Origin of deep saline groundwaters in the Vienne granitic rocks (France): constraints inferred from boron and strontium isotopes

As part of a preliminary geological characterization programme to assess the feasibility of an underground laboratory in granitic rock, a series of 17 deep boreholes (maximum depth, 900 m) was drilled by ANDRA in the Vienne district, France. A salinity gradient was demonstrated in the granitic waters with concentrations varying from approximately 1 g L^?1 at 150 m depth at the top of the basement (beneath the sedimentary cover) to 10 g L^?1 in the deeper part (from 400 to 600 m depth). Sr and B isotope ratios were measured in order to better understand the origin of the salinity and to evaluate the degree of water–rock interaction in the system. The results obtained were compared to those of mineral spring waters emerging from the granitic basement in the Massif Central. Evidence in support of a significant marine contribution include: (i) the Cl–Br investigations agree with a marine origin for the saline groundwaters without evolution from seawater; (ii) the ⁸⁷Sr/⁸⁶Sr ratio of the Vienne deep groundwaters (0.7078–0.7084) is in agreement with a palaeo‐seawater isotopic signature; (iii) measured δ¹¹B values for the deepest brine samples are enriched in ¹¹B (up to 36.1‰) relative to the granitic springs. The combined use of δ¹¹B, Cl, B, Br, Sr contents and ⁸⁷Sr/⁸⁶Sr ratios makes it possible to define and quantify a mixing model between marine and crustal end‐members in order to explain the origin of the deep saline groundwaters in the Vienne granitic rocks.     

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.     

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.     

Geochemistry and origin of natural gases dissolved in brines from gas fields in southwest Japan

Previous geochemical studies indicated that most natural gases dissolved in brines in Japan are of microbial origin, consisting of methane produced via carbonate reduction. However, some of those from gas fields in southwest Japan contain methane relatively enriched in ¹³C, whose origin remains to be clarified. To address this issue, chemical and isotopic analyses were performed on natural gases and brines from the gas fields in Miyazaki and Shizuoka prefectures, southwest Japan. Methane isotopic signatures (δ¹³C ≈ ?68‰ to ?34‰ VPDB; δ²H ≈ ?183‰ to ?149‰ VSMOW) suggest that these gases are of microbial (formed via carbonate reduction) or of mixed microbial and thermogenic origin. The relatively high δ²H‐CH₄ values and their relationship with the δ²H‐H₂O values argue against the possibility of their formation via acetate fermentation. The δ¹³C‐CO₂ values (≈?5‰), together with the slope of the correlation between δ²H‐CH₄ and δ¹³C‐CH₄ (Δδ²H‐CH₄/Δδ¹³C‐CH₄ ≈ 1), contradict the possibility of their formation via carbonate reduction followed by partial oxidation by methanotrophs. The ³He/⁴He ratios of the gases from Miyazaki (≈0.11–1.3 Ra) and their low correlation with δ¹³C‐CH₄ values do not support an abiogenic origin. It is inferred therefore that the high δ¹³C‐CH₄ values of natural gases dissolved in brines from gas fields in southwest Japan are indications of the contribution of thermogenic hydrocarbons, although whether abiogenic hydrocarbons contribute significantly to the gases from Shizuoka requires further investigation. This study has clarified that, for the future exploration of natural gases in southwest Japan, we should adopt the strategies for conventional thermogenic gas accumulations, such as checking the content, type and maturity of organic matter in the underlying sedimentary rocks.     

New and past geochemical data on fresh to brine waters of the Salar de Atacama and Andean Altiplano,northern Chile

The paper deals with the major chemistry and stable isotopes (hydrogen, oxygen, carbon, sulfur, strontium) of waters and solutes from the Salar de Atacama basin (Rio Pedro, Honar Creek and Laguna Chaxa) and Andean Altiplano (Laguna Miñique and Laguna Miscanti). The water inflows of the Salar are chemically quite different, the Rio San Pedro being of Na‐Cl type and the Honar Creek of Na‐HCO₃ type, in keeping with the sedimentary‐evaporitic and volcanic nature of the catchment rocks respectively. The δ³⁴S and δ¹⁸O values of sulfate and the ⁸⁷Sr/⁸⁶Sr ratio of strontium in the streams match those of drained rocks, whereas the δ¹³C values of dissolved carbonate are largely controlled by vegetation. The lagoons are evaporated meteoric water bodies, and the relative air humidity estimated from the slope of the isotopic evaporation line is in accordance with historical data on air humidity in the area. The Laguna Chaxa is Na‐Cl rich, and its isotopic composition are consistent with a mixed sedimentary‐volcanic provenance of sulfur and strontium solutes. The Laguna Miñique is Na‐SO₄ rich, and its sulfate δ³⁴S is nearly identical to that of Laguna Chaxa. The δ¹³C(HCO₃) values are quite different in the Laguna Chaxa and Laguna Miñique, with the former being notably enriched in ¹³C probably because of preferential uptake of ¹²C by the high biological productivity occurring in the lagoon. The limited set of new data is interpreted in the context of a much larger literature database. In particular, previous chemical data on inflows and brines in the Salar de Atacama were revisited, and compared with evaporation path models and mineral stability diagrams (boron, lithium and Mg‐minerals) computed using updated software and thermodynamic databases. The modeling shows that the removal of boron and lithium from sulfate‐rich brines possibly occurs, respectively, as ulexite and sulfate salts, and carnallite should be the final magnesium phase of the brine evolution.     

Geochemical fingerprinting of hydraulic fracturing fluids from Qusaiba Hot Shale and formation water from Paleozoic petroleum systems,Saudi Arabia

Provenance studies of produced water are essential to trace flow dynamics and reservoir compartmentalization in petroleum systems and to quantify fluid recovery rates from unconventional fracturing. Produced water from a hydraulically fractured well in the Qusaiba Hot Shale in the Northern Exploration Area, Saudi Arabia, was daily monitored and analyzed for water chemistry, and environmental (δ²H, δ¹³C, δ¹⁸O_H2O, δ¹⁸O_SO4, δ³⁴S_SO4, δ³⁷Cl, ⁸⁷Sr/⁸⁶Sr) and cosmogenic isotopes (³H, ¹⁴C, ³⁶Cl), to differentiate from reference fluids of supply water, fracturing fluids, and formation water from adjacent Paleozoic units. Initially, recovered water is composed of fracturing fluids and subsequently replaced by a homogeneous cut of pristine formation water. Formation water is composed of dominant meteoric water (approximately 84 vol%) and minor fossil evaporated seawater. The young ¹⁴C‐apparent age between 6000 and 6700 years BP and depleted δ¹⁸O/δ²H values for the meteoric component confirm the infiltration of surface water into the Qusaiba Hot Shale interval or adjacent units during the Early Holocene Pluvial Period under cooler and wetter climatic conditions than present, which suggest the presence of a very recent, dynamic hydraulic flow system. ³⁶Cl/Cl ratios between 102 × 10^?15 and 31 × 10^?15 are ambiguous and can be attributed to atmospheric recharge close to the coast, mixing of ³⁶Cl‐enriched Quaternary meteoric recharge with ³⁶Cl‐depleted fossil seawater, and/or hypogene production by U‐Th‐enriched host rock. Produced waters from Qusaiba Hot Shale are within the compositional range of Na‐Cl‐type formation water from Paleozoic reservoir units in northern Saudi Arabia with salinities from 30 000 to 130 000 mg l^?1. As a novel technological approach for exploration wells in Northern Saudi Arabia, multi‐isotopic methods were successfully implemented to quantify flowback volumes from hydraulic fracturing, and to fingerprint pristine formation water or pore water in Paleozoic systems on their provenance, residence time, migration pathways, and secondary alteration processes.     

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.     

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.     

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.     

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.     

Migration of metamorphic CO2 into a coal seam: a natural analog study to assess the long‐term fate of CO2 in Coal Bed Carbon Capture,Utilization, and Storage Projects

This study assesses the displacement of coalbed methane by CO₂ migration along a fault into the coal seam in the Yaojie coalfield. Coal and gas samples were collected continuously at various distances in NO.2 coal seam from F19 fault. Vitrinite reflectance, maceral, and pore distributions and proximate analysis of fourteen coal samples were performed. Gas components, concentrations, carbon isotopes of 28 gas samples were determined. We examined the coal–gas trace characteristics of coalbed methane displaced away from the fault by CO₂ injection after geological ages. From east to west, away from the F19 fault, the CO₂ concentration decreased, whereas the CH₄ concentration increased gradually. The δ¹³C values for CO₂ varied between ?9.94‰ and 1.12‰, suggesting a metamorphic origin. A wider range of values (from ?9.94‰ to 20‰) was associated with the mixing of microbial carbon dioxide, isotopic fractionation during CO₂ migration through the microporous structures of coals, and/or carbon isotope fractionation during gas–water exchange and dissolution of CO₂. Away from the F19 fault, the volumes of micropores, mesopores and macropores decrease gradually. The Dubinin–Radushkevich (DR) micropore volume decreased from 0.0059 to 0.0037 cm³ g^‐1, and the mesopore and macropore volumes decreased from 0.066 to 0.026 cm³ g^‐1. The CO₂ injection can mobilize aromatic hydrocarbons and mineral matter from coal matrix, resulting in the decrease in the absorption peak intensity for coal samples after supercritical CO₂ treatment, which indicates that chemical reactions occur between coal and CO₂, not only physical adsorption.     

Addressing data comparability in the creation of combined data sets of bioapatite carbon and oxygen isotopic compositions

Before amalgamating published isotope data, comparability should be demonstrated. This paper compares carbon and oxygen isotopic compositions of 30 enamel samples measured by two laboratories. The aims were to see what, if any, isotopic variation was observed, to determine the causes as needed and to correct if possible. Bioapatite was acidified at 90°C in 2006 and at 26°C in 2017, while δ values were corrected via one‐point normalization in 2006 and by two‐point normalization in 2017. One case (of the 30) produced different δ values between the analysis dates, suggesting contamination. Repeated carbon isotope ratio measurements were not meaningfully different. Repeated oxygen isotope ratio measurements were significantly different, even following correction for acid‐carbonate fractionation at different temperatures and the renormalization of 2017 δ values using one point; however, differences were not meaningful for interpretations. Results were used to calculate real interpretative differences (RIDs) for comparing enamel bioapatite as 0.6‰ for δ¹³C values and as 1.6‰ for δ¹⁸O values.     

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.     

OXYGEN AND CARBON ISOTOPE ANALYSIS OF HUMAN TOOTH ENAMEL FROM THE NEW KINGDOM SITE OF TOMBOS IN NUBIA

This study examines the feasibility of using oxygen isotope analysis of tooth carbonate to identify immigrants from the New Kingdom site of Tombos in Nubia (n = 30). In comparison with published data, the results (δ¹⁸O_ca,VSMOW = 31.4‰) imply a substantial presence of immigrants. However, further analysis of these data strongly suggests the need to consider hydrological and cultural factors such as the contribution of aquifer waters to the Nile, use of groundwater sources, and differences in handling and storage of water. The carbon isotope analysis, in conjunction with published ⁸⁷Sr/⁸⁶Sr data, provides additional support for the presence of immigrants at Tombos.     

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

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

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.     

Geochemistry of the Bagnères-de-Bigorre thermal waters from the North Pyrenean Zone (France)

Thermal springs are poorly known in the sedimentary sites of the Pyrenees. In this paper, we describe the ‘Bagnères‐de‐Bigorre’ springs which occur in a remarkably active seismotectonic context. A chemical and isotopic study of 15 spring waters (both cold and thermal, ranging in temperature from 7.0 to 49.9°C), and continuous monitoring of a single spring allow us to characterise water–rock interactions, fluids paths and mixing processes. Three groups of waters are distinguished: (I) SO₄²⁺–Ca²⁺–Cl^– thermal waters (II) SO₄²⁺–Cl^––Ca²⁺ thermal waters and (III) HCO₃^––Ca²⁺ cold shallow waters. Their characteristics suggest interactions with Mesozoic evaporite and carbonate formations. O and D isotopes from thermal waters indicate a local meteoric origin of Atlantic signature and a recharge elevation of 800 to 1000 m, which corresponds to a single feeding area. Their δ¹³C values (?2.8 to ?9.6‰) are consistent with carbonate dissolution, slight fractionation and a surficial organic input leading to δ¹³C depletion. Sr isotopes (0.70751 to 0.70777), Na⁺/Cl^– and (Ca²⁺ + Mg²⁺)/SO₄^2– ratios as well as thermodynamic calculations show that the dissolution of anhydrite and halite‐bearing Triassic layers control the chemical composition of group‐I and ‐II waters. The contrasting trends of cation/Cl^– ratios and TDS of waters from groups I and II suggest the existence of two different circulation paths at depth as well as dilution with surficial waters similar to group III. Calculated mixing proportions show that three waters from group I are diluted from 17 to 66%, whereas all waters from group II are mixed. The aquifer temperature is estimated to be in the range 55–64°C using the retrograde and prograde solubilities of anhydrite and chalcedony, respectively. Accordingly, the mean depth of the reservoir is around 1.7 km, which allows us to constrain the depth of the Triassic layer.     

Iron mineralization and dolomitization in the Paran Fault zone,Israel: implications for low‐temperature basinal fluid processes near the Dead Sea Transform

Petrography, Eh‐pH calculations and the stable isotope composition of oxygen are used to interpret geochemical processes that occurred during iron oxide mineralization and dolomitization along the Menuha Ridge segment of the Paran Fault, southern Israel, adjacent to the Dead Sea Transform (DST). Iron mineralization is strongly localized in the fault zone as ferruginous lenses, whereas Fe dolomitization spreads laterally into the Cenomanian‐Turonian carbonate host rock as stratabound beds. The average oxygen isotope fractionation between syngenetic quartz and iron oxides in the ferruginous lenses gives a temperature of 50 ± 10°C and δ¹⁸O SMOW water = ?3.5‰; consistent with an origin from metalliferous groundwater flow in the sedimentary basin. Ferroan dolomite initially formed under strongly reducing conditions, but this was followed by oxidation and pseudomorphic replacement of the dolomite by a mesh of fine‐grained iron oxides (simple zoned dolomites). This cycle of ferroan dolomite formation and replacement by iron oxides was repeated in complex zoned dolomites. Dolomite oxygen isotope compositions fall into two groups: a high δ¹⁸O group corresponding to the simple zoned dolomites and non‐ferroan dolomites and a low δ¹⁸O group corresponding to the complex zoned dolomites. Water‐rock calculations suggest that the epignetic dolomites formed under fluid‐buffered conditions: the high δ¹⁸O group are indicated to have formed at temperatures of ca. 25°C for waters with δ¹⁸O = ?4 to 0‰; the low δ¹⁸O complex zoned dolomites at 50–75°C for waters with the same isotopic composition. A kinetic calculation for a complex zoned dolomite‐bearing bed indicates that dolomitization must have occurred at high values of the dolomite saturation index. This requirement for high Mg supersaturation and the indication that epigenetic dolomitization is more protracted in stratigraphically deeper formations located closer to the DST is consistent with models proposing that Mg‐rich solutions originated in the Dead Sea Rift.     

Chlorine stable isotope ratios as tracer for pore‐water advection rates in a submarine gas‐hydrate field: implication for hydrate concentration

At Ocean Drilling Program Site 997 in Blake Ridge gas‐hydrate field in West Atlantic, pore‐water studies revealed a pronounced downward depletion of the heavy chlorine isotope to nearly ?4‰δ³⁷Cl at approximately 750 m below sea floor (mbsf) associated with a 10% downward chlorinity decrease. This is one of the stronger ³⁷Cl depletions hitherto reported for marine pore waters. Chlorinity reductions in hydrate‐bearing sediments commonly result from fresh‐water release by hydrate melting. However, in situ measurements at Site 997 suggest that >50% of the chlorinity reduction occurred prior to hydrate dissociation. Modeling the chlorinity profile shows that advection of a strongly ³⁷Cl‐depleted, low‐chlorinity water (506 mm ) from below the drilled sequence can explain the reduction prior to sampling. Fitting the model to the δ³⁷Cl curve yielded an advection rate of 0.18 mm year^?1. Diffusive mixing with near‐0‰‐δ³⁷Cl paleo‐seawater with maximum chlorinity at shallow subsurface depths (561 mm at approximately 20 mbsf) produced the smooth, steady trend. Separating that part of the freshening caused by advection and diffusion from that due to hydrate dissociation allowed estimation of average hydrate concentrations of 3.8% of the pore space (up to 24.5% in hydrate‐rich layers; near‐100% in rare massive hydrate layers). The deep‐seated source of the ³⁷Cl‐depleted, low‐chlorinity water remains unknown and might be located below the sedimentary section in the oceanic basement.     

A comprehensive review of hydrocarbons and genetic model of the sandstone‐hosted Dongsheng uranium deposit,Ordos Basin,China

The Dongsheng uranium deposit, the largest in situ leach uranium mine in the Ordos Basin, geometrically forms a roll‐front type deposit that is hosted in the Middle Jurassic Zhiluo Formation. The genesis of the mineralization, however, has long been a topic of great debate. Regional faults, epigenetic alterations in surface outcrops, natural oil seeps, and experimental findings support a reducing microenvironment during ore genesis. The bulk of the mineralization is coffinite. Based on thin‐section petrography, some of the coffinite is intimately intergrown with authigenic pyrite (ore‐stage pyrite) and is commonly juxtaposed with some late diagenetic sparry calcite (ore‐stage calcite) in primary pores, suggesting simultaneous precipitation. Measured homogenization temperatures of greater than 100°C from fluid inclusions indicate circulation of low‐temperature hydrothermal fluids in the ore zone. The carbon isotopic compositions of late calcite cement (δ¹³C_VPDB = ?31.0 to ?1.4‰) suggest that they were partly derived from sedimentary organic carbon, possibly from deep‐seated petroleum fluids emanating from nearby faults. Hydrogen and oxygen isotope data from kaolinite cement (δD = ?133 to ?116‰ and δ¹⁸O_SMOW = 12.6–13.8‰) indicate that the mineralizing fluids differed from magmatic and metamorphic fluids and were more depleted in D (²H) than modern regional meteoric waters. Such a strongly negative hydrogen isotopic signature suggests that there has been selective modification of δD by CH₄±H₂S±H₂ fluids. Ore‐stage pyrite lies within a very wide range of δ³⁴S (?39.2 to 26.9‰), suggesting that the pyrite has a complex origin and that bacterially mediated sulfate reduction cannot be precluded. Hydrocarbon migration and its role in uranium reduction and precipitation have here been unequivocally defined. Thus, a unifying model for uranium mineralization can be established: Early coupled bacterial uranium mineralization and hydrocarbon oxidation were followed by later recrystallization of ore phases in association with low‐temperature hydrothermal solutions under hydrocarbon‐induced reducing conditions.