Textural and isotopic evidence on the fluid source and transport mechanism of antitaxial fibrous microstructures from the Alps and the Appalachians

The source of fluid‐forming veins is of great importance in order to understand the hydraulic system acting in the earth's crust. The study of syntectonic antitaxial veins is one of the few methods by which the opening history can be deduced from rocks, and thus these veins are of primary importance in determining rock kinematics. Antitaxial veins were taken from black shales in two different tectonic settings in the Helvetic Alps, Switzerland, and the Taconic Appalachians, New York State. These syntectonic extension veins are regularly spaced and are oriented sub‐normal to bedding. The vein microstructure displays a symmetry around the median line in the centre of the vein, and a symmetry in cathodoluminescence banding parallel to the vein–wall interface, which suggests transport along bedding‐parallel dissolution planes from both vein‐walls. Antitaxial veins nucleated in transgranular fractures, but evidence for ongoing multiple crack‐seal increments is lacking; rather, veins grew continuously keeping close contact to the vein‐wall. Radiogenic ⁸⁷Sr/⁸⁶Sr ratios are higher in the surrounding matrix than in the vein, and higher than the corresponding seawater data in all samples. Variations are small and calcite in both the vein and the host rock were derived from the same source of fluid in the Helvetic samples. Mass balance of Sr suggests that the amount of calcite is too small in the surrounding host rock to be derived locally. Stable oxygen compositions are heavier in the host rock than in the veins, with overall low variation in both δ¹⁸O and δ¹³C values in the Mesozoic Helvetic samples. Data point to a rock‐buffered system, the precipitate most likely derived from an external source. The lower Palaeozoic Appalachian veins have lesser δ¹⁸O values than the host rock, similar to the Helvetic veins. Radiogenic ⁸⁷Sr/⁸⁶Sr data and a large heterogeneity in stable isotope values indicate an open system. Microstructural and isotopic evidence suggests that the antitaxial veins were formed by pervasive fluid flow, with the solute at least partly derived from an external source.     

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.     

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.     

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.     

Changes in fluid pathways in a calcite vein mesh (Natih Formation,Oman Mountains): insights from stable isotopes

We present a structural, microstructural, and stable isotope study of a calcite vein mesh within the Cretaceous Natih Formation in the Oman Mountains to explore changes in fluid pathways during vein formation. Stage 1 veins form a mesh of steeply dipping crack‐seal extension veins confined to a 3.5‐m‐thick stratigraphic interval. Different strike orientations of Stage 1 veins show mutually crosscutting relationships. Stage 2 veins occur in the dilatant parts of a younger normal fault interpreted to penetrate the stratigraphy below. The δ¹⁸O composition of the host rock ranges from 21.8‰ to 23.7‰. The δ¹³C composition ranges from 1.5‰ to 2.3‰. This range is consistent with regionally developed diagenetic alteration at top of the Natih Formation. The δ¹⁸O composition of vein calcite varies from 22.5‰ to 26.2‰, whereas δ¹³C composition ranges from ?0.8‰ to 2.1‰. A first trend observed in Stage 1 veins involves a decrease of δ¹³C to compositions nearly 1.3‰ lower than the host rock, whereas δ¹⁸O remains constant. A second trend observed in Stage 2 calcite has δ¹⁸O values up to 3.3‰ higher than the host rock, whereas the δ¹³C composition is similar. Stable isotope data and microstructures indicate an episodic flow regime for both stages. During Stage 1, formation of a stratabound vein mesh involved bedding‐parallel flow, under near‐lithostatic fluid pressures. The ¹⁸O fluid composition was host rock‐buffered, whereas ¹³C composition was relatively depleted. This may reflect reaction of low ¹³C CO₂ derived by fluid interaction with organic matter in the limestones. Stage 2 vein formation is associated with fault‐controlled fluid flow accessing fluids in equilibrium with limestones about 50 m beneath. We highlight how evolution of effective stress states and the growth of faults influence the hydraulic connectivity in fracture networks and we demonstrate the value of stable isotopes in tracking changes in fluid pathways.     

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.     

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.     

Fracture sealing and fluid overpressures in limestones of the Jabal Akhdar dome,Oman mountains

Fractures are important conduits for fluid flow in the Earth's crust. To better understand the spatial and temporal relations among fracturing, fracture sealing, and fluid flow, we have studied fractures, faults, and veins in a large dome (Jabal Akhdar) in the Oman mountains. Our work combines the results of meso‐ and microstructural analyses and stable isotope analyses. Seven generations of fractures and veins have been identified in the carbonate‐dominated dome. The earliest generations of veins developed during extension and subsidence of the Mesozoic basin. These veins formed in the inclined segments of bedding‐parallel stylolites and in extensional fractures that are perpendicular to bedding (#1 and #2, respectively). These extension‐related veins are truncated by bedding‐parallel veins (#4) that formed during top‐to‐north bedding‐parallel shear of both the northern and southern limbs of the dome. These veins are consistent with a change in stress regime and may be related to an earlier generation of strongly deformed pinch‐and‐swell veins (#3) that are exposed locally on the southern limb of the dome. Normal faults contain a set of en‐echelon tension gashes (#5) and veins emplaced in dilational jogs along the fault planes (#6). In the northern part of the dome, veins (#7) associated with thrusts post‐date the normal faults. Samples of veins and their host rocks were analyzed to provide information on fluid‐rock interaction in the dome and the scale(s) of fluid movement. Oxygen isotope values range from +16.2 to +29.3‰; carbon isotope values range from 0 to +3.6‰. The results of the structural and isotopic analyses are consistent with the early veins (#2–#5) having precipitated from overpressured fluid in a isotopically rock‐buffered system. During normal faulting (#5 and #6), a more open system allowed external fluid to infiltrate the dome at drained conditions and precipitate the youngest sets of veins (#6 and #7).     

Fluid systems and mineralization in the north German and Polish basin

The North European Basin hosts mineral deposits like the Kupferschiefer and the Mississippi Valley Type deposits in the Silesian sub‐basin in Poland. The basement to this basin, exposed in the Harz Mts and in the Flechtingen and Calvörde Blocks, contains Mesozoic Pb–Zn vein mineralization and barite–fluorite deposits as well as massive hematite veins in the Rotliegend volcanics. A comparison of the mineralizing models of these deposits with results from a basin‐wide petrographic, fluid inclusion and stable isotope study shows that the genesis of the mineral deposits can be explained by fluid systems that were active during different stages of basin evolution. These comprise syn‐ to post‐magmatic fluids derived from or mobilized in the course of the Rotliegend magmatism, fluids convecting in the Rotliegend units during the extensional basin subsidence in the Permo‐Triassic and originating from progressive devolatilization of the basin sequence and fluids derived from the overlying Zechstein evaporites. Deep‐reaching fault systems developing during the Cretaceous tectonic reactivation enhanced fluid percolation from the surface to the deep sections of the basin sequence. Identification and correlation of these fluids across the basin and in the mineralizations provide the base for a basin‐wide metallogenetic model.     

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.     

Contrasting paleofluid systems in the continental basement: a fluid inclusion and stable isotope study of hydrothermal vein mineralization,Schwarzwald district,Germany

An integrated fluid inclusion and stable isotope study was carried out on hydrothermal veins (Sb‐bearing quartz veins, metal‐bearing fluorite–barite–quartz veins) from the Schwarzwald district, Germany. A total number of 106 Variscan (quartz veins related to Variscan orogenic processes) and post‐Variscan deposits were studied by microthermometry, Raman spectroscopy, and stable isotope analysis. The fluid inclusions in Variscan quartz veins are of the H₂O–NaCl–(KCl) type, have low salinities (0–10 wt.% eqv. NaCl) and high T_h values (150–350°C). Oxygen isotope data for quartz range from +2.8‰ to +12.2‰ and calculated δ¹⁸O_H2O values of the fluid are between ?12.5‰ and +4.4‰. The δD values of water extracted from fluid inclusions vary between ?49‰ and +4‰. The geological framework, fluid inclusion and stable isotope characteristics of the Variscan veins suggest an origin from regional metamorphic devolatilization processes. By contrast, the fluid inclusions in post‐Variscan fluorite, calcite, barite, quartz, and sphalerite belong to the H₂O–NaCl–CaCl₂ type, have high salinities (22–25 wt.% eqv. NaCl) and lower T_h values of 90–200°C. A low‐salinity fluid (0–15 wt.% eqv. NaCl) was observed in late‐stage fluorite, calcite, and quartz, which was trapped at similar temperatures. The δ¹⁸O values of quartz range between +11.1‰ and +20.9‰, which translates into calculated δ¹⁸O_H2O values between ?11.0‰ and +4.4‰. This range is consistent with δ¹⁸O_H2O values of fluid inclusion water extracted from fluorite (?11.6‰ to +1.1‰). The δD values of directly measured fluid inclusion water range between ?29‰ and ?1‰, ?26‰ and ?15‰, and ?63‰ and +9‰ for fluorite, quartz, and calcite, respectively. Calculations using the fluid inclusion and isotope data point to formation of the fluorite–barite–quartz veins under near‐hydrostatic conditions. The δ¹⁸O_H2O and δD data, particularly the observed wide range in δD, indicate that the mineralization formed through large‐scale mixing of a basement‐derived saline NaCl–CaCl₂ brine with meteoric water. Our comprehensive study provides evidence for two fundamentally different fluid systems in the crystalline basement. The Variscan fluid regime is dominated by fluids generated through metamorphic devolatilization and fluid expulsion driven by compressional nappe tectonics. The onset of post‐Variscan extensional tectonics resulted in replacement of the orogenic fluid regime by fluids which have distinct compositional characteristics and are related to a change in the principal fluid sources and the general fluid flow patterns. This younger system shows remarkably persistent geochemical and isotopic features over a prolonged period of more than 100 Ma.     

On the homogeneity of fluids forming bedding‐parallel veins

A group of 400–500 m long, bedding‐parallel calcite veins are exposed in the central La Popa Basin of northeastern Mexico. These veins provide a unique opportunity to determine the kilometer‐scale fluid–rock system associated with bedding‐parallel vein formation, and to test for sampling bias in studies that often use one or two samples to constrain the characteristics of regional‐scale paleohydrogeological systems. We use fluid inclusion microthermometry in conjunction with measurements of δ¹³C, δ¹⁸O, and ⁸⁷Sr/⁸⁶Sr ratios to constrain the vein‐forming fluid temperatures, compositions and sources, and compare these values along and between the veins to establish the homogeneity of the vein‐forming fluids and fluid–rock system. The δ¹³C values of the veins are close to those of the host rock, and average – 3.96‰ (PDB). The δ¹⁸O values of the veins are typically 1‰ lower than those of the host rocks, and average – 9.54‰ (PDB). Fluid inclusion homogenization temperatures average 137°C and inclusion salinities are all <6 wt% NaCl equivalent. The ⁸⁷Sr/⁸⁶Sr ratios of the veins average 0.70731 and are substantially lower than the values expected for the host rock. Calculated fluid δ¹⁸O values range from 4 to 10‰ (SMOW). The isotopic and microthermometric data indicate the veins most likely formed at depths of 3–4 km when meteoric water mixed with upward migrating, warm basinal brines. Vein microstructures and field characteristics indicate they formed from multiple slip events that most likely were associated with transport of individual fluid pulses that migrated along bedding planes. The large‐scale homogeneity of vein geochemistry is remarkable and demonstrates that only one or two samples would be sufficient to accurately characterize the kilometer‐scale paleohydrogeological system for these veins.     

Role of compressive tectonics on gas charging into the Ordovician sandstone reservoirs in the Sbaa Basin,Algeria: constrained by fluid inclusions and mineralogical data

Structure‐ and tectonic‐related gas migration into Ordovician sandstone reservoirs and its impact on diagenesis history were reconstructed in two gas fields in the Sbaa Basin, in SW Algeria. This was accomplished by petrographical observations, fluid inclusion microthermometry and stable isotope geochemistry on quartz, dickite and carbonate cements and veins. Two successive phases of quartz cementation (CQ1 and CQ2) occurred in the reservoirs. Two phase aqueous inclusions show an increase in temperatures and salinities from the first CQ1 diagenetic phase toward CQ2 in both fields. Microthermometric data on gas inclusions in quartz veins reveal the presence of an average of 92 ± 5 mole% of CH₄ considering a CH₄‐CO₂ system, which is similar to the present‐day gas composition in the reservoirs. The presence of primary methane inclusions in early quartz overgrowths and in quartz and calcite veins suggests that hydrocarbon migration into the reservoir occurred synchronically with early quartz cementation in the sandstones located near the contact with the Silurian gas source rock at 100–140°C during the Late Carboniferous period and the late Hercynian episode fracturing at temperatures between 117 and 185°C, which increased in the NW‐direction of the basin. During the fracture filling, three main types of fluids were identified with different salinities and formation temperatures. A supplementary phase of higher fluid temperature (up to 226°C) recorded in late quartz, and calcite veins is related to a Jurassic thermal event. The occurrence of dickite cements close to the Silurian base near the main fault areas in both fields is mainly correlated with the sandstones where the early gas was charged. It implies that dickite precipitation is related to acidic influx. Late carbonate cements and veins (calcite – siderite – ankerite and strontianite) occurred at the same depths resulting from the same groundwater precipitation. The absence of methane inclusions in calcite cements result from methane flushing by saline waters.     

Fluid evolution along multistage composite fault systems at the southern margin of the Lower Palaeozoic Anglo-Brabant fold belt, Belgium

Mineralised vein systems have been investigated at nine localities at the southern margin of the Anglo‐Brabant fold belt in Belgium. During the late Silurian to early Middle Devonian Caledonian orogeny, shear zones formed, inferred to be associated with granitoid basement blocks in the subsurface. The circulation of a metamorphic fluid, possibly originating in the Cambrian core of the fold belt, along these shear zones resulted in the formation of mesozonal orogenic mineralisation at the southern margin of the Anglo‐Brabant fold belt. The fluid had a composition dominated by H₂O–CO₂–X–NaCl–KCl. The shear zones form part of a greater fault zone, the Nieuwpoort–Asquempont fault zone, which is characterised by normal faulting that started before the Givetian and by the reactivation of the shear zones. Two fluid generations are associated with this normal faulting. First, a low salinity H₂O–NaCl(–KCl) fluid migrated through the Palaeozoic rocks after the Silurian. Based on the isotopic composition, this fluid could be a late‐metamorphic Caledonian fluid or a younger fluid that originated from the Rhenohercynian basin and interacted with Lower Devonian rocks along its migration path. Second, a high salinity H₂O–NaCl–CaCl₂ fluid was identified in the fault systems. Similar fluids have been found in southern and eastern Belgium, where they produced Mississippi Valley‐type Zn–Pb deposits. These fluids are interpreted as evaporative brines that infiltrated the Lower Palaeozoic basement, from where they were expelled during extensional tectonism in the Mesozoic.     

Diagenesis of the Amposta offshore oil reservoir (Amposta Marino C2 well,Lower Cretaceous,Valencia Trough,Spain)

Samples from the Amposta Marino C2 well (Amposta oil field) have been investigated in order to understand the origin of fractures and porosity and to reconstruct the fluid flow history of the basin prior, during and after oil migration. Three main types of fracture systems and four types of calcite cements have been identified. Fracture types A and B are totally filled by calcite cement 1 (CC1) and 2 (CC2), respectively; fracture type A corresponds to pre‐Alpine structures, while type B is attributed to fractures developed during the Alpine compression (late Eocene‐early Oligocene). The oxygen, carbon and strontium isotope compositions of CC2 are close to those of the host‐rock, suggesting a high degree of fluid‐rock interaction, and therefore a relatively closed palaeohydrogeological system. Fracture type C, developed during the Neogene extension and enlarged by subaerial exposure, tend to be filled with reddish (CS3r) and greenish (CS3g) microspar calcite sediment and blocky calcite cement type 4 (CC4), and postdated by kaolinite, pyrite, barite and oil. The CS3 generation records lower oxygen and carbon isotopic compositions and higher ⁸⁷Sr/⁸⁶Sr ratios than the host‐limestones. These CS3 karstic infillings recrystallized early within evolved‐meteoric waters having very little interaction with the host‐rock. Blocky calcite cement type 4 (CC4 generation) has the lowest oxygen isotope ratio and the most radiogenic ⁸⁷Sr/⁸⁶Sr values, indicating low fluid‐rock interaction. The increasingly open palaeohydrogeological system was dominated by migration of hot brines with elevated oxygen isotope ratios into the buried karstic system. The main oil emplacement in the Amposta reservoir occurred after the CC4 event, closely related to the Neogene extensional fractures. Corrosion of CC4 (blocky calcite cement type 4) occurred prior to (or during) petroleum charge, possibly related to kaolinite precipitation from relatively acidic fluids. Barite and pyrite precipitation occurred after this corrosion. The sulphur source associated with the late precipitation of pyrite was likely related to isotopically light sulphur expelled, e.g. as sulphide, from the petroleum source rock (Ascla Fm). Geofluids (2010) 10 , 314–333     

Syntectonic infiltration by meteoric waters along the Sevier thrust front,southwest Montana

Structural, petrographic, and isotopic data for calcite veins and carbonate host‐rocks from the Sevier thrust front of SW Montana record syntectonic infiltration by H₂O‐rich fluids with meteoric oxygen isotope compositions. Multiple generations of calcite veins record protracted fluid flow associated with regional Cretaceous contraction and subsequent Eocene extension. Vein mineralization occurred during single and multiple mineralization events, at times under elevated fluid pressures. Low salinity (T_m = ?0.6°C to +3.6°C, as NaCl equivalent salinities) and low temperature (estimated 50–80°C for Cretaceous veins, 60–80°C for Eocene veins) fluids interacted with wall‐rock carbonates at shallow depths (3–4 km in the Cretaceous, 2–3 km in the Eocene) during deformation. Shear and extensional veins of all ages show significant intra‐ and inter‐vein variation in δ¹⁸O and δ¹³C. Carbonate host‐rocks have a mean δ¹⁸O_V‐SMOW value of +22.2 ± 3‰ (1σ), and both the Cretaceous veins and Eocene veins have δ¹⁸O ranging from values similar to those of the host‐rocks to as low as +5 to +6‰. The variation in vein δ¹³C_V‐PDB of ?1 to approximately +6‰ is attributed to original stratigraphic variation and C isotope exchange with hydrocarbons. Using the estimated temperature ranges for vein formation, fluid (as H₂O) δ¹⁸O calculated from Cretaceous vein compositions for the Tendoy and Four Eyes Canyon thrust sheets are ?18.5 to ?12.5‰. For the Eocene veins within the Four Eyes Canyon thrust sheet, calculated H₂O δ¹⁸O values are ?16.3 to ?13.5‰. Fluid–rock exchange was localized along fractures and was likely coincident with hydrocarbon migration. Paleotemperature determinations and stable isotope data for veins are consistent with the infiltration of the foreland thrust sheets by meteoric waters, throughout both Sevier orogenesis and subsequent orogenic collapse. The cessation of the Sevier orogeny was coincident with an evolving paleogeographic landscape associated with the retreat of the Western Interior Seaway and the emergence of the thrust front and foreland basin. Meteoric waters penetrated the foreland carbonate thrust sheets of the Sevier orogeny utilizing an evolving mesoscopic fracture network, which was kinematically related to regional thrust structures. The uncertainty in the temperature estimates for the Cretaceous and Eocene vein formation prevents a more detailed assessment of the temporal evolution in meteoric water δ¹⁸O related to changing paleogeography. Meteoric water‐influenced δ¹⁸O values calculated here for Cretaceous to Eocene vein‐forming fluids are similar to those previously proposed for surface waters in the Eocene, and those observed for modern‐day precipitation, in this part of the Idaho‐Montana thrust belt.     

Fluid-induced processes: metasomatism and metamorphism

Metamorphism and metasomatism both involve the reequilibration of mineral assemblages due to changes in pressure, temperature and/or chemical environment. Both processes involve material transport but on different length scales, so every metamorphic reaction is metasomatic on a local scale. Fluids provide a transport mechanism which is orders of magnitude faster than solid state diffusion and induce reequilibration through dissolution of parent phases and reprecipitation of products. Chemical weathering (kaolinitization and serpentinization), and albitization are used as examples to describe the coupling between dissolution and precipitation. Albitization of feldspars in nature and in experiments is a pseudomorphic replacement which generates porosity in the albite. Porosity generation associated with interface-coupled dissolution-precipitation allows rapid material transport and together with fluid induced fracturing, is the mechanism of pervasive fluid flow through reacting crystals. Examples of metamorphic reactions in granulite-eclogite rocks illustrate the role of fluids in inducing chemical changes along fluid pathways. Microstructural criteria for a metamorphic event (i.e. change in P , T ) are critically reviewed by describing the corona formed by reaction between kyanite and garnet, as well as partial replacement textures. We conclude that both corona structures and partial replacement textures are equally indicative of a metasomatic reaction (driven by a fluid-induced compositional change) as they may be of a metamorphic reaction driven by a change in P and/or T . This raises the question of the extent to which fluids play not only a catalytic role but also a thermodynamic role in determining the course of a metamorphic reaction.     

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.     

Red calcite: an indicator of paleo‐karst systems associated with bauxitic unconformities

A unique red calcite generation, which fills fractures/cavities, is hosted by Mesozoic carbonates in the Transdanubian Range, Hungary. Solid inclusions are located along growth zones of calcite. Hematite, the most abundant solid inclusion, gives the red colour of it. Outcrop‐scale geometry, mineralogical features and detrital mineral assemblage (hematite, gibbsite, goethite, kaolinite, smectite, illite, Cr‐spinel, monazite, xenotime, zircon, apatite and Ti‐oxide) of calcite precipitates suggest strong correlation between the calcite and nearby karst bauxite deposits. Fluid inclusion petrography and microthermometry (T < 50°C; salinity from 0 to 0.17 NaCl eq. w%) of primary fluid inclusions, and the stable isotope trend of the calcite, following the meteoric water line, clearly indicate vadose and phreatic meteoric origin in a near‐surface karst system. The late Cretaceous to mid‐Eocene unconformity‐related cavity‐filling deposits occur close to the surface; indicating that the most recent Quaternary exhumation re‐exposed those surfaces that existed at the time of calcite mineralization. Thus, red calcite precipitates are interpreted as being speleothems, vestiges of the subterranean part of the pre‐Middle Eocene karst. The infiltrated, fine bauxite particles enclosed by the calcite are the witnesses of the once areally extensive pre‐Middle Eocene bauxitic blanket that became partially eroded by the time of the deposition of the cover beds. Red calcite when found in core samples may provide good evidence on bauxite formation associated with the overlying unconformity, even if it was later removed by erosion. Therefore, presence or absence of red calcite may be used as distinguishing criteria between karst episodes with or without bauxite formation.     

Fracture mineralization and fluid flow evolution: an example from Ordovician–Devonian carbonates,southwestern Ontario,Canada

Petrography, geochemistry (stable and radiogenic isotopes), and fluid inclusion microthermometry of matrix dolomite, fracture‐filling calcite, and saddle dolomite in Ordovician to Devonian carbonates from southwestern Ontario, Canada, provide useful insights into fluid flow evolution during diagenesis. The calculated δ¹⁸O_fluid, ΣREE, and REE_SN patterns of matrix and saddle dolomite suggest diverse fluids were involved in dolomitization and/or recrystallization of dolomite. The ⁸⁷Sr/⁸⁶Sr ratios of dolomite of each succession vary from values in the range of coeval seawater to values more radiogenic than corresponding seawater, which indicate diagenetic fluids were influenced by significant water/rock interaction. High salinities (22.4–26.3 wt. % NaCl + CaCl₂) of Silurian and Ordovician dolomite–hosted fluid inclusions indicate involvement of saline waters from dissolution of Silurian evaporites. High fluid inclusion homogenization temperatures (>100°C) in all samples from Devonian to Ordovician show temperatures higher than maximum burial (60–90°C) of their host strata and suggest involvement of hydrothermal fluids in precipitation and/or recrystallization of dolomite. A thermal anomaly over the mid‐continent rift during Devonian to Mississippian time likely was the source of excess heat in the basin. Thermal buoyancy resulting from this anomaly was the driving force for migration of hydrothermal fluids through regional aquifers from the center of the Michigan Basin toward its margin. The decreasing trend of homogenization temperatures from the basin center toward its margin further supports the interpreted migration of hydrothermal fluids from the basin center toward its margin. Hydrocarbon‐bearing fluid inclusions in late‐stage Devonian to Ordovician calcite cements with high homogenization temperatures (>80°C) and their ¹³C‐depleted values (approaching ?32‰ PDB) indicate the close relationship between hydrothermal fluids and hydrocarbon migration.