Mineral precipitation associated with vertical fault zones: the interaction of solute advection,diffusion and chemical kinetics

This article is concerned with chemical reactions that occur between two interacting parallel fluid flows using mixing in vertical faults as an example. Mineral precipitation associated with fluid flow in permeable fault zones results in mineralization and chemical reaction (alteration) patterns, which in turn are strongly dependent on interactions between solute advection (controlled by fluid flow rates), solute diffusion/dispersion and chemical kinetics. These interactions can be understood by simultaneously considering two dimensionless numbers, the Damköhler number and the Z‐number. The Damköhler number expresses the interaction between solute advection (flow rate) and chemical kinetics, while the Z‐number expresses the interaction between solute diffusion/dispersion and chemical kinetics. Based on the Damköhler and Z‐numbers, two chemical equilibrium length‐scales are defined, dominated by either solute advection or by solute diffusion/dispersion. For a permeable vertical fault zone and for a given solute diffusion/dispersion coefficient, there exist three possible types of chemical reaction patterns, depending on both the flow rate and the chemical reaction rate. These three types are: (i) those dominated by solute diffusion and dispersion resulting in precipitation at the lower tip of a vertical fault and as a thin sliver within the fault, (ii) those dominated by solute advection resulting in precipitation at or above the upper tip of the fault, and (iii) those in which advection and diffusion/dispersion play similar roles resulting in wide mineralization within the fault. Theoretical analysis indicates that there exists both an optimal flow rate and an optimal chemical reaction rate, such that chemical equilibrium following focusing and mixing of two fluids may be attained within the fault zone (i.e. type 3). However, for rapid and parallel flows, such as those resulting from a lithostatic pressure gradient, it is difficult for a chemical reaction to reach equilibrium within the fault zone, if the two fluids are not well mixed before entering the fault zone. Numerical examples are given to illustrate the three possible types of chemical reaction patterns.     

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.     

Constraining the rate and extent of mantle serpentinization from seismic and petrological data: implications for chemosynthesis and tectonic processes

We used seismic velocity as a proxy for serpentinization of the mantle, which occurred beneath thinned but laterally continuous continental crust during continental break up, prior to opening of the Atlantic Ocean. The serpentinized sub‐continental mantle is now exhumed, beneath the Iberia Abyssal Plain and was accessed by scientific drilling on Ocean Drilling Program legs 149 and 173. Chromatographic modelling of kinetically limited transport of the serpentinization front yields a front displacement of 2197 ± 89 m, a time‐integrated fluid flux of 1098 ± 45 m³ m^?2 and a Damköhler number of 6.0 ± 0.2. Whether either surface reaction or chemical transport limit the rate of reaction, we calculate timescales for serpentinization of approximately 10⁵–10⁶ years. This yields time‐average fluid flux rates for H₂O, entering and reacting with the mantle, of 60–600 mol m^?2 a^?1 and for CH₄, produced as a by‐product of oxidation of Fe⁺⁺ to magnetite and exiting the mantle, of 0.55–5.5 mol m^?2 a^?1. This equates to a CH₄‐flux of 0.18–1.8 Tg a^?1 for coeval serpentinization of the mantle that was exhumed west of Iberia. This represents 0.03–0.3% of the present‐day annual CH₄‐flux from all sources and a higher fraction of pre‐anthropogenic (lower) CH₄ levels. CH₄ released by serpentinization at or beneath the seafloor could provide substrate for biological chemosynthesis and/or promote gas‐hydrate formation. Finally, noting its volumetric extent and rapidity (<10⁶ years), we interpret serpentinization to be a reckonable component of tectonic processes, contributing both diapiric and expansional forces and helping to ‘lubricate’ extensional processes. Given its anisotropic permeability, actively deforming serpentinite might impede melt migration which may be of interest, given the apparent lack of melt in some rifted margins.     

Chlorine stable isotope ratios as tracer for pore‐water advection rates in a submarine gas‐hydrate field: implication for hydrate concentration

At Ocean Drilling Program Site 997 in Blake Ridge gas‐hydrate field in West Atlantic, pore‐water studies revealed a pronounced downward depletion of the heavy chlorine isotope to nearly ?4‰δ³⁷Cl at approximately 750 m below sea floor (mbsf) associated with a 10% downward chlorinity decrease. This is one of the stronger ³⁷Cl depletions hitherto reported for marine pore waters. Chlorinity reductions in hydrate‐bearing sediments commonly result from fresh‐water release by hydrate melting. However, in situ measurements at Site 997 suggest that >50% of the chlorinity reduction occurred prior to hydrate dissociation. Modeling the chlorinity profile shows that advection of a strongly ³⁷Cl‐depleted, low‐chlorinity water (506 mm ) from below the drilled sequence can explain the reduction prior to sampling. Fitting the model to the δ³⁷Cl curve yielded an advection rate of 0.18 mm year^?1. Diffusive mixing with near‐0‰‐δ³⁷Cl paleo‐seawater with maximum chlorinity at shallow subsurface depths (561 mm at approximately 20 mbsf) produced the smooth, steady trend. Separating that part of the freshening caused by advection and diffusion from that due to hydrate dissociation allowed estimation of average hydrate concentrations of 3.8% of the pore space (up to 24.5% in hydrate‐rich layers; near‐100% in rare massive hydrate layers). The deep‐seated source of the ³⁷Cl‐depleted, low‐chlorinity water remains unknown and might be located below the sedimentary section in the oceanic basement.     

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.     

Numerical modelling of 3D fluid flow and oxygen isotope exchange in fractured media: spatial distribution of isotope patterns

An understanding of fluid flow, mass transport and isotopic exchange in fractured rock is required to understand the origin of several geological processes including hydrothermal mineral deposits. The numerical model HydroGeoSphere simulates 3D advection, molecular diffusion, mechanical dispersion and isotopic exchange in a discretely fractured porous media, and can be used to better understand the processes of mass transport and isotopic exchange in fractured rocks. Study of ¹⁸O isopleth patterns for different types of fractures and fracture networks with a range of structural complexity and hydraulic properties shows that fracture properties and geometry control mass transport and isotopic exchange. The hydraulic properties, as well as the density, spacing, and connectivity of fractures determine the isotopic patterns. Asymmetries in the geometry of oxygen isotope patterns could be used to determine the direction of hydrothermal fluid flow.     

Permeability changes in simulated granite faults during and after frictional sliding

Thermal–hydrological–mechanical coupling processes suggest that fault permeability should undergo dynamic change as a result of seismic slip. In igneous rocks, a fault's slip surface may have much higher permeability than the surrounding rock matrix and therefore operate as a conduit for fluids. We conducted laboratory experiments to investigate changes in fracture permeability (or transmissivity) of a fault in granite due to shear slip and cyclic heating and cooling. Our experiments showed that high initial fracture transmissivity (>10^?18 m³) was associated with a high friction coefficient and that transmissivity decreased during slip. We propose that this reduction in transmissivity reflects the presence of gouge in fracture voids, increasing the area of contact in the fault plane and reducing the hydraulic aperture. In contrast, when initial fracture transmissivity was low (<10^?18 m³), we observed that friction was lower and transmissivity increased during slip. The high transmissivity and high friction may be explained by large areas of bare rock being in contact on the slip surface. Slip velocity had little influence on the evolution of permeability, probably because gouge produced at different slip velocities had similar grain size distributions, or because gouge leaked from the slip surface. Transmissivity decreased with increasing temperature in heating tests, probably due to thermal expansion increasing normal stress on the fracture. Frictional heating did not influence transmissivity during the shearing tests.     

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.     

Constraining groundwater flow in the glacial drift and saginaw aquifers in the Michigan Basin through helium concentrations and isotopic ratios

³He and ⁴He concentrations in excess of those in water in solubility equilibrium with the atmosphere by up to two and three orders of magnitude are observed in the shallow Glacial Drift and Saginaw aquifers in the Michigan Basin. A simplified He transport model shows that in situ production is negligible and that most He excesses have a source external to the aquifer. Simulated results show that ³He and ⁴He fluxes entering the bottom of the Saginaw aquifer are 7.5 × 10^?14 and 6.1 × 10^?7 cm³STPcm^?2 yr^?1, both of which are lower than fluxes entering the underlying Marshall aquifer, 1.0 × 10^?13 and 1.6 × 10^?6 cm³STPcm^?2 yr^?1 for ³He and ⁴He, respectively. In contrast, He fluxes entering the Saginaw aquifer are higher than fluxes entering the overlying Glacial Drift aquifer of 5.2 × 10^?14 and 1.5 × 10^?7 cm³STPcm^?2 yr^?1 for ³He and ⁴He, respectively. The unusually high He fluxes and their decreasing values from the lower Marshall to the upper Glacial Drift aquifer strongly suggest the presence of an upward cross‐formational flow, with increasing He dilution toward the surface by recharge water. These fluxes are either comparable to or far greater than He fluxes in deeper aquifers around the world. Model simulations also suggest an exponential decrease in the horizontal groundwater velocity with recharge distance. Horizontal velocities vary from 13 to 2 myr^?1 for the Saginaw aquifer and from 18 to 6 myr^?1 for the Marshall aquifer. The highly permeable Glacial Drift aquifer displays a greater velocity range, from 250 to 5 myr^?1. While Saginaw ⁴He ages estimated based on the simulated velocity field display an overall agreement with ¹⁴C ages, ¹⁴C and ⁴He ages in the Glacial Drift and Marshall aquifers deviate significantly, possibly due to simplifications introduced in the He transport model leading to calculation of first‐order approximation He ages and high uncertainties in Glacial Drift ¹⁴C ages.     

Long‐term stability of fracture systems and their behaviour as flow paths in uplifting granitic rocks from the Japanese orogenic field

In granitic rocks, fracture networks typically provide pathways for groundwater flow and solute transport that need to be understood to assess the long‐term performance of deep underground storage or disposal facilities such as radioactive waste repositories. However, relatively little is known about the long‐term processes of fracturing and/or the longevity of flow paths (FP) in granitic rocks distributed within orogenic belts. To clarify these issues, Japanese plutons of different ages and in situ fractures in granite at the Mizunami Underground Research Laboratory (MIU) located in central Japan were studied. Detailed structural characterization and geochemical analysis of in situ fracture fillings sampled from a depth of 300 m were carried out to clarify the relationship between fracturing and mineral infilling processes. Different plutons show identical episodes of fracturing and fracture filling, consisting of: brittle tensile fracturing, due to decreasing temperature through the ductile–brittle transition after plutonic intrusion (Stage I); relatively rapid uplifting (ca. a few mm/year) accompanied by hydrothermal water circulation, which produced uncrushed layered mineral fillings (Stage II); and a period of low‐temperature meteoric water circulation following exposure after uplift (Stage III). The parageneses of carbonate mineral fracture fillings and their carbon isotopic compositions (¹⁴C, δ¹³C) show that there were distinct episodes of carbonate mineral precipitation during the rapid uplifting of a pluton. The carbonate minerals that formed during each episode incorporated carbon from a distinct source. The evolution of fillings identified here enables development of a specific model of fracturing and persistence of fluid‐conducting systems in the plutons of the orogenic field.     

Fluid inclusion and stable isotope constraints on the genesis of the Jian copper deposit,Sanandaj–Sirjan metamorphic zone,Iran

The Jian copper deposit, located on the eastern edge of the Sanandaj–Sirjan metamorphic zone, southwest of Iran, is contained within the Surian Permo‐Triassic volcano‐sedimentary complex. Retrograde metamorphism resulted in three stages of mineralization (quartz ± sulfide veins) during exhumation of the Surian metamorphic complex (Middle Jurassic time; 159–167 Ma), and after the peak of the metamorphism (Middle to Late Triassic time; approximately 187 Ma). The early stage of mineralization (stage 1) is related to a homogeneous H₂O–CO₂ (XCO₂ > 0.1) fluid characterized by moderate salinity (<10 wt.% NaCl equivalent) at high temperature and pressure (>370°C, >3 kbar). Early quartz was followed by small amounts of disseminated fine‐grained pyrite and chalcopyrite. Most of the main‐ore‐stage (stage 2) minerals, including chalcopyrite, pyrite and minor sphalerite, pyrrhotite, and galena, precipitated from an aqueous‐carbonic fluid (8–18 wt.% NaCl equivalent) at temperatures ranging between 241 and 388°C during fluid unmixing process (CO₂ effervescence). Fluid unmixing in the primary carbonaceous fluid at pressures of 1.5–3 kbar produced a high XCO₂ (>0.05) and a low XCO₂ (<0.01) aqueous fluid in ore‐bearing quartz veins. Oxygen and hydrogen isotope compositions suggest mineralization by fluids derived from metamorphic dehydration (δ¹⁸O_fluid = +7.6 to +10.7‰ and δD = ?33.1 to ?38.5‰) during stage 2. The late stage (stage 3) is related to a distinct low salinity (1.5–8 wt.% NaCl equivalent) and temperatures of (120–230°C) aqueous fluid at pressures below 1.5 kbar and the deposition of post‐ore barren quartz veins. These fluids probably derived from meteoric waters, which circulated through the metamorphic pile at sufficiently high temperatures and acquire the characteristics of metamorphic fluids (δ¹⁸O_fluid = +4.7 to +5.1‰ and δD = ?52.3 to ?53.9‰) during waning stages of the postearly Cimmerian orogeny in Surian complex. The sulfide‐bearing quartz veins are interpreted as a small‐scale example of redistribution of mineral deposits by metamorphic fluids. This study suggests that mineralization at the Jian deposit is metamorphogenic in style, probably related to a deep‐seated mesothermal system.     

Multiphase flow simulation through porous media with explicitly resolved fractures

Accurate simulation of multiphase flow in fractured porous media remains a challenge. An important problem is the representation of the discontinuous or near discontinuous behaviour of saturation in real geological formations. In the classical continuum approach, a refined mesh is required at the interface between fracture and porous media to capture the steep gradients in saturation and saturation‐dependent transport properties. This dramatically increases the computational load when large numbers of fractures are present in the numerical model. A discontinuous finite element method is reported here to model flow in fractured porous media. The governing multiphase porous media flow equations are solved in the adaptive mesh computational fluid dynamics code IC‐FERST on unstructured meshes. The method is based on a mixed control volume – discontinuous finite element formulation. This is combined with the P_N+1DG‐P_NDG element pair, which has discontinuous (order N+1) representation for velocity and discontinuous (order N) representation for pressure. A number of test cases are used to evaluate the method's ability to model fracture flow. The first is used to verify the performance of the element pair on structured and unstructured meshes of different resolution. Multiphase flow is then modelled in a range of idealised and simple fracture patterns. Solutions with sharp saturation fronts and computational economy in terms of mesh size are illustrated.     

Hydrologic and geochemical controls on soluble benzene migration in sedimentary basins

The effects of groundwater flow and biodegradation on the long‐distance migration of petroleum‐derived benzene in oil‐bearing sedimentary basins are evaluated. Using an idealized basin representation, a coupled groundwater flow and heat transfer model computes the hydraulic head, stream function, and temperature in the basin. A coupled mass transport model simulates water washing of benzene from an oil reservoir and its miscible, advective/dispersive transport by groundwater. Benzene mass transfer at the oil–water contact is computed assuming equilibrium partitioning. A first‐order rate constant is used to represent aqueous benzene biodegradation. A sensitivity study is used to evaluate the effect of the variation in aquifer/geochemical parameters and oil reservoir location on benzene transport. Our results indicate that in a basin with active hydrodynamics, miscible benzene transport is dominated by advection. Diffusion may dominate within the cap rock when its permeability is less than 10^?19 m². Miscible benzene transport can form surface anomalies, sometimes adjacent to oil fields. Biodegradation controls the distance of transport down‐gradient from a reservoir. We conclude that benzene detected in exploration wells may indicate an oil reservoir that lies hydraulically up‐gradient. Geochemical sampling of hydrocarbons from springs and exploration wells can be useful only when the oil reservoir is located within about 20 km. Benzene soil gas anomalies may form due to regional hydrodynamics rather than separate phase migration. Diffusion alone cannot explain the elevated benzene concentration observed in carrier beds several km away from oil fields.     

Geochemical fingerprinting of hydraulic fracturing fluids from Qusaiba Hot Shale and formation water from Paleozoic petroleum systems,Saudi Arabia

Provenance studies of produced water are essential to trace flow dynamics and reservoir compartmentalization in petroleum systems and to quantify fluid recovery rates from unconventional fracturing. Produced water from a hydraulically fractured well in the Qusaiba Hot Shale in the Northern Exploration Area, Saudi Arabia, was daily monitored and analyzed for water chemistry, and environmental (δ²H, δ¹³C, δ¹⁸O_H2O, δ¹⁸O_SO4, δ³⁴S_SO4, δ³⁷Cl, ⁸⁷Sr/⁸⁶Sr) and cosmogenic isotopes (³H, ¹⁴C, ³⁶Cl), to differentiate from reference fluids of supply water, fracturing fluids, and formation water from adjacent Paleozoic units. Initially, recovered water is composed of fracturing fluids and subsequently replaced by a homogeneous cut of pristine formation water. Formation water is composed of dominant meteoric water (approximately 84 vol%) and minor fossil evaporated seawater. The young ¹⁴C‐apparent age between 6000 and 6700 years BP and depleted δ¹⁸O/δ²H values for the meteoric component confirm the infiltration of surface water into the Qusaiba Hot Shale interval or adjacent units during the Early Holocene Pluvial Period under cooler and wetter climatic conditions than present, which suggest the presence of a very recent, dynamic hydraulic flow system. ³⁶Cl/Cl ratios between 102 × 10^?15 and 31 × 10^?15 are ambiguous and can be attributed to atmospheric recharge close to the coast, mixing of ³⁶Cl‐enriched Quaternary meteoric recharge with ³⁶Cl‐depleted fossil seawater, and/or hypogene production by U‐Th‐enriched host rock. Produced waters from Qusaiba Hot Shale are within the compositional range of Na‐Cl‐type formation water from Paleozoic reservoir units in northern Saudi Arabia with salinities from 30 000 to 130 000 mg l^?1. As a novel technological approach for exploration wells in Northern Saudi Arabia, multi‐isotopic methods were successfully implemented to quantify flowback volumes from hydraulic fracturing, and to fingerprint pristine formation water or pore water in Paleozoic systems on their provenance, residence time, migration pathways, and secondary alteration processes.     

Precipitation of fracture fillings and cements in the Buntsandstein (NW Germany)

The relationship between fracturing and fracture filling in opening‐mode fractures in the Triassic Buntsandstein in the Lower Saxony Basin (LSB; NW Germany) has been studied by an integration of petrographic and structural analysis of core samples, strontium isotope analysis and microthermometry on fluid inclusions. This revealed the relationship between the timing of the fracturing and the precipitation of different mineral phases in the fractures by constraining the precipitation conditions and considering the possible fluid transport mechanisms. The core was studied from four different boreholes, located in different structural settings across the LSB. In the core samples from the four boreholes, fractures filled with calcite, quartz and anhydrite were found, in addition to pore‐filling calcite cementation. In boreholes 2 and 3, calcite‐filled fractures have a fibrous microstructure whereas in borehole 1, fractures are filled with elongate‐blocky calcite crystals. Anhydrite‐filled fractures have, in all samples, a blocky to elongate‐blocky microstructure. Fractures that are filled with quartz are observed in borehole 2 only where the quartz crystals are ‘stretched’ with an elongated habit. Fluid inclusion microthermometry of fracturing‐filling quartz crystals showed that quartz precipitation took place at temperatures of at least 140°C, from a fluid with NaCl–CaCl₂–H₂O composition. Melting phases are meta‐stable and suggest growth from high salinity formation water. Strontium isotopes, measured in leached host rock, indicate that, in boreholes 2 and 3, the fluid which precipitated the calcite cements and calcite‐filled fractures is most likely locally derived whereas in borehole 1, the ⁸⁷Sr/⁸⁶Sr ratios from the pore‐filling cements and in the elongate‐blocky calcite‐filled fracture can only be explained by mixing with externally derived fluids. The elongate‐blocky anhydrite‐filled fractures, present in boreholes 1, 3 and 4, precipitated from a mixture of locally derived pore fluids and a significant quantity of fluid with a lower, less radiogenic, ⁸⁷Sr/⁸⁶Sr ratio. Taking into account the structural evolution of the basin and accompanying salt tectonics, it is likely that the underlying Zechstein is a source for the less radiogenic fluids. Based on the samples in the LSB, it is probable that fibrous fracture fillings in sedimentary rocks most likely developed from locally derived pore fluids whereas elongate‐blocky fracture fillings with smooth walls developed from externally derived pore fluids.     

Experimental study of polycrystal growth from an advecting supersaturated fluid in a model fracture

We present real‐time observations of polycrystal growth experiments in transmitted light in an accurately controlled flow system with the analogue material alum [KAl(SO₄)₂·12H₂O]. The aim of the experiments is to obtain a better insight into the evolution of vein microstructures. A first series of experiments shows the evolution of a polycrystal at supersaturations between 0.095 and 0.263. The average growth rate of the crystals is influenced by growth competition and the depletion of the solute along fracture length. Growth competition is controlled by crystallographic orientation, crystal size and crystal location. In addition, the growth rate of an individual crystal facet also shows variations depending on the facet index, facet size and flow velocity. These variations can influence the morphology of the grain boundaries and the microstructures. The aim of the second series of experiments is to investigate the growth evolution of rough/dissolved facets in detail. The growth distance required for the development of facets is around 15 μm. In all the experiments, we observe that the measured growth rates have a much larger range than predicted by alum single‐crystal growth kinetics. This is due to the combined effect of the facet index and the crystal size. Furthermore, at high supersaturations, the facet growth rate measurements do not fit the same growth rate equation as for the experiments at lower supersaturations (<0.176). This can be explained by a change in the growth mechanism at high supersaturations with more influence of volume diffusion, relative to advection of the bulk solution on the growth rate. This effect can also cause a more homogeneous sealing pattern over fracture length. At high supersaturations, the larger crystals in these experiments incorporate regularly spaced fluid inclusion bands and we propose that these can be used as an indicator for high palaeo‐supersaturation. The final microstructures of the experiments show no asymmetry with respect to the flow direction.     

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.     

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.     

Permeability of the Mercia Mudstone: suitability as caprock to carbon capture and storage sites

The Upper Triassic Mercia Mudstone is the caprock to potential carbon capture and storage (CCS) sites in porous and permeable Lower Triassic Sherwood Sandstone reservoirs and aquifers in the UK (primarily offshore). This study presents direct measurements of vertical (k_v) and horizontal (k_h) permeability of core samples from the Mercia Mudstone across a range of effective stress conditions to test their caprock quality and to assess how they will respond to changing effective stress conditions that may occur during CO₂ injection and storage. The Mercia samples analysed were either clay‐rich (muddy) siltstones or relatively clean siltstones cemented by carbonate and gypsum. Porosity is fairly uniform (between 7.4 and 10.7%). Porosity is low either due to abundant depositional illite or abundant diagenetic carbonate and gypsum cements. Permeability values are as low as 10^?20 m² (10nD), and therefore, the Mercia has high sealing capacity. These rocks have similar horizontal and vertical permeabilities with the highest k_h/k_v ratio of 2.03 but an upscaled k_h/k_v ratio is 39, using the arithmetic mean of k_h and the harmonic mean of k_v. Permeability is inversely related to the illite clay content; the most clay‐rich (illite‐rich) samples represent very good caprock quality; the cleaner Mercia Mudstone samples, with pore‐filling carbonate and gypsum cements, represent fair to good caprock quality. Pressure sensitivity of permeability increases with increasing clay mineral content. As pore pressure increases during CO₂ injection, the permeability of the most clay‐rich rocks will increase more than carbonate‐ and gypsum‐rich rocks, thus decreasing permeability heterogeneity. The best quality Mercia Mudstone caprock is probably not geochemically sensitive to CO₂ injection as illite, the cause of the lowest permeability, is relatively stable in the presence of CO₂–water mixtures.     

Morphological evolution of three‐dimensional chemical dissolution front in fluid‐saturated porous media: a numerical simulation approach

This paper is concerned with the morphological evolution of three‐dimensional chemical dissolution fronts that occur in fluid‐saturated porous media. A fully coupled system between porosity, pore‐fluid flow and reactive chemical species transport is considered to describe this phenomenon. Using the newly presented concept of the generalized dimensionless pore fluid pressure‐gradient, which can be used to represent the interaction between solute advection, solute diffusion, chemical kinetics and the shape factor of the soluble mineral, a theoretical criterion has been established to assess the likelihood of instability at a chemical dissolution front in the reactive transport system. To simulate the chemical dissolution front evolution in a three‐dimensional fluid‐saturated porous medium, a numerical procedure combining both the finite difference method and the finite element method has been proposed. As the problem belongs to a complex system science problem, a small randomly generated perturbation of porosity is added to the initial porosity of a three‐dimensional homogeneous domain to trigger instability of a planar chemical dissolution front during its propagation within the fluid‐saturated porous medium. To test the correctness and accuracy of the proposed numerical procedure, a three‐dimensional benchmark problem has been constructed and the related analytical solution has been derived. This enables using the proposed numerical procedure for simulating the morphological evolution of a three‐dimensional chemical dissolution front from a stable, planar state into an unstable, fingering state. The related numerical results demonstrate that the proposed numerical procedure is useful for, and capable of, simulating the morphological instability of a three‐dimensional chemical dissolution front within a fluid‐saturated porous medium.