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.     

Reconstructing Diet of the Early Qin (ca. 700–400 BC) at Xishan,Gansu Province,China

Here we report the bone collagen carbon and nitrogen isotopic results of humans (n = 33) and animals (n = 58) to reconstruct the dietary practices of an early Qin population dating to the Zhou Dynasty (Late Western–Early Eastern period ca. 700–400 BC ) at the Xishan site in Gansu Province, China. The humans have a very large range of δ¹³C (−23.3‰ to −7.1‰) and δ¹⁵N (4.3‰ to 10.9‰) values which reflects extraordinarily diverse diets and included individuals with predominately C₃ as well as those with exclusive C₄ diets. This wide span of isotopic results produced a subtle linear trend (R² = 0.62) in the human data, which paralleled the animals across the C₃ and C₄ environmental gradient. However, the majority of the individuals had a predominately C₄ diet based on millet with δ¹⁵N results only slightly elevated above the animals, except for the pigs and cattle. This is evidence that many of the animals were likely used for their secondary products, labour or as sacrificial offerings and that pork and beef were the main sources of animal protein for the population. High status individuals had elevated δ¹⁵N values (10.2 ± 0.6‰) compared to medium (8.9 ± 0.3‰) and lower status (8.8 ± 0.8‰) individuals, possibly related to increased animal protein in the diet. Differences related to gender were also found with females having elevated δ¹³C (−11.2 ± 1.9‰) and δ¹⁵N (9.4 ± 0.8‰) values compared to the males (δ¹³C = −14.1 ± 4.2‰; δ¹⁵N = 7.9 ± 1.9‰), but these results necessitate caution given the large number of individuals that could not be sexed. The results of this study support the view that the early Qin people were a more sedentary society focused on millet agriculture and animal husbandry, and that they were influenced by the pre‐existing populations of the central Gansu region. Copyright © 2015 John Wiley & Sons, Ltd.     

Oxygen isotopes in cellulose identify source water for archaeological maize in the American Southwest

Maize (Zea mays) was a primary food crop for aboriginal societies of the arid American Southwest. Water used for maize production in these arid zones could have come from precipitation and runoff during the summer monsoon, from perennial streams and springs, or from stored soil water fed by snowmelt. The oxygen stable isotope ratio (δ¹⁸O) of summer and winter precipitation on the Colorado Plateau naturally differ by more than 10‰ providing a powerful tool for distinguishing winter- from summer-derived water sources used in cultivation of maize. We investigated whether variation in δ¹⁸O of potential source waters is preserved in the δ¹⁸O of cellulose (δ¹⁸O_cellulose) of maize cobs by growing four aboriginal and one modern maize variety in pots irrigated with water of known δ¹⁸O composition. The δ¹⁸O_cellulose values of cobs ranged from 26.8 to 36.4‰ (averaged within varieties) and were highly correlated with δ¹⁸O values of the source irrigation water (−15.8 to −8.2‰). Cob δ¹⁸O_cellulose from five archaeological sites on the Colorado Plateau in southeastern Utah ranged from 27.3 to 34.6‰, closely matching the range of values observed in experimental plants. A δ¹⁸O_cellulose model developed originally for tree rings was parameterized and applied to the archaeological maize cobs. The model indicated that monsoonal precipitation accounted for 0–20% of the moisture for archaeological cob samples from a site adjacent to a perennial stream and 43–98% for samples from an upland site, more distant from a perennial water source. These results reveal the potential for using δ¹⁸O_cellulose to investigate prehistoric irrigation practices and source water used for maize production in the American Southwest.     

Investigating Dietary Patterns with Stable Isotope Ratios of Collagen and Starch Grain Analysis of Dental Calculus at the Iron Age Cemetery Site of Heigouliang,Xinjiang, China

Here, we present δ¹³C and δ¹⁵N results for the dietary reconstruction of nomadic pastoralists from the Iron Age (ca. 1000 bc –8 ad ) site of Heigouliang. The human (n = 27) δ¹³C values range from −19.6‰ to −17.0‰ with a mean value of −18.5 ± 0.5‰, and the δ¹⁵N results range from 11.5‰ to 13.8‰ with a mean value of 12.4 ± 0.6‰. The results indicated that animals, like sheep, were part of the predominately C₃ terrestrial diet, but two individuals have values greater than −18‰ that is indicative of some input of C₄ foods in their diets. Because of a lack of faunal samples and to supply complementary information concerning plant consumption, teeth from four individuals were analysed for dental calculus microfossils. Starch grains were found to correspond to Triticeae and Poaceae, possibly including wheat (Triticum aestivum), barley (Hordeum vulgare), highland barley (H. vulgare L var. nudum), foxtail millet (Setaria italica) and/or common millet (Panicum miliaceum). At the population level, no dietary differences were detected between burial owners and sacrificial victims, but variations were found when specific tombs were analysed. In particular, individuals with bone trauma associated with armed conflict also had distinct isotopic signatures possibly suggesting that some of the sacrificial victims could have been captured warriors that were sacrificed for the burial owners. While limited, the results are some of the first from an Iron Age population from Xinjiang and contribute to our understanding of the dietary patterns of this region. Copyright © 2015 John Wiley & Sons, Ltd.     

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.     

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.     

Chicken and Egg: Testing the Carbon Isotopic Effects of Carnivory and Herbivory

In bone, the spacing between δ¹³C in collagen and bioapatite carbonate is greater in herbivores than carnivores, with implications for understanding animal dietary ecology from surviving hard tissues. Two explanations have been proposed: varying diet composition or differences in physiology between herbivores and carnivores. We measured the isotopic effects of carnivorous and herbivorous diets on a single species, to test the effect of diet composition alone. Protein δ¹³C and δ¹⁵N and carbonate δ¹³C were measured on egg and bone from hens on different diets. Herbivorous hens had a +14.3‰ spacing between egg albumen and shell δ¹³C, compared to +12.4‰ for omnivorous hens, and +11.5‰ for carnivorous hens. The bioapatite–collagen Δ¹³C spacing was measured as +6.2‰ for herbivorous hens, and calculated as +4.3‰ for omnivorous hens, and +3.4‰ for carnivorous hens—similar to observed mammalian herbivore and carnivore bioapatite–collagen Δ¹³C differences. We conclude that a shift in diet composition from herbivory to carnivory in a single species does alter the bioapatite–collagen carbon isotopic spacing. Our data strongly suggest that this results from differences in the Δ¹³C_{bioapatite–diet} spacing, and not that of Δ¹³C_{collagen–diet}.     

Molecular transport of methane, ethane and nitrogen and the influence of diffusion on the chemical and isotopic composition of natural gas accumulations

Laboratory experiments have been performed to determine diffusion coefficients of natural gas components (methane, ethane and nitrogen) and isotope fractionation effects under simulated in situ pressure (up to 45 MPa effective stress) and temperature conditions (50–200°C) in water‐saturated pelitic and coarse‐grained rocks. Effective diffusion coefficients of molecular nitrogen (0.39 × 10^?11 to 21.6 × 10^?11 m² sec^?1 at 90°C) are higher than those for methane (0.18 × 10^?11 to 18.2 × 10^?11 m² sec^?1 at 90°C). Diffusive flux rates expressed in mass units are generally higher for N₂ than for CH₄. Both methane and (to a lesser extent) nitrogen diffusion coefficients decrease with increasing total organic carbon (TOC) content of the rock samples because of sorption processes on the organic matter. This effect decreases with increasing temperature. Effective diffusion coefficients increase upon a temperature increase from 50 to 200°C by a factor of four. Effective diffusion coefficients and steady‐state diffusive flux decrease with effective stress. Stationary diffusive fluxes drop by 50–70% for methane and 45–62% for nitrogen while effective diffusion coefficients are reduced by 38% (CH₄) and 32–48% (N₂), respectively. Isotope fractionation coefficients of diffusive transport are higher for methane (?1.56 and ?2.77‰) than for ethane (?0.84 and ?1.62‰). Application of the experimental results to geological systems show that diffusive transport has only a low transport efficiency. Significant depletion of natural gas reservoirs by molecular diffusion is only expected in cases of very poor caprock qualities (in terms of thickness and/or porosity) and over extended periods of geological time. Under these circumstances, the chemical and isotopic composition of a gas reservoir will change and maturity estimates based on these parameters may be deceptive. To account for these potential effects, nomograms have been developed to estimate diffusive losses and apply maturity corrections.     

Temperature‐dependent Li isotope ratios in Appalachian Plateau and Gulf Coast Sedimentary Basin saline water

Lithium (Li) concentrations of produced water from unconventional (horizontally drilled and hydraulically fractured shale) and conventional gas wells in Devonian reservoirs in the Appalachian Plateau region of western Pennsylvania range from 0.6 to 17 mmol kg^?1, and Li isotope ratios, expressed as in δ⁷Li, range from +8.2 to +15‰. Li concentrations are as high as 40 mmol kg^?1 in produced waters from Plio‐Pleistocene through Jurassic‐aged reservoirs in the Gulf Coast Sedimentary Basin analyzed for this study, and δ⁷Li values range from about +4.2 to +16.6‰. Because of charge‐balance constraints and rock buffering, Li concentrations in saline waters from sedimentary basins throughout the world (including this study) are generally positively correlated with chloride (Cl), the dominant anion in these fluids. Li concentrations also vary with depth, although the extent of depth dependence differs among sedimentary basins. In general, Li concentrations are higher than expected from seawater or evaporation of seawater and therefore require water–mineral reactions that remove lithium from the minerals. Li isotope ratios in these produced waters vary inversely with temperature. However, calculations of temperature‐dependent fractionation of δ⁷Li between average shale δ⁷Li (?0.7‰) and water result in δ⁷Li_water that is more positive than that of most produced waters. This suggests that aqueous δ⁷Li may reflect transport of water from depth and/or reaction with rocks having δ⁷Li lighter than average shale.     

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.     

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.     

Application of boron isotopes to the understanding of fluid–rock interactions in a hydrothermally stimulated oil reservoir in the Alberta Basin, Canada

Boron isotope ratios of reservoir minerals and fluids can be a useful geothermometer and monitor of fluid–rock interactions. In Cold Lake oil sands of northern Alberta, there is a large variation in δ¹¹B of the produced waters generated during steam injection and recovery of oil and water. The higher temperature waters (～ 200 °C) have isotopically light δ¹¹B values (+ 3‰ to + 14‰) and high B contents (～150 p.p.m.). It is inferred that the range of δ¹¹B values of the hydrothermal fluids results from reaction with the reservoir rock, and is a function of the temperature of the fluid–rock interaction. The distinct B geochemistry of the produced waters can be used to show that there is no detectable mixing of the oil recovery waters with the regional formation waters or shallow groundwater aquifers containing potable water. Examination of B isotope ratios of reservoir minerals, before and after steam injection, allows the evaluation of sources of B in the reservoir. The only significant phase containing B is pumice. It shows generally positive δ¹¹B values before steam injection and negative values after steam, with δ¹¹B as low as ? 28‰. Other possibly reactive phases include clay minerals and organic matter, but their abundance is not great enough to impact on the isotopic composition of the produced waters. This information makes it possible to evaluate the boron isotope fractionation equation derived from experimental data ( Williams LB (2000) Boron isotope geochemistry during burial diagenesis. PhD Dissertation. The University of Calgary, Alberta, Canada; Williams LB, Hervig RL, Holloway JR, Hutcheon I (2001a) Boron isotope geochemistry during diagenesis: Part 1. Experimental determination of fractionation during illitization of smectite. Geochimica et Cosmochimica Acta, in press). The results show that the fractionation curve predicts the difference between δ¹¹B of the pumice and hydrothermal fluids in the Cold Lake reservoir. This not only indicates that the reservoir fluids have approached boron isotope equilibrium with the reservoir rock, but also shows that B isotopes provide a useful geothermometer for hydrothermally stimulated oil reservoirs.     

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.     

Horticulturists and oxygen ecozones in the tropical and subtropical forests of Southeast South America

We analyse the isotopic values (δ¹³C, δ¹⁵N) of the diet of pre-Columbian horticulturalist populations from tropical and subtropical areas of southeastern South America, belonging to the Guarani and Taquara archaeological units. The data indicate different trends in each one (T?=?4.21; P?=?0.0004), showing a mixed diet with maize consumption in the Guarani samples (δ¹³C_co?=??15.5?±?1.8‰; δ¹³C_ap ?10.4?±?0.8‰) and a depleted one in the Taquara ones (δ¹³C_co ?18.2?±?1.7‰; δ¹³C_ap ?11.9?±?0.9‰), with a significant internal dispersion in both populations. The first population has higher nitrogen values (δ¹⁵N 11.1?±?0.6‰) compared to the Taquara samples (δ¹⁵N 9.3?±?1‰), suggesting a more carnivorous diet. The recognition of these pre-Columbian mixed diets involves the identification of maize cultivation on the Atlantic side of the southernmost area of South America (Parana Delta, 34° SL). Through the analysis of δ¹⁸O we have identified two isotopic ecozones, the first along the Paraná River Valley, with an average value of δ¹⁸O ?3.7?±?0.5‰ (CV?=?13.5%; CI?=??3.83 / ?3.16), and the second one, located in the Planalto of southern Brazil (Araucaria Forest), with a mean value of δ¹⁸O ?1.5?±?0.3‰ (CV?=?16.5%; CI?=??1.69 / ?1.29). The isotopic data (δ¹³C, δ¹⁵N and δ¹⁸O) suggest human movements between these two ecozones.     

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.     

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.     

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.     

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.     

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.     

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.