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.     

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.     

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 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.     

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.     

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.     

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.     

Fracture-fill calcite as a record of microbial methanogenesis and fluid migration: a case study from the Devonian Antrim Shale, Michigan Basin

The Devonian Antrim Shale is an organic‐rich, naturally fractured black shale in the Michigan Basin that serves as both a source and reservoir for natural gas. A well‐developed network of major, through‐going vertical fractures controls reservoir‐scale permeability in the Antrim Shale. Many fractures are open, but some are partially sealed by calcite cements that retain isotopic evidence of widespread microbial methanogenesis. Fracture filling calcite displays an unusually broad spectrum of δ¹³C values (+34 to ?41‰ PDB), suggesting that both aerobic and anaerobic bacterial processes were active in the reservoir. Calcites with high δ¹³C values (>+15‰) record cementation of fractures from dissolved inorganic carbon (DIC) generated during bacterial methanogenesis. Calcites with low δ¹³C values (13C values between ?10 and ?30‰ can be attributed to variable organic matter oxidation pathways, methane oxidation, and carbonate rock buffering. Identification of ¹³C‐rich calcite provides unambiguous evidence of biogenic methane generation and may be used to identify gas deposits in other sedimentary basins. It is likely that repeated glacial advances and retreats exposed the Antrim Shale at the basin margin, enhanced meteoric recharge into the shallow part of the fractured reservoir, and initiated multiple episodes of bacterial methanogenesis and methanotrophic activity that were recorded in fracture‐fill cements. The δ¹⁸O values in both formation waters and calcite cements increase with depth in the basin (?12 to ?4‰ SMOW, and +21 to +27‰ PDB, respectively). Most fracture‐fill cements from outcrop samples have δ¹³C values between ?41 and ?15‰ PDB. In contrast, most cement in cores have δ¹³C values between +15 and +34‰ PDB. Radiocarbon and ²³⁰Th dating of fracture‐fill calcite indicates that the calcite formed between 33 and 390 ka, well within the Pleistocene Epoch.     

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.     

Source and character of syntaxial hydrothermal calcite veins in Paleoproterozoic crystalline rocks revealed by fine‐scale investigations

Calcite veins in Paleoproterozoic granitoids on the Baltic Shield are the focus of this study. These veins are distinguished by their monomineralic character, unusual thickness and closeness to Neoproterozoic dolerite dykes and therefore have drawn attention. The aim of this study was to define the source of these veins and to unravel their isotopic and chemical nature by carrying out fine‐scale studies. Seven calcite veins covering a depth interval of 50–420 m below the ground surface and composed of breccias or crack‐sealed fillings typically expressing syntaxial growth were sampled and analysed for a variety of physicochemical variables: homogenization temperature (T_h) and salinity of fluid inclusions, and stable isotopes (⁸⁷Sr/⁸⁶Sr, ¹³C/¹²C, ¹⁸O/¹⁶O), trace‐element concentrations (Fe, Mn, Mg, Sr, rare earth elements) and cathodoluminescence (CL) of the solid phase. The fluid‐inclusion data show that the calcites were precipitated mainly from relatively low‐temperature (T_h = 73–106°C) brines (13.4–24.5 wt.% CaCl₂), and the ⁸⁷Sr/⁸⁶Sr is more radiogenic than expected for Rb‐poor minerals precipitated from Neoproterozoic fluids. These features, together with the distribution of δ¹³C and δ¹⁸O values, provide evidence that the calcite veins are not genetic with the nearby Neoproterozoic dolerite dykes, but are of Paleozoic age and were precipitated from warm brines expressing a rather large variability in salinity. Whereas the isotopic and chemical variables express rather constant average values among the individual veins, they vary considerably on fine‐scale across individual veins. This has implications for understanding processes causing calcite‐rich veins to form and capture trace metals in crystalline bedrock settings.     

Fluid mixing induced by hydrothermal activity in the ordovician carbonates in Tarim Basin,China

Permian hydrothermal activity in the Tarim Basin may have been responsible for the invasion of hot brines into Ordovician carbonate reservoirs. Studies have been undertaken to explain the origin and geochemical characteristics of the diagenetic fluid present during this hydrothermal event although there is no consensus on it. We present a genetic model resulting from the study of δ¹³C, δ¹⁸O, δ³⁴S, and ⁸⁷Sr/⁸⁶Sr isotope values and fluid inclusions (FIs) from fracture‐ and vug‐filling calcite, saddle dolomite, fluorite, barite, quartz, and anhydrite from Ordovician outcrops in northwest (NW) Tarim Basin and subsurface cores in Central Tarim Basin. The presence of hydrothermal fluid was confirmed by minerals with fluid inclusion homogenization temperatures being >10°C higher than the paleo‐formation burial temperatures both in the NW Tarim and in the Central Tarim areas. The mixing of hot (>200°C), high‐salinity (>24 wt% NaCl), ⁸⁷Sr‐rich (up to 0.7104) hydrothermal fluid with cool (60–100°C), low‐salinity (0 to 3.5 wt% NaCl), also ⁸⁷Sr‐rich (up to 0.7010) meteoric water in the Ordovician unit was supported by the salinity of fluid inclusions, and δ¹³C, δ¹⁸O, and ⁸⁷Sr/⁸⁶Sr isotopic values of the diagenetic minerals. Up‐migrated hydrothermal fluids from the deeper Cambrian strata may have contributed to the hot brine with high sulfate concentrations which promoted thermochemical sulfate reduction (TSR) in the Ordovician, resulting in the formation of ¹²C‐rich (δ¹³C as low as ?13.8‰) calcite and ³⁴S‐rich (δ³⁴S values from 21.4‰ to 29.7‰) H₂S, pyrite, and elemental sulfur. Hydrothermal fluid mixing with fresh water in Ordovician strata in Tarim Basin was facilitated by deep‐seated faults and up‐reaching faults due to the pervasive Permian magmatic activity. Collectively, fluid mixing, hydrothermal dolomitization, TSR, and faulting may have locally dissolved the host carbonates and increased the reservoir porosity and permeability, which has significant implications for hydrocarbon exploration.     

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.     

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.     

Fluid inclusion and isotopic constraints on the origin of ore‐forming fluid of the Jinman–Liancheng vein Cu deposit in the Lanping Basin,western Yunnan,China

Extensive quartz–carbonate–Cu sulfide veins occur in clastic rocks and are spatially related to Paleocene granites in the western border of the Lanping Basin, western Yunnan, China. Abundant aqueous‐carbonic fluid inclusions occur in these veins but their origin is debated. In the Jinman–Liancheng deposit, individual primary inclusion groups contain either exclusively liquid‐rich inclusions (Gl), or coexisting liquid‐rich and vapor‐rich inclusions (Glv). Microthermometry and estimate of CO₂ content indicate that type Gl inclusions either have homogenization temperatures (Th) 238–263°C and contain c. 3.9–5.5 mole % CO₂, or have Th 178–222°C and contain c. 1.6–3.2 mole % CO₂. Type Glv inclusions are thought to represent samples of fluid unmixing that occurred at 183–218°C. At that time, the liquid phase in the unmixing fluid may contain c. 2.0–3.3 mole % CO₂. As such, the correlation of CO₂ content with Th for type Gl inclusions is thought to be caused by fluid unmixing with decreasing temperature and subsequent CO₂ escape. δ¹⁸O and δD values of the parent water mainly fall in the field below that of primary magmatic water, indicative of fluid derivation from degassed (in open system) magmatic water, with no contributions from basinal or meteoric water. Initial Sr isotopic compositions of hydrothermal carbonates suggest that the fluid was magmatic, probably derived from the Paleogene granites. δ¹³C_PDB values (?4‰ to ?7‰) of the hydrothermal carbonates and δ³⁴S_V‐CDT values of sulfides (mainly ?11‰ to +5‰) indicate that the carbon and sulfur can be derived from (degassed) magma and/or nonmagmatic sources. The CO₂‐rich and magmatic‐water‐derived fluid at Jinman–Liancheng differs from the CO₂‐poor and basinally derived fluid in sediment‐hosted stratiform Cu (SSC) deposits, which suggests that there are no genetic linkages between the vein Cu and SSC deposits in the Lanping Basin.     

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.     

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.     

Ancient hydrocarbon seeps from the Mesozoic convergent margin of California: carbonate geochemistry, fluids and palaeoenvironments

More than a dozen hydrocarbon seep‐carbonate occurrences in late Jurassic to late Cretaceous forearc and accretionary prism strata, western California, accumulated in turbidite/fault‐hosted or serpentine diapir‐related settings. Three sites, Paskenta, Cold Fork of Cottonwood Creek and Wilbur Springs, were analyzed for their petrographic, geochemical and palaeoecological attributes, and each showed a three‐stage development that recorded the evolution of fluids through reducing–oxidizing–reducing conditions. The first stage constituted diffusive, reduced fluid seepage (CH₄, H₂S) through seafloor sediments, as indicated by Fe‐rich detrital micrite, corroded surfaces encrusted with framboidal pyrite, anhedral yellow calcite and negative cement stable isotopic signatures (δ¹³C as low as ?35.5‰ PDB; δ¹⁸O as low as ?10.8‰ PDB). Mega‐invertebrates, adapted to reduced conditions and/or bacterial chemosymbiosis, colonized the sites during this earliest period of fluid seepage. A second, early stage of centralized venting at the seafloor followed, which was coincident with hydrocarbon migration, as evidenced by nonluminescent fibrous cements with δ¹³C values as low as ?43.7‰ PDB, elevated δ¹⁸O (up to +2.3‰ PDB), petroleum inclusions, marine borings and lack of pyrite. Throughout these early phases of hydrocarbon seepage, microbial sediments were preserved as layered and clotted, nondetrital micrites. A final late‐stage of development marked a return to reducing conditions during burial diagenesis, as implied by pore‐associated Mn‐rich cement phases with bright cathodoluminescent patterns, and negative δ¹⁸O signatures (as low as ?14‰ PDB). These recurring patterns among sites highlight similarities in the hydrogeological evolution of the Mesozoic convergent margin of California, which influenced local geochemical conditions and organism responses. A comparison of stable carbon and oxygen isotopic data for 33 globally distributed seep‐carbonates, ranging in age from Devonian to Recent, delineated three groupings that reflect variable fluid input, different tectono‐sedimentary regimes and time–temperature‐dependent burial diagenesis.     

Thermochemical and bacterial sulfate reduction in the Cambrian and Lower Ordovician carbonates in the Tazhong Area,Tarim Basin,NW China: evidence from fluid inclusions,C, S,and Sr isotopic data

Petrographic features, C, O, S, and Sr isotopes were determined, and fluid inclusions (FI) were analyzed on various stages of vug‐ and fracture‐fillings from the Cambrian and Lower Ordovician reservoirs in the Tazhong area, Tarim basin, NW China. The aim was to assess the origin of pyrite and anhydrite and the processes affecting sulfur during diagenesis of the carbonates. Pyrite from seven wells has δ³⁴S values from ?22‰ to +31‰. The pyrites with low δ³⁴S values from ?21.8‰ to ?12.3‰ were found close to fracture‐filling calcites with vapor‐liquid double‐phase aqueous fluid inclusions homogenization temperatures (FI‐Th) from 55.7 to 73.2°C, salinities from 1.4wt% to 6.59wt% NaCl equiv and δ¹³C values from ?2.3‰ to ?14.2‰, indicating an origin from bacterial sulfate reduction by organic matter. Other sulfides with heavier δ³⁴S values may have formed by thermochemical sulfate reduction (TSR) during two episodes. The earlier TSR in the Middle and Lower Cambrian resulted in pyrites and H₂S having δ³⁴S values from 30 to 33‰, close to those of bedded anhydrite and oilfield water (approximately 34‰). The later TSR is represented by calcites with δ¹³C values as light as ?17.7‰ and FI‐Th of about 120–145°C, and pyrite and H₂S with δ³⁴S values close to those of the Upper Cambrian burial‐diagenetic anhydrite (between +14.8‰ and +22.6‰). The values of the anhydrite are significantly lighter than contemporary seawater sulfates. This together with ⁸⁷Sr/⁸⁶Sr values of anhydrite and TSR calcites from 0.7091 to 0.7125 suggests a source from the underlying Ediacaran seawater sulfate and detrital Sr contribution.     

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.     

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.