Br/Cl signature of hydrothermal fluids: liquid–vapour fractionation of bromine revisited

Br/Cl ratios of hydrothermal fluids are widely used as geochemical tracers in marine hydrothermal systems to prove fluid phase separation processes. However, previous results of the liquid–vapour fractionation of bromine are ambiguous. Here we report new experimental results of the liquid–vapour fractionation of bromine in the system H₂O–NaCl–NaBr at 380–450°C and 22.9–41.7 MPa. Our data indicate that bromine is generally more enriched than chlorine in the liquid phase. Calculated exchange coefficients K_D(Br‐Cl)^{liquid‐vapour} for the reaction Br^vapour + Cl^liquid = Br^liquid + Cl^vapour are between 0.94 ± 0.08 and 1.66 ± 0.14 within the investigated P–T range. They correlate positively with D_Cl^{liquid‐vapour} and suggest increasing bromine–chlorine fractionation with increasing opening of the liquid–vapour solvus, i.e. increasing distance to the critical curve in the H₂O–NaCl system. An empirical fit of the form K_D(Br‐Cl)^{liquid‐vapour} = a*ln[b*(D_Cl^{liquid‐vapour}?1) + e^1/a] yields a = 0.349 and b = 1.697. Based on this empirical fit and the well‐constrained phase relations in the H₂O–NaCl system we calculated the effect of fluid phase separation on the Br/Cl signature of a hydrothermal fluid with initial seawater composition for closed and open adiabatic ascents along the 4.5 and 4.8 J g^?1 K^?1 isentropes. The calculations indicate that fluid phase separation can significantly alter the Br/Cl ratio in hydrothermal fluids. The predicted Br/Cl evolutions are in accord with the Br/Cl signatures in low‐salinity vent fluids from the 9 to 10°N East Pacific Rise.     

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).     

Exploring the potential linkages between oil‐field brine reinjection,crystalline basement permeability,and triggered seismicity for the Dagger Draw Oil field,southeastern New Mexico,USA, using hydrologic modeling

We used hydrologic models to explore the potential linkages between oil‐field brine reinjection and increases in earthquake frequency (up to M_d 3.26) in southeastern New Mexico and to assess different injection management scenarios aimed at reducing the risk of triggered seismicity. Our analysis focuses on saline water reinjection into the basal Ellenburger Group beneath the Dagger Draw Oil field, Permian Basin. Increased seismic frequency (>M_d 2) began in 2001, 5 years after peak injection, at an average depth of 11 km within the basement 15 km to the west of the reinjection wells. We considered several scenarios including assigning an effective or bulk permeability value to the crystalline basement, including a conductive fault zone surrounded by tighter crystalline basement rocks, and allowing permeability to decay with depth. We initially adopted a 7 m (0.07 MPa) head increase as the threshold for triggered seismicity. Only two scenarios produced excess heads of 7m five years after peak injection. In the first, a hydraulic diffusivity of 0.1 m² s^?1 was assigned to the crystalline basement. In the second, a hydraulic diffusivity of 0.3 m² s^?1 was assigned to a conductive fault zone. If we had considered a wider range of threshold excess heads to be between 1 and 60 m, then the range of acceptable hydraulic diffusivities would have increased (between 0.1–0.01 m² s^?1 and 1–0.1 m² s^?1 for the bulk and fault zone scenarios, respectively). A permeability–depth decay model would have also satisfied the 5‐year time lag criterion. We also tested several injection management scenarios including redistributing injection volumes between various wells and lowering the total volume of injected fluids. Scenarios that reduced computed excess heads by over 50% within the crystalline basement resulted from reducing the total volume of reinjected fluids by a factor of 2 or more.     

Hydrothermal dolomitization,mixing corrosion and deep burial porosity formation: numerical results from 1‐D reactive transport models

Major corrosion has been found at depth in carbonate hydrocarbon reservoirs from different geologic provinces. Fluid inclusion microthermometry and stable isotopic compositions of carbonate cements, predating major corrosion, constrain the interpretation of the evolution of parental fluids during progressive burial and prior to the major corrosion event. Post‐major corrosion mineral paragenesis includes pyrite (‐marcasite), anhydrite, kaolinite (dickite) and fluorite. Although the post‐corrosion mineral paragenesis represents minor volumes of rock, it may provide valuable insights into the post‐corrosion brine chemistry. Using reactive transport numerical models, the roles of cooling and/or mixing of brines on corrosion have been evaluated as controls for dolomitization, deep burial corrosion and precipitation of the post‐corrosion mineral paragenesis. Modelling results show that cooling of deep‐seated fluids moving upward along a fracture may cause minor calcite dissolution and porosity generation. Significant dolomitization along a fracture zone and nearby host‐rock only occurs when deep‐seated fluids have high salinities (4 mol Cl kg^?1 of solution) and Darcian flow rates are relatively high (1 m³ m^?2 year^?1). Only minor volumes of quartz and fluorite precipitate in the newly formed porosity. Moreover, modelling results cannot reproduce the authigenic precipitation of kaolinite (dickite at high temperatures) by cooling. As an alternative to cooling as a cause of corrosion, mixing between two brines of different compositions and salinities is represented by two main cases. One case consists of the flow up along a fracture of deep‐seated fluids with higher salinities than the fluid in the wall rock. Dolomite does not precipitate at a fracture zone. Nevertheless, minor volumes of dolomite are formed away from the fracture. The post‐corrosion mineral paragenesis can be partly reproduced, and the results are comparable to those obtained from cooling calculations. Minor volumes of quartz and fluorite are formed, and kaolinite‐dickite does not precipitate. The major outputs of this scenario are calcite dissolution and slight net increase in porosity. A second case corresponds to the mixing of low salinity deep‐seated fluids, flowing up along fractures, with high salinity brines within the wall rock. Calculations predict major dissolution of calcite and precipitation of dolomite. The post‐corrosion mineral paragenesis can be reproduced. High volumes of quartz, fluorite and kaolinite‐dickite precipitate and may even completely occlude newly formed porosity.     

Indications of formation water flow and compartmentalization on the flank of a salt structure derived from salinity and seismic data

Vertical and lateral variations in lithology, salinity, temperature, and pressure determined from wireline LAS logs, produced water samples, and seismic data on the south flank of a salt structure on the continental shelf, offshore Louisiana indicate three hydrogeologic zones in the study area: a shallow region from 0 to 1.1 km depth with hydrostatically pressured, shale‐dominated Pleistocene age sediments containing pore waters with sea water (35 g l^?1) or slightly above sea water salinity; a middle region from 1.1 to 3.2 km depth with near hydrostatically pressured, sand‐dominated Pliocene age sediments that contain pore waters that range from seawater salinity to up to 5 times sea water salinity (180 g l^?1); and a deep section below 3.2 km depth with geopressured, shale‐dominated Miocene age sediments containing pore waters that range from sea water salinity to 125 g l^?1. Salt dissolution has generated dense, saline waters that appear to be migrating down dip preferentially through the thick Pliocene sandy section. Sand layers that come in contact with salt contain pore waters with high salinity. Isolated sands have near sea water salinity. Salinity information in conjunction with seismic data is used to infer fluid compartmentalization. Both vertical and lateral lithologic barriers to fluid flow at tens to hundreds of meters scale are observed. Fluid compartmentalization is also evident across a supradomal normal fault. Offset of salinity contours are consistent with the throw of the fault, which suggests that saline fluids migrated before fault formation.     

Gas breakthrough experiments on fine-grained sedimentary rocks

The capillary sealing efficiency of fine‐grained sedimentary rocks has been investigated by gas breakthrough experiments on fully water saturated claystones and siltstones (Boom Clay from Belgium, Opalinus Clay from Switzerland and Tertiary mudstone from offshore Norway) of different lithological compositions. Sand contents of the samples were consistently below 12%, major clay minerals were illite and smectite. Porosities determined by mercury injection lay between 10 and 30% while specific surface areas determined by nitrogen adsorption (BET method) ranged from 20 to 48 m² g ^{? 1}. Total organic carbon contents were below 2%. Prior to the gas breakthrough experiments the absolute (single phase) permeability (k_abs) of the samples was determined by steady state flow tests with water or NaCl brine. The k_abs values ranged between 3 and 550 nDarcy (3 × 10^?21 and 5.5 × 10^?19 m²). The maximum effective permeability to the gas‐phase (k_eff) measured after gas breakthrough on initially water‐saturated samples extended from 0.01 nDarcy (1 × 10^?23 m²) up to 1100 nDarcy (1.1 × 10^?18 m²). The residual differential pressures after re‐imbibition of the water phase, referred to as the ‘minimum capillary displacement pressures’ (P_d), ranged from 0.06 to 6.7 MPa. During the re‐imbibition process the effective permeability to the gas phase decreases with decreasing differential pressure. The recorded permeability/pressure data were used to derive the pore size distribution (mostly between 8 and 60 nm) and the transport porosity of the conducting pore system (10^‐5–10^‐2%). Correlations could be established between (i) absolute permeability coefficients and the maximum effective permeability coefficients and (ii) effective or absolute permeability coefficients and capillary sealing efficiency. No correlation was found between the capillary displacement pressures determined from gas breakthrough experiments and those derived theoretically by mercury injection.     

High‐temperature magmatic fluid exsolved from magma at the Duobuza porphyry copper–gold deposit,Northern Tibet

The Duobuza porphyry copper–gold deposit (proven Cu resources of 2.7 Mt, 0.94% Cu and 13 t gold, 0.21 g t^?1 Au) is located at the northern margin of the Bangong‐Nujiang suture zone separating the Qiangtang and Lhasa Terranes. The major ore‐bearing porphyry consists of granodiorite. The alteration zone extends from silicification and potassic alteration close to the porphyry stock to moderate argillic alteration and propylitization further out. Phyllic alteration is not well developed. Sericite‐quartz veins only occur locally. High‐temperature, high‐salinity fluid inclusions were observed in quartz phenocrysts and various quartz veins. These fluid inclusions are characterized by sylvite dissolution between 180 and 360°C and halite dissolution between 240 and 540°C, followed by homogenization through vapor disappearance between 620 and 960°C. Daughter minerals were identified by SEM as chalcopyrite, halite, sylvite, rutile, K–feldspar, and Fe–Mn‐chloride. They indicate that the fluid is rich in ore‐forming elements and of high oxidation state. The fluid belongs to a complex hydrothermal system containing H₂O – NaCl – KCl ± FeCl₂ ± CaCl₂ ± MnCl₂. With decreasing homogenization temperature, the fluid salinity tends to increase from 34 to 82 wt% NaCl equiv., possibly suggesting a pressure or Cl/H₂O increase in the original magma. No coexisting vapor‐rich fluid inclusions with similar homogenization temperatures were found, so the brines are interpreted to have formed by direct exsolution from magma rather than trough boiling off of a low‐salinity vapor. Estimated minimum pressure of 160 MPa imply approximately 7‐km depth. This indicates that the deposit represents an orthomagmatic end member of the porphyry copper deposit continuum. Two key factors are proposed for the fluid evolution responsible for the large size of the gold‐rich porphyry copper deposit of Duobuza: (i) ore‐forming fluids separated early from the magma, and (ii) the hydrothermal fluid system was of magmatic origin and highly oxidized.     

Origin of deep saline groundwaters in the Vienne granitic rocks (France): constraints inferred from boron and strontium isotopes

As part of a preliminary geological characterization programme to assess the feasibility of an underground laboratory in granitic rock, a series of 17 deep boreholes (maximum depth, 900 m) was drilled by ANDRA in the Vienne district, France. A salinity gradient was demonstrated in the granitic waters with concentrations varying from approximately 1 g L^?1 at 150 m depth at the top of the basement (beneath the sedimentary cover) to 10 g L^?1 in the deeper part (from 400 to 600 m depth). Sr and B isotope ratios were measured in order to better understand the origin of the salinity and to evaluate the degree of water–rock interaction in the system. The results obtained were compared to those of mineral spring waters emerging from the granitic basement in the Massif Central. Evidence in support of a significant marine contribution include: (i) the Cl–Br investigations agree with a marine origin for the saline groundwaters without evolution from seawater; (ii) the ⁸⁷Sr/⁸⁶Sr ratio of the Vienne deep groundwaters (0.7078–0.7084) is in agreement with a palaeo‐seawater isotopic signature; (iii) measured δ¹¹B values for the deepest brine samples are enriched in ¹¹B (up to 36.1‰) relative to the granitic springs. The combined use of δ¹¹B, Cl, B, Br, Sr contents and ⁸⁷Sr/⁸⁶Sr ratios makes it possible to define and quantify a mixing model between marine and crustal end‐members in order to explain the origin of the deep saline groundwaters in the Vienne granitic rocks.     

A simulation of the hydrothermal response to the Chesapeake Bay bolide impact

Groundwater more saline than seawater has been discovered in the tsunami breccia of the Chesapeake Bay Impact Crater. One hypothesis for the origin of this brine is that it may be a liquid residual following steam separation in a hydrothermal system that evolved following the impact. Initial scoping calculations have demonstrated that it is feasible such a residual brine could have remained in the crater for the 35 million years since impact. Numerical simulations have been conducted using the code HYDROTHERM to test whether or not conditions were suitable in the millennia following the impact for the development of a steam phase in the hydrothermal system. Hydraulic and thermal parameters were estimated for the bedrock underlying the crater and the tsunami breccia that fills the crater. Simulations at three different breccia permeabilities suggest that the type of hydrothermal system that might have developed would have been very sensitive to the permeability. A relatively low breccia permeability (1 × 10^?16 m²) results in a system partitioned into a shallow water phase and a deeper superheated steam phase. A moderate breccia permeability (1 × 10^?15 m²) results in a system with regionally extensive multiphase conditions. A relatively high breccia permeability (1 × 10^?14 m²) results in a system dominated by warm‐water convection cells. The permeability of the crater breccia could have had any of these values at given depths and times during the hydrothermal system evolution as the sediments compacted. The simulations were not able to take into account transient permeability conditions, or equations of state that account for the salt content of seawater. Results suggest, however, that it is likely that steam conditions existed at some time in the system following impact, providing additional evidence that is consistent with a hydrothermal origin for the crater brine.     

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.     

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.     

Salt tectonics and shallow subseafloor fluid convection: models of coupled fluid‐heat‐salt transport

Thermohaline convection associated with salt domes has the potential to drive significant fluid flow and mass and heat transport in continental margins, but previous studies of fluid flow associated with salt structures have focused on continental settings or deep flow systems of importance to petroleum exploration. Motivated by recent geophysical and geochemical observations that suggest a convective pattern to near‐seafloor pore fluid flow in the northern Gulf of Mexico (GoMex), we devise numerical models that fully couple thermal and chemical processes to quantify the effects of salt geometry and seafloor relief on fluid flow beneath the seafloor. Steady‐state models that ignore halite dissolution demonstrate that seafloor relief plays an important role in the evolution of shallow geothermal convection cells and that salt at depth can contribute a thermal component to this convection. The inclusion of faults causes significant, but highly localized, increases in flow rates at seafloor discharge zones. Transient models that include halite dissolution show the evolution of flow during brine formation from early salt‐driven convection to later geothermal convection, characteristics of which are controlled by the interplay of seafloor relief and salt geometry. Predicted flow rates are on the order of a few millimeters per year or less for homogeneous sediments with a permeability of 10^?15 m², comparable to compaction‐driven flow rates. Sediment permeabilities likely fall below 10^?15 m² at depth in the GoMex basin, but such thermohaline convection can drive pervasive mass transport across the seafloor, affecting sediment diagenesis in shallow sediments. In more permeable settings, such flow could affect methane hydrate stability, seafloor chemosynthetic communities, and the longevity of fluid seeps.     

Numerical model of pore‐pressure diffusion associated with the initiation of the 2010–2011 Guy–Greenbrier,Arkansas earthquakes

We model pore‐pressure diffusion caused by pressurized waste‐fluid injection at two nearby wells and then compare the buildup of pressure with the observed initiation and migration of earthquakes during the early part of the 2010–2011 Guy–Greenbrier earthquake swarm. Pore‐pressure diffusion is calculated using MODFLOW 2005 that allows the actual injection histories (volume/day) at the two wells to diffuse through a fractured and faulted 3D aquifer system representing the eastern Arkoma basin. The aquifer system is calibrated using the observed water‐level recovery following well shut‐in at three wells. We estimate that the hydraulic conductivities of the Boone Formation and Arbuckle Group are 2.2 × 10^?2 and 2.03 × 10^?3 m day^?1, respectively, with a hydraulic conductivity of 1.92 × 10^?2 m day^?1 in the Hunton Group when considering 1.72 × 10^?3 m day^?1 in the Chattanooga Shale. Based on the simulated pressure field, injection near the relatively conductive Enders and Guy–Greenbrier faults (that hydraulically connect the Arbuckle Group with the underlying basement) permits pressure diffusion into the crystalline basement, but the effective radius of influence is limited in depth by the vertical anisotropy of the hydraulic diffusivity. Comparing spatial/temporal changes in the simulated pore‐pressure field to the observed seismicity suggests that minimum pore‐pressure changes of approximately 0.009 and 0.035 MPa are sufficient to initiate seismic activity within the basement and sedimentary sections of the Guy–Greenbrier fault, respectively. Further, the migration of a second front of seismicity appears to follow the approximately 0.012 MPa and 0.055 MPa pore‐pressure fronts within the basement and sedimentary sections, respectively.     

Regional groundwater flow and interactions with deep fluids in western Apennine: the case of Narni‐Amelia chain (Central Italy)

The elemental fluxes and heat flow associated with large aquifer systems can be significant both at local and at regional scales. In fact, large amounts of heat transported by regional groundwater flow can affect the subsurface thermal regime, and the amount of matter discharged towards the surface by large spring systems can be significant relative to the elemental fluxes of surface waters. The Narni‐Amelia regional aquifer system (Central Italy) discharges more than 13 m³ sec^?1 of groundwater characterised by a slight thermal anomaly, high salinity and high pCO₂. During circulation in the regional aquifer, groundwater reacts with the host rocks (dolostones, limestones and evaporites) and mixes with deep CO₂‐rich fluids of mantle origin. These processes transfer large amounts of dissolved substances, in particular carbon dioxide, and a considerable amount of heat towards the surface. Because practically all the water circulating in the Narni‐Amelia system is discharged by few large springs (Stifone‐Montoro), the mass and energy balance of these springs can give a good estimation of the mass and heat transported from the entire system towards the surface. By means of a detailed mass and balance of the aquifer and considering the soil CO₂ fluxes measured from the main gas emission of the region, we computed a total CO₂ discharge of about 7.8 × 10⁹ mol a^?1 for the whole Narni‐Amelia system. Finally, considering the enthalpy difference between infiltrating water and water discharged by the springs, we computed an advective heat transfer related to groundwater flow of 410 ± 50 MW.     

Effective gas permeability of Tight Gas Sandstones as a function of capillary pressure – a non‐steady‐state approach

Single‐ and two‐phase (gas/water) fluid transport in tight sandstones has been studied in a series of permeability tests on core plugs of nine tight sandstones of the southern North Sea. Absolute (Klinkenberg‐corrected) gas permeability coefficients (k_gas__inf) ranged between 3.8 × 10^?16 and 6.2 × 10^?19 m² and decreased with increasing confining pressure (10–30 MPa) by a factor 3–5. Klinkenberg‐corrected (intrinsic) gas permeability coefficients were consistently higher by factors from 1.4 to 10 than permeability coefficients determined with water. Non‐steady‐state two‐phase (He/water) flow experiments conducted up to differential pressures of 10 MPa document the dynamically changing conductivity for the gas phase, which is primarily capillary‐controlled (drainage and imbibition). Effective gas permeability coefficients in the two‐phase flow tests ranged between 1.1 × 10^?17 and 2.5 × 10^?22 m², corresponding to relative gas permeabilities of 0.03% and 10%. In the early phase of the nonstationary flow regime (before establishment of steady‐state conditions), they may be substantially (>50%) lower. Effective gas permeability measurements are affected by the following factors: (i) Capillary‐controlled drainage/imbibition, (ii) viscous–dynamic effects (iii) and slip flow.     

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.     

Simulation of the impact of faults on CO2 injection into sandstone reservoirs

Numerical simulations of multiphase CO₂ behavior within faulted sandstone reservoirs examine the impact of fractures and faults on CO₂ migration in potential subsurface injection systems. In southeastern Utah, some natural CO₂ reservoirs are breached and CO₂‐charged water flows to the surface along permeable damage zones adjacent to faults; in other sites, faulted sandstones form barriers to flow and large CO₂‐filled reservoirs result. These end‐members serve as the guides for our modeling, both at sites where nature offers ‘successful’ storage and at sites where leakage has occurred. We consider two end‐member fault types: low‐permeability faults dominated by deformation‐band networks and high‐permeability faults dominated by fracture networks in damage zones adjacent to clay‐rich gouge. Equivalent permeability (k) values for the fault zones can range from <10^?14 m² for deformation‐band‐dominated faults to >10^?12 m² for fracture‐dominated faults regardless of the permeability of unfaulted sandstone. Water–CO₂ fluid‐flow simulations model the injection of CO₂ into high‐k sandstone (5 × 10^?13 m²) with low‐k (5 × 10^?17 m²) or high‐k (5 × 10^?12 m²) fault zones that correspond to deformation‐band‐ or fracture‐dominated faults, respectively. After 500 days, CO₂ rises to produce an inverted cone of free and dissolved CO₂ that spreads laterally away from the injection well. Free CO₂ fills no more than 41% of the pore space behind the advancing CO₂ front, where dissolved CO₂ is at or near geochemical saturation. The low‐k fault zone exerts the greatest impact on the shape of the advancing CO₂ front and restricts the bulk of the dissolved and free CO₂ to the region upstream of the fault barrier. In the high‐k aquifer, the high‐k fault zone exerts a small influence on the shape of the advancing CO₂ front. We also model stacked reservoir seal pairs, and the fracture‐dominated fault acts as a vertical bypass, allowing upward movement of CO₂ into overlying strata. High‐permeability fault zones are important pathways for CO₂ to bypass unfaulted sandstone, which leads to reduce sequestration efficiency. Aquifer compartmentalization by low‐permeability fault barriers leads to improved storativity because the barriers restrict lateral CO₂ migration and maximize the volume and pressure of CO₂ that might be emplaced in each fault‐bound compartment. As much as a 3.5‐MPa pressure increase may develop in the injected reservoir in this model domain, which under certain conditions may lead to pressures close to the fracture pressure of the top seal.     

The upper continental crust, an aquifer and its fluid: hydaulic and chemical data from 4 km depth in fractured crystalline basement rocks at the KTB test site

Detailed information on the hydrogeologic and hydraulic properties of the deeper parts of the upper continental crust is scarce. The pilot hole of the deep research drillhole (KTB) in crystalline basement of central Germany provided access to the crust for an exceptional pumping experiment of 1‐year duration. The hydraulic properties of fractured crystalline rocks at 4 km depth were derived from the well test and a total of 23100 m³ of saline fluid was pumped from the crustal reservoir. The experiment shows that the water‐saturated fracture pore space of the brittle upper crust is highly connected, hence, the continental upper crust is an aquifer. The pressure–time data from the well tests showed three distinct flow periods: the first period relates to wellbore storage and skin effects, the second flow period shows the typical characteristics of the homogeneous isotropic basement rock aquifer and the third flow period relates to the influence of a distant hydraulic border, probably an effect of the Franconian lineament, a steep dipping major thrust fault known from surface geology. The data analysis provided a transmissivity of the pumped aquifer T = 6.1 × 10^?6 m² sec^?1, the corresponding hydraulic conductivity (permeability) is K = 4.07 × 10^?8 m sec^?1 and the computed storage coefficient (storativity) of the aquifer of about S = 5 × 10^?6. This unexpected high permeability of the continental upper crust is well within the conditions of possible advective flow. The average flow porosity of the fractured basement aquifer is 0.6–0.7% and this range can be taken as a representative and characteristic values for the continental upper crust in general. The chemical composition of the pumped fluid was nearly constant during the 1‐year test. The total of dissolved solids amounts to 62 g l^?1 and comprise mainly a mixture of CaCl₂ and NaCl; all other dissolved components amount to about 2 g l^?1. The cation proportions of the fluid (X_Ca approximately 0.6) reflects the mineralogical composition of the reservoir rock and the high salinity results from desiccation (H₂O‐loss) due to the formation of abundant hydrate minerals during water–rock interaction. The constant fluid composition suggests that the fluid has been pumped from a rather homogeneous reservoir lithology dominated by metagabbros and amphibolites containing abundant Ca‐rich plagioclase.     

3D numerical modeling of hydrothermal processes during the lifetime of a deep geothermal reservoir

Understanding hydrothermal processes during production is critical to optimal geothermal reservoir management and sustainable utilization. This study addresses the hydrothermal (HT) processes in a geothermal research doublet consisting of the injection well E GrSk3/90 and production well Gt GrSk4/05 at the deep geothermal reservoir of Groß Schönebeck (north of Berlin, Germany) during geothermal power production. The reservoir is located between ?4050 to ?4250 m depth in the Lower Permian of the Northeast German Basin. Operational activities such as hydraulic stimulation, production (T = 150°C; Q = ?75 m³ h^?1; C = 265 g l^?1) and injection (T = 70°C; Q = 75 m³ h^?1; C = 265 g l^?1) change the HT conditions of the geothermal reservoir. The most significant changes affect temperature, mass concentration and pore pressure. These changes influence fluid density and viscosity as well as rock properties such as porosity, permeability, thermal conductivity and heat capacity. In addition, the geometry and hydraulic properties of hydraulically induced fractures vary during the lifetime of the reservoir. A three‐dimensional reservoir model was developed based on a structural geological model to simulate and understand the complex interaction of such processes. This model includes a full HT coupling of various petrophysical parameters. Specifically, temperature‐dependent thermal conductivity and heat capacity as well as the pressure‐, temperature‐ and mass concentration‐dependent fluid density and viscosity are considered. These parameters were determined by laboratory and field experiments. The effective pressure dependence of matrix permeability is less than 2.3% at our reservoir conditions and therefore can be neglected. The results of a three‐dimensional thermohaline finite‐element simulation of the life cycle performance of this geothermal well doublet indicate the beginning of thermal breakthrough after 3.6 years of utilization. This result is crucial for optimizing reservoir management. Geofluids (2010) 10 , 406–421     

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.