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.     

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.     

Lithium extractivism and water injustices in the Salar de Atacama,Chile: The colonial shadow of green electromobility

This paper analyzes the linkages and feedback between green electromobility, lithium extractivism, and water injustices affecting the Atacameño's indigenous communities in the Salar de Atacama basin (Atacama Salt Flats). Currently, lithium is in high demand in the international markets as a strategic resource for the green electromobility industry, which represents part of the Global North policies established by the Paris Agreement to mitigate climate change's effects. Using both documentary and ethnographic methods based mainly on semi-structured interviews conducted with Atacameño people, public officials, and lithium companies' representatives and workers, we propose a decolonial interpretation of lithium extractivism in brine mining through the lens of Latin American political ecology combined with a decolonial and water justice approach. The results demonstrate how the linkages and feedback between global and local dynamics of lithium mining in the Salar de Atacama constitute a form of green extractivism that further replicates the historical inequalities between the Northern and Southern hemispheres and especially affects the indigenous Andean territories and the water ecosystems in the Global South. We call this phenomenon the colonial shadow of green electromobility. We conclude by exposing the need to rethink global proposals addressing climate change by reducing the commodity demand and aiming for water justice at global and local levels.     

Secular variations in seawater chemistry as a control on the chemistry of basinal brines: test of the hypothesis

The hypothesis that basinal brines inherited their major ion chemistries and elevated salinities from evaporated paleoseawaters is tested by comparing the compositions of basinal brines in Silurian (Michigan basin, Illinois basin, Appalachian basin in eastern Ohio) and Jurassic/Cretaceous (Central Mississippi Salt Dome basin, Arkansas shelf, and south‐central Texas) host rocks, when the world oceans were ‘CaCl₂ seas’, with those from Permian and Pennsylvanian rocks (Palo Duro basin, Central Basin Platform, and Delaware basin, Texas and New Mexico) when the world oceans were ‘MgSO₄ seas’. Basinal brines examined are assumed to have originally formed from evaporation of the same seawaters that produced major evaporites. Sulfate, Mg and K levels in basinal brines are below the concentrations expected from evaporation of seawater of any type, which emphasizes the importance of diagenetic mineral–brine interactions in controlling basinal brine chemistry. There are no major differences in SO₄, Mg and K concentrations between basinal brines hosted by rocks originally formed during ages when the world oceans were MgSO₄ seas versus CaCl₂ seas. Basinal brines in Pennsylvanian–Permian rocks are compositionally distinct (relatively high Na and low Ca) from basinal brines in Silurian, Jurassic and Cretaceous host rocks, which may reflect original differences in seawater chemistry. Basinal brines enriched in Ca and depleted in Na relative to evaporated seawater of any type have traditionally been interpreted to form by albitization of plagioclase feldspar. A new explanation for Ca enrichment and Na depletion of basinal brines is the mixing of evaporated CaCl₂‐type seawater with more dilute water. Some basinal brines are similar in major ion composition to evaporated seawater of a particular age, for example basinal brines in the Cretaceous Edwards Group carbonates, Texas, where dolomitization is the only reaction required to convert evaporated Mesozoic CaCl₂ seawater into Edwards Group brine.     

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.     

Isotopic Evidence for Marine Consumption and Mobility in the Atacama Desert (Quillagua,Northern Chile)

Archaeological research in the Atacama Desert has recovered evidence of considerable cultural variability. This variability seems to have increased during the Late Intermediate Period (AD 950–1400). The oasis of Quillagua, located at the margins of the Loa River in northern Chile, between the Andes and the coast (70 km from the Pacific Ocean), has shown important evidence regarding this cultural diversity. The variety in the archaeological evidence found at Quillagua has been interpreted as the result of two different cultural influences at the oasis: the Pica‐Tarapacá who occupied the coastal and inland regions to the north of Quillagua and the Atacama who occupied the oasis and fertile areas southeast of Quillagua. Here, we present the results of stable carbon, nitrogen and oxygen isotope analyses of 23 individuals recovered from the Cementerio Oriente in Quillagua, in order to test whether the observed cultural variability is also reflected in diet and mobility patterns. Results from carbon and nitrogen isotope measurements indicate the importance of marine protein, as well as a contribution of maize in the diet of some individuals. Four individuals show low δ¹⁸O values, suggesting a possible highland or non‐local origin, whereas values for the remaining individuals are consistent with lowland populations. Together, the results support the idea that the Quillagua oasis represented an important site of interaction between the Tarapacá and Atacama cultures, with close contacts with the coast but also with the presence of individuals from the highlands. Copyright © 2015 John Wiley & Sons, Ltd.     

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.     

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.     

Sensitivity of bulk sedimentary stable carbon isotopes to prehistoric forest clearance and maize agriculture

The stable carbon isotope compositions (δ¹³C) of tropical lake sediments and soils have been used to reconstruct the occurrence of prehistoric maize cultivation and its relative importance through time. This study assesses some of the possible variables affecting the response of lake sediment bulk organic carbon isotope (δ¹³C_TOC) values to variations in the scale of prehistoric maize cultivation and the potential of this proxy to yield quantitative estimates of the scale of prehistoric maize agriculture in small tropical watersheds. High resolution analyses of δ¹³C_TOC values, maize pollen concentrations, and mineral influx were conducted on sediments deposited during a ∼220 year period of prehistoric maize agriculture in the watershed of Laguna Castilla, a small lake in the mid-elevations of the Cordillera Central, Dominican Republic. Close correspondence between δ¹³C_TOC values and maize pollen concentrations in the Laguna Castilla sediment record indicates a close relationship between the isotopic values and the scale of prehistoric maize cultivation. Correlations between the δ¹³C_TOC signature and mineral influx indicate that the isotope record is also sensitive to variations in allochthonous carbon delivery. This study establishes that sedimentary δ¹³C_TOC values can provide a highly sensitive proxy of the spatial scale of prehistoric maize agriculture in small tropical watersheds, but emphasizes the need for a better understanding of sediment dynamics and carbon cycling in anthropogenically modified landscapes before this proxy can be widely employed in diverse archaeological settings.     

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

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

Introducing δSr analysis in archaeology: a demonstration of the utility of strontium isotope fractionation in paleodietary studies

Isotopic methods are widely used in archaeology to investigate paleodiet. Here, we present a new method to identify trophic level in archaeological human populations and to investigate paleodiet. We demonstrate that strontium isotope compositions (reported as δ^88/86Sr) vary in a mass-dependent manner with increasing trophic level and can elucidate paleodiet in archaeological human populations. We present new mass-dependent strontium isotope data from tooth enamel and bone from individuals buried during the Late Intermediate Period (c. AD 1000–1300) in the large cemeteries of Chiribaya Alta, Chiribaya Baja, San Gerónimo, and El Yaral in the Ilo and Moquegua Valleys of southern Peru. We compare these data to radiogenic strontium isotope data (⁸⁷Sr/⁸⁶Sr) and light stable isotope data (δ¹⁵N_col and δ¹³C_col) from the same individuals to investigate geologic variability in strontium sources as well as marine food consumption among the Chiribaya. Our results demonstrate the utility of measurements of strontium isotope fractionation as a new tool for archaeological investigation of paleodiet. Importantly, this new technique can be used to generate paleodietary (δ^88/86Sr) and paleomobility (⁸⁷Sr/⁸⁶Sr) data from the same specimen, minimizing destructive analyses of invaluable archaeological material, and provides a new way to examine paleodiet through hydroxyapatite, which is particularly important when collagen is poorly preserved.     

Assessing the life history of an andean traveller through biogeochemistry: Stable and radiogenic isotope analyses of archaeological human remains from Northern Chile

Bioarchaeology and biogeochemistry can elucidate aspects of individual life histories that are often lost in the archaeological record. Here, we use stable and radiogenic isotope analyses of enamel, bone and hair to reconstruct paleodiet and paleomobility in an adult male interred along a pre‐Columbian route connecting the northern Chilean coast to the inland Loa River Valley. Although this well‐preserved burial included mortuary goods typical of coastal cultures, it was discovered in a vast, uninhabited part of northern Chile's hyper‐arid Atacama Desert. Variation in carbon and nitrogen isotopes reflects dietary differences, while strontium and oxygen isotopes vary geologically and geographically. We use these data to examine paleodiet and paleomobility and to assess whether this was a coastal traveller seeking provisions from the interior or vice versa. Enamel stable isotope analysis is consistent with the consumption of a mixture of terrestrial and marine resources during the first years of life. Bone stable isotope analyses indicate habitual consumption of marine foodstuffs over the last 10–30 years of this individual's life. Interestingly, stable isotope analysis of hair samples provides more fine‐grained information on this individual, suggesting movements between the coast and highlands in the months before his death. Radiogenic strontium isotope data are consistent with residence on the coast or in the Atacama Desert, but are lower than strontium isotope values from higher altitudes. These dietary and geological patterns are reconcilable with coastal residency; the isotopic data are consistent with foodstuffs and textiles found with the burial. Therefore, we argue that this individual was regularly moving from the coast to inland areas, crossing the hyper‐arid Atacama Desert by following strategic interzonal routes that provided access to particular resources. Copyright © 2010 John Wiley & Sons, Ltd.     

Strontium isotopic characterization of the Palmottu hydrosystem (Finland): water–rock interaction and geochemistry of groundwaters

The Palmottu hydrosystem is located in a granitic host rock in southern Finland. Along well‐defined pathways in the fractured crystalline rock, strontium isotopes are used to trace the degree of water–rock interaction (WRI) and mixing processes in groundwaters. The ⁸⁷Sr/⁸⁶Sr ratios range between 0.716910 and 0.735606 in the surface waters and between 0.719991 and 0.750787 in the groundwaters, but are between 0.720 and 0.735 in most of the samples. Moreover, the results show a lack of correlation between the water chemistries determining the classification into different water‐types (Na–Cl, Na–SO₄, etc.) and the results of the strontium (Sr) contents and Sr isotopic ratios. From a WRI standpoint, this implies that the Sr behaviour is independent of the water chemistry; the occurrence of large ⁸⁷Sr/⁸⁶Sr variations is site specific and mainly dependent on the lithology. A model to determine the ⁸⁷Sr/⁸⁶Sr ratio of water after interaction with granite was developed. This model is based on the assumption that Sr was derived from three minerals: plagioclase, K‐feldspar and biotite. The results of the calculation indicate that around half of the water analysed within the Palmottu hydrosystem can be explained by the weathering of the granites. However, clearly lower ⁸⁷Sr/⁸⁶Sr are observed in waters when compared to the calculated ⁸⁷Sr/⁸⁶Sr and other sources of Sr, with low ⁸⁷Sr/⁸⁶Sr, rather than the calculated granite–water interaction, which may be suspected. When comparing the ⁸⁷Sr/⁸⁶Sr and ion ratios (Ca/Na, Mg/Na, Sr/Na, Cl/Na), the scattering of the data can be explained by the presence of four end‐members: a brine component (low ⁸⁷Sr/⁸⁶Sr and Ca/Na ratios…), a deep granitic component (high ⁸⁷Sr/⁸⁶Sr ratios and low Ca/Na ratios…), a subsurface component (intermediate ⁸⁷Sr/⁸⁶Sr ratios associated with high Ca/Na ratios…) and a surface end‐member:snow and river drainage (low ⁸⁷Sr/⁸⁶Sr and low Ca/Na ratios…). These extreme end‐members define a series of WRI‐mixing line within a rather complex hydrosystem.     

The Use of Hunting and Herding Spaces: Stable Isotope Analysis of Late Archaic and Early Formative Camelids in the Tulan Transect (Puna de Atacama,Chile)

We present the results of analysing stable carbon and nitrogen isotopes in camelid remains found at the Late Archaic site TU‐52 (ca. 5000–3800 bp ), the Tarajne Phase site TU‐94 and the Early Formative sites TU‐54, TU‐85 and TU‐122 (ca. 3100–2400 bp ). All of the sites are located in the Puna de Atacama (Northern Chile) along the 14 km Tulan transect, between the head of Tulan ravine (ca. 3000 m.a.s.l.) and the border of the Salar de Atacama (2317 m.a.s.l.). Our aim is to understand how the space was used by hunter‐gatherers and early herders from the beginning of camelid domestication to the consolidation of herding practices. Isotopic analyses were complemented with osteometric data in order to correlate changes in animal size and isotopic values with the initiation of animal husbandry. Isotopic and osteometric results show less variability of δ¹³C and δ¹⁵N values during the Late Archaic and Tarajne Phase, whereas variability is higher during the Early Formative. We postulate that during the latter period, there was more widespread use of hunting and herding spaces along the Tulan ravine, including areas above 3000 m.a.s.l. as result of more consolidated herding practices, while the highlands were used as a complementary space to hold livestock near ritual sites and residential settlements. Copyright © 2017 John Wiley & Sons, Ltd.     

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

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

Fluid inclusion and stable isotope constraints on the genesis of the Jian copper deposit,Sanandaj–Sirjan metamorphic zone,Iran

The Jian copper deposit, located on the eastern edge of the Sanandaj–Sirjan metamorphic zone, southwest of Iran, is contained within the Surian Permo‐Triassic volcano‐sedimentary complex. Retrograde metamorphism resulted in three stages of mineralization (quartz ± sulfide veins) during exhumation of the Surian metamorphic complex (Middle Jurassic time; 159–167 Ma), and after the peak of the metamorphism (Middle to Late Triassic time; approximately 187 Ma). The early stage of mineralization (stage 1) is related to a homogeneous H₂O–CO₂ (XCO₂ > 0.1) fluid characterized by moderate salinity (<10 wt.% NaCl equivalent) at high temperature and pressure (>370°C, >3 kbar). Early quartz was followed by small amounts of disseminated fine‐grained pyrite and chalcopyrite. Most of the main‐ore‐stage (stage 2) minerals, including chalcopyrite, pyrite and minor sphalerite, pyrrhotite, and galena, precipitated from an aqueous‐carbonic fluid (8–18 wt.% NaCl equivalent) at temperatures ranging between 241 and 388°C during fluid unmixing process (CO₂ effervescence). Fluid unmixing in the primary carbonaceous fluid at pressures of 1.5–3 kbar produced a high XCO₂ (>0.05) and a low XCO₂ (<0.01) aqueous fluid in ore‐bearing quartz veins. Oxygen and hydrogen isotope compositions suggest mineralization by fluids derived from metamorphic dehydration (δ¹⁸O_fluid = +7.6 to +10.7‰ and δD = ?33.1 to ?38.5‰) during stage 2. The late stage (stage 3) is related to a distinct low salinity (1.5–8 wt.% NaCl equivalent) and temperatures of (120–230°C) aqueous fluid at pressures below 1.5 kbar and the deposition of post‐ore barren quartz veins. These fluids probably derived from meteoric waters, which circulated through the metamorphic pile at sufficiently high temperatures and acquire the characteristics of metamorphic fluids (δ¹⁸O_fluid = +4.7 to +5.1‰ and δD = ?52.3 to ?53.9‰) during waning stages of the postearly Cimmerian orogeny in Surian complex. The sulfide‐bearing quartz veins are interpreted as a small‐scale example of redistribution of mineral deposits by metamorphic fluids. This study suggests that mineralization at the Jian deposit is metamorphogenic in style, probably related to a deep‐seated mesothermal system.     

Monitoring fluid chemistry in iron oxide–copper–gold‐related metasomatic processes,eastern Mt Isa Block,Australia

Most researchers in the Proterozoic eastern Mt Isa Block, NW Queensland, Australia, favour magmatic fluid and salt sources for sodic‐(calcic) alteration and iron oxide–copper–gold mineralization. Here we compare spatial, mineralogic and stable isotope data from regional alteration assemblages with magmatic and magmatic‐hydrothermal interface rocks in order to track chemical and isotopic variations in fluid composition away from inferred fluid sources. Tightly clustered δ¹⁸O values for magnetite, quartz, feldspar and actinolite for igneous‐hosted samples reflect high temperature equilibration in the magmatic‐hydrothermal environment. In contrast, these minerals record predominantly higher δ¹⁸O values in regional alteration and Cu–Au mineralization. This dichotomy reflects partial equilibration with isotopically heavier wallrocks and slightly lower temperatures. Increases in Si concentrations of metasomatic amphiboles relative to igneous amphiboles in part reflect cooling of metasomatic fluids away from igneous rocks. Variations in X_Mg for metasomatic amphiboles indicate local wallrock controls on amphibole chemistry, while variations in X_Cl/X_OH ratios for amphiboles (at constant X_Mg) indicate variable aH₂O/aHCl ratios for metasomatic fluids. Biotite geochemistry also reflects cooling and both increases and decreases in aH₂O/aHCl for fluids away from plutonic rocks. Decreased aH₂O/aHCl ratios for metasomatic fluids reflect in part scavenging of chlorine out of meta‐evaporite sequences, although this process requires already saline fluids. Local increases in aH₂O/aHCl ratios, as well as local decreases in δ¹⁸O values for some minerals (most notably haematite and epithermal‐textured quartz), may indicate ingress of low salinity, low δ¹⁸O fluids of possible meteoric origin late in the hydrothermal history of the region. Taken together, our observations are most consistent with predominantly magmatic sources for metasomatic fluids in the eastern Mt Isa Block, but record chemical and isotopic variations along fluid flow paths that may be important in explaining some of the diversity in alteration and mineralization styles in the district.     

Paleonutritional and paleodietary survey on prehistoric humans from Las Cañadas del Teide (Tenerife,Canary Islands) based on chemical and histological analysis of bone

The aim of the present study is to perform a paleodietary and paleonutritional survey on 17 individuals buried in accordance with the prehispanic ritual in the central plateau of the island Tenerife, called Las Cañadas del Teide. We recorded hydrogen, nitrogen and carbon isotope compositions of human bone collagen, bone barium and strontium, and histomorphometrically assessed trabecular bone mass (TBM). Bone trace elements and TBM were compared with reference data derived from a modern sample consisting of 13 individuals. In addition, δ¹⁵N and δ¹³C values were determined in several modern indigenous plants, bone collagen of prehistoric domestic animals (goat and pig), and prehistoric wild animals (a giant lizard, Gallotia goliath and a giant rat, Canaryomis bravoi), which represent food sources potentially consumed by the prehistoric population of the Island. The carbon stable isotope composition of bone collagen ranged between ?20.5 and ?18.6‰ (VPDB), indicating a diet based on C₃ plants. Nitrogen isotope values ranged from 8.2 to 12.4‰ (AIR), suggesting a general meat-enriched diet, most likely domestic goats, of higher level consumers. Hydrogen isotope values ranged from ?18 to +4‰, whereas log Ba/Sr was greater than ?0.40 in the vast majority of cases. TBM showed a tendency to osteoporosis in 30% of the individuals analyzed. C-14 dating showed that two burial sites, including 5 individuals, belonged to the post-conquest era (after the 15th century), despite a fully “prehispanic” burial ritual, which lends credenceto the oral tradition that some of the prehispanic population fled to the highlands at the time of the Spanish conquest, and lived there during decades or even centuries. These individuals showed lower δD, δ¹³C and δ¹⁵N, and higher log Ba/Sr values than those buried before the Spanish conquest, suggesting dietary differences between the two groups. Also, women showed a trend to a higher consumption of vegetables than men.     

Long‐term chemical evolution and modification of continental basement brines – a field study from the Schwarzwald,SW Germany

Highly saline, deep‐seated basement brines are of major importance for ore‐forming processes, but their genesis is controversial. Based on studies of fluid inclusions from hydrothermal veins of various ages, we reconstruct the temporal evolution of continental basement fluids from the Variscan Schwarzwald (Germany). During the Carboniferous (vein type i), quartz–tourmaline veins precipitated from low‐salinity (<4.5wt% NaCl + CaCl₂), high‐temperature (≤390°C) H₂O‐NaCl‐(CO₂‐CH₄) fluids with Cl/Br mass ratios = 50–146. In the Permian (vein type ii), cooling of H₂O‐NaCl‐(KCl‐CaCl₂) metamorphic fluids (T ≤ 310°C, 2–4.5wt% NaCl + CaCl₂, Cl/Br mass ratios = 90) leads to the precipitation of quartz‐Sb‐Au veins. Around the Triassic–Jurassic boundary (vein type iii), quartz–haematite veins formed from two distinct fluids: a low‐salinity fluid (similar to (ii)) and a high‐salinity fluid (T = 100–320°C, >20wt% NaCl + CaCl₂, Cl/Br mass ratios = 60–110). Both fluids types were present during vein formation but did not mix with each other (because of hydrogeological reasons). Jurassic–Cretaceous veins (vein type iv) record fluid mixing between an older bittern brine (Cl/Br mass ratios ~80) and a younger halite dissolution brine (Cl/Br mass ratios >1000) of similar salinity, resulting in a mixed H₂O‐NaCl‐CaCl₂ brine (50–140°C, 23–26wt% NaCl + CaCl₂, Cl/Br mass ratios = 80–520). During post‐Cretaceous times (vein type v), the opening of the Upper Rhine Graben and the concomitant juxtaposition of various aquifers, which enabled mixing of high‐ and low‐salinity fluids and resulted in vein formation (multicomponent fluid H₂O‐NaCl‐CaCl₂‐(SO₄‐HCO₃), 70–190°C, 5–25wt% NaCl‐CaCl₂ and Cl/Br mass ratios = 2–140). The first occurrence of highly saline brines is recorded in veins that formed shortly after deposition of halite in the Muschelkalk Ocean above the basement, suggesting an external source of the brine's salinity. Hence, today's brines in the European basement probably developed from inherited evaporitic bittern brines. These were afterwards extensively modified by fluid–rock interaction on their migration paths through the crystalline basement and later by mixing with younger meteoric fluids and halite dissolution brines.     

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

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