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.     

Inferring intermediate‐scale fluid flow in a heterogeneous metasedimentary multilayer sequence during progressive deformation: evidence from the Monts d’Arrée slate belt (Brittany,France)

Quartz veins in the early Variscan Monts d’Arrée slate belt (Central Armorican Terrane, Western France), have been used to determine fluid‐flow characteristics. A combination of a detailed structural analysis, fluid inclusion microthermometry and stable isotope analyses provides insights in the scale of fluid flow and the water–rock interactions. This research suggests that fluids were expelled during progressive deformation and underwent an evolution in fluid chemistry because of changing redox conditions. Seven quartz‐vein generations were identified in the metasedimentary multilayer sequence of the Upper Silurian to Lower Devonian Plougastel Formation, and placed within the time frame of the deformation history. Fluid inclusion data of primary inclusions in syn‐ to post‐tectonic vein generations indicate a gradual increase in methane content of the aqueous–gaseous H₂O–CO₂–NaCl–CH₄–N₂ fluid during similar P–T conditions (350–400°C and 2–3.5 kbar). The heterogeneous centimetre‐ to metre‐scale multilayer sequence of quartzites and phyllites has a range of oxygen‐isotope values (8.0–14.1‰ Vienna Standard Mean Ocean Water), which is comparable with the range in the crosscutting quartz veins (10.5–14.7‰ V‐SMOW). Significant differences between oxygen‐isotope values of veins and adjacent host rock (Δ = ?2.8‰ to +4.9‰ V‐SMOW) suggest an absence of host‐rock buffering on a centimetre scale, but based on the similar range of isotope values in the Plougastel Formation, an intraformational buffering and an intermediate‐scale fluid‐flow system could be inferred. The abundance of veins, their well‐distributed and isolated occurrence, and their direct relationship with the progressive deformation suggests that the intermediate‐scale fluid‐flow system primarily occurred in a dynamically generated network of temporarily open fractures.     

Comparing closed system, flow-through and fluid infiltration geochemical modelling: examples from K-alteration in the Ernest Henry Fe-oxide–Cu–Au system

Potassic alteration of rocks adjacent to, and within the Ernest Henry Fe‐oxide–Cu–Au deposit is used here as a test case to investigate fluid–rock interactions using various equilibrium dynamic geochemical modelling approaches available in the HCh code. Reaction of a simple K–Fe–(Na,Ca) brine (constrained by published fluid inclusion analysis) with an albite‐bearing felsic volcanic rock, resulted in predicted assemblages defined by (i) K‐feldspar–muscovite–magnetite, (ii) biotite–K‐feldspar–magnetite, (iii) biotite–quartz–albite and (iv) albite–biotite–actinolite–pyroxene with increasing rock buffering (decreasing log w/r). Models for isothermal–isobaric conditions (450°C and 2500 bars) were compared with models run over a T–P gradient (450 to 200°C and 2500 to 500 bars). Three principal equilibrium dynamic simulation methods have been used: (i) static closed system, where individual steps are independent of all others, (ii) flow‐through and flush, where a part of the result is passed as input further along the flow line, and (iii) fluid infiltration models that simulate fluid moving through a rock column. Each type is best suited to a specific geological fluid–rock scenario, with increasing complexity, computation requirements and approximation to different parts of the natural system. Static closed system models can be used to quickly ascertain the broad alteration assemblages related to changes in the water/rock ratio, while flow‐through models are better suited to simulating outflow of reacted fluid into fresh rock. The fluid infiltration model can be used to simulate spatially controlled fluid metasomatism of rock, and we show that, given assumptions of porosity relationships and spatial dimensions, this model is a first‐order approximation to full reactive transport, without requiring significant computational time. This work presents an overview of the current state of equilibrium dynamic modelling technology using the HCh code with a view to applying these techniques to predictive modelling in exploration for mineral deposits. Application to the Ernest Henry Fe‐oxide–Cu–Au deposit demonstrates that isothermal fluid–rock reaction can account for some of the alteration zonation around the deposit.     

Geometry‐coupled reactive fluid transport at the fracture scale: application to CO2 geologic storage

Water acidification follows CO₂ injection and leads to reactive fluid transport through pores and rock fractures, with potential implications to reservoirs and wells in CO₂ geologic storage and enhanced oil recovery. Kinetic rate laws for dissolution reactions in calcite and anorthite are combined with the Navier‐Stokes law and advection–diffusion transport to perform geometry‐coupled numerical simulations in order to study the evolution of chemical reactions, species concentration, and fracture morphology. Results are summarized as a function of two dimensionless parameters: the Damköhler number Da which is the ratio between advection and reaction times, and the transverse Peclet number Pe defined as the ratio between the time for diffusion across the fracture and the time for advection along the fracture. Reactant species are readily consumed near the inlet in a carbonate reservoir when the flow velocity is low (low transverse Peclet number and Da > 10^?1). At high flow velocities, diffusion fails to homogenize the concentration field across the fracture (high transverse Peclet number Pe > 10^?1). When the reaction rate is low as in anorthite reservoirs (Da < 10^?1), reactant species are more readily transported toward the outlet. At a given Peclet number, a lower Damköhler number causes the flow channel to experience a more uniform aperture enlargement along the length of the fracture. When the length‐to‐aperture ratio is sufficiently large, say l/d > 30, the system response resembles the solution for 1D reactive fluid transport. A decreased length‐to‐aperture ratio slows the diffusive transport of reactant species to the mineral fracture surface, and analyses of fracture networks must take into consideration both the length and slenderness of individual fractures in addition to Pe and Da numbers.     

Electron backscatter diffraction investigation of length‐fast chalcedony in agate: implications for agate genesis and growth mechanisms

Agates of volcanic origin contain a range of silica minerals, with chalcedony and quartz arranged in concentric bands. Although agates are abundant worldwide, little is known about the genesis of their characteristic banding patterns. Current hypotheses suggest the bands result either from precipitation from convecting siliceous hydrothermal influxes or by in situ crystallization of a silica gel. This study combines the use of a variety of analytical techniques, including electron backscatter diffraction (EBSD), cathodoluminescence (CL), and Fourier transform infrared (FT‐IR) spectroscopy, to characterize the silica minerals present and investigate their spatial and crystallographic relationships in the banding arrangement. Microstructural and spectroscopic observations reveal that chalcedony bands are composed of amorphous silica that also contains nanocrystalline and later‐formed microcrystalline quartz. Nano‐ and microcrystalline quartz grew with a‐axes perpendicular to the growth substrate, typical of length‐fast chalcedony. The bands formed as a result of discrete influxes of silica‐rich fluid. Within these individual bands, there is a sequence of minerals: chalcedony‐A (with amorphous silica and nanocrystalline quartz) → chalcedony‐MQ (with microcrystalline quartz) → quartz. This sequence is reflected in the degree of crystallinity, crystal orientations and water content and is analogous to a diagenetic cycle; the initial chalcedony portion of the band commences with amorphous silica with nanocrystalline quartz followed by fibrous microcrystalline quartz crystals; chalcedony then grades into larger equiaxial mesoquartz crystals. This paragenetic sequence suggests a viable model for the growth of chalcedony in agates.     

A vector of high‐temperature paleo‐fluid flow deduced from mass transfer across permeability barriers (quartz veins)

Quartz veins acted as impermeable barriers to regional fluid flow and not as fluid‐flow conduits in Mesoproterozoic rocks of the Mt Painter Block, South Australia. Systematically distributed asymmetric alteration selvedges consisting of a muscovite‐rich zone paired with a biotite‐rich zone are centered on quartz veins in quartz–muscovite–biotite schist. Geometric analysis of the orientation and facing of 126 veins at Nooldoonooldoona Waterhole reveals a single direction along which a maximum of all veins have a muscovite‐rich side, irrespective of their specific individual orientation. This direction represents a Mesoproterozoic fluid‐flow vector and the veins represent permeability barriers to the flow. The pale muscovite‐rich zones formed on the downstream side of the vein and the dark biotite‐rich zones mark the upstream side. The alteration couplets formed from mica schist at constant Zr, Ga, Sc, and involved increases in Si, Na, Al and decreases in K, Fe, Mg for pale alteration zones, and inverse alteration within dark zones. The asymmetry of the alteration couplets is best explained by the pressure dependence of mineral–fluid equilibria. These equilibria, in combination with a Darcian flow model for coupled advection and diffusion, and with permeability barriers imposed by the quartz veins, simulate the pattern of both fluid flow and differential, asymmetric metasomatism. The determined vector of fluid flow lies along the regional foliation and is consistent with the known distribution of regional alteration products. The presence of asymmetric alteration zones in rock containing abundant pre‐alteration veins suggests that vein‐rich material may have generally retarded regional fluid flow.     

Chemical modification of pyroclastic rock by hot water: an experimental investigation of mass transport at the fluid–solid interface

Hydrothermal water–(pyroclastic) rock interactions were examined using flow-through experiments to deduce the effect of mass transport phenomena on the reaction process. A series of experiments were conducted over the temperature range 75–250°C, with a constant temperature for each experiment, and at saturated vapour pressure, to estimate the apparent rate constants as a function of temperature.
Based on the chemistry of analysed solutions, the water–rock interaction in the experiments was controlled by diffusion from the reaction surface and by the existence of a surface layer at the rock–fluid interface, which regulated the chemical reaction rate. The reaction progress depended to a high degree on flow velocity and temperature conditions, with element abundances in the fluid significantly affected by these factors. Mass transport coefficients for diffusion from the rock surface to the bulk solution have been estimated. Ca is selectively depleted under lower temperature conditions ( T  < 150°C), whereas Na is greatly depleted under higher temperature conditions ( T  > 150°C), and K reaction rates are increased when flow velocity increases. Using these conditions, specific alkali and alkali earth cations were selectively leached from mineral surfaces. The 'surface layer' comprised a 0.5–1.8 mm boundary film on the solution side (the thickness of this layer has no dependence on chemical character) and a reaction layer. The reaction layer was composed of a Si, Al-rich cation-leached layer, whose thickness was dependent on temperature, flow velocity and reaction length. The reaction layer varied in thickness from about 10⁻⁴ to 10⁻⁷ mm under high temperature/low fluid velocity and low temperature/high fluid velocity conditions, respectively.     

Quantifying secondary migration efficiencies

Exploration success relies on properly risking the hydrocarbon system relevant for each prospect. Accurate risking of secondary migration efficiencies has been difficult due to lack of simple procedures that relate rock properties such as permeability and entry pressures to migration velocities, oil stringer heights and saturations. In order to achieve improved estimates of charge probabilities, equations for the secondary migration process are formulated based upon the Darcy flow and buoyancy conditions. An analytical solution of the formulated equations is shown, making it possible to construct charts for efficiently assessing the column height of secondary migration hydrocarbon stringers. The average oil (hydrocarbon) saturation of the migrating stringer can be computed, making it easy to compute the permeability related, secondary migration losses. Inputs to the chart are hydrocarbon flow‐rates and flow‐path width, hydrocarbon viscosity and density, carrier bed dip, permeability and entry pressures. Outputs are stringer heights, hydrocarbon saturation, relative permeability, migration velocities and migration losses. A procedure for including the new equations into existing basin scale fluid flow simulators is outlined and a Java applet for calculating the properties is described. The Java applet is useful for sensitivity studies, and can also be used to test results from basin simulators with the new migration efficiency equations. The analytical solution suggests that many published methods for calculating hydrocarbon migration in fluid flow simulators will over‐estimate hydrocarbon saturations and therefore losses. Calculated migration velocities will also be too low.     

Massive dolomitization of a Messinian reef in the Great Bahama Bank: a numerical modelling evaluation of Kohout geothermal convection

The hypothesis that Kohout thermal convection may have induced the massive dolomitization of the 60 m thick lowest more reefal unit in well Unda [top of Great Bahama Bank (GBB)] is evaluated through numerical modelling. A two‐dimensional (2‐D) section, including lithological and petrophysical data, together with datings for the sediments of the GBB, was used in the basin model TEMISPACK to reconstruct the history of the whole platform, with a focus on the reef unit. Simulations showed that during high sea‐level periods, Kohout convection is a valid mechanism in the settings of the GBB, although the convection cell remains flat in most cases because of high permeability anisotropy. This mechanism induces rapid fluid flow in the superficial as well as in the deeper parts of the platform, with velocities of at least two orders of magnitude higher than with compaction alone. Lithology appears as a strong control of fluid circulations at the margin scale through the permeability anisotropy, for which a critical value lies between values of 10 and 100. The reefal unit in Unda is part of a larger area determined by the lithologic distribution, in which flow velocities are significantly higher than in the rest of the platform. These velocities are high enough to bring the magnesium necessary to precipitate the observed amounts of dolomite, within durations in agreement with the available time of post‐reef deposition high sea level(s). However, neither fluid flow pattern nor flow velocities are able to explain the preferential massive dolomitization of the lower reef unit and the complete absence of dolomite in the upper one.     

Spatial coupling between spilitization and carbonation of basaltic sills in SW Scottish Highlands: evidence of a mineralogical control of metamorphic fluid flow

In a geochemical and petrological analysis of overprinting episodes of fluid–rock interaction in a well‐studied metabasaltic sill in the SW Scottish Highlands, we show that syn‐deformational access of metamorphic fluids and consequent fluid–rock interaction is at least in part controlled by preexisting mineralogical variations. Lithological and structural channelling of metamorphic fluids along the axis of the Ardrishaig Anticline, SW Scottish Highlands, caused carbonation of metabasaltic sills hosted by metasedimentary rocks of the Argyll Group in the Dalradian Supergroup. Analysis of chemical and mineralogical variability across a metabasaltic sill at Port Cill Maluaig shows that carbonation at greenschist to epidote–amphibolites facies conditions caused by infiltration of H₂O‐CO₂ fluids was controlled by mineralogical variations, which were present before carbonation occurred. This variability probably reflects chemical and mineralogical changes imparted on the sill during premetamorphic spilitization. Calculation of precarbonation mineral modes reveals heterogeneous spatial distributions of epidote, amphibole, chlorite and epidote. This reflects both premetamorphic spilitization and prograde greenschist facies metamorphism prior to fluid flow. Spilitization caused albitization of primary plagioclase and spatially heterogeneous growth of epidote ± calcic amphibole ± chlorite ± quartz ± calcite. Greenschist facies metamorphism caused breakdown of primary pyroxene and continued, but spatially more homogeneous, growth of amphibole + chlorite ± quartz. These processes formed diffuse epidote‐rich patches or semi‐continuous layers. These might represent precursors of epidote segregations, which are better developed elsewhere in the SW Scottish Highlands. Chemical and field analyses of epidote reveal the evidence of local volume fluctuations associated with these concentrations of epidote. Transient permeability enhancement associated with these changes may have permitted higher fluid fluxes and therefore more extensive carbonation. This deflected metamorphic fluid such that its flow direction became more layer parallel, limiting propagation of the reaction front into the sill interior.     

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.     

The relevance of vein texture in understanding the past hydraulic behaviour of a crystalline rock mass: reconstruction of the palaeohydrology of the Mecsekalja Zone,south Hungary

This study reconstructs the palaeohydrogeologic evolution of the shallow‐to‐moderate Mesozoic subsidence history for the Mecsekalja Zone (MZ), a narrow metamorphic belt in the eastern Mecsek Mountains, Hungary. Brittle deformation of the MZ produced a vein system with a cement history consisting of five sequential carbonate generations and one quartz phase. Vein textures suggest different fluid‐flow mechanisms for the parent fluids of subsequent cement generations. Combined microthermometric and stable‐isotope measurements permit reconstruction of the character of subsequent fluid generations with different flow types, as defined by vein textures, yielding new information regarding the hydraulic behaviour of a metamorphic crystalline complex. Textural observations and geochemical data suggest that fracture‐controlled flow pathways and externally derived fluids were typical of some flow events, while percolation through the rock matrix and the relationship to the Cretaceous volcanism and dyke emplacement were typical of others. The difference in the mode of calcite deposition from pervasive fluids (i.e. pervasive carbonatisation along grain boundaries versus deposition in antitaxial veins) between two calcite generations related to the volcanism inspired a stress‐dependent model of antitaxial vein growth. Textural and isotope variations in a vein generation produced by the same parent fluid indicate rock‐dependent hydraulic behaviour for different rock types, distinct action of the contemporaneous fracture systems and different extents of fluid–rock interaction. Cathodoluminescence microscopy and fluid‐inclusion microthermometry shed light on the possible role of hydraulic fracturing in the formation of massive calcite. The time of formation was estimated from the isotope composition of the oldest calcite generation and its presumptive relationship with the sedimentary sequences to the north, whereas microthermometry permitted conciliation of the reconstructed flow sequence with the Mesozoic subsidence history of the Mórágy Block (including the MZ).     

Evaluation of recoverable energy potential from enhanced geothermal systems: a sensitivity analysis in a poro‐thermo‐elastic framework

This study presents application of an efficient approach to simulate fluid flow and heat transfer in naturally fractured geothermal reservoirs. Fluid flow is simulated by combining single continuum and discrete fracture approaches. The local thermal nonequilibrium approach is used to simulate heat transfer by conduction in the rock matrix and convection (including conduction) in the fluid. Fluid flow and heat transfer models are integrated within a coupled poro‐thermo‐elastic framework. The developed model is used to evaluate the long‐term response of a geothermal reservoir with specific boundary conditions and injection/production schedule. A comparative study and a sensitivity analysis are carried out to evaluate the capability of the integrated approach and understand the degree by which different reservoir parameters affect thermal depletion of Soultz geothermal reservoir, respectively. Also observed, there exists an optimum fracture permeability after which the reservoir stimulation does not change the recovery factor significantly. Estimation of fluid temperature by the assumption of local thermal nonequilibrium heat transfer between the fracture fluid and the rock matrix gives fluid temperature of about 3°C less than that of estimated by thermal equilibrium heat transfer at early stage of hot water production.     

Basin‐scale fluid movement patterns revealed by veins: Wessex Basin,UK

Calcite veins at outcrop in the Mesozoic, oil‐bearing Wessex Basin, UK, have been studied using field characterization, petrography, fluid inclusions and stable isotopes to help address the extent, timing and spatial and stratigraphic variability of basin‐scale fluid flow. The absence of quartz shows that veins formed at low temperature without an influence of hydrothermal fluids. Carbon isotopes suggest that the majority of vein calcite was derived locally from the host rock but up to one quarter of the carbon in the vein calcite came from CO₂ from petroleum source rocks. Veins become progressively enriched in source‐rock‐derived CO₂ from the outer margin towards the middle, indicating a growing influence of external CO₂. The carbon isotope data suggest large‐scale migration of substantial amounts of CO₂ around the whole basin. Fluid inclusion salinity data and interpreted water‐δ¹⁸O data show that meteoric water penetrated deep into the western part of the basin after interacting with halite‐rich evaporites in the Triassic section before entering fractured Lower and Middle Jurassic rocks. This large‐scale meteoric invasion of the basin probably happened during early Cenozoic uplift. A similar approach was used to reveal that, in the eastern part of the basin close to the area that underwent most uplift, uppermost Jurassic and Cretaceous rocks underwent vein formation in the presence of marine connate water suggesting a closed system. Stratigraphically underlying Upper Jurassic mudstone and Lower Cretaceous sandstone, in the most uplifted part of the basin, contain veins that resulted from intermediate behaviour with input from saline meteoric water and marine connate waters. Thus, while source‐rock‐derived CO₂ seems to have permeated the entire section, water movement has been more restricted. Oil‐filled inclusions in vein calcite have been found within dominant E‐W trending normal faults, suggesting that these may have facilitated oil migration.     

Timescales for reaching steady-state fluid flow in systems perturbed by formation of highly permeable faults

We consider the case of an isothermal, fluid‐saturated, homogeneous rock layer with transverse fluid flow driven by an imposed constant fluid pressure gradient. A rupture in the centre of the rock layer generates a highly permeable fault and results in a change of the initially homogeneous permeability distribution. This leads to a perturbation of the fluid flow field and its gradual transition to a new steady‐state corresponding to the new permeability distribution. An examination of this transitional process permits us to obtain an analytical estimation of the transition stage duration. The application of the results obtained to km‐scale faults in crystalline rock bodies leads to the conclusion that the evolution of the fluid velocity field is rather rapid compared with geological timescales.     

Chemical evolution of metamorphic fluids in the Central Alps,Switzerland: insight from LA‐ICPMS analysis of fluid inclusions

The chemical evolution of fluids in Alpine fissure veins (open cavities with large free‐standing crystals) has been studied by combination of fluid inclusion petrography, microthermometry, LA‐ICPMS microanalysis, and thermodynamic modeling. The quartz vein systems cover a metamorphic cross section through the Central Alps (Switzerland), ranging from subgreenschist‐ to amphibolite‐facies conditions. Fluid compositions change from aqueous inclusions in subgreenschist‐ and greenschist‐facies rocks to aqueous–carbonic inclusions in amphibolite‐facies rocks. The fluid composition is constant for each vein, across several fluid inclusion generations that record the growth history of the quartz crystals. Chemical solute geothermometry, fluid inclusion isochores, and constraints from fluid–mineral equilibria modeling were used to reconstruct the pressure–temperature conditions of the Alpine fissure veins and to compare them with the metamorphic path of their host rocks. The data demonstrate that fluids in the Aar massif were trapped close to the metamorphic peak whereas the fluids in the Penninic nappes record early cooling, consistent with retrograde alteration. The good agreement between the fluid–mineral equilibria modeling and observed fluid compositions and host‐rock mineralogy suggests that the fluid inclusions were entrapped under rock‐buffered conditions. The molar Cl/Br ratios of the fluid inclusions are below the seawater value and would require unrealistically high degrees of evaporation and subsequent dilution if they were derived from seawater. The halogen data may thus be better explained by interaction between metamorphic fluids and organic matter or graphite in metasedimentary rocks. The volatile content (CO₂, sulfur) in the fluid inclusions increases systematically as function of the metamorphic grade, suggesting that the fluids have been produced by prograde devolatilization reactions. Only the fluids in the highest grade rocks were partly modified by retrograde fluid–rock interactions, and all major element compositions reflect equilibration with the local host rocks during the earliest stages of postmetamorphic uplift.     

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

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

Origin of palaeofluids in a normal fault setting in the Aegean region

The province of Burdur (SW Turkey) is seismically an active region. A structural, geochronological, petrographical, geochemical and fluid inclusion study of extension veins and fault‐related calcite precipitates has been undertaken to reconstruct the palaeofluid flow pattern in this normal fault setting in the Aegean region. A palaeostress analysis and U/Th dating of the precipitates reveals the neotectonic significance of the sampled calcites. Fluid inclusion microthermometry of calcites‐filling extension veins shows final melting temperatures (T_m ice) of 0°C. This indicates pure water, most likely of meteoric origin. The oxygen isotope values (?9.8‰ to ?6.5‰ VPDB) and the carbon isotopic composition (?10.4‰ to ?2.9‰ VPDB) of these calcites also show a near‐surface meteoric origin of the fluid responsible for precipitation. The microstructural characteristics of fault‐related calcites indicate that calcite precipitation was linked with fault activity. Final melting temperature of fault‐related calcites ranges between 0 and ?1.9°C. The oxygen isotope values show a broad range between ?15.0‰ and ?2.2‰ VPDB. Several of these calcites have a δ¹⁸O composition that is higher or lower than the oxygen isotopic composition of meteoric calcites in the area (i.e. between ?10‰ and ?6‰ VPDB). The δ¹³C composition largely falls within the range of the host limestones and reflects a rock‐buffered system. Microthermometry and stable isotopic study indicate a meteoric origin of the fluids with some degree of water–rock interaction or mixing with another fluid. Temperatures deduced from microthermometry and stable isotope analyses indicate precipitation temperatures around 50°C. These higher temperatures and the evidence for water–rock interaction indicate a flow path long enough to equilibrate with the host–rock limestone and to increase the temperature. The combined study of extension vein‐ and fault‐related calcite precipitates enables determining the origin of the fluids responsible for precipitation in a normal fault setting. Meteoric water infiltrated in the limestones to a depth of at least 1 km and underwent water–rock interaction or mixing with a residual fluid. This fluid was, moreover, tapped during fault activity. The extension veins, on the contrary, were passively filled with calcites precipitating from the downwards‐migrating meteoric water.     

Hydraulic and hydrochemical properties of deep sedimentary reservoirs of the Upper Rhine Graben,Europe

Hydraulic and hydrochemical data from several hundred wells mostly drilled by the oil and gas industry within the four deep carbonate and siliciclastic reservoirs of the Upper Rhine Graben area in France and Germany have been compiled, examined, validated and analysed with the aim to characterize fluids and reservoir properties. Due to enhanced temperatures in the subsurface of the Upper Rhine Graben, this study on hydraulic and hydrochemical properties has been motivated by an increasing interest in deep hydrogeothermal energy projects in the Rhine rift valley. The four examined geothermal reservoir formations are characterized by high hydraulic conductivity reflecting the active tectonic setting of the rift valley and its fractured and karstified reservoirs. The hydraulic conductivity decreases only marginally with depth in each of the reservoirs, because the Upper Rhine Graben is a young tectonically active structure. The generally high hydraulic conductivity of the reservoir rocks permits cross‐formation advective flow of thermal water. Water composition data reflect the origin and hydrochemical evolution of deep water. Shallow water to 500 m depth is, in general, weakly mineralized. The chemical signature of the water is controlled by fluid–rock geochemical interactions. With increasing depth, the total of dissolved solids (TDS) increases. In all reservoirs, the fluids evolve to a NaCl‐dominated brine. The high salinity of the reservoirs is partly derived from dissolution of halite in evaporitic Triassic and Cenozoic formations, and partly from the fluids residing in the crystalline basement. Water of all four reservoirs is saturated with respect to calcite and other minerals including quartz and barite.     

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.