 5 mol % CO₂ were synthesized, and their halite dissolution temperatures, T_m(halite), were measured. The solubilities of NaCl in CO₂-bearing aqueous fluid were obtained at 160–320C under vapor-saturated pressures. The T_m(halite) value in aqueous fluid with 5 mol % CO₂ obtained in this study agrees with that of Schmidt et al. (1995), showing that 5 mol % CO₂ reduces the solubility of NaCl by about 1 wt%.
Calculation of magnetite solubility suggests that 5–10 mol % CO2 decreases magnetite solubility by 4.5–8.9 % relative to the magnetite solubility in CO2-free solution. Therefore, an increase of CO2 content in ore-forming solutions may cause deposition of iron minerals and produce ore deposits.     

CO2 transfer between the upper mantle and the atmosphere: temporary storage in the lower continental crust

The CO₂ atmospheric content has shown large variations over geological times. High contents (up to one order of magnitude more than present-day values) ultimately correspond to discrete episodes of mantle degassing, either juvenile, or subduction-related (carbon recycling). A number of arguments (e.g. the continuous volume increase of carbonate-bearing sediments with time) suggest that, throughout the Earth's history, juvenile CO₂ has formed a major contribution to the global carbon budget of the Earth.
The absence of a direct relationship between major volcanic episodes and the average CO₂ atmospheric content suggests that volcanoes might not be the only way by which mantle CO₂ is transported to the surface. It is proposed that large quantities of juvenile CO₂ could temporarily be stored in the lower continental crust during major episodes of granulite formation. These are primarily caused by magmatic underplating and they result in a vertical accretion of the crust by accumulation of CO₂-bearing, mantle-derived magmas. Most of the CO₂ migrates through the crust during post-metamorphic evolution and isostatic restoration of the normal continental thickness. However, large quantities of CO₂ can still be present in some areas, notably as high-density fluids enclosed in minerals.     

Thermochemical sulphate reduction in the Upper Devonian Cairn Formation of the Fairholme carbonate complex (South-West Alberta, Canadian Rockies): evidence from fluid inclusions and isotopic data

The Fairholme carbonate complex is part of the extensively dolomitized Upper Devonian carbonate reefs in west-central Alberta. The studied formations contain moulds (up to 10 cm in diameter), which are filled partially with (saddle) dolomite, quartz and calcite cements. These cements precipitated from a mixture of brines that acquired high salinity by dissolution of halite and brines derived from evaporated sea water. The fluids were warm (homogenization temperature of primary fluid inclusions of 76 to 200 °C) and saline (20 to 25 wt% NaCl equivalent) and testify to thermochemical sulphate reduction processes. The latter is deduced from S in solid inclusions, CO₂ and H₂S in volatile-rich aqueous inclusions and depleted δ¹³C values down to −26‰ Vienna Pee Dee Belemnite. High ⁸⁷Sr/⁸⁶Sr values (0·7094 to 0·7110) of the cements also indicate interaction of the fluids with siliciclastic sequences. The thermochemical sulphate reduction-related cements probably formed during early Laramide burial. Another (younger) calcite phase, characterized by depleted δ¹⁸O values (−23·9‰ to −13·9‰ Vienna Pee Dee Belemnite), low Na (27 to 37 p.p.m.) and Sr (39 to 150 p.p.m.) concentrations and non-saline (∼0 wt% NaCl equivalent) fluid inclusions, is attributed to post-Laramide meteoric water.