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.     

Diffuse hydrothermal methane output and evidence of methanotrophic activity within the soils at Sousaki (Greece)

Methane soil flux measurements have been made in 38 sites at the geothermal system of Sousaki (Greece) with the closed chamber method. Fluxes range from ?47.6 to 29 150 mg m^?2 day^?1, and the diffuse CH₄ output of the system has been estimated at 19 t a^?1. Contemporaneous CO₂ flux measurements showed a moderate positive correlation between CO₂ and CH₄ fluxes. Comparison of the CO₂/CH₄ soil flux ratios with the CO₂/CH₄ ratio of the gases of the main gas manifestations provided evidence for methanotrophic activity within the soil. Laboratory CH₄ consumption experiments confirmed the presence of methanotrophic microorganisms in soil samples collected at Sousaki. Consumption was generally in the range from ?4.9 to ?38.9 pmolCH₄ h^?1 g^?1 but could sometimes reach extremely high values (?33 000 pmolCH₄ h^?1 g^?1). These results are consistent with recent studies on other geothermal systems that revealed the existence of thermoacidophilic bacteria exerting methanotrophic activity in hot, acid soils, thereby reducing methane emissions to the atmosphere.     

Low‐temperature dunite hydration: evaluating CH4 and H2 production from H2O and CO2

Abiotic methane (CH₄) and hydrogen (H₂) produced after hydration of mafic/ultramafic rocks represent energy sources for microbes that may thrive in the deep subsurface regions of Earth and possibly on other planets. While H₂ is a direct product of serpentinization, CH₄ can form via Fischer–Tropsch Type (FTT) reactions (carbon reduction) that, due to potential H₂ migration, can be spatially and temporally detached from serpentinization. We tested an alternative process hypothesized by some scholars, in which CO₂ can be reduced through dunite hydration without initially added H₂, implying that CH₄ can form in the same serpentinized fluid–rock system. The experiment used natural dunite sand (Forsterite 92), CO₂ with δ¹³C ~ ?25‰ (VPDB), and a 1 mm dissolved SiO₂ solution mixed in 30 glass bottles (118 mL) stored for up to 8 months at low temperature (50°C) to simulate land‐based serpentinization systems. In addition, 30 control bottles without olivine were used as blanks. Trivial amounts of CH₄ (orders of 0.2–0.9 ppmv) were detected in both samples and blanks, likely representing analytical noise; essentially, no significant amount of CH₄ formed under the experimental conditions used in this work. Low amounts of H₂ (~2.55 ± 1.39 ppmv) were generated, with production yields that were one order of magnitude lower than in previously published experiments. Moderate concentrations of SiO₂ appeared to hinder low‐temperature H₂ production. Our experiment confirms that the low‐temperature reduction of CO₂ into CH₄ through direct olivine hydration, without initial H₂, is sluggish and not straightforward, which is consistent with previous studies. The presence of substantial amounts of H₂, as well as suitable metal catalysts, appears to be essential in the low‐temperature production of abiotic CH₄, as observed in published FTT experiments.     

Modeling of hydrogen production by serpentinization in ultramafic‐hosted hydrothermal systems: application to the Rainbow field

The production of hydrogen by serpentinization in ultramafic‐hosted hydrothermal systems is simulated by coupling thermodynamic and dynamic modeling in the framework of a thermo‐hydraulic single‐pass model where a high‐temperature hydrothermal fluid moves preferentially through a main canal of high permeability. The alteration of ultramafic rocks is modeled with a first‐order kinetic formulation, wherein the serpentinization rate coefficient, K_r, takes the form: K_r = A exp(?α(T ? T₀)²). In this formulation, α determines the temperature range of the reaction and T₀ is the temperature at which the serpentinization rate reaches its maximum. This model is applied to the Rainbow hydrothermal system, which is situated on the Mid‐Atlantic Ridge, and characterized by a high temperature, a high mass flux, and a very high hydrogen concentration. The results show that a first‐order kinetic law gives a useful representation of the kinetics of serpentinization. The estimated value for the parameter A in the temperature‐dependent formulation of the serpentinization rate coefficient lies in the range (1–5) × 10^?11 s^?1. This effective parameter is several orders of magnitude lower than the values obtained from small grain‐size experiments, but in agreement with other published modeling studies of natural systems. Numerical simulations show that the venting site is able to produce the observed high concentration of hydrogen during the whole continuous lifetime of the Rainbow site.     

Molecular transport of methane, ethane and nitrogen and the influence of diffusion on the chemical and isotopic composition of natural gas accumulations

Laboratory experiments have been performed to determine diffusion coefficients of natural gas components (methane, ethane and nitrogen) and isotope fractionation effects under simulated in situ pressure (up to 45 MPa effective stress) and temperature conditions (50–200°C) in water‐saturated pelitic and coarse‐grained rocks. Effective diffusion coefficients of molecular nitrogen (0.39 × 10^?11 to 21.6 × 10^?11 m² sec^?1 at 90°C) are higher than those for methane (0.18 × 10^?11 to 18.2 × 10^?11 m² sec^?1 at 90°C). Diffusive flux rates expressed in mass units are generally higher for N₂ than for CH₄. Both methane and (to a lesser extent) nitrogen diffusion coefficients decrease with increasing total organic carbon (TOC) content of the rock samples because of sorption processes on the organic matter. This effect decreases with increasing temperature. Effective diffusion coefficients increase upon a temperature increase from 50 to 200°C by a factor of four. Effective diffusion coefficients and steady‐state diffusive flux decrease with effective stress. Stationary diffusive fluxes drop by 50–70% for methane and 45–62% for nitrogen while effective diffusion coefficients are reduced by 38% (CH₄) and 32–48% (N₂), respectively. Isotope fractionation coefficients of diffusive transport are higher for methane (?1.56 and ?2.77‰) than for ethane (?0.84 and ?1.62‰). Application of the experimental results to geological systems show that diffusive transport has only a low transport efficiency. Significant depletion of natural gas reservoirs by molecular diffusion is only expected in cases of very poor caprock qualities (in terms of thickness and/or porosity) and over extended periods of geological time. Under these circumstances, the chemical and isotopic composition of a gas reservoir will change and maturity estimates based on these parameters may be deceptive. To account for these potential effects, nomograms have been developed to estimate diffusive losses and apply maturity corrections.     

Gas breakthrough experiments on pelitic rocks: comparative study with N2, CO2 and CH4

The capillary‐sealing efficiency of intermediate‐ to low‐permeable sedimentary rocks has been investigated by N₂, CO₂ and CH₄ breakthrough experiments on initially fully water‐saturated rocks of different lithological compositions. Differential gas pressures up to 20 MPa were imposed across samples of 10–20 mm thickness, and the decline of the differential pressures was monitored over time. Absolute (single‐phase) permeability coefficients (k_abs), determined by steady‐state fluid flow tests, ranged between 10^?22 and 10^?15 m². Maximum effective permeabilities to the gas phase k_eff(max), measured after gas breakthrough at maximum gas saturation, extended from 10^?26 to 10^?18 m². Because of re‐imbibition of water into the interconnected gas‐conducting pore system, the effective permeability to the gas phase decreases with decreasing differential (capillary) pressure. At the end of the breakthrough experiments, a residual pressure difference persists, indicating the shut‐off of the gas‐conducting pore system. These pressures, referred to as the ‘minimum capillary displacement pressures’ (P_d), ranged from 0.1 up to 6.7 MPa. Correlations were established between (i) absolute and effective permeability coefficients and (ii) effective or absolute permeability and capillary displacement pressure. Results indicate systematic differences in gas breakthrough behaviour of N₂, CO₂ and CH₄, reflecting differences in wettability and interfacial tension. Additionally, a simple dynamic model for gas leakage through a capillary seal is presented, taking into account the variation of effective permeability as a function of buoyancy pressure exerted by a gas column underneath the 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.     

Low‐temperature catalytic CO2 hydrogenation with geological quantities of ruthenium: a possible abiotic CH4 source in chromitite‐rich serpentinized rocks

Metal‐catalysed CO₂ hydrogenation is considered a source of methane in serpentinized (hydrated) igneous rocks and a fundamental abiotic process germane to the origin of life. Iron, nickel, chromium and cobalt are the catalysts typically employed in hydrothermal simulation experiments to obtain methane at temperatures >200°C. However, land‐based present‐day serpentinization and abiotic gas apparently develop below 100°C, down to approximately 40–50°C. Here, we document considerable methane production in thirteen CO₂ hydrogenation experiments performed in a closed dry system, from 20 to 90°C and atmospheric pressure, over 0.9–122 days, using concentrations of non‐pretreated ruthenium equivalent to those occurring in chromitites in ophiolites or igneous complexes (from 0.4 to 76 mg of Ru, equivalent to the amount occurring approximately in 0.4–760 kg of chromitite). Methane production increased with time and temperature, reaching approximately 87 mg CH₄ per gram of Ru after 30 days (2.9 mgCH₄/g_ru/day) at 90°C. At room temperature, CH₄ production rate was approximately three orders of magnitude lower (0.003 mgCH₄/g_ru/day). We report the first stable carbon and hydrogen isotope ratios of abiotic CH₄ generated below 100°C. Using initial δ¹³C_CO2 of ‐40‰, we obtained room temperature δ¹³C_CH4 values as ¹³C depleted as ?142‰. With time and temperature, the C‐isotope separation between CO₂ and CH₄ decreased significantly and the final δ¹³C_CH4 values approached that of initial δ¹³C_CO2. The presence of minor amounts of C₂‐C₆ hydrocarbons is consistent with observations in natural settings. Comparative experiments at the same temperatures with iron and nichel catalysts did not generate CH₄. Ru‐enriched chromitites could potentially generate methane at low temperatures on Earth and on other planets.     

Groundwater discharges in the Baltic Sea: survey and quantification using a schlieren technique application

Groundwater seeps are known to occur in Eckernförde Bay, Baltic Sea. Their discharge rate and dispersion were investigated with a new schlieren technique application, which is able to visualize heterogeneous water parcels with density anomalies down to Δσ_t = 0.049 on the scale of millimeters. With the use of an inverted funnel, discharged fluids can be captured and the outflow velocity can be determined. Overall, 46 stations could be categorized by three different cases: active vent sites, seep‐influenced sites, and non‐seep sites. New seep locations were discovered, even at shallow near‐shore sites, lacking prominent sediment depression, which indicate submarine springs. The detection of numerous seeps was possible and the groundwater‐influenced area was defined to be approximately 6.3 km². Flow rates of between 0.05 and 0.71 l m^?2 min^?1 were measured. A single focused fluid plume, which was not disturbed by the funnel was recorded and revealed a flux of 59.6 ± 20 ml cm^?2 min^?1 and it was calculated that this single focused plume would be strong enough to produce a flow rate through the funnel of 1.32 ± 0.44 l m^?2 min^?1. The effect of different seep‐meter funnel sizes is discussed.     

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.     

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.     

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.     

Soil and organic carbon losses from varying land uses: a global meta‐analysis

Soil (SL) and organic carbon losses (SOC_L) have increased with human population and climate change linked extreme events. While SL and SOC_L are clearly associated with surface run‐off, the impact of land use is still not well understood. This article elucidates the effects of land use, surface cover, and other environmental factors on SL and SOC_L using data from 55 published studies. The overall SL (12.34 ± 2.25 Mg ha^?1 year^?1) and SOC_L (21.80 ± 0.91 g C m^?2 year^?1) suggests substantial losses of the fertile topsoil globally. Grasslands (4.19 ± 1.22 Mg ha^?1 year^?1) had 77%, 66%, and 41% lower SL than orchards, croplands, and forests, respectively, which is attributable to higher soil organic matter and surface cover. Croplands had the highest SOC_L at 22.78 ± 2.22 g C m^?2 year^?1. Natural vegetation had 98% and 70% lower run‐off and SL than did plant residue mulched plots, indicating its great potential for surface run‐off and soil erosion control. Rainfall and slope were key drivers of soil erosion, while soil surface cover, SOC, and clay content decreased. These findings improve our knowledge on soil and organic carbon losses, which is useful for fostering sustainable management of soils and natural vegetation to enhance ecosystems functionality.     

Solubility of corundum + kyanite in H2O at 700°C and 10 kbar: evidence for Al‐Si complexing at high pressure and temperature

The solubility of the assemblage corundum + kyanite in H₂O was determined at 700°C and 10 kbar, using a piston‐cylinder apparatus and rapid‐quench/fluid‐extraction techniques. Weighted mean concentrations of total Al and Si were 5.80 ± 0.03 mmol kg^?1 H₂O and 0.308 ± 0.003 mol kg^?1 H₂O, respectively (1σ errors). The Al concentration is nearly five times higher than that of corundum solubility in pure H₂O. This difference is interpreted to arise from complexing between Si and Al to form HAlSiO_4,aq species. Charged or more polymerized species are also possible, but their abundance cannot be constrained based on these experiments. Assumption of a single aqueous aluminosilicate complex permits calculation of the thermodynamic consequences of Al‐Si interaction in high‐pressure fluids, as well as phase diagrams for the system Al‐Si‐O‐H. Formation of Al‐Si complexes leads to a large increase in dissolved Al with increasing Si in solution, such that Al concentration in equilibrium with kyanite + quartz is predicted to be 7.1 mmolal, higher than with kyanite + corundum. The elevated concentration of Si in deep‐crustal and mantle aqueous fluids suggests that Al must readily be dissolved and transported by Al‐Si complexing in high‐pressure metamorphic and metasomatic environments. The results provide a simple explanation for the common observation of kyanite + quartz segregations in eclogites and Barrovian metamorphic rocks.     

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.     

Experimental study of aqueous fluid infiltration into quartzite: implications for the kinetics of fluid redistribution and grain growth driven by interfacial energy reduction

To investigate the kinetics of interfacial energy‐driven fluid infiltration, experiments were carried out in a quartzite–water system at 621–925°C and 0.8 GPa. Infiltration couples were made by juxtaposing presynthesized dry quartzite cylinders and fluid reservoirs. The infiltration process was confirmed by the presence of pores at the quartzite grain edges. As predicted from theoretical considerations and previous experiments, wetting fluids such as pure water and NaCl aqueous solution infiltrated into quartzite, whereas nonwetting CO₂‐rich fluids did not. Newly precipitated quartz layers at the surfaces of the infiltrated sample proved that infiltration took place by a dissolution–precipitation mechanism. The enhancement of grain growth by fluid infiltration was observed over the entire range of experimental temperatures. The fluid fraction, gauged by the porosity of the run products, increases at the infiltration front and then decreases towards the fluid reservoir to form a high‐porosity zone with a maximum porosity of 2.3–2.9%. As infiltration proceeds, the high‐porosity zone advances like a travelling wave. This porosity wave is probably caused by a grain curvature gradient resulting from preferential grain growth in the infiltrated part of the quartzite, perhaps combined with other factors. The infiltration kinetics were modelled with a steady‐state diffusion model over the high‐porosity zone. The solubility difference between dissolving and precipitating grains was deduced to be 2 × 10^?2?3 × 10^?1 wt %. The experimentally obtained infiltration rate of aqueous fluid in the steady‐state diffusion regime (2 ± 0.5 × 10^?8 m sec^?1 at 823°C) is much faster than the estimated metamorphic fluid flux rates, so that interfacial energy‐driven fluid redistribution in quartz‐rich layers could significantly contribute to the fluid flux in high‐grade metamorphism, at least over a short distance. Cathodoluminescence observations of the run products revealed that the grain growth of quartzite in the presence of fluid proceeds extensively, which would promote the chemical equilibration between fluid and rock more effectively than would volume diffusion in quartz crystals.     

Modelling the Lost City hydrothermal field: influence of topography and permeability structure

The Lost City hydrothermal field (LCHF) is hosted in serpentinite at the crest of the Atlantis Massif, an oceanic core complex close to the mid‐Atlantic Ridge. It is remarkable for its longevity and for venting low‐temperature (40–91°C) alkaline fluids rich in hydrogen and methane. IODP Hole U1309D, 5 km north of the LCHF, penetrated 1415 m of gabbroic rocks and contains a near‐conductive thermal gradient close to 100°C km^?1. This is remarkable so close to an active hydrothermal field. We present hydrothermal modelling using a topographic profile through the vent field and IODP site U1309. Long‐lived circulation with vent temperatures similar to the LCHF can be sustained at moderate permeabilities of 10^?14 to 10^?15 m² with a basal heatflow of 0.22 W m^?2. Seafloor topography is an important control, with vents tending to form and remain in higher topography. Models with a uniform permeability throughout the Massif cannot simultaneously maintain circulation at the LCHF and the near‐conductive gradient in the borehole, where permeabilities <10^?16 m² are required. A steeply dipping permeability discontinuity between the LCHF and the drill hole is required to stabilize venting at the summit of the massif by creating a lateral conductive boundary layer. The discontinuity needs to be close to the vent site, supporting previous inferences that high permeability is most likely produced by faulting related to the transform fault. Rapid increases in modelled fluid temperatures with depth beneath the vent agree with previous estimates of reaction temperature based on geochemical modelling.     

The effect of deformation on permeability development in anhydrite and implications for caprock integrity during geological storage of CO2

Geological storage of CO₂ in depleted oil and gas reservoirs is one of the most promising options to reduce atmospheric CO₂ concentrations. Of great importance to CO₂ mitigation strategies is maintaining caprock integrity. Worldwide many current injection sites and potential storage sites are overlain by anhydrite‐bearing seal formations. However, little is known about the magnitude of the permeability change accompanying dilatation and failure of anhydrite under reservoir conditions. To this extent, we have performed triaxial compression experiments together with argon gas permeability measurements on Zechstein anhydrite, which caps many potential CO₂ storage sites in the Netherlands. Our experiments were performed at room temperature at confining pressures of 3.5–25 MPa. We observed a transition from brittle to semi‐brittle behaviour over the experimental range, and peak strength could be described by a Mogi‐type failure envelope. Dynamic permeability measurements showed a change from ‘impermeable’ (<10^?21 m²) to permeable (10^?16 to 10^?19 m²) as a result of mechanical damage. The onset of measurable permeability was associated with an increase in the rate of dilatation at low pressures (3.5–5 MPa), and with the turning point from compaction to dilatation in the volumetric versus axial strain curve at higher pressures (10–25 MPa). Sample permeability was largely controlled by the permeability of the shear faults developed. Static, postfailure permeability decreased with increasing effective mean stress. Our results demonstrated that caprock integrity will not be compromised by mechanical damage and permeability development. Geofluids (2010) 10 , 369–387     

Geochemistry and origin of natural gases dissolved in brines from gas fields in southwest Japan

Previous geochemical studies indicated that most natural gases dissolved in brines in Japan are of microbial origin, consisting of methane produced via carbonate reduction. However, some of those from gas fields in southwest Japan contain methane relatively enriched in ¹³C, whose origin remains to be clarified. To address this issue, chemical and isotopic analyses were performed on natural gases and brines from the gas fields in Miyazaki and Shizuoka prefectures, southwest Japan. Methane isotopic signatures (δ¹³C ≈ ?68‰ to ?34‰ VPDB; δ²H ≈ ?183‰ to ?149‰ VSMOW) suggest that these gases are of microbial (formed via carbonate reduction) or of mixed microbial and thermogenic origin. The relatively high δ²H‐CH₄ values and their relationship with the δ²H‐H₂O values argue against the possibility of their formation via acetate fermentation. The δ¹³C‐CO₂ values (≈?5‰), together with the slope of the correlation between δ²H‐CH₄ and δ¹³C‐CH₄ (Δδ²H‐CH₄/Δδ¹³C‐CH₄ ≈ 1), contradict the possibility of their formation via carbonate reduction followed by partial oxidation by methanotrophs. The ³He/⁴He ratios of the gases from Miyazaki (≈0.11–1.3 Ra) and their low correlation with δ¹³C‐CH₄ values do not support an abiogenic origin. It is inferred therefore that the high δ¹³C‐CH₄ values of natural gases dissolved in brines from gas fields in southwest Japan are indications of the contribution of thermogenic hydrocarbons, although whether abiogenic hydrocarbons contribute significantly to the gases from Shizuoka requires further investigation. This study has clarified that, for the future exploration of natural gases in southwest Japan, we should adopt the strategies for conventional thermogenic gas accumulations, such as checking the content, type and maturity of organic matter in the underlying sedimentary rocks.     

Interpretation of observed fluid potential patterns in a deep sedimentary basin under tectonic compression: Hungarian Great Plain, Pannonian Basin

The ≈ 40 000 km² Hungarian Great Plain portion of the Pannonian Basin consists of a basin fill of 100 m to more than 7000 m thick semi‐ to unconsolidated marine, deltaic, lacustrine and fluviatile clastic sediments of Neogene age, resting on a strongly tectonized Pre‐Neogene basement of horst‐and‐graben topography of a relief in excess of 5000 m. The basement is built of a great variety of brittle rocks, including flysch, carbonates and metamorphics. The relatively continuous Endr?d Aquitard, with a permeability of less than 1 md (10^?15 m²) and a depth varying between 500 and 5000 m, divides the basin's rock framework into upper and lower sequences of highly permeable rock units, whose permeabilities range from a few tens to several thousands of millidarcy. Subsurface fluid potential and flow fields were inferred from 16 192 water level and pore pressure measurements using three methods of representation: pressure–elevation profiles; hydraulic head maps; and hydraulic cross‐sections. Pressure–elevation profiles were constructed for eight areas. Typically, they start from the surface with a straight‐line segment of a hydrostatic gradient (γ_st = 9.8067 MPa km^?1) and extend to depths of 1400–2500 m. At high surface elevations, the gradient is slightly smaller than hydrostatic, while at low elevations it is slightly greater. At greater depths, both the pressures and their vertical gradients are uniformly superhydrostatic. The transition to the overpressured depths may be gradual, with a gradient of γ_dyn = 10–15 MPa km^?1 over a vertical distance of 400–1000 m, or abrupt, with a pressure jump of up to 10 MPa km^?1 over less than 100 m and a gradient of γ_dyn > 20 MPa km^?1. According to the hydraulic head maps for 13 100–500 m thick horizontal slices of the rock framework, the fluid potential in the near‐surface domains declines with depth beneath positive topographic features, but it increases beneath depressions. The approximate boundary between these hydraulically contrasting regions is the 100 m elevation contour line in the Duna–Tisza interfluve, and the 100–110 m contours in the Nyírség uplands. Below depths of ≈ 600 m, islets of superhydrostatic heads develop which grow in number, areal extent and height as the depth increases; hydraulic heads may exceed 3000 m locally. A hydraulic head ‘escarpment’ appears gradually in the elevation range of ? 1000 to ? 2800 m along an arcuate line which tracks a major regional fault zone striking NE–SW: heads drop stepwise by several hundred metres, at places 2000 m, from its north and west sides to the south and east. The escarpment forms a ‘fluid potential bank’ between a ‘fluid potential highland’ (500–2500 m) to the north and west, and a ‘fluid potential basin’ (100–500 m) to the south and east. A ‘potential island’ rises 1000 m high above this basin further south. According to four vertical hydraulic sections, groundwater flow is controlled by the topography in the upper 200–1700 m of the basin; the driving force is orientated downwards beneath the highlands and upwards beneath the lowlands. However, it is directed uniformly upwards at greater depths. The transition between the two regimes may be gradual or abrupt, as indicated by wide or dense spacing of the hydraulic head contours, respectively. Pressure ‘plumes’ or ‘ridges’ may protrude to shallow depths along faults originating in the basement. The basement horsts appear to be overpressured relative to the intervening grabens. The principal thesis of this paper is that the two main driving forces of fluid flow in the basin are gravitation, due to elevation differences of the topographic relief, and tectonic compression. The flow field is unconfined in the gravitational regime, whereas it is confined in the compressional regime. The nature and geometry of the fluid potential field between the two regimes are controlled by the sedimentary and structural features of the rock units in that domain, characterized by highly permeable and localized sedimentary windows, conductive faults and fracture zones. The transition between the two potential fields can be gradual or abrupt in the vertical, and island‐like or ridge‐like in plan view. The depth of the boundary zone can vary between 400 and 2000 m. Recharge to the gravitational regime is inferred to occur from infiltrating precipitation water, whereas that to the confined regime is from pore volume reduction due to the basement's tectonic compression.