Stable Isotope Record of Human and Sheep Enamel Carbonate from the Ancient Middle Euphrates Valley (Syria)

Stable isotope analyses of human tooth enamel have allowed us to reconstruct the isotope composition of dietary carbon, changes in the oxygen isotope composition of drinking water and the possible migration of humans in ancient Terqa and Tell Masaikh (SE Syria). δ¹⁸O_carbonate values of human tooth enamel from the interval comprising the Neo‐Assyrian to the modern Islamic periods (from 900 BC to AD 1949) generally mirror the isotope composition of Euphrates water, which is believed to have been a major drinking water source. Lower δ¹⁸O_carbonate values of human Bronze Age apatite are linked to a different hydrologic system that was present in the Middle Euphrates valley at that time (2650–1700 BC). Higher δ¹⁸O_carbonate values of some individuals in the Neo‐Assyrian (900–700 BC) and Islamic periods (AD 600–1200) may indicate human migration from the interior of the Near East. Low δ¹³C_carbonate values (−11.3 to −12.4‰) of human tooth enamel from the interval comprising the Early Bronze to the Islamic periods (from 2650 BC to AD 1200) indicate C₃ plants as a predominant source of dietary carbon. Changes in human dietary customs in SE Syria (with inferred usage of C₄ plants) occurred in the modern Islamic period only (AD 1850–1949). Oxygen and carbon isotope data of sheep enamel show the usage of water bodies characterised by an enhanced evaporation rate during the Neo‐Assyrian time (900–700 BC) and grazing sheep herds on drier areas during the Islamic and the modern Islamic periods (after AD 600). Copyright © 2015 John Wiley & Sons, Ltd.     

Significance and Limitations of Stable Oxygen Isotope Ratios in the Apatite Phosphate of Archaeological Vertebrate Finds for Provenance Analysis in an Alpine Reference Region

A multi‐isotope fingerprint consisting of δ¹⁸O_phosphate, ⁸⁷Sr/⁸⁶Sr, ²⁰⁸Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁸Pb/²⁰⁷Pb and ²⁰⁶Pb/²⁰⁷Pb was established in the bioapatite of 219 individual archaeofaunal remains (cattle, pig, red deer) excavated from sites located along a specific transect of the European Alps, namely the Inn–Eisack–Adige–Brenner Passage, that has been of eminent importance since European prehistory. This reference area is vertically stratified, and since δ¹⁸O in the skeleton is influenced by climate, water source, physiology and even culture, we tested the relative contribution and importance of δ¹⁸O as a component of the multi‐isotope fingerprint for provenance analysis in this alpine region by a novel mathematical approach. In particular, we adapted a supervised learning approach through expectation–maximization (EM) clustering for fingerprint extraction and evaluated the contribution of each isotopic ratio to the data structure. While an altitude effect was evident in δ¹⁸O, its overall structural importance in the complete isotopic fingerprint was rather low. Therefore, provenance analysis of bioarchaeological finds in this region is possible by measuring stable Sr and Pb ratios alone, which is of considerable importance when δ¹⁸O values are not available, e.g., in cremated finds, although some information is lost. Whether this is tolerable depends on the scientific question to be solved.     

Stable isotopic analysis of human bones from Jiahu site,Henan, China: implications for the transition to agriculture

We have investigated change in subsistence during the transition to agriculture in the site of Jiahu, Henan Province, China, using stable isotopic analysis of collagen and apatite in human bones. Millet agriculture is well documented at drier high latitudes of the Yellow River Valley, while rice agriculture predominated at wetter lower latitudes of the Yangtze Valley region. The early Neolithic site of Jiahu lies near the boundary between the drier north and wetter south. Archaeobotanical evidence shows that rice was a significant component of diet at Jiahu, but its δ¹³C value is similar to that of other foods, and therefore cannot be conclusively identified by carbon isotope analysis. Foxtail and broomcorn millets are the only C₄ crops known for the Chinese Neolithic. Because of their high δ¹³C values, their consumption can be evaluated by stable carbon isotope analysis of human bone. Collagen reflects mainly the δ¹³C value of dietary protein, and apatite accurately records that of the whole diet. Isotopic analysis of 15 well-preserved samples from three periods shows that collagen δ¹³C values were very low for almost all individuals, suggesting C₃-based foods dominated their diets. However, apatite carbonate δ¹³C values and δ¹³C spacing between collagen and apatite (Δ¹³C_ap-co) indicate that millet may have been a minor component of the diet in this region. Individuals, who consumed the smallest amounts of animal protein, as indicated by low δ¹⁵N, generally had the highest apatite δ¹³C values. Archaeobotanical evidence for millet at Jiahu is needed to support this interpretation.     

Method-dependent variations in stable isotope results for structural carbonate in bone bioapatite

Stable carbon and oxygen isotope values (δ¹³C, δ¹⁸O) were obtained for structural carbonate in the bioapatite of archaeological bones from Guatemala and Sudan using several common analytical methods. For the Sudan samples, the different methods produced δ¹³C values within ±0.1‰ and δ¹⁸O values within ±0.7‰, on average. The isotopic results for the Guatemala samples were similar in reproducibility to the Sudan samples when obtained using methods that employed lower reaction temperatures and reactions in sealed vessels. However, many Guatemala samples had highly variable and extremely low δ¹⁸O values when reacted at higher temperatures in vessels that remained open to cryogenic traps. The latter arrangement caused reaction products to be removed immediately upon their production. The anomalously low δ¹⁸O values are related to the production of a contaminant gas that causes the m/z 46/44 ratio to be lowered, either by adding to the m/z 44 peak or subtracting from the m/z 46 peak. That said, potential contaminant materials were not detectable in “anomalous” bones using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction, or inductively-coupled plasma atomic emission spectroscopy. However, subtle structural and chemical differences between “normal” and “anomalous” samples were observed, most notably in the FTIR ν₂ CO₃ domain. We suggest that these changes promote volatilization of an oxyphosphorus compound and oxygen isotope fractionation between PO⁻ derived from this compound and CO₂ derived from bone carbonate. Production of the contaminant gas and the related “anomalous” δ¹⁸O values is reversible if the reaction occurs within a sealed vessel for a sufficient period of time, which allows a “back-reaction” to occur.     

A Late Neolithic vertebrate food web based on stable isotope analyses

Stable carbon and nitrogen isotope analyses of bone collagen, and stable carbon and oxygen isotope analyses of the bone's structural carbonate, were performed on 120 individuals representing 33 vertebrate species, including a single human bone find, collected from the Late Neolithic settlement at Pestenacker, Bavaria, Germany. We were thus capable of reconstructing a rather complex food web and could also address particular issues, such as whether humans influenced the diet of their domestic animals as opposed to their wild relatives, or whether humans perhaps had to compete over food with their domesticates. A rather unexpected result was that freshwater fish, which could be captured in the nearby river Lech, a major tributary of the Danube, contributed to the human diet only occasionally. As for mammals, it was also possible to recognise different trophic levels for birds and aquatic vertebrates, applying stable isotope analyses to both bone collagen and structural carbonate. In the case of fish, δ¹⁸O values at least revealed a physiological regularity in terms of temperature preference, besides diet. Conceivably, variability of δ¹⁸O in surface water as reflected, for example, by species that avoided human settlements, may help to characterise past ecosystems and to define site catchment exploited by Neolithic man in the course of food acquisition. Copyright © 2006 John Wiley & Sons, Ltd.     

FOCUS: effect of diet and protein source on carbon stable isotope ratios in collagen: follow up to

We analyzed carbon stable isotope data from bone collagen of animals consuming varied experimental diets, including recently published data from Warinner and Tuross [Warinner, C., Tuross, N., 2009. Alkaline cooking and stable isotope tissue–diet spacing in swine: archaeological implications. Journal of Archaeological Science 36, 1690–1697; this journal]. Comparing regression lines for the relationship between collagen and diet δ¹³C, we show that protein source, and not physiology, explains the apparent taxonomic difference between swine and rodents reported in that paper. Our results reveal a complex relationship between whole diet and dietary protein in determining collagen δ¹³C values, such that in many cases, collagen alone may not provide reliable reconstructions of paleodiet. We advocate the simultaneous use of both collagen and apatite δ¹³C, whenever possible, to assess the diets of prehistoric peoples.     

Human Response to Climate Change during the Umm an‐Nar/Wadi Suq Transition in the United Arab Emirates

Stable oxygen isotope ratios in archaeological human dental enamel represent an under‐utilised tool in the examination of changing climatic patterns in the ancient world. In the Oman Peninsula at the end of the third millennium bc , rapid aridification was accompanied by a breakdown in interregional trade relations; however, the human response to these changes is poorly understood. At the Bronze Age necropolis at Shimal in the United Arab Emirates, dental enamel from individuals interred in both Umm an‐Nar (ca 2700–2000 bc ) and Wadi Suq (ca 2000–1300 bc ) tombs underwent oxygen, strontium and carbon isotope analyses to examine how local inhabitants of southeastern Arabia responded to both environmental and socioeconomic change. While individuals from Shimal exhibit a clear shift in mean δ¹⁸O_c(VPDB) values from the Umm an‐Nar (−3.5 ± 0.6‰, 1σ) to the Wadi Suq (−2.4 ± 0.9‰, 1σ), corresponding ⁸⁷Sr/⁸⁶Sr and δ¹³C_ap signatures display homogeneity indicative of continuity in Bronze Age lifeways. Together, these data highlight the ability of local communities to successfully adapt to their changing environs (in lieu of societal collapse or a shift to a more mobile lifestyle) in an effort to maintain their way of life. Copyright © 2014 John Wiley & Sons, Ltd.     

Hydrogeology of the Krafla geothermal system,northeast Iceland

The Krafla geothermal system is located in Iceland's northeastern neovolcanic zone, within the Krafla central volcanic complex. Geothermal fluids are superheated steam closest to the magma heat source, two‐phase at higher depths, and sub‐boiling at the shallowest depths. Hydrogen isotope ratios of geothermal fluids range from ?87‰, equivalent to local meteoric water, to ?94‰. These fluids are enriched in ¹⁸O relative to the global meteoric line by +0.5–3.2‰. Calculated vapor fractions of the fluids are 0.0–0.5 wt% (~0–16% by volume) in the northwestern portion of the geothermal system and increase towards the southeast, up to 5.4 wt% (~57% by volume). Hydrothermal epidote sampled from 900 to 2500 m depth has δD values from ?127 to ?108‰, and δ¹⁸O from ?13.0 to ?9.6‰. Fluids in equilibrium with epidote have isotope compositions similar to those calculated for the vapor phase of two‐phase aquifer fluids. We interpret the large range in δD_EPIDOTE and δ¹⁸O_EPIDOTE across the system and within individual wells (up to 7‰ and 3.3‰, respectively) to result from variable mixing of shallow sub‐boiling groundwater with condensates of vapor rising from a deeper two‐phase reservoir. The data suggest that meteoric waters derived from a single source in the northwest are separated into the shallow sub‐boiling reservoir, and deeper two‐phase reservoir. Interaction between these reservoirs occurs by channelized vertical flow of vapor along fractures, and input of magmatic volatiles further alters fluid chemistry in some wells. Isotopic compositions of hydrothermal epidote reflect local equilibrium with fluids formed by mixtures of shallow water, deep vapor condensates, and magmatic volatiles, whose ionic strength is subsequently derived from dissolution of basalt host rock. This study illustrates the benefits of combining phase segregation effects in two‐phase systems during analysis of wellhead fluid data with stable isotope values of hydrous alteration minerals when evaluating the complex hydrogeology of volcano‐hosted geothermal systems.     

The effect of growth on stable nitrogen isotope ratios in subadult bone collagen

Stable nitrogen isotopes have been used to reconstruct infant feeding practices as nursing infants have elevated δ¹⁵N ratios compared with their mothers. However, infancy is also a time of rapid growth, which may alter nitrogen isotope diet‐to‐tissue spacing. Several studies have documented a decrease in δ¹⁵N during growth in tissues with relatively fast accretion rates. This study investigates the effect that the growth of long bones, via collagen accretion, has on δ¹⁵N ratios. Long bones from individuals aged seven to nineteen years were obtained from a protohistoric ossuary in Ontario, Canada. Analysis of juveniles and adolescents permitted the examination of growth in a group who were not also nursing. It is concluded that a nitrogen isotope growth effect is not detectable in bone collagen from juveniles and adolescents, because: (1) δ¹⁵N ratios are not significantly different among the epiphyses, metaphyses and diaphysis of a growing long bone; (2) δ¹⁵N ratios are not significantly different between faster‐growing versus slower‐growing metaphyses; and (3) δ¹⁵N ratios are not significantly different between bones (or areas of a bone) that are still undergoing growth, versus bones that have ceased growing. The relatively slow speed of collagen accretion may explain why a growth effect is not manifested. Ultimately this research lends support to the use of nitrogen isotopes from bone collagen for infant feeding reconstructions. Copyright © 2009 John Wiley & Sons, Ltd.     

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.     

Preliminary evidence for medieval Polish diet from carbon and nitrogen stable isotopes

In this pilot study, stable carbon and nitrogen isotopes from bone collagen and apatite of skeletons from the 11th and 12th century cemetery in Giecz, Poland are interpreted. Isotope values from a small number of fish and animal bones from the same archaeological site are also examined. The goal of this research is to provide preliminary evidence of diet for a group of medieval Polish peasants, with particular emphasis on sex-based differences in diet. Results of isotope analyses suggest diet of this early medieval population was omnivorous and terrestrial-based. Fish bones sampled exhibit low δ¹³C ratios, and in half of the cases are significantly enriched in ¹⁵N, indicating they are freshwater species. Human bones do not reflect these signatures, suggesting freshwater fish were not a significant source of dietary protein at Giecz. The ¹³C_coll from some human bones is enriched beyond what might be expected from an exclusively C₃ diet. Associated mammal bones do not exhibit similarly elevated δ¹³C_coll ratios, suggesting enrichment among humans is not due to consumption of animals foddered on C₄ plants. Two possible sources of ¹³C_coll enrichment are marine fish in diet and direct consumption of a C₄ plant, such as millet. The δ¹³C values obtained from bone apatite of a small subset of humans suggest that millet contributes to ¹³C_coll enrichment, although at least three individuals may have also consumed small amounts of marine fish. Sex-based differences in δ¹⁵N ratios indicate that men consumed relatively more animal products (meat or dairy) than did women. There is also a correlation between δ¹³C_coll and δ¹⁵N values in skeletons of men that is absent in women. These carbon and nitrogen isotope data are the first reported for any Polish population and contribute to a more complete picture of dietary adaptation and social organization in medieval Europe.     

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

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

Preservation assessment of Miocene–Pliocene tooth enamel from Tugen Hills (Kenyan Rift Valley) through FTIR,chemical and stable-isotope analyses

We investigated fossil tooth enamel of mammals and crocodiles from two Mio-Pliocene East-African formations (Lukeino and Mabaget Fms) using infrared spectroscopy and chemical and stable-isotope analyses. Infrared spectra indicate that the fossil enamel contains biological apatite (bioapatite), without significant secondary carbonate contaminations. Several empirical infrared indexes were used to analyze the crystal–chemical characteristics of enamel. Fossil enamel has less organic matter, water and structural carbonate of apatite than modern enamel with which it was compared. Fossil apatite has a better crystallinity than bioapatite. The calcium/phosphorus mass ratio and the fluorine content of fossil apatite show intermediate values between bioapatite and geological fluorapatite. The samples also display significant crystal-chemical variations, depending on the vertebrate group (mammals vs. reptiles) and the taphonomic context (Lukeino Fm vs. Mabaget Fm). In spite of these changes, no relationship was observed between the chemical contents (carbonate and fluorine) and the stable-isotope ratios of carbonate (δ¹³C and δ¹⁸O) in fossil enamel. Preservation of the palaeoenvironmental signals is strongly supported by the fact that the stable-isotope composition of the three investigated fossil mammalian taxa (deinotheres, equids and hippos) is consistent with their ecological features. For instance, typical C₃- and C₄-plant isotope compositions are reflected in the deinotheres and equids, respectively, and amphibious hippos display lower δ¹⁸O values than terrestrial herbivores, as expected.     

Isotopically distinct modern carbonates in abandoned livestock corrals in northern Kenya

We report δ¹⁸O and δ¹³C data from modern carbonate in soils and dung samples from 3 recently abandoned livestock corrals in northern Kenya. Calcium carbonate content is higher within ∼5 cm depth that contains a mixture of dung and surface soils of corrals than in soils below 5 cm depth. We radiocarbon dated carbonates from 0.5 to 40 cm depths in two corrals and one control site. Surface carbonates (0.5 cm) from the two corrals were formed from modern carbon (>1955) when the corrals were active, while all other carbon is >16,000 years (BP) old. Shallow carbonate is also enriched in ¹⁸O (δ¹⁸O up to 3.0‰) and depleted in ¹³C (δ¹³C up to −12.0‰) with respect to carbonate at deeper levels and at two control sites. The δ¹⁸O and δ¹³C of soil carbonates (δ¹⁸O_SC and δ¹³C_SC respectively) in corrals are inversely correlated for depths up to about 15 cm where organic carbon is greater than 0.5%. Below that depth, there is a positive correlation between δ¹⁸O_SC and δ¹³C_SC values, similar to that observed in a control site.     

Oxygen isotopic evidence of residence and migration in a Greek colonial population on the Black Sea

Oxygen isotope analysis was performed on the enamel of the first and third permanent molars of 60 individuals excavated from the Kalfata-Budjaka necropolis associated with the ancient Greek colony of Apollonia Pontica (5th–3rd centuries BC) on the Black Sea coast of Bulgaria. The objective of this study was to examine the geographic origins and residential histories of these individuals and to compare the isotopic data with archaeological evidence derived from the burials in an attempt to distinguish ‘locals’ from ‘non-locals’. The analysis revealed that 55 of the 60 individuals sampled were either locally born or came from areas outside of Apollonia with isotopically similar δ¹⁸O values. Five individuals were identified as ‘non-local’, and their isotope values suggest that they originated from areas with higher δ¹⁸O_w of precipitation, most likely the Aegean region. Unfortunately, the archaeological evidence associated with these five skeletons provides no clues as to their place of origin.     

Provisioning Inka feasts at Tiwanaku, Bolivia: the geographic origins of camelids in the Pumapunku complex

While political integration can be achieved by many means, here we focus on the use of feasting and statecraft in the Inka Empire of the Andean Late Horizon (c. AD 1400-1532) in South America. In order to examine Inka political integration of the Lake Titicaca Basin of Bolivia, we examine paleomobility and paleodiet through radiogenic strontium and stable oxygen and carbon isotope data in archaeological camelid remains from the site of Tiwanaku. Mean radiogenic strontium isotope values from all archaeological camelid enamel and bone samples is ⁸⁷Sr/⁸⁶Sr = 0.70998 ± 0.00179 (1σ, n = 48), mean stable oxygen isotope values from a sub-set of archaeological camelid enamel and bone samples is δ¹⁸O_{carbonate (VPDB)} = −10.0‰ ± 2.6‰ (1σ, n = 18) and mean stable carbon isotope values from a sub-set of archaeological camelid enamel and bone samples is δ¹³C_{carbonate (VPDB)} = −9.0‰ ± 1.7‰ (1σ, n = 18). While many camelids consumed in these feasting events were likely local to the Lake Titicaca Basin, others came from a variety of different geologic zones, elucidating our understanding of Inka statecraft and the role of feasting in political integration in empires in the past.     

Evidence of physico–chemical and isotopic modifications in archaeological bones during controlled acid etching

It has been repeatedly shown that palaeoecological inferences from the elemental and isotopic content of carbonate hydroxylapatite of fossil teeth and bones are unrecoverable without removing diagenetic overprinting by chemical pretreatments. Such pretreatments may in turn cause modification of the biogenic signature. In this paper, we focus upon optimal removal of Ca–bearing carbonates (mainly calcite). In order to control the progress with time of calcite dissolution, we perform leaching under vacuum, and we monitor the evolution of the pH, pCO₂, δ¹³C of released CO₂, %C, δ¹³C and δ¹⁸O of the remaining mineral. For a set of different Quaternary bones and teeth, mass and isotopic balances indicate that 1 hour at most is necessary for complete dissolution of calcite with an optimal conservation of carbonate hydroxylapatite. Long–lasting experiments lead to a fractionation of hydroxylapatite ¹⁸O/¹⁶O carbonates.     

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.     

REFINING ESTIMATES FOR THE SEASON OF SHELLFISH COLLECTION ON THE PACIFIC NORTHWEST COAST: APPLYING HIGH‐RESOLUTION STABLE OXYGEN ISOTOPE ANALYSIS AND SCLEROCHRONOLOGY

Stable oxygen isotopes from estuarine bivalve carbonate from Saxidomus gigantea were analysed combined with high‐resolution sclerochronology from modern and archaeological shells from British Columbia, Canada, to determine the seasonality of shellfish collection from the archaeological site of Namu. The combination of high‐resolution sclerochronology and a micro‐milled sampling strategy for δ¹⁸O analysis permits a precise estimate of archaeological seasonality, because seasonal freshwater influxes and changes in temperature have dual effects on the δ¹⁸O value of the shell. Sclerochronological analysis identifies the timing and duration of growth that is temporally aligned to stable oxygen isotope results, since δ¹⁸O_shell appears to be strongly influenced by seasonal inputs of very low δ¹⁸O snowmelt‐water from adjacent coastal mountain ranges. The results show that shellfish were collected year‐round at this site over a 4000‐year period, and these data combined with other zooarchaeological lines of evidence support the interpretation of year‐round occupation.     

Stable oxygen (δO) and hydrogen (δD) isotopes in ovicaprid dentinal collagen record seasonal variation

Understanding paleoenvironmental conditions, including the frequency and amplitude of seasonal variation, is crucial to understanding a wide array of human behaviors in prehistory. In vertebrate calcified tissue, inorganic oxygen isotopes derived from apatite have been widely used as a proxy for paleoenvironment and seasonality in the archaeological record. However, organic sources of δ¹⁸O and δD in mineralized tissue have remained largely unexplored. Here we measure the oxygen (δ¹⁸O) and hydrogen (δD) composition of dentin collagen sequentially sampled from the lower cheek teeth of four modern ovicaprids from the Baga Gazar'in Chuluu (BGC) region of the Gobi Desert of Mongolia. A significant correlation between trends in hydrogen and oxygen isotope values within individual teeth was identified. The amplitude of isotopic variation observed in sampled tooth dentin is similar to the yearly range of hydrogen and oxygen isotopic variation observed in meteoric precipitation for the region. These data indicate that dentin collagen δ¹⁸O and δD isotopic values reflect seasonal variation in the organic oxygen and hydrogen isotopic composition of diet and ingested water. We argue that paired measurements of dentin collagen δ¹⁸O and δD appear to be reliable seasonal climatic indicators.