Syntectonic infiltration by meteoric waters along the Sevier thrust front,southwest Montana

Structural, petrographic, and isotopic data for calcite veins and carbonate host‐rocks from the Sevier thrust front of SW Montana record syntectonic infiltration by H₂O‐rich fluids with meteoric oxygen isotope compositions. Multiple generations of calcite veins record protracted fluid flow associated with regional Cretaceous contraction and subsequent Eocene extension. Vein mineralization occurred during single and multiple mineralization events, at times under elevated fluid pressures. Low salinity (T_m = ?0.6°C to +3.6°C, as NaCl equivalent salinities) and low temperature (estimated 50–80°C for Cretaceous veins, 60–80°C for Eocene veins) fluids interacted with wall‐rock carbonates at shallow depths (3–4 km in the Cretaceous, 2–3 km in the Eocene) during deformation. Shear and extensional veins of all ages show significant intra‐ and inter‐vein variation in δ¹⁸O and δ¹³C. Carbonate host‐rocks have a mean δ¹⁸O_V‐SMOW value of +22.2 ± 3‰ (1σ), and both the Cretaceous veins and Eocene veins have δ¹⁸O ranging from values similar to those of the host‐rocks to as low as +5 to +6‰. The variation in vein δ¹³C_V‐PDB of ?1 to approximately +6‰ is attributed to original stratigraphic variation and C isotope exchange with hydrocarbons. Using the estimated temperature ranges for vein formation, fluid (as H₂O) δ¹⁸O calculated from Cretaceous vein compositions for the Tendoy and Four Eyes Canyon thrust sheets are ?18.5 to ?12.5‰. For the Eocene veins within the Four Eyes Canyon thrust sheet, calculated H₂O δ¹⁸O values are ?16.3 to ?13.5‰. Fluid–rock exchange was localized along fractures and was likely coincident with hydrocarbon migration. Paleotemperature determinations and stable isotope data for veins are consistent with the infiltration of the foreland thrust sheets by meteoric waters, throughout both Sevier orogenesis and subsequent orogenic collapse. The cessation of the Sevier orogeny was coincident with an evolving paleogeographic landscape associated with the retreat of the Western Interior Seaway and the emergence of the thrust front and foreland basin. Meteoric waters penetrated the foreland carbonate thrust sheets of the Sevier orogeny utilizing an evolving mesoscopic fracture network, which was kinematically related to regional thrust structures. The uncertainty in the temperature estimates for the Cretaceous and Eocene vein formation prevents a more detailed assessment of the temporal evolution in meteoric water δ¹⁸O related to changing paleogeography. Meteoric water‐influenced δ¹⁸O values calculated here for Cretaceous to Eocene vein‐forming fluids are similar to those previously proposed for surface waters in the Eocene, and those observed for modern‐day precipitation, in this part of the Idaho‐Montana thrust belt.     

Mobilization of ore fluids during Alpine metamorphism: evidence from hydrothermal veins in the Variscan basement of Western Carpathians,Slovakia

Hydrothermal polymetallic veins of the Gemeric unit of the Western Carpathians are oriented coherently with the foliation of their low‐grade Variscan basement host. Early siderite precipitated from homogeneous NaCl‐KCl‐CaCl₂‐H₂O brines with minor CO₂, while immiscible gas–brine mixtures are indicative of the superimposed barite, quartz–tourmaline and quartz–sulphide stages. The high‐salinity aqueous fluid (18–35 wt%) found in all mineralization stages corresponds to formation water modified by interaction with crystalline basement rocks at temperatures between 140 and 300°C. High brominity (around 1000 ppm in average) resulted from evaporation and anhydrite precipitation in a Permo‐Triassic marine basin, and from secondary enrichment by dissolution of organic matter in the marine sediments at diagenetic temperatures. Sulphate depletion reflects thermogenic reduction during infiltration of the formation waters into the Variscan crystalline basement. Crystallization temperatures of the siderite fill (140–300°C) and oxygen isotope ratios of the parental fluids (4–10‰) increase towards the centre of the Gemeric cleavage fan, probably as a consequence of decreasing water/rock ratios in rock‐buffered hydrothermal systems operating during the initial stages of vein evolution. In contrast, buoyant gas–water mixtures, variable salinities and strongly fluctuating P–T parameters in the successive mineralization stages reflect transition from a closed to an open hydrothermal system and mixing of fluids from various sources. Depths of burial were 6–14 km (1.7–4.4 kbar, in a predominantly lithostatic fluid regime) during the siderite and barite sub‐stages of the north‐Gemeric veins, and up to 16 km (1.6–4.5 kbar, in a hydrostatic to lithostatic fluid regime) in the quartz–tourmaline stage of the south‐Gemeric veins. The fluid pressure decreased down to approximately 0.6 kbar during crystallization of sulphides. U‐Pb‐Th, ⁴⁰Ar/³⁹Ar and K/Ar geochronology applied to hydrothermal muscovite–phengite and monazite, as well as cleavage phyllosilicates in the adjacent basement rocks and deformed Permian conglomerates corroborated the opening of hydrothermal veins during Lower Cretaceous thrusting and their rejuvenation during Late Cretaceous sinistral transpressive shearing and extension.     

Hydrogeology of the Krafla geothermal system,northeast Iceland

The Krafla geothermal system is located in Iceland's northeastern neovolcanic zone, within the Krafla central volcanic complex. Geothermal fluids are superheated steam closest to the magma heat source, two‐phase at higher depths, and sub‐boiling at the shallowest depths. Hydrogen isotope ratios of geothermal fluids range from ?87‰, equivalent to local meteoric water, to ?94‰. These fluids are enriched in ¹⁸O relative to the global meteoric line by +0.5–3.2‰. Calculated vapor fractions of the fluids are 0.0–0.5 wt% (~0–16% by volume) in the northwestern portion of the geothermal system and increase towards the southeast, up to 5.4 wt% (~57% by volume). Hydrothermal epidote sampled from 900 to 2500 m depth has δD values from ?127 to ?108‰, and δ¹⁸O from ?13.0 to ?9.6‰. Fluids in equilibrium with epidote have isotope compositions similar to those calculated for the vapor phase of two‐phase aquifer fluids. We interpret the large range in δD_EPIDOTE and δ¹⁸O_EPIDOTE across the system and within individual wells (up to 7‰ and 3.3‰, respectively) to result from variable mixing of shallow sub‐boiling groundwater with condensates of vapor rising from a deeper two‐phase reservoir. The data suggest that meteoric waters derived from a single source in the northwest are separated into the shallow sub‐boiling reservoir, and deeper two‐phase reservoir. Interaction between these reservoirs occurs by channelized vertical flow of vapor along fractures, and input of magmatic volatiles further alters fluid chemistry in some wells. Isotopic compositions of hydrothermal epidote reflect local equilibrium with fluids formed by mixtures of shallow water, deep vapor condensates, and magmatic volatiles, whose ionic strength is subsequently derived from dissolution of basalt host rock. This study illustrates the benefits of combining phase segregation effects in two‐phase systems during analysis of wellhead fluid data with stable isotope values of hydrous alteration minerals when evaluating the complex hydrogeology of volcano‐hosted geothermal systems.     

Modeling thermal convection in supradetachment basins: example from western Norway

The juxtaposition of fault‐bounded sedimentary basins, above crustal‐scale detachments, with warmer exhumed footwalls can lead to thermal convection of the fluids in the sediments. The Devonian basins of western Norway are examples of supradetachment basins that formed in the hanging wall of the Nordfjord‐Sogn Detachment Zone. In the central part of the Hornelen and Kvamshesten basins, the basin‐fill is chiefly represented by fluvial sandstones and minor lacustrine siltstones, whereas the fault margins are dominated by fanglomerates along the detachment contact. Prominent alteration and low‐greenschist facies metamorphic conditions are associated with the peak temperature estimates of the sediments close to the detachment shear zone. Fluid circulation may have been active during the burial of the sediments, and we quantify the potential role played by thermal convection in redistributing heat within the basins. Different models are tested with homogeneous and layered basin‐fill and with material transport properties corresponding to sandstones and siltstones. We found that thermally driven fluid flow is expected in supradetachment basins as a transient process during the exhumation of warmer footwalls. We demonstrate that the fluid flow may have significantly affected the temperature distribution in the upper five kilometers of the Devonian basins of western Norway. The temperature anomaly induced by the flow may locally reach about 80°C. The sedimentary layering formed by sand‐ and siltstones strata does not inhibit fluid circulation at the scale of the basin. The presence of fluid pathways along the detachment has an important impact on the flow and allows an efficient drainage of the basin by channelizing fluids upward along the detachment.     

Numerical modeling of the origin of calcite mineralization in the Refugio‐Carneros fault,Santa Barbara Basin,California

Many faults in active and exhumed hydrocarbon‐generating basins are characterized by thick deposits of carbonate fault cement of limited vertical and horizontal extent. Based on fluid inclusion and stable isotope characteristics, these deposits have been attributed to upward flow of formation water and hydrocarbons. The present study sought to test this hypothesis by using numerical reactive transport modeling to investigate the origin of calcite cements in the Refugio‐Carneros fault located on the northern flank of the Santa Barbara Basin of southern California. Previous research has shown this calcite to have low δ¹³C values of about ?40 to ?30‰PDB, suggesting that methane‐rich fluids ascended the fault and contributed carbon for the mineralization. Fluid inclusion homogenization temperatures of 80–125°C in the calcite indicate that the fluids also transported significant quantities of heat. Fluid inclusion salinities ranging from fresh water to seawater values and the proximity of the Refugio‐Carneros fault to a zone of groundwater recharge in the Santa Ynez Mountains suggest that calcite precipitation in the fault may have been induced by the oxidation of methane‐rich basinal fluids by infiltrating meteoric fluids descending steeply dipping sedimentary layers on the northern basin flank. This oxidation could have occurred via at least two different mixing scenarios. In the first, overpressures in the central part of the basin may have driven methane‐rich formation waters derived from the Monterey Formation northward toward the basin flanks where they mixed with meteoric water descending from the Santa Ynez Mountains and diverted upward through the Refugio‐Carneros fault. In the second scenario, methane‐rich fluids sourced from deeper Paleogene sediments would have been driven upward by overpressures generated in the fault zones because of deformation, pressure solution, and flow, and released during fault rupture, ultimately mixing with meteoric water at shallow depth. The models in the present study were designed to test this second scenario, and show that in order for the observed fluid inclusion temperatures to be reached within 200 m of the surface, moderate overpressures and high permeabilities were required in the fault zone. Sudden release of overpressure may have been triggered by earthquakes and led to transient pulses of accelerated fluid flow and heat transport along faults, most likely on the order of tens to hundreds of years in duration. While the models also showed that methane‐rich fluids ascending the Refugio‐Carneros fault could be oxidized by meteoric water traversing the Vaqueros Sandstone to form calcite, they raised doubts about whether the length of time and the number of fault pulses needed for mineralization by the fault overpressuring mechanism were too high given existing geologic constraints.     

Evolution of deformation and fault‐related fluid flow within an ancient methane seep system (Eocene,Varna, Bulgaria)

Faults are often important in fuelling methane seep systems; however, little is known on how different components in fault zones control subsurface fluid circulation paths and how they evolve through time. This study provides insight into fault‐related fluid flow systems that operated in the shallow subsurface of an ancient methane seep system. The Pobiti Kamani area (NE Bulgaria) encloses a well‐exposed, fault‐related seep system in unconsolidated Lower Eocene sandy deposits of the Dikilitash Formation. The Beloslav quarry and Beloslav N faults displace the Dikilitash Formation and are typified by broad, up to 80 m wide, preferentially lithified hanging wall damage zones, crosscut by deformation bands and deformation band zones, smaller slip planes and fault‐related joints. The formation of a shallow plumbing system and chimney‐like concretions in the Dikilitash Formation was followed by at least two phases of fault‐related methane fluid migration. Widespread fluid circulation through the Dikilitash sands caused massive cementation of the entire damage zones in the fault hanging walls. During this phase, paths of ascending methane fluids were locally obstructed by decimetre‐thick, continuous deformation band zones that developed in the partly lithified sands upon the onset of deformation. Once the entire damage zone was pervasively cemented, deformation proceeded through the formation of slip planes and joints. This created a new network of more localized conduits in close vicinity to the main fault plane and around through‐going slip planes. ¹³C‐depleted crustiform calcite cements in several joints record the last phase of focused methane fluid ascent. Their formation predated Neogene uplift and later meteoric water infiltration along the joint network. This illustrates how fault‐related fluid pathways evolved, over time, from ‘plumes’ in unconsolidated sediments above damage zones, leading to chimney fields, over widespread fluid paths, deflected by early deformation structures, to localized paths along fracture networks near the main fault.     

Monitoring fluid chemistry in iron oxide–copper–gold‐related metasomatic processes,eastern Mt Isa Block,Australia

Most researchers in the Proterozoic eastern Mt Isa Block, NW Queensland, Australia, favour magmatic fluid and salt sources for sodic‐(calcic) alteration and iron oxide–copper–gold mineralization. Here we compare spatial, mineralogic and stable isotope data from regional alteration assemblages with magmatic and magmatic‐hydrothermal interface rocks in order to track chemical and isotopic variations in fluid composition away from inferred fluid sources. Tightly clustered δ¹⁸O values for magnetite, quartz, feldspar and actinolite for igneous‐hosted samples reflect high temperature equilibration in the magmatic‐hydrothermal environment. In contrast, these minerals record predominantly higher δ¹⁸O values in regional alteration and Cu–Au mineralization. This dichotomy reflects partial equilibration with isotopically heavier wallrocks and slightly lower temperatures. Increases in Si concentrations of metasomatic amphiboles relative to igneous amphiboles in part reflect cooling of metasomatic fluids away from igneous rocks. Variations in X_Mg for metasomatic amphiboles indicate local wallrock controls on amphibole chemistry, while variations in X_Cl/X_OH ratios for amphiboles (at constant X_Mg) indicate variable aH₂O/aHCl ratios for metasomatic fluids. Biotite geochemistry also reflects cooling and both increases and decreases in aH₂O/aHCl for fluids away from plutonic rocks. Decreased aH₂O/aHCl ratios for metasomatic fluids reflect in part scavenging of chlorine out of meta‐evaporite sequences, although this process requires already saline fluids. Local increases in aH₂O/aHCl ratios, as well as local decreases in δ¹⁸O values for some minerals (most notably haematite and epithermal‐textured quartz), may indicate ingress of low salinity, low δ¹⁸O fluids of possible meteoric origin late in the hydrothermal history of the region. Taken together, our observations are most consistent with predominantly magmatic sources for metasomatic fluids in the eastern Mt Isa Block, but record chemical and isotopic variations along fluid flow paths that may be important in explaining some of the diversity in alteration and mineralization styles in the district.     

Invasion of a karst aquifer by hydrothermal fluids: evidence from stable isotopic compositions of cave mineralization

Mineral deposits in the Cupp‐Coutunn/Promeszutochnaya cave system (Turkmenia, central Asia) record a phase of hydrothermal activity within a pre‐existing karstic groundwater conduit system. Hydrothermal fluids entered the caves through fault zones and deposited sulphate, sulphide and carbonate minerals under phreatic conditions. Locally, intense alteration of limestone wall rocks also occurred at this stage. Elsewhere in the region, similar faults contain economic quantities of galena and elemental sulphur mineralization. Comparisons between the Pb and S isotope compositions of minerals found in cave and ore deposits confirm the link between economic mineralization and hydrothermal activity at Cupp‐Coutunn. The predominance of sulphate mineralization in Cupp‐Coutunn implies that the fluids were more oxidized in the higher permeability zone associated with the karst aquifer. A slight increase in the δ³⁴S of sulphate minerals and a corresponding δ³⁴S decrease in sulphides suggest that partial isotopic equilibration occurred during oxidation. Carbonate minerals indicate that the hydrothermal fluid was enriched in ¹⁸O (δ¹⁸O_SMOW ～ + 10‰) relative to meteoric groundwater and seawater. Estimated values for δ¹³C_DIC (δ¹³C_PDB ～ ? 13‰) are consistent with compositions expected for dissolved inorganic carbon (DIC) derived from the products of thermal decomposition of organic matter and dissolution of marine carbonate. Values derived for δ¹³C_DIC and δ¹⁸O_water indicate that the hydrothermal fluid was of basinal brine origin, generated by extensive water–rock interaction. Following the hydrothermal phase, speleothemic minerals were precipitated under vadose conditions. Speleothemic sulphates show a bimodal sulphur isotope distribution. One group has compositions similar to the hydrothermal sulphates, whilst the second group is characterized by higher δ³⁴S values. This latter group may either record the effects of microbial sulphate reduction, or reflect the introduction of sulphate‐rich groundwater generated by the dissolution of overlying evaporites. Oxygen isotope compositions show that calcite speleothems were precipitated from nonthermal groundwater of meteoric origin. Carbonate speleothems are relatively enriched in ¹³C compared to most cave deposits, but can be explained by normal speleothem‐forming processes under thin, arid‐zone soils dominated by C4 vegetation. However, the presence of sulphate speleothems, with isotopic compositions indicative of the oxidation of hydrothermal sulphide, implies that CO₂ derived by reaction of limestone with sulphuric acid (‘condensation corrosion’) contributed to the formation of ¹³C‐enriched speleothem deposits.     

Principal features of impact-generated hydrothermal circulation systems: mineralogical and geochemical evidence

Any hypervelocity impact generates a hydrothermal circulation system in resulting craters. Common characteristics of hydrothermal fluids mobilized within impact structures are considered, based on mineralogical and geochemical investigations, to date. There is similarity between the hydrothermal mineral associations in the majority of terrestrial craters; an assemblage of clay minerals–zeolites–calcite–pyrite is predominant. Combining mineralogical, geochemical, fluid inclusion, and stable isotope data, the distinctive characteristics of impact‐generated hydrothermal fluids can be distinguished as follows: (i) superficial, meteoric and ground water and, possibly, products of dehydration and degassing of minerals under shock are the sources of hot water solutions; (ii) shocked target rocks are sources of the mineral components of the solutions; (iii) flow of fluids occurs mainly in the liquid state; (iv) high rates of flow are likely (10^?4 to 10^?3 m s^?1); (v) fluids are predominantly aqueous and of low salinity; (vi) fluids are weakly alkaline to near‐neutral (pH 6–8) and are supersaturated in silica during the entire hydrothermal process because of the strong predominance of shock‐disordered aluminosilicates and fusion glasses in the host rocks; and (vii) variations in the properties of the circulating solutions, as well as the spatial distribution of secondary mineral assemblages are controlled by temperature gradients within the circulation cell and by a progressive cooling of the impact crater. Products of impact‐generated hydrothermal processes are similar to the hydrothermal mineralization in volcanic areas, as well as in modern geothermal systems, but impacts are always characterized by a retrograde sequence of alteration minerals.     

Pyrophyllite formation in the thermal aureole of a hydrothermal system in the Lower Saxony Basin,Germany

A combined clay mineralogical, fluid inclusion, and K‐Ar study of Upper Jurassic metasediments at the Gehn (Lower Saxony Basin, Germany) provides evidence for a transient hydrothermal event during Upper Cretaceous basin inversion centered on a prominent gravimetric anomaly. Kaolinite and smectite in Oxfordian pelitic parent rocks that cap a deltaic sandstone unit were locally transformed into pyrophyllite, 2M₁ illite, R3 illite–smectite, chlorite, and berthierine at the Ueffeln quarry. The pyrophyllite‐bearing metapelites lack bedding‐parallel preferred orientation of sheet silicates and experienced peak temperatures of about 260–270°C consistent with microthermometric data on quartz veins in the underlying silicified sandstones. The presence of expandable layers in illite–smectite and high Kübler Index values indicate that the thermal event was rather short‐lived. K‐Ar dating of the <0.2 μm fraction of the pyrophyllite‐bearing Ueffeln metapelite yields a maximum illitization age of 117 ± 2 Ma. Lower trapping temperatures of aqueous fluid inclusions in quartz veins and the absence of pyrophyllite in metapelites of the Frettberg quarry in a distance of about 2.5 km from the Ueffeln quarry infer maximum paleotemperatures of only 220°C. The highly localized thermal anomaly at Ueffeln suggests fault‐controlled fluid migration and heat transfer that provided a thermal aureole for pyrophyllite formation in the metapelites rather than metamorphism due to deep burial. A pH neutral hydrothermal fluid that formed by devolatilization reactions or less likely by mixing of meteoric and marine waters that interacted at depth with shales is indicated by the low salinity (3–5 wt. % NaCl equiv.) of aqueous inclusions, their coexistence with methane–carbon dioxide‐dominated gas inclusions as well as carbon, hydrogen, and oxygen isotope data. The upwelling zone of hydrothermal fluids and the thermal maximum is centered on a gravimetric anomaly interpreted as an igneous intrusion (‘Bramsche Massif’) providing the heat source for the intrabasinal hydrothermal system.     

Possible isotopic fractionation of argon in source obsidians and archeological artifacts from Kulkuletti, Ethiopia

Despite uniform geochemistry ⁴⁰Ar/³⁹Ar ages of 0.6, 1.25, and 1.3 Ma on obsidians from a source flow (Worja) and from archeological artifacts at the sites of Kulkuletti (near Gademotta, Ethiopia) have been interpreted to suggest that they derive from different source flows of different ages. A further suggestion is that the magmatic source of the obsidian flows was chemically homogeneous between 1.3 Ma and 0.6 Ma. Chemical analysis of these obsidians indeed suggests that they derive from a single flow. Reexamination of the argon isotopic data reveals that argon isotopes may have been fractionated within the flow, so that the assumption of an atmospheric ⁴⁰Ar/³⁶Ar ratio of 295.5 is inappropriate to use for computing ages. Three groups of data are apparent, and internally all yield ages near 1.3 Ma if the intercept value for ⁴⁰Ar/³⁶Ar from an isotope correlation plot is used for computation instead of using the atmospheric ratio. The Soret thermal diffusion effect provides a possible mechanism of fractionation of argon within the obsidian flow that is of approximately the right magnitude to explain the observations by in-diffusion of already fractionated atmospheric argon.     

A comprehensive review of hydrocarbons and genetic model of the sandstone‐hosted Dongsheng uranium deposit,Ordos Basin,China

The Dongsheng uranium deposit, the largest in situ leach uranium mine in the Ordos Basin, geometrically forms a roll‐front type deposit that is hosted in the Middle Jurassic Zhiluo Formation. The genesis of the mineralization, however, has long been a topic of great debate. Regional faults, epigenetic alterations in surface outcrops, natural oil seeps, and experimental findings support a reducing microenvironment during ore genesis. The bulk of the mineralization is coffinite. Based on thin‐section petrography, some of the coffinite is intimately intergrown with authigenic pyrite (ore‐stage pyrite) and is commonly juxtaposed with some late diagenetic sparry calcite (ore‐stage calcite) in primary pores, suggesting simultaneous precipitation. Measured homogenization temperatures of greater than 100°C from fluid inclusions indicate circulation of low‐temperature hydrothermal fluids in the ore zone. The carbon isotopic compositions of late calcite cement (δ¹³C_VPDB = ?31.0 to ?1.4‰) suggest that they were partly derived from sedimentary organic carbon, possibly from deep‐seated petroleum fluids emanating from nearby faults. Hydrogen and oxygen isotope data from kaolinite cement (δD = ?133 to ?116‰ and δ¹⁸O_SMOW = 12.6–13.8‰) indicate that the mineralizing fluids differed from magmatic and metamorphic fluids and were more depleted in D (²H) than modern regional meteoric waters. Such a strongly negative hydrogen isotopic signature suggests that there has been selective modification of δD by CH₄±H₂S±H₂ fluids. Ore‐stage pyrite lies within a very wide range of δ³⁴S (?39.2 to 26.9‰), suggesting that the pyrite has a complex origin and that bacterially mediated sulfate reduction cannot be precluded. Hydrocarbon migration and its role in uranium reduction and precipitation have here been unequivocally defined. Thus, a unifying model for uranium mineralization can be established: Early coupled bacterial uranium mineralization and hydrocarbon oxidation were followed by later recrystallization of ore phases in association with low‐temperature hydrothermal solutions under hydrocarbon‐induced reducing conditions.     

Isotopic and petrological evidence of fluid–rock interaction at a Tethyan ocean–continent transition in the Alps: implications for tectonic processes and carbon transfer during early ocean formation

We report overprinting stable isotope evidence of fluid–rock interaction below two detachment faults along which mantle rocks were exhumed to the seafloor, between the respective landward and seaward limits of oceanic and continental crust, at a Tethyan ocean–continent transition (OCT). This OCT, which is presently exposed in the Tasna nappe (south‐eastern Switzerland) is considered an on‐land analogue of the well‐studied Iberian OCT. We compare our results with the fault architecture (fault core–damage zone–protolith) described by Caine et al. [Geology (1996) Vol. 24, pp. 1025–1028]. We confirm the existence of a sharp boundary between the fault core and damage zone based on isotopic data, but the boundary between the damage zone and protolith is gradational. We identify evidence for: (1) pervasive isotopic modification to 8.4 ± 0.1‰ which accompanied or post‐dated serpentinization of these mantle rocks at an estimated temperature of 67–109°C, (2) either (i) partial isolation of some highly strained regions [fault core(s) and mylonite] from this pervasive isotopic modification, because of permeability reduction (Caine et al.) or (ii) subsequent isotopic modification caused by structurally channelled flow of warm fluids within these highly strained regions, because of permeability enhancement, and (3) isotopic modification, which is associated with extensive calcification at T = 54–100°C, primarily beneath the younger of the two detachment faults and post‐dating initial serpentinization. By comparing the volumetric extent of calcification with an experimentally verified model for calcite precipitation in veins, we conclude that calcification could have occurred in response to seawater infiltration, with a calculated flux rate of 0.1–0.2 m year^?1 and a minimum duration of 0.2–4.0 × 10⁴ years. The associated time‐averaged uptake flux of carbon during this period was 8–120 mol m^?2 year^?1. By comparison with the estimated area of exhumed mantle rocks at the Iberian OCT, we calculate a maximum annual uptake flux for carbon of 2–30 Tg year^?1. This is an order of magnitude greater than that for carbon exchange at the mid‐ocean ridges and 0.1–1.4% of the global oceanic uptake flux for carbon.     

Carbon dioxide controlled earthquake distribution pattern in the NW Bohemian swarm earthquake region,western Eger Rift,Czech Republic – gas migration in the crystalline basement

The ascent of magmatic carbon dioxide in the western Eger (Oh?e) Rift is interlinked with the fault systems of the Variscian basement. In the Cheb Basin, the minimum CO₂ flux is about 160 m³ h^?1, with a diminishing trend towards the north and ceasing in the main epicentral area of the Northwest Bohemian swarm earthquakes. The ascending CO₂ forms Ca‐Mg‐HCO₃ type waters by leaching of cations from the fault planes and creates clay minerals, such as kaolinite, as alteration products on affected fault planes. These mineral reactions result in fault weakness and in hydraulically interconnected fault network. This leads to a decrease in the friction coefficient of the Coulomb failure stress (CFS) and to fault creep as stress build‐up cannot occur in the weak segments. At the transition zone in the north of the Cheb Basin, between areas of weak, fluid conductive faults and areas of locked faults with frictional strength, fluid pressure can increase resulting in stress build‐up. This can trigger strike‐slip swarm earthquakes. Fault creep or movements in weak segments may support a stress build‐up in the transition area by transmitting fluid pressure pulses. Additionally to fluid‐driven triggering models, it is important to consider that fluids ascending along faults are CO₂‐supersaturated thus intensifying the effect of fluid flow. The enforced flow of CO₂‐supersaturated fluids in the transitional zone from high to low permeability segments through narrowings triggers gas exsolution and may generate pressure fluctuations. Phase separation starts according to the phase behaviour of CO₂‐H₂O systems in the seismically active depths of NW Bohemia and may explain the vertical distribution of the seismicity. Changes in the size of the fluid transport channels in the fault systems caused, or superimposed, by fault movements, can produce fluid pressure increases or pulses, which are the precondition for triggering fluid‐induced swarm earthquakes.     

Hydrothermal control on organic matter alteration and illite precipitation, Mt Isa Basin, Australia

Abundant illite precipitation in Proterozoic rocks from Northern Lawn Hill Platform, Mt Isa Basin, Australia, occurred in organic matter‐rich black shales rather than in sandstones, siltstones and organic matter‐poor shales. Sandstones and siltstones acted as impermeable rocks, as early diagenetic quartz and carbonate minerals reduced the porosity–permeability. Scanning and transmission electron microscopy (SEM and TEM) studies indicate a relation between creation of microporosity–permeability and organic matter alteration, suitable for subsequent mineral precipitation. K–Ar data indicate that organic matter alteration and the subsequent illite precipitation within the organic matter occurred during the regional hydrothermal event at 1172 ± 50 (2σ) Ma. Hot circulating fluids are considered to be responsible for organic matter alteration, migration and removal of volatile hydrocarbon, and consequently porosity–permeability creation. Those rocks lacking sufficient porosity–permeability, such as sandstones, siltstones and organic matter poor shales, may not have been affected by fluid movement. In hydrothermal systems, shales and mudstones may not be impermeable as usually assumed because of hydrocarbons being rapidly removed by fluid, even with relatively low total organic carbon.     

Fracture mineralization and fluid flow evolution: an example from Ordovician–Devonian carbonates,southwestern Ontario,Canada

Petrography, geochemistry (stable and radiogenic isotopes), and fluid inclusion microthermometry of matrix dolomite, fracture‐filling calcite, and saddle dolomite in Ordovician to Devonian carbonates from southwestern Ontario, Canada, provide useful insights into fluid flow evolution during diagenesis. The calculated δ¹⁸O_fluid, ΣREE, and REE_SN patterns of matrix and saddle dolomite suggest diverse fluids were involved in dolomitization and/or recrystallization of dolomite. The ⁸⁷Sr/⁸⁶Sr ratios of dolomite of each succession vary from values in the range of coeval seawater to values more radiogenic than corresponding seawater, which indicate diagenetic fluids were influenced by significant water/rock interaction. High salinities (22.4–26.3 wt. % NaCl + CaCl₂) of Silurian and Ordovician dolomite–hosted fluid inclusions indicate involvement of saline waters from dissolution of Silurian evaporites. High fluid inclusion homogenization temperatures (>100°C) in all samples from Devonian to Ordovician show temperatures higher than maximum burial (60–90°C) of their host strata and suggest involvement of hydrothermal fluids in precipitation and/or recrystallization of dolomite. A thermal anomaly over the mid‐continent rift during Devonian to Mississippian time likely was the source of excess heat in the basin. Thermal buoyancy resulting from this anomaly was the driving force for migration of hydrothermal fluids through regional aquifers from the center of the Michigan Basin toward its margin. The decreasing trend of homogenization temperatures from the basin center toward its margin further supports the interpreted migration of hydrothermal fluids from the basin center toward its margin. Hydrocarbon‐bearing fluid inclusions in late‐stage Devonian to Ordovician calcite cements with high homogenization temperatures (>80°C) and their ¹³C‐depleted values (approaching ?32‰ PDB) indicate the close relationship between hydrothermal fluids and hydrocarbon migration.     

Fluid circulation related to post‐Messinian extension,Thassos Island,North Aegean

In the North Aegean Domain, Thassos Island contains a Plio‐Pleistocene basin controlled by a large‐scale flat‐ramp extensional system with a potential décollement located at depth within a marble unit. Numerous mineralizations associated with normal faults of Plio‐Pleistocene age are the sign of fluid circulation during extension. Two main generations of fluid flow are recognized, related to Plio‐Pleistocene extension. A first circulation under high‐temperature conditions (about 100–200°C) resulted in dolomitization of marbles near the base of the Plio‐Pleistocene basin. The dolomites are characterized by low δ¹⁸O values (down to 11‰ versus Standard Mean Ocean Water). Some cataclastic deformation affected the dolomites. Hydrothermal quartz that crystallized in extension veins above a blind ramp also has low δ¹⁸O values (about 13‰). This shows that high‐temperature fluids moved up from the décollement level toward the surface. A second downward circulation of continental waters at near‐surface temperature is documented by calcite veins in fault zones and at the base of the Plio‐Pleistocene basin. These veins have O isotope values relatively constant at about 23–25‰ and C isotope values intermediate between the high δ¹³C value of the carbonate host rock (about 1–3‰ versus Peedee Belemnite) and the low δ¹³C value of soil‐derived carbon (?10‰). The calcites associated with the oxidative remobilization of primary sulphide Zn–Pb mineralization of Thassos carbonates have comparable O and C isotope compositions. Hot fluids, within the 100–200°C temperature range, have likely contributed to the weakening of the lower marble unit of Thassos and, thus, to the process of décollement.     

Composition and evolution of fluids during skarn development in the Monte Capanne thermal aureole,Elba Island,central Italy

We describe the chemistry of the fluids circulating during skarn formation by focusing on fluids trapped in calcsilicate minerals of the inner thermal aureole of the Late Miocene Monte Capanne intrusion of western Elba Island (central Italy). Primary, CH₄‐dominant, C‐O‐H‐S‐salt fluid inclusions formed during prograde growth of the main skarn‐forming mineral phases: grossular/andradite and vesuvianite. The variable phase ratios attest to heterogeneous entrapment of fluid, with co‐entrapment of an immiscible hydrocarbon–brine mixture. Chemical elements driving skarn metasomatism such as Na, K, Ca, S and Cl, Fe and Mn were dominantly partitioned into the circulating fluid phase. The high salinity (apparent salinity between 58 and 70 wt% NaCl eq.) and the C‐component of the fluids are interpreted as evidence for a composite origin of the skarn‐forming fluids that involves both fluids derived from the crystallizing intrusion and contributions from metamorphic devolatilization. Oxidation of a Fe‐rich brine in an environment dominated by fluctuation in pressure from lithostatic to hydrostatic conditions (maintained by active crack‐sealing) contributed to skarn development. Fluid infiltration conformed to a geothermal gradient of about 100°C km^?1, embracing the transition from high‐temperature contact metamorphism and fluid‐assisted skarn formation (at ca 600°C) to a barren hydrothermal stage (at ca 200°C).     

Geological setting, nature of ore fluids and sulphur isotope geochemistry of the Fu Ning Carlin-type gold deposits, Yunnan Province, China

Carlin‐type gold deposits in southern China are present in Palaeozoic to Mesozoic siliciclastic and carbonate rocks. The border region of Yunnan, Guizhou and Guangxi Provinces contains gold deposits on the south‐western margin of the Pre‐Cambrian South China Craton in south‐eastern Yunnan Province. The Fu Ning gold deposits host epigenetic, micron‐sized disseminated gold in: (i) Middle Devonian (D₁p) black carbonaceous mudstone at the Kuzhubao gold deposit and (ii) fault breccia zones at the contact between Triassic gabbro (β ) and the Devonian mudstone (D₁p) at the Bashishan gold deposit. The deposits are associated with zones of intense deformation with enhanced permeability and porosity that focused hydrothermal fluid flow, especially where low‐angle N‐S striking thrust faults are cut by NW striking strike‐slip and/or NE striking normal faults. Major sulphide ore minerals in the Fu Ning gold deposits are pyrite, arsenopyrite, arsenic‐rich pyrite, stibnite and minor iron‐poor sphalerite. Gangue minerals are quartz, sericite, calcite, ankerite and chlorite. Hypogene ore grades range from 1 to 7 g t^?1 Au and up to 18 g t^?1 Au at the Kuzhubao gold deposit and are generally less than 3 g t^?1 Au at the Bashishan gold deposit. Sub‐microscopic gold mineralization is associated with finely disseminated arsenic‐rich pyrite in the Stage III mineral assemblage. Two types of primary fluid inclusions have been recorded: Type I liquid–vapour inclusions with moderate‐to‐high liquid/vapour ratios, and Type II inclusions containing moderate liquid/vapour ratios with CO₂ as determined from laser Raman analysis. Temperature of homogenization (T_h) data collected from these primary fluid inclusions in gold‐ore Stage III quartz ranged from 180 to 275°C at the Kuzhubao gold deposit and 210 to 330°C at the Bashishan gold deposit. Salinity results indicate that there were possibly two fluids present during gold deposition, including: (i) an early fluid with 0.8–6.5 wt.% NaCl equivalent, similar to salinity in shear‐zone‐hosted gold deposits with metamorphic derived fluids; and (ii) a late fluid with 11.8–13.4 wt.% NaCl equivalent, indicating possible derivation from connate waters and/or brine sources. CO₂ and trace CH₄ were only detected by laser Raman spectrometry in gold‐ore‐stage primary fluid inclusions. Results of sulphur isotope studies showed that δ³⁴S values for pyrite and arsenopyrite associated with gold‐ore mineralization during Stage III at the Kuzhubao and Bashishan gold deposits are isotopically similar and moderately heavy with a range from +9 to +15 per mil, and also fall into the range of δ³⁴S values reported for Carlin‐type gold deposits. Sulphur isotopes suggest that the Fu Ning gold deposits were formed from connate waters and/or basinal brines. Fluid geochemistry data from the Fu Ning gold deposits suggest a Carlin‐type genetic model, involving fluid mixing between: (i) deep CO₂‐rich metamorphic fluids, (ii) moderately saline, reduced connate waters and/or basinal brines; and (iii) evolved meteoric waters.     

Application of boron isotopes to the understanding of fluid–rock interactions in a hydrothermally stimulated oil reservoir in the Alberta Basin, Canada

Boron isotope ratios of reservoir minerals and fluids can be a useful geothermometer and monitor of fluid–rock interactions. In Cold Lake oil sands of northern Alberta, there is a large variation in δ¹¹B of the produced waters generated during steam injection and recovery of oil and water. The higher temperature waters (～ 200 °C) have isotopically light δ¹¹B values (+ 3‰ to + 14‰) and high B contents (～150 p.p.m.). It is inferred that the range of δ¹¹B values of the hydrothermal fluids results from reaction with the reservoir rock, and is a function of the temperature of the fluid–rock interaction. The distinct B geochemistry of the produced waters can be used to show that there is no detectable mixing of the oil recovery waters with the regional formation waters or shallow groundwater aquifers containing potable water. Examination of B isotope ratios of reservoir minerals, before and after steam injection, allows the evaluation of sources of B in the reservoir. The only significant phase containing B is pumice. It shows generally positive δ¹¹B values before steam injection and negative values after steam, with δ¹¹B as low as ? 28‰. Other possibly reactive phases include clay minerals and organic matter, but their abundance is not great enough to impact on the isotopic composition of the produced waters. This information makes it possible to evaluate the boron isotope fractionation equation derived from experimental data ( Williams LB (2000) Boron isotope geochemistry during burial diagenesis. PhD Dissertation. The University of Calgary, Alberta, Canada; Williams LB, Hervig RL, Holloway JR, Hutcheon I (2001a) Boron isotope geochemistry during diagenesis: Part 1. Experimental determination of fractionation during illitization of smectite. Geochimica et Cosmochimica Acta, in press). The results show that the fractionation curve predicts the difference between δ¹¹B of the pumice and hydrothermal fluids in the Cold Lake reservoir. This not only indicates that the reservoir fluids have approached boron isotope equilibrium with the reservoir rock, but also shows that B isotopes provide a useful geothermometer for hydrothermally stimulated oil reservoirs.