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.     

Precipitation of fracture fillings and cements in the Buntsandstein (NW Germany)

The relationship between fracturing and fracture filling in opening‐mode fractures in the Triassic Buntsandstein in the Lower Saxony Basin (LSB; NW Germany) has been studied by an integration of petrographic and structural analysis of core samples, strontium isotope analysis and microthermometry on fluid inclusions. This revealed the relationship between the timing of the fracturing and the precipitation of different mineral phases in the fractures by constraining the precipitation conditions and considering the possible fluid transport mechanisms. The core was studied from four different boreholes, located in different structural settings across the LSB. In the core samples from the four boreholes, fractures filled with calcite, quartz and anhydrite were found, in addition to pore‐filling calcite cementation. In boreholes 2 and 3, calcite‐filled fractures have a fibrous microstructure whereas in borehole 1, fractures are filled with elongate‐blocky calcite crystals. Anhydrite‐filled fractures have, in all samples, a blocky to elongate‐blocky microstructure. Fractures that are filled with quartz are observed in borehole 2 only where the quartz crystals are ‘stretched’ with an elongated habit. Fluid inclusion microthermometry of fracturing‐filling quartz crystals showed that quartz precipitation took place at temperatures of at least 140°C, from a fluid with NaCl–CaCl₂–H₂O composition. Melting phases are meta‐stable and suggest growth from high salinity formation water. Strontium isotopes, measured in leached host rock, indicate that, in boreholes 2 and 3, the fluid which precipitated the calcite cements and calcite‐filled fractures is most likely locally derived whereas in borehole 1, the ⁸⁷Sr/⁸⁶Sr ratios from the pore‐filling cements and in the elongate‐blocky calcite‐filled fracture can only be explained by mixing with externally derived fluids. The elongate‐blocky anhydrite‐filled fractures, present in boreholes 1, 3 and 4, precipitated from a mixture of locally derived pore fluids and a significant quantity of fluid with a lower, less radiogenic, ⁸⁷Sr/⁸⁶Sr ratio. Taking into account the structural evolution of the basin and accompanying salt tectonics, it is likely that the underlying Zechstein is a source for the less radiogenic fluids. Based on the samples in the LSB, it is probable that fibrous fracture fillings in sedimentary rocks most likely developed from locally derived pore fluids whereas elongate‐blocky fracture fillings with smooth walls developed from externally derived pore fluids.     

Chemical and isotopic signatures of Na/HCO3/CO2‐rich geofluids,North Portugal

Geochemical and isotopic studies have been undertaken to assess the origin of CO₂‐rich waters issuing in the northern part of Portugal. These solutions are hot (76°C) to cold (17°C) Na–HCO₃ mineral waters. The δ²H and δ¹⁸O signatures of the mineral waters reflect the influence of altitude on meteoric recharge. The lack of an ¹⁸O‐shift indicates there has been no high temperature water–rock interaction at depth, corroborating the results of several chemical geothermometers (reservoir temperature of about 120°C). The low ¹⁴C activity (up to 9.9 pmC) measured in some of the cold CO₂‐rich mineral waters (total dissolved inorganic carbon) is incompatible with the presence of ³H (from 1.7 to 4.1 TU) in those waters, which indicates relatively short subsurface circulation times. The δ¹³C values of CO₂ gas and dissolved inorganic carbon range between ?6‰ and ?1‰ versus Vienna‐Peedee Belemnite, indicating that the total carbon in the recharge waters is being diluted by larger quantities of CO₂ (¹⁴C‐free) introduced from deep‐seated (upper mantle) sources, masking the ¹⁴C‐dating values. The differences in the ⁸⁷Sr/⁸⁶Sr ratios of the studied thermal and mineral waters seem to be caused by water–rock interaction with different granitic rocks. Chlorine isotope signatures (?0.4‰ < δ³⁷Cl < +0.4‰ versus standard mean ocean chloride) indicate that Cl in these waters could be derived from mixing of a small amount of igneous Cl from leaching of granitic rocks.     

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.     

Permeability of the Mercia Mudstone: suitability as caprock to carbon capture and storage sites

The Upper Triassic Mercia Mudstone is the caprock to potential carbon capture and storage (CCS) sites in porous and permeable Lower Triassic Sherwood Sandstone reservoirs and aquifers in the UK (primarily offshore). This study presents direct measurements of vertical (k_v) and horizontal (k_h) permeability of core samples from the Mercia Mudstone across a range of effective stress conditions to test their caprock quality and to assess how they will respond to changing effective stress conditions that may occur during CO₂ injection and storage. The Mercia samples analysed were either clay‐rich (muddy) siltstones or relatively clean siltstones cemented by carbonate and gypsum. Porosity is fairly uniform (between 7.4 and 10.7%). Porosity is low either due to abundant depositional illite or abundant diagenetic carbonate and gypsum cements. Permeability values are as low as 10^?20 m² (10nD), and therefore, the Mercia has high sealing capacity. These rocks have similar horizontal and vertical permeabilities with the highest k_h/k_v ratio of 2.03 but an upscaled k_h/k_v ratio is 39, using the arithmetic mean of k_h and the harmonic mean of k_v. Permeability is inversely related to the illite clay content; the most clay‐rich (illite‐rich) samples represent very good caprock quality; the cleaner Mercia Mudstone samples, with pore‐filling carbonate and gypsum cements, represent fair to good caprock quality. Pressure sensitivity of permeability increases with increasing clay mineral content. As pore pressure increases during CO₂ injection, the permeability of the most clay‐rich rocks will increase more than carbonate‐ and gypsum‐rich rocks, thus decreasing permeability heterogeneity. The best quality Mercia Mudstone caprock is probably not geochemically sensitive to CO₂ injection as illite, the cause of the lowest permeability, is relatively stable in the presence of CO₂–water mixtures.     

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.     

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.     

Hydrothermal dolomitization,mixing corrosion and deep burial porosity formation: numerical results from 1‐D reactive transport models

Major corrosion has been found at depth in carbonate hydrocarbon reservoirs from different geologic provinces. Fluid inclusion microthermometry and stable isotopic compositions of carbonate cements, predating major corrosion, constrain the interpretation of the evolution of parental fluids during progressive burial and prior to the major corrosion event. Post‐major corrosion mineral paragenesis includes pyrite (‐marcasite), anhydrite, kaolinite (dickite) and fluorite. Although the post‐corrosion mineral paragenesis represents minor volumes of rock, it may provide valuable insights into the post‐corrosion brine chemistry. Using reactive transport numerical models, the roles of cooling and/or mixing of brines on corrosion have been evaluated as controls for dolomitization, deep burial corrosion and precipitation of the post‐corrosion mineral paragenesis. Modelling results show that cooling of deep‐seated fluids moving upward along a fracture may cause minor calcite dissolution and porosity generation. Significant dolomitization along a fracture zone and nearby host‐rock only occurs when deep‐seated fluids have high salinities (4 mol Cl kg^?1 of solution) and Darcian flow rates are relatively high (1 m³ m^?2 year^?1). Only minor volumes of quartz and fluorite precipitate in the newly formed porosity. Moreover, modelling results cannot reproduce the authigenic precipitation of kaolinite (dickite at high temperatures) by cooling. As an alternative to cooling as a cause of corrosion, mixing between two brines of different compositions and salinities is represented by two main cases. One case consists of the flow up along a fracture of deep‐seated fluids with higher salinities than the fluid in the wall rock. Dolomite does not precipitate at a fracture zone. Nevertheless, minor volumes of dolomite are formed away from the fracture. The post‐corrosion mineral paragenesis can be partly reproduced, and the results are comparable to those obtained from cooling calculations. Minor volumes of quartz and fluorite are formed, and kaolinite‐dickite does not precipitate. The major outputs of this scenario are calcite dissolution and slight net increase in porosity. A second case corresponds to the mixing of low salinity deep‐seated fluids, flowing up along fractures, with high salinity brines within the wall rock. Calculations predict major dissolution of calcite and precipitation of dolomite. The post‐corrosion mineral paragenesis can be reproduced. High volumes of quartz, fluorite and kaolinite‐dickite precipitate and may even completely occlude newly formed porosity.     

Geometry‐coupled reactive fluid transport at the fracture scale: application to CO2 geologic storage

Water acidification follows CO₂ injection and leads to reactive fluid transport through pores and rock fractures, with potential implications to reservoirs and wells in CO₂ geologic storage and enhanced oil recovery. Kinetic rate laws for dissolution reactions in calcite and anorthite are combined with the Navier‐Stokes law and advection–diffusion transport to perform geometry‐coupled numerical simulations in order to study the evolution of chemical reactions, species concentration, and fracture morphology. Results are summarized as a function of two dimensionless parameters: the Damköhler number Da which is the ratio between advection and reaction times, and the transverse Peclet number Pe defined as the ratio between the time for diffusion across the fracture and the time for advection along the fracture. Reactant species are readily consumed near the inlet in a carbonate reservoir when the flow velocity is low (low transverse Peclet number and Da > 10^?1). At high flow velocities, diffusion fails to homogenize the concentration field across the fracture (high transverse Peclet number Pe > 10^?1). When the reaction rate is low as in anorthite reservoirs (Da < 10^?1), reactant species are more readily transported toward the outlet. At a given Peclet number, a lower Damköhler number causes the flow channel to experience a more uniform aperture enlargement along the length of the fracture. When the length‐to‐aperture ratio is sufficiently large, say l/d > 30, the system response resembles the solution for 1D reactive fluid transport. A decreased length‐to‐aperture ratio slows the diffusive transport of reactant species to the mineral fracture surface, and analyses of fracture networks must take into consideration both the length and slenderness of individual fractures in addition to Pe and Da numbers.     

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.     

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.     

Geological setting, nature of ore fluids and sulphur isotope geochemistry of the Fu Ning Carlin-type gold deposits, Yunnan Province, China

Carlin‐type gold deposits in southern China are present in Palaeozoic to Mesozoic siliciclastic and carbonate rocks. The border region of Yunnan, Guizhou and Guangxi Provinces contains gold deposits on the south‐western margin of the Pre‐Cambrian South China Craton in south‐eastern Yunnan Province. The Fu Ning gold deposits host epigenetic, micron‐sized disseminated gold in: (i) Middle Devonian (D₁p) black carbonaceous mudstone at the Kuzhubao gold deposit and (ii) fault breccia zones at the contact between Triassic gabbro (β ) and the Devonian mudstone (D₁p) at the Bashishan gold deposit. The deposits are associated with zones of intense deformation with enhanced permeability and porosity that focused hydrothermal fluid flow, especially where low‐angle N‐S striking thrust faults are cut by NW striking strike‐slip and/or NE striking normal faults. Major sulphide ore minerals in the Fu Ning gold deposits are pyrite, arsenopyrite, arsenic‐rich pyrite, stibnite and minor iron‐poor sphalerite. Gangue minerals are quartz, sericite, calcite, ankerite and chlorite. Hypogene ore grades range from 1 to 7 g t^?1 Au and up to 18 g t^?1 Au at the Kuzhubao gold deposit and are generally less than 3 g t^?1 Au at the Bashishan gold deposit. Sub‐microscopic gold mineralization is associated with finely disseminated arsenic‐rich pyrite in the Stage III mineral assemblage. Two types of primary fluid inclusions have been recorded: Type I liquid–vapour inclusions with moderate‐to‐high liquid/vapour ratios, and Type II inclusions containing moderate liquid/vapour ratios with CO₂ as determined from laser Raman analysis. Temperature of homogenization (T_h) data collected from these primary fluid inclusions in gold‐ore Stage III quartz ranged from 180 to 275°C at the Kuzhubao gold deposit and 210 to 330°C at the Bashishan gold deposit. Salinity results indicate that there were possibly two fluids present during gold deposition, including: (i) an early fluid with 0.8–6.5 wt.% NaCl equivalent, similar to salinity in shear‐zone‐hosted gold deposits with metamorphic derived fluids; and (ii) a late fluid with 11.8–13.4 wt.% NaCl equivalent, indicating possible derivation from connate waters and/or brine sources. CO₂ and trace CH₄ were only detected by laser Raman spectrometry in gold‐ore‐stage primary fluid inclusions. Results of sulphur isotope studies showed that δ³⁴S values for pyrite and arsenopyrite associated with gold‐ore mineralization during Stage III at the Kuzhubao and Bashishan gold deposits are isotopically similar and moderately heavy with a range from +9 to +15 per mil, and also fall into the range of δ³⁴S values reported for Carlin‐type gold deposits. Sulphur isotopes suggest that the Fu Ning gold deposits were formed from connate waters and/or basinal brines. Fluid geochemistry data from the Fu Ning gold deposits suggest a Carlin‐type genetic model, involving fluid mixing between: (i) deep CO₂‐rich metamorphic fluids, (ii) moderately saline, reduced connate waters and/or basinal brines; and (iii) evolved meteoric waters.     

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.     

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 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.     

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

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

Fracture spacing during hydro‐fracturing of cap‐rocks

Layered low permeability rock units, like shales, represent seals or ‘cap‐rocks’ in a variety of geological settings. A continuous increase in the fluid pressure gradients across a virtually impermeable rock layer will ultimately lead to hydro‐fracturing. Depending on the boundary conditions, such fracturing may lead to the formation of a set of sub‐parallel cracks oriented more or less perpendicular to the cap‐rock layer. In this article, we propose a new numerical model that describes interactions between multiple cross‐cutting fractures in an elastic low permeability rock layer. The width of each fracture and the spacing between them are modeled as a force balance between the fluid pressure and the elastic forces in the cap‐rock and between each fracture. The model indicates that the system of fractures evolves toward a spatially periodic steady‐state distribution with a fixed fracture spacing and aperture. The results are similar for incompressible and compressible fluids. The steady‐state conditions depend on only two dimensionless parameters, and the fracture spacing is only weakly dependent on the cap‐rock thickness. This is in contrast to fracturing produced by simple extension of an elastic rock layer beyond the fracture strength, in which case fracture spacing is proportional to layer thickness.     

Infiltration of basinal fluids into high-grade basement, South Norway: sources and behaviour of waters and brines

Quartz veins hosted by the high‐grade crystalline rocks of the Modum complex, Southern Norway, formed when basinal fluids from an overlying Palaeozoic foreland basin infiltrated the basement at temperatures of c. 220°C (higher in the southernmost part of the area). This infiltration resulted in the formation of veins containing both two‐phase and halite‐bearing aqueous fluid inclusions, sometimes with bitumen and hydrocarbon inclusions. Microthermometric results demonstrate a very wide range of salinities of aqueous fluids preserved in these veins, ranging from c. 0 to 40 wt% NaCl equivalent. The range in homogenization temperatures is also very large (99–322°C for the entire dataset) and shows little or no correlation with salinity. A combination of aqueous fluid microthermometry, halogen geochemistry and oxygen isotope studies suggest that fluids from a range of separate aquifers were responsible for the quartz growth, but all have chemistries comparable to sedimentary formation waters. The bulk of the quartz grew from relatively low δ¹⁸O fluids derived directly from the basin or equilibrated in the upper part of the basement (T < 200°C). Nevertheless, some fluids acquired higher salinities due to deep wall‐rock hydration reactions leading to salt saturation at high temperatures (>300°C). The range in fluid inclusion homogenization temperatures and densities, combined with estimates of the ambient temperature of the basement rocks suggests that at different times veins acted as conduits for influx of both hotter and colder fluids, as well as experiencing fluctuations in fluid pressure. This is interpreted to reflect episodic flow linked to seismicity, with hotter dry basement rocks acting as a sink for cooler fluids from the overlying basin, while detailed flow paths reflected local effects of opening and closing of individual fractures as well as reaction with wall rocks. Thermal considerations suggest that the duration of some flow events was very short, possibly in the order of days. As a result of the complex pattern of fracturing and flow in the Modum basement, it was possible for shallow fluids to penetrate basement rocks at significantly higher temperatures, and this demonstrates the potential for hydrolytic weakening of continental crust by sedimentary fluids.     

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.     

OPTICAL DATING OF GRANITIC STONE SURFACES*

A novel luminescence methodology for dating surfaces of granitoid rocks is presented, with encouraging results for archaeological stone structures. It is based on the zeroing of the latent signal of optically stimulated luminescence (OSL) in feldspar and quartz grains of the stone surface during exposure to daylight. When after bleaching the surface is shielded from light, the OSL signal builds up again, such that its intensity provides an age for the event of the last exposure to light. This event could be the construction or the destruction of stone structures or, for example, sedimentary deposition of granitic boulders, such as in fan deposits. The experimental approach utilizes a high spatial resolution detection technique (HR‐OSL) for OSL of minerals that are left in their original petrological context; that is, without any mineral separation. With this approach, steep gradients in microdosimetry at the surface and at grain boundaries become important and are discussed in detail. The new dating technique is successfully applied to a stone wall of the medieval castle of Lindenfels in southwestern Germany and the pre‐Columbian Nasca lines (geoglyphs) around Palpa in southern Peru.