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.     

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.     

Retrograde P–T evolution and high temperature–low pressure fluid circulation in relation to late Hercynian intrusions: a mineralogical and fluid inclusion study of the Charroux-Civray plutonic complex (north-western Massif Central, France)

The calc‐alkaline plutonic complex from Charroux‐Civray (north‐western part of the French Massif Central) displays multiphase hydrothermal alteration. Plutonic rocks, as well as early retrograde Ca–Al silicate assemblages, which have crystallized during cooling and uplifting of the plutonic series, are affected by multiphase chlorite–phengite–illite–carbonate alteration linked to intense pervasive fluid circulation through microfractures. The petrographic study of alteration sequences and their associated fluid inclusions in microfissures of the plutonic rocks, as well as in mineral fillings of the veins, yields a reconstruction of the P–T–X evolution of the Hercynian basement after the crystallization of the main calc‐alkaline plutonic bodies. This reconstruction covers the uplift of the basement to its exposure and the subsequent burial by Mesozoic sediments. Cooling of the calc‐alkaline plutonic series started at solidus temperatures (～650°C), at a pressure of about 4 kbar (1 bar = 10⁵ N m^?2), as indicated by magmatic epidote stability, hornblende barometry and fluid inclusion data. Cooling continued under slightly decreasing pressure during uplift down to 2–3 kbar at 200–280°C (prehnite–pumpellyite paragenesis). Then, a hot geothermal circulation of CO₂‐bearing fluids was induced within the calc‐alkaline rocks leading to the formation of greisen‐like mineralizations. During this stage, temperatures around 400–450°C were still high for the inferred depths (～2 kbar). They imply abnormal heat flows and thermal gradients of 60–80°C km^?1. The hypothesis of the existence of one large or a succession of smaller peraluminous plutons at depth, supported by geophysical data, suggests that localized heat flows were linked to concealed leucogranite intrusions. As uplift continued, greisen mineralization was subsequently affected by the chlorite–phengite–dolomite assemblage, correlated with aqueous and nitrogen‐bearing fluid circulations in the temperature range of 400–450°C. In a later stage, a continuous temperature decrease at constant pressure (～0.5 kbar) led to the alteration of the dolomite–illite–chlorite type in the 130–250°C temperature range.     

Petroleum infiltration of high-grade basement, South Norway: Pressure-Temperature-time-composition (P–T–t–X) constraints

Fluid inclusion data provide pressure–temperature–time–composition (P–T–t–X) constraints for an episode of petroleum infiltration of the crystalline basement in South Norway. Petroleum inclusions associated with pyrobitumen occur in postmetamorphic quartz veins in the Modum Complex. Three groups of fluid compositions have been shown, ranging from CH₄ ± CO₂ to condensates with alkanes up to C₁₅. The range in fluid composition is a result of petroleum decomposition at high temperature. Globular and massive pyrobitumen occurs in the quartz veins or in associated vein systems. Reflectance (%Rm) measurements of 3.20–3.35 correspond to a maximum temperature of 207–214°C for the pyrobitumen associated with group II and III inclusions. Geothermometry of chlorites included in the quartz show results of 226–231°C. Pressure conditions of trapping for all three groups of inclusion fluids have been estimated to 520–985 bar at 220°C. The pressure range is probably a result of fluctuations caused by repeated fracture opening and sealing due to seismic activity coupled with mineral growth. A lack of systematic textural relationships between the three groups of inclusions and similar pressure–temperature estimates for all fluid types indicate trapping at similar times and a process of rapid change. Fluid migration in fractures from an overlying, overpressured sedimentary basin into a dry, crystalline basement best explains the observed P–T–t–X constraints.     

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.     

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.     

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.     

The link between fluids and rank variation in the South Wales Coalfield: evidence from fluid inclusions and stable isotopes

Fluid inclusion and stable isotope data from quartz and carbonate minerals in fracture fillings and ‘ironstone’ nodules from the South Wales Coalfield have been used to characterise the fluids generated during basin evolution and associated coalification. Carbonates grew first, probably at relatively shallow depths and low temperatures (<100°C). The carbonates exhibit a trend of increasing C‐isotopic values across the coalfield, ranging from δ¹³C = ?12‰ VPDB in the SE of the coalfield to 0‰ VPDB in the NW, possibly as a result of increasing methanogenesis in the deeper (NW) parts of the coalfield. Quartz formed at a later stage of basin formation, probably at temperatures between 150 and 200°C. Fluid inclusions in these minerals suggest that burial and coalification of the sediments were associated with mixed aqueous–petroleum fluids. Furthermore, the density of these petroleum fluids decreases towards the NW of the coalfield, where the rank of the associated coal increases to anthracite grade. The study confirms that the composition and temperature of these fluids closely correlate with the variations in coal rank, indicating a possible causal link. The data also give general support to models that propose regional fluid flow in the basin. and are consistent with the erosion of approximately 2 km of section which is not preserved today. A geothermal gradient (at maximum burial) of 45°C km^?1 is proposed, and thus no exceptionally anomalous thermal regime is required to explain coal rank variation.     

Long‐term chemical evolution and modification of continental basement brines – a field study from the Schwarzwald,SW Germany

Highly saline, deep‐seated basement brines are of major importance for ore‐forming processes, but their genesis is controversial. Based on studies of fluid inclusions from hydrothermal veins of various ages, we reconstruct the temporal evolution of continental basement fluids from the Variscan Schwarzwald (Germany). During the Carboniferous (vein type i), quartz–tourmaline veins precipitated from low‐salinity (<4.5wt% NaCl + CaCl₂), high‐temperature (≤390°C) H₂O‐NaCl‐(CO₂‐CH₄) fluids with Cl/Br mass ratios = 50–146. In the Permian (vein type ii), cooling of H₂O‐NaCl‐(KCl‐CaCl₂) metamorphic fluids (T ≤ 310°C, 2–4.5wt% NaCl + CaCl₂, Cl/Br mass ratios = 90) leads to the precipitation of quartz‐Sb‐Au veins. Around the Triassic–Jurassic boundary (vein type iii), quartz–haematite veins formed from two distinct fluids: a low‐salinity fluid (similar to (ii)) and a high‐salinity fluid (T = 100–320°C, >20wt% NaCl + CaCl₂, Cl/Br mass ratios = 60–110). Both fluids types were present during vein formation but did not mix with each other (because of hydrogeological reasons). Jurassic–Cretaceous veins (vein type iv) record fluid mixing between an older bittern brine (Cl/Br mass ratios ~80) and a younger halite dissolution brine (Cl/Br mass ratios >1000) of similar salinity, resulting in a mixed H₂O‐NaCl‐CaCl₂ brine (50–140°C, 23–26wt% NaCl + CaCl₂, Cl/Br mass ratios = 80–520). During post‐Cretaceous times (vein type v), the opening of the Upper Rhine Graben and the concomitant juxtaposition of various aquifers, which enabled mixing of high‐ and low‐salinity fluids and resulted in vein formation (multicomponent fluid H₂O‐NaCl‐CaCl₂‐(SO₄‐HCO₃), 70–190°C, 5–25wt% NaCl‐CaCl₂ and Cl/Br mass ratios = 2–140). The first occurrence of highly saline brines is recorded in veins that formed shortly after deposition of halite in the Muschelkalk Ocean above the basement, suggesting an external source of the brine's salinity. Hence, today's brines in the European basement probably developed from inherited evaporitic bittern brines. These were afterwards extensively modified by fluid–rock interaction on their migration paths through the crystalline basement and later by mixing with younger meteoric fluids and halite dissolution brines.     

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

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

Fluid circulation related to post‐Messinian extension,Thassos Island,North Aegean

In the North Aegean Domain, Thassos Island contains a Plio‐Pleistocene basin controlled by a large‐scale flat‐ramp extensional system with a potential décollement located at depth within a marble unit. Numerous mineralizations associated with normal faults of Plio‐Pleistocene age are the sign of fluid circulation during extension. Two main generations of fluid flow are recognized, related to Plio‐Pleistocene extension. A first circulation under high‐temperature conditions (about 100–200°C) resulted in dolomitization of marbles near the base of the Plio‐Pleistocene basin. The dolomites are characterized by low δ¹⁸O values (down to 11‰ versus Standard Mean Ocean Water). Some cataclastic deformation affected the dolomites. Hydrothermal quartz that crystallized in extension veins above a blind ramp also has low δ¹⁸O values (about 13‰). This shows that high‐temperature fluids moved up from the décollement level toward the surface. A second downward circulation of continental waters at near‐surface temperature is documented by calcite veins in fault zones and at the base of the Plio‐Pleistocene basin. These veins have O isotope values relatively constant at about 23–25‰ and C isotope values intermediate between the high δ¹³C value of the carbonate host rock (about 1–3‰ versus Peedee Belemnite) and the low δ¹³C value of soil‐derived carbon (?10‰). The calcites associated with the oxidative remobilization of primary sulphide Zn–Pb mineralization of Thassos carbonates have comparable O and C isotope compositions. Hot fluids, within the 100–200°C temperature range, have likely contributed to the weakening of the lower marble unit of Thassos and, thus, to the process of décollement.     

Sources and composition of fluids associated with fluorite deposits of Asturias (N Spain)

The fluorite deposits of Asturias (northern Iberian Peninsula) are hosted by rocks of Permo‐Triassic and Palaeozoic age. Fluid inclusions in ore and gangue minerals show homogenization temperatures from 80 to 170°C and the presence of two types of fluids: an H₂O–NaCl low‐salinity fluid (<8 eq. wt% NaCl) and an H₂O–NaCl–CaCl₂ fluid (7–13 wt% NaCl and 11–14 wt% CaCl₂). The low salinity and the Cl/Br and Na/Br ratios (Cl/Br_molar 100–700 and Na/Br_molar 20–700) are consistent with an evaporated sea water origin of this fluid. The other end‐member of the mixture was highly saline brine with high Cl/Br and Na/Br ratios (Cl/Br_molar 700–13 000 and Na/Br_molar 700–11 000) generated after dissolution of Triassic age evaporites. LA‐ICP‐MS analyses of fluid inclusions in fluorite reveal higher Zn, Pb and Ba contents in the high‐salinity fluids (160–500, 90–170, 320–480 p.p.m. respectively) than in the low‐salinity fluid (75–230, 25–150 and 100–300 p.p.m. respectively). The metal content of the fluids appears to decrease from E to W, from Berbes to La Collada and to Villabona. The source of F is probably related to leaching of volcanic rocks of Permian age. Brines circulated along faults into the Palaeozoic basement. Evaporated sea water was present in permeable rocks and faults along or above the unconformity between the Permo‐Triassic sediments and the Palaeozoic basement. Mineralization formed when the deep brines mixed with the surficial fluids in carbonates, breccias and fractures resulting in the formation of veins and stratabound bodies of fluorite, barite, calcite, dolomite and quartz and minor amounts of sulphides. Fluid movement and mineralization occurred between Late Triassic and Late Jurassic times, probably associated with rifting events related to the opening of the Atlantic Ocean. This model is also consistent with the geodynamic setting of other fluorite‐rich districts in Europe.     

Pyrophyllite formation in the thermal aureole of a hydrothermal system in the Lower Saxony Basin,Germany

A combined clay mineralogical, fluid inclusion, and K‐Ar study of Upper Jurassic metasediments at the Gehn (Lower Saxony Basin, Germany) provides evidence for a transient hydrothermal event during Upper Cretaceous basin inversion centered on a prominent gravimetric anomaly. Kaolinite and smectite in Oxfordian pelitic parent rocks that cap a deltaic sandstone unit were locally transformed into pyrophyllite, 2M₁ illite, R3 illite–smectite, chlorite, and berthierine at the Ueffeln quarry. The pyrophyllite‐bearing metapelites lack bedding‐parallel preferred orientation of sheet silicates and experienced peak temperatures of about 260–270°C consistent with microthermometric data on quartz veins in the underlying silicified sandstones. The presence of expandable layers in illite–smectite and high Kübler Index values indicate that the thermal event was rather short‐lived. K‐Ar dating of the <0.2 μm fraction of the pyrophyllite‐bearing Ueffeln metapelite yields a maximum illitization age of 117 ± 2 Ma. Lower trapping temperatures of aqueous fluid inclusions in quartz veins and the absence of pyrophyllite in metapelites of the Frettberg quarry in a distance of about 2.5 km from the Ueffeln quarry infer maximum paleotemperatures of only 220°C. The highly localized thermal anomaly at Ueffeln suggests fault‐controlled fluid migration and heat transfer that provided a thermal aureole for pyrophyllite formation in the metapelites rather than metamorphism due to deep burial. A pH neutral hydrothermal fluid that formed by devolatilization reactions or less likely by mixing of meteoric and marine waters that interacted at depth with shales is indicated by the low salinity (3–5 wt. % NaCl equiv.) of aqueous inclusions, their coexistence with methane–carbon dioxide‐dominated gas inclusions as well as carbon, hydrogen, and oxygen isotope data. The upwelling zone of hydrothermal fluids and the thermal maximum is centered on a gravimetric anomaly interpreted as an igneous intrusion (‘Bramsche Massif’) providing the heat source for the intrabasinal hydrothermal system.     

Re‐equilibration of fluid inclusions in diagenetic‐anchizonal rocks of the Ciñera‐Matallana coal basin (NW Spain)

Thermally re‐equilibrated fluid inclusions are reported in natural fissure quartz (qtz1) from polymineralic veins in the diagenetic‐anchizonal clastic sedimentary rocks of the Ciñera‐Matallana coal basin (Variscan, NW Spain). Euhedral quartz formed during early fissure opening from an immiscible fluid mixture composed of a low salinity aqueous solution and a CH₄‐rich vapour phase, at temperatures of about 110–120°C and pressures ranging from 15 to 56 MPa. Five textural types of re‐equilibration are recognised in progressive order of inclusion modification: scalloped, hairy, annular‐ring shaped, haloes and decrepitation clusters. These textures resulted from a combination of brittle fracturing and dissolution and re‐precipitation of quartz, with preferential loss of water. The thermal peak was short‐lived, but was high enough to induce extensive decrepitation of fluid inclusions in vein quartz throughout the entire basin. Enhanced temperatures can be related to the intrusion of diorites in the basin. Careful analysis of textural features in fluid inclusions from diagenetic and very low‐grade metamorphism environments constitutes a useful tool for recording basin thermal history.     

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.     

Reconstruction of palaeo-burial history and pore fluid pressure in foothill areas: a sensitivity test in the Hammam Zriba (Tunisia) and Koh-i-Maran (Pakistan) ore deposits

The burial and pore fluid pressure history of fluorite ore deposits is reconstructed: (i) at Hammam Zriba–Djebel Guebli along the eastern margin of the Tunisian Atlas; and (ii) at Koh‐i‐Maran within the northern part of the Kirthar Range in Pakistan. Both the deposits are hosted by Late Jurassic carbonate reservoirs, unconformably overlain by Late Cretaceous seals. Microthermometric analyses on aqueous and petroleum fluid inclusions with pressure–volume–temperature–composition (PVTX) modeling of hydrocarbon fluid isochores are integrated with kinematics and thermal 2D basin modeling in order to determine the age of mineralization. The results suggest a Cenozoic age for the fluorite mineralization and a dual fluid migration model for both ore deposits. The PVTX modeling indicates that the initial stage of fluorite cementation at Hammam Zriba occurred under fluid pressures of 115 ± 5 bars and at a temperature close to 130°C. At Koh‐i‐Maran, the F3 geodic fluorite mineralization developed under hydrostatic pressures of 200 ± 10 bars, and at temperatures of 125–130°C. The late increase in temperature recorded in the F3 fluorites can be accounted for by rapid rise of hotter fluids (up to 190°C) along open fractures, resulting from hydraulic fracturing of overpressured sedimentary layers.     

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.     

Fluids and halogens at the diagenetic–metamorphic boundary: evidence from veins in continental basins, western Norway

Seven vein types are recognized in three continental Devonian molasse basins (the Hornelen, Kvamshesten and Solund basins) in western Norway. These include calcite‐, quartz‐ and epidote‐dominated veins. The salinities of fluid inclusions from quartz‐dominated veins in the Hornelen and Kvamshesten basins are close to or slightly higher than those for modern seawater, whereas the fluids from quartz‐ and calcite‐dominated veins in the Solund basin range from seawater values to 20 wt % NaCl equivalent. Minerals such as biotite, amphibole, titanite, chlorite and epidote are abundant in the latter veins, and are important constituents of the authigenic mineral assemblages. A combination of fluid inclusion and petrological data suggest that at least some of the veins formed at depths around 12–14 km. The Cl/Br ratios and the salinity of the fluid inclusions can be explained by interactions with evaporites, implying that the sedimentary environment forming the basin fill had the strongest influence upon low‐grade metamorphic fluid Cl and Br contents. Differences in the Cl/I and Na/Br ratios between the Solund basin and the Hornelen and Kvamshesten basins are best explained by local mass transfer between pore fluids and the surrounding rock matrix during burial and increasing temperatures.     

Palaeo‐formation water evolution in the Latrobe aquifer,Gippsland Basin,south‐eastern Australia continental shelf

Offshore fresh or brackish groundwater has been observed around the globe and represents an interesting but unusual freshwater reserve. Formation waters in sedimentary basins evolve at geological time through fluid–rock interactions and water movements in aquifers. However, the mechanism and timing of freshwater displacing and mixing with pre‐existing formation water offshore under the seafloor has not been investigated in many cases. The growing need for developing freshwater resources in deeper parts of sedimentary basins that have not been economic or technically feasible in the past, may potentially lead to an increasing conflict with petroleum production or injection of carbon dioxide. For being able to assess and mitigate possible impacts of fluid production or injection on groundwater flow and quality, a better understanding of the natural history of the interaction between fresh meteoric water and deep basin formation water is necessary. A low‐salinity wedge of meteoric origin with less than 5000 ppm currently extends to about 20 km offshore in the confined Latrobe aquifer in the Gippsland Basin (Australia). The Latrobe aquifer is a freshwater resource in the onshore, hosts major petroleum reservoirs and has been considered for carbon dioxide storage in the offshore parts of the basin. The objective of this study is to constrain the evolution of formation water in the Latrobe aquifer by investigating the water naturally trapped in fluid inclusions during burial. The measured palaeo‐salinities from onshore and offshore rock samples have a minimum of about 12 500 ppm (NaCl equivalent) and a maximum of about 50 000 ppm. Most of the salinities are in the 32 000–35 000 ppm range. There is no evidence for freshwater in fluid inclusions and the variation in palaeo‐salinity across the basin is consistent with the palaeogeography of deposition of the sedimentary rocks. The current low‐salinity water wedge must have started to form recently after most of the diagenetic processes that led to the trapping of water in fluid inclusions happened. The minimum homogenisation temperatures (T_h) recorded are consistent with current formation temperature. However, they are generally higher than present day suggesting that hotter temperatures were attained in the past. The T_h and salinity data together suggest that the fluid inclusions record the diagenetic modification of connate water to higher salinities over a time period that was accompanied by an increase in temperature, consistent with a westward palaeo‐fluid flow from the deeper part of the basin through the aquifer. Subsequent pore‐water evolution from palaeo‐ to current day conditions is consistent with an influx of fresher and cooler meteoric water into the Latrobe Group. The meteoric recharge originates from the area of the Baragwanath anticline in the onshore part of the basin where the Latrobe Group subcrops at high elevations.     

Origin of palaeo‐waters in the Ordovician carbonates in Tahe oilfield,Tarim Basin: constraints from fluid inclusions and Sr,C and O isotopes

Petrographic features, isotopes, and trace elements were determined, and fluid inclusions were analyzed on fracture‐filling, karst‐filling and interparticle calcite cement from the Ordovician carbonates in Tahe oilfield, Tarim basin, NW China. The aim was to assess the origin and evolution of palaeo‐waters in the carbonates. The initial water was seawater diluted by meteoric water, as indicated by bright cathodoluminescence (CL) in low‐temperature calcite. The palaeoseawater was further buried to temperatures from 57 to 110°C, nonluminescent calcite precipitated during the Silurian to middle Devonian. Infiltration of meteoric water of late Devonian age into the carbonate rocks was recorded in the first generation of fracture‐ and karst‐filling dull red CL calcite with temperatures from <50°C to 83°C, low salinities (<9.0 wt%), high Mn contents and high ⁸⁶Sr/⁸⁷Sr ratios from 0.7090 to 0.7099. During the early Permian, ⁸⁷Sr‐rich hydrothermal water may have entered the carbonate rocks, from which precipitated a second generation of fracture‐filling and interparticle calcite and barite cements with salinities greater than 22.4 wt%, and temperatures from 120°C to 180°C. The hydrothermal water may have collected isotopically light CO₂ (possibly of TSR‐origin) during upward migration, resulting in hydrothermal calcite and the present‐day oilfield water having δ¹³C values from ?4.3 to ?13.8‰ and showing negative relationships of ⁸⁷Sr/⁸⁶Sr ratios to δ¹³C and δ¹⁸O values. However, higher temperatures (up to 187°C) and much lower salinities (down to 0.5 wt%) measured from some karst‐filling, giant, nonluminescent calcite crystals may suggest that hydrothermal water was deeply recycled, reduced (Fe‐bearing) meteoric water heated in deeper strata, or water generated from TSR during hydrothermal water activity. Mixing of hydrothermal and local basinal water (or diagenetically altered connate water) with meteoric waters of late Permian age and/or later may have resulted in large variations in salinity of the present oilfield waters with the lowest salinity formation waters in the palaeohighs.