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.     

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.     

Invasion of a karst aquifer by hydrothermal fluids: evidence from stable isotopic compositions of cave mineralization

Mineral deposits in the Cupp‐Coutunn/Promeszutochnaya cave system (Turkmenia, central Asia) record a phase of hydrothermal activity within a pre‐existing karstic groundwater conduit system. Hydrothermal fluids entered the caves through fault zones and deposited sulphate, sulphide and carbonate minerals under phreatic conditions. Locally, intense alteration of limestone wall rocks also occurred at this stage. Elsewhere in the region, similar faults contain economic quantities of galena and elemental sulphur mineralization. Comparisons between the Pb and S isotope compositions of minerals found in cave and ore deposits confirm the link between economic mineralization and hydrothermal activity at Cupp‐Coutunn. The predominance of sulphate mineralization in Cupp‐Coutunn implies that the fluids were more oxidized in the higher permeability zone associated with the karst aquifer. A slight increase in the δ³⁴S of sulphate minerals and a corresponding δ³⁴S decrease in sulphides suggest that partial isotopic equilibration occurred during oxidation. Carbonate minerals indicate that the hydrothermal fluid was enriched in ¹⁸O (δ¹⁸O_SMOW ～ + 10‰) relative to meteoric groundwater and seawater. Estimated values for δ¹³C_DIC (δ¹³C_PDB ～ ? 13‰) are consistent with compositions expected for dissolved inorganic carbon (DIC) derived from the products of thermal decomposition of organic matter and dissolution of marine carbonate. Values derived for δ¹³C_DIC and δ¹⁸O_water indicate that the hydrothermal fluid was of basinal brine origin, generated by extensive water–rock interaction. Following the hydrothermal phase, speleothemic minerals were precipitated under vadose conditions. Speleothemic sulphates show a bimodal sulphur isotope distribution. One group has compositions similar to the hydrothermal sulphates, whilst the second group is characterized by higher δ³⁴S values. This latter group may either record the effects of microbial sulphate reduction, or reflect the introduction of sulphate‐rich groundwater generated by the dissolution of overlying evaporites. Oxygen isotope compositions show that calcite speleothems were precipitated from nonthermal groundwater of meteoric origin. Carbonate speleothems are relatively enriched in ¹³C compared to most cave deposits, but can be explained by normal speleothem‐forming processes under thin, arid‐zone soils dominated by C4 vegetation. However, the presence of sulphate speleothems, with isotopic compositions indicative of the oxidation of hydrothermal sulphide, implies that CO₂ derived by reaction of limestone with sulphuric acid (‘condensation corrosion’) contributed to the formation of ¹³C‐enriched speleothem deposits.     

Low‐temperature catalytic CO2 hydrogenation with geological quantities of ruthenium: a possible abiotic CH4 source in chromitite‐rich serpentinized rocks

Metal‐catalysed CO₂ hydrogenation is considered a source of methane in serpentinized (hydrated) igneous rocks and a fundamental abiotic process germane to the origin of life. Iron, nickel, chromium and cobalt are the catalysts typically employed in hydrothermal simulation experiments to obtain methane at temperatures >200°C. However, land‐based present‐day serpentinization and abiotic gas apparently develop below 100°C, down to approximately 40–50°C. Here, we document considerable methane production in thirteen CO₂ hydrogenation experiments performed in a closed dry system, from 20 to 90°C and atmospheric pressure, over 0.9–122 days, using concentrations of non‐pretreated ruthenium equivalent to those occurring in chromitites in ophiolites or igneous complexes (from 0.4 to 76 mg of Ru, equivalent to the amount occurring approximately in 0.4–760 kg of chromitite). Methane production increased with time and temperature, reaching approximately 87 mg CH₄ per gram of Ru after 30 days (2.9 mgCH₄/g_ru/day) at 90°C. At room temperature, CH₄ production rate was approximately three orders of magnitude lower (0.003 mgCH₄/g_ru/day). We report the first stable carbon and hydrogen isotope ratios of abiotic CH₄ generated below 100°C. Using initial δ¹³C_CO2 of ‐40‰, we obtained room temperature δ¹³C_CH4 values as ¹³C depleted as ?142‰. With time and temperature, the C‐isotope separation between CO₂ and CH₄ decreased significantly and the final δ¹³C_CH4 values approached that of initial δ¹³C_CO2. The presence of minor amounts of C₂‐C₆ hydrocarbons is consistent with observations in natural settings. Comparative experiments at the same temperatures with iron and nichel catalysts did not generate CH₄. Ru‐enriched chromitites could potentially generate methane at low temperatures on Earth and on other planets.     

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.     

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.     

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.     

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.     

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.     

Isotopic Reconstruction of the Late Longshan Period (ca. 4200–3900 BP) Dietary Complexity before the Onset of State‐Level Societies at the Wadian Site in the Ying River Valley,Central Plains,China

During the late Longshan period (ca. 4200–3900 BP) settlements on the Central Plains of China underwent a diversification in food production technologies, which set the stage for rapid economic and social development. The introduction of novel domesticates such as rice, wheat, cattle, and sheep not only provided more food choices, but also changed ideas concerning land use, farming techniques, and the use and mobilization of large scale labor forces. To better understand the contribution that these new dietary items and practices made to shaping the late Longshan period societies, a stable isotope ratio study of humans (n = 12) and animals (n = 42) was conducted at the late Longshan period site of Wadian. The human δ¹³C and δ¹⁵N values are clustered into two distinct groups. One group of nine individuals (δ¹³C = −9.9 ± 0.7‰; δ¹⁵N = 7.5 ± 0.5‰) had a predominately C₄ diet based on millet grains with little protein input from the domestic animals. The other group of three individuals (δ¹³C = −14.3 ± 0.8‰; δ¹⁵N = 10.2 ± 0.3‰) had a mixed C₃/C₄ diet of millets and rice and were consuming sheep and cattle. The animals also displayed dietary diversity with the pigs (δ¹³C = −11.3 ± 2.5‰; δ¹⁵N = 6.9 ± 1.0‰, n = 10) and dogs (δ¹³C = −10.1 ± 1.0‰; δ¹⁵N = 7.2 ± 1.1‰, n = 7) having mostly a C₄ plant based diet (millets). In contrast, the cattle (δ¹³C = −12.8 ± 2.1‰; δ¹⁵N = 7.6 ± 0.7‰, n = 9), sheep (δ¹³C = −16.7 ± 0.9‰; δ¹⁵N = 7.6 ± 0.1‰, n = 2), and cervids (δ¹³C = −20.8 ± 0.9‰; δ¹⁵N = 5.0 ± 1.2‰, n = 10) had diets with a greater contribution from C₃ sources such as rice and wild plants. The discovery that humans and animals had different subsistence patterns indicates dietary complexity at Wadian and that rice agriculture, and cattle and sheep husbandry practices were already an important part of the local economy by the late Longshan period in the southern region of the Central Plains of China. Copyright © 2015 John Wiley & Sons, Ltd.     

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.     

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.     

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.     

On the geochemistry of gases and noble gas isotopes (including 222Rn) in deep crustal fluids: the 4000 m KTB-pilot hole fluid production test 2002–03

The concentrations of H₂, O₂, CO₂, and concentrations and isotopic composition of the noble gases (including ²²²Rn), N₂, CH₄, and higher hydrocarbons dissolved in 4000 m deep‐seated fluids from a 12‐month fluid production test in the KTB pilot hole were analyzed. This determination of the gas geochemistry during the test in combination with the knowledge of the hydraulic data provides relevant information about the fluid hydraulics of the deep system. All gas concentrations and isotopic signatures, except for ²²²Rn, showed constancy during the course of the test. This, in combination with large fluid flow rates at a moderate water table drawdown, imply an almost infinite fluid reservoir in 4000 m depth. From the change in ²²²Rn‐activity as a function of pump rate, the contribution of smaller and wider pores to the overall fluid flow in an aquifer can be deduced. This ²²²Rn‐activity monitoring proved therefore to be a valuable instrument for the qualitative observation of the scavenging of pore and fracture surfaces, a hydraulic feature invisible to standard hydraulic testing tools. The observance of this scavenging effect is due to (i) the continuous on‐line geochemical monitoring, (ii) the durability of the test, (iii) a change in pump rate during the course of the test, and (iv) due to the short half‐life of ²²²Rn. The fluids have a 5.9% mantle He component, and a δ²¹Ne excess of 14%, and a noble gas model age of about (5.5–6.2) ± 2.0 Myr. The mean N₂/Ar‐ratio of 516 and δ¹⁵N‐data of about +1.5‰ indicates sedimentary or metamorphic origin of N₂. The hydrocarbons, amounting to 33 vol.% in the gas phase, are derived from thermal decomposition of marine organic matter of low maturity. But a key question, the identification of the potential source region of the fluids and the migration pathway, is still unidentified.     

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.     

The stable isotopic composition of historical black powder applicable to a Japanese Tanegashima matchlock

The objective of the present study is to employ stable isotope ratio measurements (δ¹⁵N, δ³⁴S and δ¹³C) of the nitrogen, sulphur and carbon in black powder (a mixture of saltpetre, native sulphur and charcoal) as a means of source identification. A sum total of 20 samples of historical black powder applicable to matchlocks were collected from six locations throughout Japan. This classic type of hand gun prevailed up to the introduction of the modern rifles, with quicker loading and higher efficiency, in the mid‐to‐late 19th century. δ¹³C_{charcoal carbon} values showed the predominant use of C₃ plants as a source material. Except for a few unusual samples with a probable exotic origin, δ¹⁵N_{saltpetre nitrogen} values were largely consistent with those of domestic products using classical biotechnology. The isotopic analysis for native sulphur (δ³⁴S_{native sulphur}) indicates a complicated marketing route.     

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

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

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.     

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.     

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.