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.     

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

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

Dry CO2–CO fluid as an important potential deep Earth solvent

Transport properties of reduced carbonic fluid have been studied experimentally at P = 2 kbar and T = 700–1000°C in internally heated pressure vessel (IHPV). Synthetic FeCO₃ and natural siderite were used to generate fluid during experiments using a platinum double‐capsule technique. A natural CaTiSiO₅ aggregate was placed into the inner capsule as an additional source of trace elements. The outer capsule was loaded with albite glass. No water was introduced to the system and oxygen fugacity was established near to graphite–oxygen (CCO) buffer due to transformation of FeCO₃ into a magnetite aggregate during decarbonation to yield CO and CO₂. The carbonates decomposed during initial heating of the experiments, causing their some constituent components to be dissolved in and transferred by the fluid to the pore space of the albite glass matrix. After temperature reached 1000°C glass, the shards annealed and then melted, as evidenced by a vesiculated glass in the quench products. Micro‐Raman investigation of the fluid in bubbles in the albite glass in experiments with decomposition of natural siderite yielded CO–CO₂ mixture where CO mole fraction was 0.15–0.16. We observe significant concentrations of Pt, Mn, P, and REE in the albite glass; in contrast, no Fe or Mg transfer was detected. LA‐ICP‐MS analysis of the albite glass product yielded the average Pt content of 2 ppm. Such high Pt signal came from Pt particles (100–500 nm in size), which were observed on the walls of the bubbles embedded in the glass. Olivines and aluminous spinel were observed in the Fe‐oxide aggregate, demonstrating transfer of SiO₂ and Al₂O₃ from the albite melt by the reduced carbonic fluid from the albite glass (large capsule). Our results demonstrate that dry CO–CO2 fluid can be important agents of dissolution and transport, especially for Pt and other metals. The data imply that metals are chiefly dissolved as carbonyl complexes.     

Growth and albitization of K‐feldspar in crystalline rocks in the shallow crust: a tracer for fluid circulation during exhumation?

A general feature of medium‐ to coarse‐grained, sheet‐silicate bearing, quartzo‐feldspathic rocks of either metamorphic or igneous affinity is the retrograde development of lenses of pure K‐feldspar at the grain boundaries between sheet silicate (0 0 1) faces and original feldspar grains. The growth of these lenses acts to displace and deform the sheet silicate grain by a force of crystallization, although the substrate feldspar and adjacent quartz are not deformed. Subsequent to the growth of the lenses they are replaced to variable degrees by pure albite, which grows into the lens from the substrate feldspar behind an irregular replacement front. The composition and texture of both K‐feldspar and replacive albite suggest a strong affinity with authigenic feldspars, although it is considered likely that the K‐feldspar of the lenses is derived from low‐temperature biotite‐breakdown reactions. A model is proposed whereby the lenses grow into open pores at dilatant sites in response to infiltration of aqueous fluids as the crystalline rocks are exhumed under brittle conditions. Continued circulation of infiltrating fluids in a temperature gradient results in the replacement of K‐feldspar by albite via an alkali exchange process. The lenses point to a significant grain‐scale permeability in crystalline rock at shallow levels in the crust.     

Granite‐related overpressure and volatile release in the mid crust: fluidized breccias from the Cloncurry District,Australia

The source and transport regions of fluidized (transported) breccias outcrop in the Cloncurry Fe‐oxide–Cu–Au district. Discordant dykes and pipes with rounded clasts of metasedimentary calc–silicate rocks and minor felsic and mafic intrusions extend several kilometres upwards and outwards from the contact aureole of the 1530 Ma Williams Batholith into overlying schists and amphibolites. We used analytical equations for particle transport to estimate clast velocities (≥20 m sec^?1), approaching volcanic ejecta rates. An abrupt release of overpressured magmatic‐hydrothermal fluid is suggested by the localization of the base of the breccias in intensely veined contact aureoles (at around 10 km, constrained by mineral equilibria), incorporation of juvenile magmatic clasts, the scale and discordancy of the bodies, and the wide range of pressure variation (up to 150 MPa) inferred from CO₂ fluid inclusion densities and related decrepitation textures. The abundance of clasts derived from depth, rather than from the adjacent wallrocks, suggests that the pressure in the pipes was sufficient to restrict the inwards spalling of fragments from breccia walls; that is, the breccias were explosive rather than implosive, and some may have vented to the surface. At these depths, such extreme behaviour may have been achieved by release of dissolved fluids from crystallizing magma, in combination with a strongly fractured and fluid‐laden carapace, sitting under a strong, low permeability barrier. The relationship of these breccias to the Ernest Henry iron‐oxide–Cu–Au deposit suggests they may have been sources of fluids or mechanical energy for ore genesis, or alternately provided permeable pathways for later ore fluids.     

New insights from reactive transport modelling: the formation of the sericitic vein envelopes during early hydrothermal alteration at Butte, Montana

A reactive transport computer code has been employed to model hydrothermal alteration of a granitoid rock bordering a discrete vein channel. The model suggests that the grey sericitic and sericitic with remnant biotite alteration envelopes at the porphyry copper deposit at Butte, Montana, can be formed by a reducing, low pH, and low salinity fluid under constant temperature and pressure conditions of approximately 400 °C and less than 100 MPa during a time span of approximately 100 years or less. Hydrothermal alteration has little effect on the porosity of the host rock (Butte Quartz Monzonite), and the diffusivity of the aqueous species also changes little. A sequence of mineral reaction fronts characterizes the alteration envelopes. The biotite dissolution front occurs closest to the vein channel and marks the transition from the grey sericitic to sericitic with remnant biotite envelope. The plagioclase dissolution front occurs farthest into the matrix and marks the edge of relatively fresh Butte Quartz Monzonite. From the properties of the quasi‐stationary state approximation ( Lichtner 1988 ; Lichtner 1991 ), it follows that once the sequence of reaction fronts is fully established, their relative locations remain constant and the widths of the reaction zones increase with the square root of time.     

Decreasing CO2 partial pressure triggered Mg–Fe–Ca carbonate formation in ancient Martian crust preserved in the ALH84001 Meteorite

We retrace hydrogeochemical processes leading to the formation of Mg–Fe–Ca carbonate concretions (first distinct carbonate population, FDCP) in Martian meteorite ALH84001 by generic hydrogeochemical equilibrium and mass transfer modeling. Our simple conceptual models assume isochemical equilibration of orthopyroxenite minerals with pure water at varying water‐to‐rock ratios, temperatures and CO₂ partial pressures. Modeled scenarios include CO₂ partial pressures ranging from 10.1325 to 0.0001 MPa at water‐to‐rock ratios between 4380 and 43.8 mol mol^?1 and different temperatures (278, 303 and 348 K) and enable the precipitation of Mg–Fe–Ca solid solution carbonate. Modeled range and trend of carbonate compositional variation from magnesio‐siderite (core) to magnesite (rim), and the precipitation of amorphous SiO₂ and magnetite coupled to magnesite‐rich carbonate are similar to measured compositional variation. The results of this study suggest that the early Martian subsurface had been exposed to a dynamic gas pressure regime with decreasing CO₂ partial pressure at low temperatures (approximately 1.0133 to 0.0001 MPa at 278 K or 6 to 0.0001 MPa at 303 K). Moderate water‐to‐rock ratios of ca. 438 mol mol^?1 and isochemical weathering of orthopyroxenite are additional key prerequisites for the formation of secondary phase assemblages similar to ALH84001’s ‘FDCP’. Outbursts of water and CO_2(g) from confined ground water in fractured orthopyroxenite rocks below an unstable CO₂ hydrate‐containing cryosphere provide adequate environments on the early Martian surface.     

Monitoring fluid chemistry in iron oxide–copper–gold‐related metasomatic processes,eastern Mt Isa Block,Australia

Most researchers in the Proterozoic eastern Mt Isa Block, NW Queensland, Australia, favour magmatic fluid and salt sources for sodic‐(calcic) alteration and iron oxide–copper–gold mineralization. Here we compare spatial, mineralogic and stable isotope data from regional alteration assemblages with magmatic and magmatic‐hydrothermal interface rocks in order to track chemical and isotopic variations in fluid composition away from inferred fluid sources. Tightly clustered δ¹⁸O values for magnetite, quartz, feldspar and actinolite for igneous‐hosted samples reflect high temperature equilibration in the magmatic‐hydrothermal environment. In contrast, these minerals record predominantly higher δ¹⁸O values in regional alteration and Cu–Au mineralization. This dichotomy reflects partial equilibration with isotopically heavier wallrocks and slightly lower temperatures. Increases in Si concentrations of metasomatic amphiboles relative to igneous amphiboles in part reflect cooling of metasomatic fluids away from igneous rocks. Variations in X_Mg for metasomatic amphiboles indicate local wallrock controls on amphibole chemistry, while variations in X_Cl/X_OH ratios for amphiboles (at constant X_Mg) indicate variable aH₂O/aHCl ratios for metasomatic fluids. Biotite geochemistry also reflects cooling and both increases and decreases in aH₂O/aHCl for fluids away from plutonic rocks. Decreased aH₂O/aHCl ratios for metasomatic fluids reflect in part scavenging of chlorine out of meta‐evaporite sequences, although this process requires already saline fluids. Local increases in aH₂O/aHCl ratios, as well as local decreases in δ¹⁸O values for some minerals (most notably haematite and epithermal‐textured quartz), may indicate ingress of low salinity, low δ¹⁸O fluids of possible meteoric origin late in the hydrothermal history of the region. Taken together, our observations are most consistent with predominantly magmatic sources for metasomatic fluids in the eastern Mt Isa Block, but record chemical and isotopic variations along fluid flow paths that may be important in explaining some of the diversity in alteration and mineralization styles in the district.     

The Ixtacamaxtitlán kaolinite deposit and sinter (Puebla State, Mexico): a magmatic-hydrothermal system telescoped by a shallow paleoaquifer

The Ixtacamaxtitlán hydrothermal deposit is made up of a succession, from bottom to top, of: (1) a porphyritic subvolcanic body, crosscut by quartz veins, and a stockwork with subordinate sulfides (pyrite and chalcopyrite), showing propylitic alteration haloes overprinting a previous potassic alteration event (biotitization); (2) an overlying, kaolinized lithic‐rich rhyolitic tuff; and (3) a layered opal deposit with preserved sedimentary structures. This vertical zonation, coupled with the distribution of the alteration assemblages, lead us to the interpretation of the whole as a porphyry‐type deposit grading upwards to a barren, steam‐heated, acid‐leached, kaolinite blanket with a partially preserved silica sinter on top. Both the fluid inclusion study carried out on the veins and stockwork, and the stable isotopic analyses of the kaolinized bodies, suggest the presence of two major hydrothermal events. The older event is characterized by the occurrence of hot hypersaline fluids (up to 320°C and 36 wt% NaCl equivalents), likely of magmatic origin, closely associated with the emplacement of the underlying early Miocene porphyry‐type deposit. The later event is characterized by the presence of cooler and dilute fluids (up to 140°C and 4 wt% NaCl equivalents) and by advanced argillic alteration close to the paleosurface. The calculated isotopic composition of water in equilibrium with the kaolinitic sequence plots close to and underneath the meteoric water line, partially overlapping the Los Humeros present‐day geothermal fluids. This evidence coupled with the petrographic observations suggests that steam‐heated phreatic waters altered the lithic‐rich rhyolitic tuff. This would have occurred when acid vapors, exsolved from deeper hydrothermal fluids by boiling, reached the local paleowater table and condensed, after a sector collapse that changed the system from lithostatic to hydrostatic conditions.     

Barite–pyrite mineralization of the Wiesbaden thermal spring system, Germany: a 500-kyr record of geochemical evolution

Barite–(pyrite) mineralizations from the thermal springs of Wiesbaden, Rhenish Massif, Germany, have been studied to place constraints on the geochemical evolution of the hydrothermal system in space and time. The thermal springs, characterized by high total dissolved solids (TDS) contents and predominance of NaCl, ascend from aquifers at 3–4 km depth and discharge at a temperature of 65–70°C. The barite–(pyrite) mineralization is found in upflow and discharge zones of the present‐day thermal springs as well as at elevations up to 50 m above the current water table. Hence, this mineralization style constitutes a continuous record of the hydrothermal activity, linking the past evolution with the present state of this geothermal system. The sulphur isotope signatures of the mineralization indicate a continuous decrease of the δ³⁴S of sulphate from +16.9‰ in the oldest barite to +10.1‰ in the present‐day thermal water. The δ³⁴S values of barite closely resemble various recently active thermal springs along the southern margin of the Rhenish Massif and contrast strongly with different regional ground and mineral waters. The mineralogical and isotopic signatures, combined with calculations based on uplift rates and the regional geological history, indicate a minimum activity of the thermal spring system at Wiesbaden of about 500 000 years. This timeframe is considerably larger than conservative models, which estimate the duration of thermal spring systems in continental intraplate settings to last for several 10 000 years. The calculated equilibrium sulphur isotope temperatures of coexisting barite and pyrite range between 65 and 80°C, close to the discharge temperature of the springs, which would indicate apparent equilibrium precipitation. Kinetic modelling of the re‐equilibration of the sulphate–sulphide pair during water ascent shows that this process would require 220 Myr. Therefore, we conclude that pyrite is formed from precursor Fe monosulphide phases, which rapidly precipitate in the near‐surface environment, preserving the isotope fractionation between dissolved sulphate and sulphide established in the deep aquifer. Equilibrium modelling of water–mineral reactions shows slight supersaturation of barite at the discharge temperature. Pyrite is already strongly supersaturated at the temperatures estimated for the aquifer (110°C) and processes in the near‐surface environment are most probably related to contact of the thermal water with atmospheric oxygen, resulting in formation of oxidized intermediate sulphur species and precipitation of Fe monosulphide phases, which subsequently recrystallize to pyrite.     

Hydrogeochemical modelling of CO2 equilibria and mass transfer induced by organic–inorganic interactions in siliciclastic petroleum reservoirs

Different feldspar types control complex hydrogeochemical processes in hydrocarbon‐bearing siliciclastic reservoirs, which have undergone different degrees of degradation. To test such processes generically, carbon dioxide equilibria and mass transfers induced by organic–inorganic interactions have been modelled for different hydrogeochemical scenarios. The approach is based on and compared with data from the Norwegian continental shelf ( Smith & Ehrenberg 1989 ) and assumes local thermodynamic equilibrium among solids and fluids. Equilibrating mineral assemblages (different feldspar types, quartz, kaolinite, calcite) are based on the primary reservoir composition. Equilibration and coupled mass transfer were triggered by the addition and reaction of different amounts of CO₂, CH₄ and H₂ (plus acetic acid) at temperatures between 50 and 95°C (323 and 368 K). These components occur in oil fields as products of anaerobic bacterial degradation, hydrolytic disproportionation of hydrocarbons and/or thermal maturation of kerogen. We apply two different computer codes and two different thermodynamic data bases to calculate the results. Reaction of 0.32–0.6 mol CO₂, 0.16–0.3 mol CH₄ and 0.8–1.5 mol H₂ with K‐feldspar, quartz, kaolinite and calcite in 1 l of pore water results in modelled values of 0.3–2.3 mol% CO₂ in a multicomponent gas phase that resembles measured data (0.2–1.5 mol%). Similar CO₂ contents result from acetic acid addition (CO₂, CH₄, H₂ + 0.016 mol CH₃COOH). Equilibration with albite or anorthite reduces the release of CO₂ into the multicomponent gas phase dramatically, by 1 or 4 orders of magnitude compared with the equilibration with K‐feldspar. Minor differences in the modelled CO₂ content (0.1–0.2 mol%) result from calculations with different computer codes if the same thermodynamic data base is applied. Relevant differences (up to 1.9 mol% CO₂) result from calculations using different thermodynamic data bases.     

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.     

Hydrogeology of the Krafla geothermal system,northeast Iceland

The Krafla geothermal system is located in Iceland's northeastern neovolcanic zone, within the Krafla central volcanic complex. Geothermal fluids are superheated steam closest to the magma heat source, two‐phase at higher depths, and sub‐boiling at the shallowest depths. Hydrogen isotope ratios of geothermal fluids range from ?87‰, equivalent to local meteoric water, to ?94‰. These fluids are enriched in ¹⁸O relative to the global meteoric line by +0.5–3.2‰. Calculated vapor fractions of the fluids are 0.0–0.5 wt% (~0–16% by volume) in the northwestern portion of the geothermal system and increase towards the southeast, up to 5.4 wt% (~57% by volume). Hydrothermal epidote sampled from 900 to 2500 m depth has δD values from ?127 to ?108‰, and δ¹⁸O from ?13.0 to ?9.6‰. Fluids in equilibrium with epidote have isotope compositions similar to those calculated for the vapor phase of two‐phase aquifer fluids. We interpret the large range in δD_EPIDOTE and δ¹⁸O_EPIDOTE across the system and within individual wells (up to 7‰ and 3.3‰, respectively) to result from variable mixing of shallow sub‐boiling groundwater with condensates of vapor rising from a deeper two‐phase reservoir. The data suggest that meteoric waters derived from a single source in the northwest are separated into the shallow sub‐boiling reservoir, and deeper two‐phase reservoir. Interaction between these reservoirs occurs by channelized vertical flow of vapor along fractures, and input of magmatic volatiles further alters fluid chemistry in some wells. Isotopic compositions of hydrothermal epidote reflect local equilibrium with fluids formed by mixtures of shallow water, deep vapor condensates, and magmatic volatiles, whose ionic strength is subsequently derived from dissolution of basalt host rock. This study illustrates the benefits of combining phase segregation effects in two‐phase systems during analysis of wellhead fluid data with stable isotope values of hydrous alteration minerals when evaluating the complex hydrogeology of volcano‐hosted geothermal systems.     

A COMBINED MULTI‐ANALYTICAL APPROACH FOR THE STUDY OF ROMAN GLASS FROM SOUTH‐WEST IBERIA: SYNCHROTRON μ‐XRF,EXTERNAL‐PIXE/PIGE AND BSEM–EDS

An integrated, multi‐analytical approach combining the high sensitivity of SR‐μXRF, the light element capability of PIXE/PIGE under a helium flux and the spatial resolution of BSEM + EDS was used to characterize chemical composition and corrosion of glass samples (first to fourth centuries ad ) from an important, but scarcely investigated, Roman region of south‐west Iberia (southern Portugal). The geochemical trends and associations of major, minor and trace elements were investigated to shed light on production techniques, the provenance of raw materials and decay mechanisms. The results, while confirming a production technique common to Roman glasses throughout the Empire—that is, a silica‐soda‐lime low‐Mg, low‐K composition, with glass additives as colouring and/or decolouring agents (Fe, Cu, Mn, Sb)—show at one site high Zr–Ti contents, suggesting a more precise dating for these glasses to the second half of the fourth century. The Ti–Fe–Zr–Nb geochemical correlations in the pristine glass indicate the presence of minerals such as ilmenite, zircon, Ti‐rich Fe oxides and columbite in the sands used as raw materials for the glass former: these minerals are typical of granitic‐type source rocks. The unusually high K content in the corrosion layers is consistent with burial conditions in K‐rich soils derived from the alteration of 2:1 clays in K‐bearing rock sequences.     

Metamorphic and basin fluids in quartz–carbonate–sulphide veins in the SW Scottish Highlands: a stable isotope and fluid inclusion study

Metalliferous (Fe–Cu–Pb–Zn) quartz–carbonate–sulphide veins cut greenschist to epidote–amphibolite facies metamorphic rocks of the Dalradian, SW Scottish Highlands, with NE–SW to NW–SE trends, approximately parallel or perpendicular to regional structures. Early quartz was followed by pyrite, chalcopyrite, sphalerite, galena, barite, late dolomite–ankerite and clays. Both quartz–sulphide and carbonate vein mineralisation is associated with brecciation, indicating rapid release of fluid overpressure and hydraulic fracturing. Two distinct mineralising fluids were identified from fluid inclusion and stable isotope studies. High temperature (>350°C) quartz‐precipitating fluids were moderately saline (4.0–12.7 wt.% NaCl equivalent) with low (approximately 0.05). Quartz δ¹⁸O (+11.7 to +16.5‰) and sulphide δ³⁴S (?13.6 to ?1.1‰) indicate isotopic equilibrium with host metasediments (rock buffering) and a local metasedimentary source of sulphur. Later, low‐temperature (T_H = 120–200°C) fluids, probably associated with secondary carbonate, barite and clay formation, were also moderately saline (3.8–9.1 wt.% NaCl equivalent), but were strongly enriched in ¹⁸O relative to host Dalradian lithologies, as indicated by secondary dolomite–ankerite (δ¹⁸O = +17.0 to +29.0‰, δ¹³C = ?1.0 to ?3.0‰). Compositions of carbonate–forming fluids were externally buffered. The veins record the fluid–rock interaction history of metamorphic host rocks during cooling, uplift and later extension. Early vein quartz precipitated under retrograde greenschist facies conditions from fluids probably derived by syn‐metamorphic dehydration of deeper, higher‐grade rocks during uplift and cooling of the Caledonian metamorphic complex. Veins are similar to those of mesothermal veins in younger Phanerozoic metamorphic belts, but are rare in the Scottish Dalradian. Early quartz veins were reactivated by deep penetration of low‐temperature basin fluids that precipitated carbonate and clays in veins and adjacent Dalradian metasediments throughout the SW Highlands, probably in the Permo‐Carboniferous. This event is consistent with paragenetically ambiguous barite with δ³⁴S characteristic of late Palaeozoic basinal brines.     

Fracture‐focused fluid flow in an acid and redox‐influenced system: diagenetic controls on cement mineralogy and geomorphology in the Navajo Sandstone

Differential cement mineralogy is influenced by depositional textures, structural deformation, pore fluid chemistry, and ultimately influences landscape evolution by introducing heterogeneities in erodibility. In Southern Utah, the region West of the Kaibab uplift known as Mollies Nipple (Mollies) in Grand Staircase‐Escalante National Monument exhibits a complex history of fluid–sediment interactions, which has resulted in a localized zone of anomalous diagenetic iron sulfate (jarosite) mineralogy in a well‐exposed dune–interdune deposit within the Navajo Sandstone. Mineralogy and geochemistry of cements within this region are examined using reflectance and imaging spectroscopy, field investigations, microscopy, and whole‐rock geochemical analyses. These data show that the in‐situ jarosite cement is localized to a plane along the highest ridge of the butte, providing an armor along with other secondary cements, which controls the butte's geomorphic evolution. The jarosite cement is associated with other mineralogies suggesting that the sulfate was one of the latest fluid‐related precipitates in the paragenetic sequence. It was preceded by a regional bleaching event, precipitation of clay cements, some localized concretionary iron oxide precipitation, and formation of deformation bands. At least one generation of dense iron oxide mineralization is associated with cataclastic brittle deformation predating the sulfate precipitation. Trace element geochemistry of cements shows certain metal oxide populations associated with extremely high (>2000 ppm) arsenic values. We interpret the combination of spatial mineral distribution, observed paragenetic sequence, and trace element geochemistry to suggest this region experienced acid sulfate diagenesis along fracture‐controlled fluid conduits related to weathering of proximal, unidentified, sulfides, or H₂S associated with deep source beds. Jarosite is highly soluble, and its presence suggests that abundant fluid flow has not occurred in this region since its formation. This terminal cement‐forming event must have occurred prior to sandstone exhumation and erosion to form the current extreme landscape at Mollies. This site exhibits the influence that fluid geochemistry, sedimentary mineralogy, and structural fabric have on geomorphic evolution.     

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.     

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.     

Hydrothermal palaeofluid circulation in the fracture network of the Baksa Gneiss Complex of SW Pannonian Basin,Hungary

A well‐developed fracture‐filling network is filled by dominantly Ca‐Al‐silicate minerals that can be found in the polymetamorphic rock body of the Baksa Gneiss Complex (SW Hungary). Detailed investigation of this vein network revealed a characteristic diopside→epidote→sphalerite→albite ± kfeldspar→chlorite1 ± prehnite ± adularia→chlorite2→chlorite3→pyrite→calcite1→calcite2→calcite3 fracture‐filling mineral succession. Thermobarometric calculations (two feldspar: 230–336°C; chlorites: approximately 130–300°C) indicate low‐temperature vein formation conditions. The relative succession of chlorites in the mineral sequence combined with the calculated formation temperatures reveals a cooling trend during precipitation of the different chlorite phases (T_chlorite1: 260 ± 32°C →T_chlorite2: 222 ± 20°C →T_chlorite3: 154 ± 13°C). This cooling trend can be supported by the microthermometry data of primary fluid inclusions in diopside (T_h: 276–362°C) and epidote (T_h: 181–359°C) phases. The identical chemical character (0.2–1.5 eq. wt% NaCl) of these inclusions mean that vein mineralization occurred in a same fluid environment. The high trace element content (e.g. As, Cu, Zn, Mn) and Co/Ni ratio approximately 1–5 of pyrite grains support the postmagmatic hydrothermal origin of the veins. The vein microstructure and identical fluid composition indicate that vein mineralization occurred in an interconnected fracture system where crystals grew in fluid filled cracks. Vein system formed at approximately <200 MPa pressure conditions during cooling from approximately 480°C to around 150°C. The rather different fluid characteristics (T_h: 75–124°C; 17.5–22.6 eq. wt% CaCl₂) of primary inclusions of calcite1 combining with the special δ¹⁸O signature of fluid from which this mineral phase precipitated refer to hydrological connection between the crystalline basement and the sedimentary cover.     

Precipitation of lead–zinc ores in the Mississippi Valley‐type deposit at Trèves,Cévennes region of southern France

The Trèves zinc–lead deposit is one of several Mississippi Valley‐type (MVT) deposits in the Cévennes region of southern France. Fluid inclusion studies show that the ore was deposited at temperatures between approximately 80 and 150°C from a brine that derived its salinity mainly from the evaporation of seawater past halite saturation. Lead isotope studies suggest that the metals were extracted from local basement rocks. Sulfur isotope data and studies of organic matter indicate that the reduced sulfur in the ores was derived from the reduction of Mesozoic marine sulfate by thermochemical sulfate reduction or bacterially mediated processes at a different time or place from ore deposition. The large range of δ³⁴S values determined for the minerals in the deposit (12.2–19.2‰ for barite, 3.8–13.8‰ for sphalerite and galena, and 8.7 to ?21.2‰ for pyrite), are best explained by the mixing of fluids containing different sources of sulfur. Geochemical reaction path calculations, based on quantitative fluid inclusion data and constrained by field observations, were used to evaluate possible precipitation mechanisms. The most important precipitation mechanism was probably the mixing of fluids containing different metal and reduced sulfur contents. Cooling, dilution, and changes in pH of the ore fluid probably played a minor role in the precipitation of ores. The optimum results that produced the most metal sulfide deposition with the least amount of fluid was the mixing of a fluid containing low amounts of reduced sulfur with a sulfur‐rich, metal poor fluid. In this scenario, large amounts of sphalerite and galena are precipitated, together with smaller quantities of pyrite precipitated and dolomite dissolved. The relative amounts of metal precipitated and dolomite dissolved in this scenario agree with field observations that show only minor dolomite dissolution during ore deposition. The modeling results demonstrate the important control of the reduced sulfur concentration on the Zn and Pb transport capacity of the ore fluid and the volumes of fluid required to form the deposit. The studies of the Trèves ores provide insights into the ore‐forming processes of a typical MVT deposit in the Cévennes region. However, the extent to which these processes can be extrapolated to other MVT deposits in the Cévennes region is problematic. Nevertheless, the evidence for the extensive migration of fluids in the basement and sedimentary cover rocks in the Cévennes region suggests that the ore forming processes for the Trèves deposit must be considered equally viable possibilities for the numerous fault‐controlled and mineralogically similar MVT deposits in the Cévennes region.