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.     

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.     

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.     

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.     

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.     

Hydrogeochemical dynamics affecting steam‐heated pools at El Chichón Crater (Chiapas – Mexico)

El Chichón is an active volcano located in the north‐western Chiapas, southern Mexico. The crater hosts a lake, a spring, named Soap Pool, emerging from the underlying volcanic aquifer and several mud pools/hot springs on the internal flanks of the crater which strongly interact with the current fumarolic system (steam‐heated pools). Some of these pools, the crater lake and a cold spring emerging from the 1982 pumice deposits, have been sampled and analysed. Water–volcanic gas interactions determine the heating (43–99°C) and acidification (pH 2–4) of the springs, mainly by H₂S oxidation. Significantly, in the study area, a significant NH₃ partial pressure has been also detected. Such a geochemically aggressive environment enhances alteration of the rock in situ and strongly increases the mineralization of the waters (and therefore their electrical conductivity). Two different mineralization systems were detected for the crater waters: the soap pool‐lake (Na⁺/Cl^? = 0.4, Na/Mg>10) and the crater mud pools (Na⁺/Cl^? > 10, Na/Mg < 4). A deep boiling, Na⁺‐K⁺‐Cl^?‐rich water reservoir generally influences the Soap Pool‐lake, while the mud pool is mainly dominated by water‐gas–rock interactions. In the latter case, conductivity of sampled water is directly proportional to the presence of reactive gases in solution. Therefore, chemical evolution proceeds through neutralization due to both rock alteration and bacterial oxidation of ammonium to nitrate. The chemical compositions show that El Chichón aqueous fluids, within the crater, interact with gases fed by a geothermal reservoir, without clear additions of deep magmatic fluids. This new geochemical dataset, together with previously published data, can be used as a base line with which to follow‐up the activity of this deadly volcano.     

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.     

Large‐scale chemical stratification of fluids in the crust: hydraulic and chemical data from the geothermal research site Urach,Germany

The Urach 3 research borehole in SW Germany has been drilled through a sedimentary cover sequence and reached gneisses of the Variscan crystalline basement at 1604 m below surface. An additional 2840 m has been drilled through fractured basement rocks. The borehole has been used for hydraulic tests in the context of a ‘hot dry rock’ (HDR) project. The sedimentary cover ranges from the Carboniferous to the Middle Jurassic (Dogger) in age and comprises mostly clastic sediments in the Paleozoic and limestone and shale in the Mesozoic. Water composition data from 10 different depths include samples from all major lithological units. The total dissolved solids (TDS) increases from the surface to about 650 m where it reaches 4.1 g l^?1 in Triassic limestone. In lower Triassic sandstones, TDS increases very sharply to 28.5 g l^?1 and the water is saturated with pure CO₂ gas. With increasing depth, TDS does not change much in the clastic sediments of the Permian and Carboniferous. The crystalline basement is marked by a very sharp increase in TDS to 55.5 g l^?1 at about 1770 m depth. TDS increases within the basement to more than 78.5 g l^?1 at about 3500 m depth. The data suggest that there is limited vertical chemical communication over long periods of time. The CO₂ gas cap in the lower Triassic sandstones requires a gastight cover. The chemical stratification of the fluids relates to the permeability structure of the crust at the Urach site and fits well with hydraulic and thermal data from the site.     

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.     

Pore pressure evolution and fluid flow during visco‐elastic single‐layer buckle folding

Pore pressure and fluid flow during the deformational history of geologic structures are directly influenced by tectonic deformation events. In this contribution, 2D plane strain finite element analysis is used to study the influence of different permeability distributions on the pore pressure field and associated flow regimes during the evolution of visco‐elastic single‐layer buckle folds. The buckling‐induced fluid flow regimes indicate that flow directions and, to a lesser degree, their magnitudes vary significantly throughout the deformation and as a function of the stratigraphic permeability distribution. The modelling results suggest that the volumetric strain and the permeability distribution significantly affect the resulting flow regime at different stages of fold development. For homogeneous permeability models (k > 10^?21 m²), low strain results in a mostly pervasive fluid flow regime and is in agreement with previous studies. For larger strain conditions, fluid focusing occurs in the buckling layer towards the top of the fold hinge. For low permeabilities (<10^?21 m²), local focused flow regimes inside the buckling layer emerge throughout the deformation history. For models featuring a low‐permeability layer embedded in a high‐permeability matrix or sandwiched between high‐permeability layers, focused flow regimes inside the folded layer result throughout the deformation history, but with significant differences in the flow vectors of the surrounding layers. Fluid flow vectors induced by the fold can result in different, even reversed, directions depending on the amount of strain. In summary, fluid flow regimes during single‐layer buckling can change from pervasive to focused and fluid flow vectors can be opposite at different strain levels, that is the flow vectors change significantly through time. Thus, a complete understanding of fluid flow regimes associated with single‐layer buckle folds requires consideration of the complete deformation history of the fold.     

Effects of episodic fluid flow on hydrocarbon migration in the Newport‐Inglewood Fault Zone,Southern California

Fault permeability may vary through time due to tectonic deformations, transients in pore pressure and effective stress, and mineralization associated with water‐rock reactions. Time‐varying permeability will affect subsurface fluid migration rates and patterns of petroleum accumulation in densely faulted sedimentary basins such as those associated with the borderland basins of Southern California. This study explores the petroleum fluid dynamics of this migration. As a multiphase flow and petroleum migration case study on the role of faults, computational models for both episodic and continuous hydrocarbon migration are constructed to investigate large‐scale fluid flow and petroleum accumulation along a northern section of the Newport‐Inglewood fault zone in the Los Angeles basin, Southern California. The numerical code solves the governing equations for oil, water, and heat transport in heterogeneous and anisotropic geologic cross sections but neglects flow in the third dimension for practical applications. Our numerical results suggest that fault permeability and fluid pressure fluctuations are crucial factors for distributing hydrocarbon accumulations associated with fault zones, and they also play important roles in controlling the geologic timing for reservoir filling. Episodic flow appears to enhance hydrocarbon accumulation more strongly by enabling stepwise build‐up in oil saturation in adjacent sedimentary formations due to temporally high pore pressure and high permeability caused by periodic fault rupture. Under assumptions that fault permeability fluctuate within the range of 1–1000 millidarcys (10^?15–10^?12 m²) and fault pressures fluctuate within 10–80% of overpressure ratio, the estimated oil volume in the Inglewood oil field (approximately 450 million barrels oil equivalent) can be accumulated in about 24 000 years, assuming a seismically induced fluid flow event occurs every 2000 years. This episodic petroleum migration model could be more geologically important than a continuous‐flow model, when considering the observed patterns of hydrocarbons and seismically active tectonic setting of the Los Angeles basin.     

Experimental determination of CePO4 and YPO4 solubilities in H2O–NaF at 800°C and 1 GPa: implications for rare earth element transport in high‐grade metamorphic fluids

Monazite (CePO₄) and xenotime (YPO₄) are important accessory minerals in metasediments. They host significant rare earth elements (REE) and are useful for geochronology and geothermometry, so it is essential to understand their behavior during the metasomatic processes that attend high‐grade metamorphism. It has been proposed that F‐bearing fluids enhance solubility and mobility of REE and Y during high‐grade metamorphism. We assessed this possibility by determining the solubility of synthetic CePO₄ and YPO₄ crystals in H₂O–NaF fluids at 800°C and 1 GPa. Experiments used hydrothermal piston‐cylinder and weight‐loss methods. Compared to the low solubilities of CePO₄ and YPO₄ in pure H₂O (0.04 ± 0.04 and 0.25 ± 0.04 millimolal, respectively), our results indicate an enormous increase in the solubility of both phosphates with increasing NaF concentration in H₂O: CePO₄ solubility reaches 0.97 molal in 20 mol.% NaF, and YPO₄ shows an even stronger solubility enhancement to 0.45 molal in only 10 mol.% NaF. The greatest relative solubility increases occur at the lowest NaF concentration. The solubilities of CePO₄ and YPO₄ show similar quadratic dependence on NaF, consistent with possible dissolution reactions of: CePO₄ + 2NaF =  CeF₂⁺ + Na₂PO₄^? and YPO₄ + 2NaF = YF₂⁺ + Na₂PO₄^?. Solubilities of both REE phosphates are significantly greater in NaF than in NaCl at equivalent salt concentration. A fluid with 10 mol.% NaCl and multiply saturated with fluorite, CePO₄, and YPO₄ would contain 1.7 millimolal Ce and 3.3 millimolal Y, values that are respectively 2.1–2.4 times greater than in NaCl‐H₂O alone. The results indicate that Y, and by extension heavy rare earth elements (HREE), can be fractionated from LREE in fluorine‐bearing saline brines which may accompany granulite‐facies metamorphism. The new data support previous indications that REE/Y mobility at these conditions is enhanced by complexing with F in the aqueous phase.     

Hydraulic observations from a 1 year fluid production test in the 4000 m deep KTB pilot borehole

A long‐term pump test was conducted in the KTB pilot borehole (KTB‐VB), located in the Oberpfalz area, Germany. It produced 22 300 m³ of formation fluid. Initially, fluid production rate was 29 l min^?1 for 4 months, but was then raised to an average of 57 l min^?1 for eight more months. The aim of this study was to examine the fluid parameters and hydraulic properties of fractured, crystalline crusts as part of the new KTB programme ‘Energy and Fluid Transport in Continental Fault Systems’. KTB‐VB has an open‐hole section from 3850 to 4000 m depth that is in hydraulic contact with a prominent continental fault system in the area, called SE2. Salinity and temperature of the fluid inside the borehole, and consequently hydrostatic pressure, changed significantly throughout the test. Influence of these quantities on variations in fluid density had to be taken into account for interpretation of the pump test. Modelling of the pressure response related to the pumping was achieved assuming the validity of linear Darcy flow and permeability to be independent of the flow rate. Following the principle ‘minimum in model dimension’, we first examined whether the pressure response can be explained by an equivalent model where rock properties around the borehole are axially symmetric. Calculations show that the observed pressure data in KTB‐VB can in fact be reproduced through such a configuration. For the period of high pumping rate (57 l min^?1) and the following recovery phase, the resulting parameters are 2.4 × 10^?13 m³ in hydraulic transmissivity and 3.7 × 10^?9 m Pa^?1 in storativity for radial distances up to 187 m, and 4.7 × 10^?14 m³ and 6.0 × 10^?9 m Pa^?1, respectively, for radial distances between 187 and 1200 m. The former pair of values mainly reflect the hydraulic properties of the fault zone SE2. For a more realistic hydraulic study on a greater scale, program FEFLOW was used. Parameter values were obtained by matching the calculated induced pressure signal to fluid‐level variations observed in the KTB main hole (KTB‐HB) located at 200 m radial distance from KTB‐VB. KTB‐HB is uncased from 9031 to 9100 m and shows indications of leakage in the casing at depths 5200–5600 m. Analysis of the pressure record and hydraulic modelling suggest the existence of a weak hydraulic communication between the two boreholes, probably at depths around the leakage. Hydraulic modelling of a major slug‐test in KTB‐HB that was run during the pumping in KTB‐VB reveals the effective transmissivity of the connected formation to be 1 to 2 orders of magnitude lower than the one determined for the SE2 fault zone.     

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     

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.     

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.     

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.     

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.