The effects of PVAc treatment and organic solvent removal on δ13C, δ15N,and δ18O values of collagen and hydroxyapatite in a modern bone

The stable isotopic analysis of archaeological and paleontological bones has become a common method to examine questions of ecology, climate, and physiology. As researchers addressing such questions incorporate museum collections in their studies, it is necessary to understand the isotopic effects of common preservation techniques utilized in such collections to ensure the preservation of original isotopic values. This study examines the effects of PVAc glue (polyvinyl acetate) applied in acetone solution and the subsequent removal of PVAc using various organic solvents on the δ¹³C and δ¹⁵N values of extracted bone collagen, the δ¹³C and δ¹⁸O values of carbonate in bone hydroxyapatite, and the δ¹⁸O values of phosphate in hydroxyapatite. The data demonstrate that isotopic values in the collagen and phosphate are unaffected by any combination of PVAc treatment and solvent application. The carbonates show little variation in δ¹³C values, but exhibit variable δ¹⁸O values upon exposure to the PVAc solution. It is here suggested that δ¹⁸O values from carbonates in PVAc-treated bones do not retain an original isotopic value and should not be included in future studies.     

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.     

Stable Carbon and Oxygen Isotope Spacing Between Bone and Tooth Collagen and Hydroxyapatite in Human Archaeological Remains

Spacing between stable isotope values in bones and teeth is a valuable tool for examining dietary influences and diagenesis. This study examines carbon and oxygen isotope values from collagen and hydroxyapatite (structural carbonate and phosphate) in archaeological human bones and teeth to derive species‐specific correlation equations and isotope spacing values. The δ¹³C_collagen and δ¹³C_{structural carbonate} in bone and dentin collagen show a strong correlation (R = 0.87, 0.90, respectively) with an average Δ¹³C_carb‐coll spacing of 5.4‰. The consistency of this isotope spacing with other large mammals and in humans with both low and high protein intake (as indicated by enriched δ¹⁵N values) suggests a similar allocation of protein‐derived carbon and whole diet‐derived carbon to collagen and structural carbonates, respectively, as other terrestrial mammals regardless of absolute meat intake. The δ¹⁸O_{structural carbonate} and δ¹⁸O_phosphate show the strongest correlation in enamel (R = 0.65), weaker correlations in dentin (R = 0.59) and bone (R = 0.35), with an average Δ¹⁸O_carb‐phos of 7.8‰. This isotope spacing is slightly lower than previously reported for large mammals and limited available data for humans. The results potentially indicate species‐specific fractionations and differing access to body water and blood‐dissolved inorganic carbonates in the presence of collagen formation. The use of correlation between δ¹⁸O_{structural carbonate} and δ¹⁸O_phosphate to determine diagenetic state is not recommended. The strength of this correlation observed in bones and teeth is variable and alternate indicators of diagenetic state (i.e. C:N ratios of collagen) provide more robust and independent evidence of isotope preservation despite presence/absence of a strong isotope correlation. Published 2012. This article is a U.S. Government work and is in the public domain in the USA.     

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.     

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.     

Origin of palaeo‐waters in the Ordovician carbonates in Tahe oilfield,Tarim Basin: constraints from fluid inclusions and Sr,C and O isotopes

Petrographic features, isotopes, and trace elements were determined, and fluid inclusions were analyzed on fracture‐filling, karst‐filling and interparticle calcite cement from the Ordovician carbonates in Tahe oilfield, Tarim basin, NW China. The aim was to assess the origin and evolution of palaeo‐waters in the carbonates. The initial water was seawater diluted by meteoric water, as indicated by bright cathodoluminescence (CL) in low‐temperature calcite. The palaeoseawater was further buried to temperatures from 57 to 110°C, nonluminescent calcite precipitated during the Silurian to middle Devonian. Infiltration of meteoric water of late Devonian age into the carbonate rocks was recorded in the first generation of fracture‐ and karst‐filling dull red CL calcite with temperatures from <50°C to 83°C, low salinities (<9.0 wt%), high Mn contents and high ⁸⁶Sr/⁸⁷Sr ratios from 0.7090 to 0.7099. During the early Permian, ⁸⁷Sr‐rich hydrothermal water may have entered the carbonate rocks, from which precipitated a second generation of fracture‐filling and interparticle calcite and barite cements with salinities greater than 22.4 wt%, and temperatures from 120°C to 180°C. The hydrothermal water may have collected isotopically light CO₂ (possibly of TSR‐origin) during upward migration, resulting in hydrothermal calcite and the present‐day oilfield water having δ¹³C values from ?4.3 to ?13.8‰ and showing negative relationships of ⁸⁷Sr/⁸⁶Sr ratios to δ¹³C and δ¹⁸O values. However, higher temperatures (up to 187°C) and much lower salinities (down to 0.5 wt%) measured from some karst‐filling, giant, nonluminescent calcite crystals may suggest that hydrothermal water was deeply recycled, reduced (Fe‐bearing) meteoric water heated in deeper strata, or water generated from TSR during hydrothermal water activity. Mixing of hydrothermal and local basinal water (or diagenetically altered connate water) with meteoric waters of late Permian age and/or later may have resulted in large variations in salinity of the present oilfield waters with the lowest salinity formation waters in the palaeohighs.     

Diagenesis in bone and enamel apatite carbonate; the potential of density separation to assess the original composition

This paper presents a new approach to the isotopic measurement of diagenetically altered archaeological bone apatite carbonate. We describe how the existing differential dissolution method may be combined with a new approach to remove diagenetically reformed material on the basis of its greater specific gravity. We show that heavier, more diagenetically altered fraction has a higher (altered) δ¹³C and also increased crystallinity within one individual. In addition, we proposed one potential tool to check the validity of bone carbonate by comparing bone collagen, enamel carbonate and bone carbonate values of δ¹³C and radiocarbon content from the same individual. In the case of Danebury cattle, we estimated the biogenic δ¹³C_apa value for DC83 and DC89, although it is still difficult to overcome diagenesis in order to meet the expected value, which is shown to be 1.9‰ (DC83) and 3.5‰ (DC89).     

Fracture-fill calcite as a record of microbial methanogenesis and fluid migration: a case study from the Devonian Antrim Shale, Michigan Basin

The Devonian Antrim Shale is an organic‐rich, naturally fractured black shale in the Michigan Basin that serves as both a source and reservoir for natural gas. A well‐developed network of major, through‐going vertical fractures controls reservoir‐scale permeability in the Antrim Shale. Many fractures are open, but some are partially sealed by calcite cements that retain isotopic evidence of widespread microbial methanogenesis. Fracture filling calcite displays an unusually broad spectrum of δ¹³C values (+34 to ?41‰ PDB), suggesting that both aerobic and anaerobic bacterial processes were active in the reservoir. Calcites with high δ¹³C values (>+15‰) record cementation of fractures from dissolved inorganic carbon (DIC) generated during bacterial methanogenesis. Calcites with low δ¹³C values (13C values between ?10 and ?30‰ can be attributed to variable organic matter oxidation pathways, methane oxidation, and carbonate rock buffering. Identification of ¹³C‐rich calcite provides unambiguous evidence of biogenic methane generation and may be used to identify gas deposits in other sedimentary basins. It is likely that repeated glacial advances and retreats exposed the Antrim Shale at the basin margin, enhanced meteoric recharge into the shallow part of the fractured reservoir, and initiated multiple episodes of bacterial methanogenesis and methanotrophic activity that were recorded in fracture‐fill cements. The δ¹⁸O values in both formation waters and calcite cements increase with depth in the basin (?12 to ?4‰ SMOW, and +21 to +27‰ PDB, respectively). Most fracture‐fill cements from outcrop samples have δ¹³C values between ?41 and ?15‰ PDB. In contrast, most cement in cores have δ¹³C values between +15 and +34‰ PDB. Radiocarbon and ²³⁰Th dating of fracture‐fill calcite indicates that the calcite formed between 33 and 390 ka, well within the Pleistocene Epoch.     

Intra-skeletal variability in trace elemental content of Precolumbian Chupicuaro human bones: the record of post-mortem alteration and a tool for palaeodietary reconstruction

This study applies an intra-skeletal sampling strategy to examine post-mortem alteration of archaeological human bone from west Mexico, and to reconstruct ancient diet. Human bone from the Chupicuaro culture (Mexico, Preclassic period) constitutes an ideal material with which to examine subsistence strategies because the specific hydrothermal environment in which the population lived would have provided certain food components (hydrothermal waters and carbonates) with distinct signature in Ca, Mg, F, Li, Sr, Mn, V and U values. Four to ten samples were taken from the long bones of six skeletons. Bone trace element content (Ca, P, F, Mn, Mg, Na, Li, V, Zn, Rb, Sr, Ba, Y, La, Ce, Nd, Th, U) and bone alteration parameters (crystallinity, organic matter and secondary calcite content) were analysed at the intra-skeletal level. Stable isotopic signatures (bone δ¹³C and δ¹⁸O_carbonate) and histological analyses were also performed on a single bone from each individual. Results indicate that all of the skeletons were affected by post-mortem mineralogical, structural and geochemical transformations. Biological bone δ¹³C values seem preserved for most of the individuals but an increase in crystallinity accompanies depletion in bone δ¹⁸O values. The combination of bone alteration parameters with bone elemental content shows that in this very specific context, a widespread dissolution-recrystallisation is unlikely. Of the hydrothermal tracers, Sr, F and Li were of particular interest because their retention in living tissues is related to the amount ingested. The intra-skeletal Li content does not reveal any pattern but Li depletion is not excluded. In contrast, Sr and F show a progressive intra-skeletal diagenetic enrichment likely due to gradual diffusion–adsorption processes. The bones with the lowest concentrations in these elements are assumed to yield the best representative ante-mortem values. The signal extracted from each skeleton, a very unusually high bone Sr, F and Li content, is interpreted as reflecting the consumption of the local hydrothermal products, which are also enriched in these elements.     

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.     

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.     

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.     

Development of successive karstic systems within the Baix Penedès Fault zone (onshore of the Valencia Trough,NW Mediterranean)

The Baix Penedès Fault zone records successive karstic systems. The outcrops studied correspond to different segments of the fault, which were temporarily connected and disconnected, allowing for different diagenetic processes to occur. The first karstic system affected the Mesozoic rocks due to subaerial exposure after Paleogene compression, an event characterized by widespread dissolution and the generation of vug and cavern porosity. The δ¹⁸O values of the dolomitic sediment filling the initial vuggy porosity are similar to those of the host dolomite, indicating that the sediment comes from the erosion and reworking of the host rock. The second karstic system is related to the upward propagation of the Baix Penedès Fault. This deformation was characterized by random‐fracture fabrics with dolomite cement and sediment. The stable isotopes values and Sr/Ca ratios of both the dolomite cement and sediments are similar to those of the host rock. In contrast, the more depleted δ¹³C values indicate the influence of soil‐derived CO₂ and the opening of the system to meteoric waters. During the third karstic event, the δ¹⁸O, δ¹³C, Sr/Ca ratios, and ⁸⁷Sr/⁸⁶Sr values of diagenetic cements suggest a marine signature, indicating that the karstic sediments were dolomitized under the influence of late Burdigalian‐Langhian marine waters. These marine waters were probably expelled from poorly buried sediments and circulated through faults producing dolomitization of the karstic sediments. A final karst system developed during a period of uplift and subaerial exposure. The δ¹⁸O values, the Mg/Ca and Sr/Ca ratios, and the high radiogenic values of the calcite cements formed during this period indicate precipitation from meteoric waters. The results of this study have implications for carbonate hydrocarbon reservoir analogs subject to karstic influence in the Valencia Trough and elsewhere.     

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.     

Stable carbon and oxygen isotopic compositions of wood ash: an experimental study with archaeological implications

Wood ash, composed mainly of the mineral calcite, is an important component in many archaeological sites. Identification of wood ash in the archaeological record is often difficult due to mixing of ash with other calcitic components of geogenic origin and/or due to diagenetic changes. A recent empirical study using the stable isotope compositions of carbon (δ¹³C) and oxygen (δ¹⁸O) in wood ash enabled the identification of mixtures of wood ash with geogenic calcite and to follow diagenetic changes due to partial dissolution and re-precipitation of ash in two prehistoric cave sites in Israel. Little however is known about the processes responsible for the isotopic compositions of wood ash in relation to formation at various temperatures and the influence on isotopic composition of ash from a variety of plant species. Here we present an experimental study of wood ash formed by burning three C3 tree species and one C4 desert bush at different temperatures. The results indicate that there are significant differences in the isotopic compositions of carbon and oxygen between wood ash that forms by combustion at a relatively low temperature (500 °C) and at a higher temperature (900 °C). In addition, we show that the isotopic composition of carbon and oxygen in high temperature wood ash approaches equilibrium over a period of several months and that the carbon isotopic composition of low temperature wood ash may reflect the photosynthetic pathway of the burnt woody species. Lastly, we show that the isotopic compositions obtained from wood ash prepared at different temperatures do not reflect a temperature dependent fractionation process, but a mixing line between calcite that formed by low temperature combustion and calcite formed by high temperature combustion which later underwent re-carbonation with atmospheric CO₂. In addition, we suggest that exchange processes may possibly occur during combustion between decomposing calcium-oxalate and atmospheric O₂, CO₂ and CO. The archaeological implications of this study are discussed in relation to identification of wood ash in the archaeological record, identification of fuel sources and burning temperatures, and diagenetic changes expected in karstic cave environments. The method presented here can be applied at any archaeological site.     

Fluid inclusion and isotopic constraints on the origin of ore‐forming fluid of the Jinman–Liancheng vein Cu deposit in the Lanping Basin,western Yunnan,China

Extensive quartz–carbonate–Cu sulfide veins occur in clastic rocks and are spatially related to Paleocene granites in the western border of the Lanping Basin, western Yunnan, China. Abundant aqueous‐carbonic fluid inclusions occur in these veins but their origin is debated. In the Jinman–Liancheng deposit, individual primary inclusion groups contain either exclusively liquid‐rich inclusions (Gl), or coexisting liquid‐rich and vapor‐rich inclusions (Glv). Microthermometry and estimate of CO₂ content indicate that type Gl inclusions either have homogenization temperatures (Th) 238–263°C and contain c. 3.9–5.5 mole % CO₂, or have Th 178–222°C and contain c. 1.6–3.2 mole % CO₂. Type Glv inclusions are thought to represent samples of fluid unmixing that occurred at 183–218°C. At that time, the liquid phase in the unmixing fluid may contain c. 2.0–3.3 mole % CO₂. As such, the correlation of CO₂ content with Th for type Gl inclusions is thought to be caused by fluid unmixing with decreasing temperature and subsequent CO₂ escape. δ¹⁸O and δD values of the parent water mainly fall in the field below that of primary magmatic water, indicative of fluid derivation from degassed (in open system) magmatic water, with no contributions from basinal or meteoric water. Initial Sr isotopic compositions of hydrothermal carbonates suggest that the fluid was magmatic, probably derived from the Paleogene granites. δ¹³C_PDB values (?4‰ to ?7‰) of the hydrothermal carbonates and δ³⁴S_V‐CDT values of sulfides (mainly ?11‰ to +5‰) indicate that the carbon and sulfur can be derived from (degassed) magma and/or nonmagmatic sources. The CO₂‐rich and magmatic‐water‐derived fluid at Jinman–Liancheng differs from the CO₂‐poor and basinally derived fluid in sediment‐hosted stratiform Cu (SSC) deposits, which suggests that there are no genetic linkages between the vein Cu and SSC deposits in the Lanping Basin.     

Diet and death in times of war: isotopic and osteological analysis of mummified human remains from southern Mongolia

This study presents the results of an isotopic analysis of nine naturally mummified individuals—three adults, two adolescents, one juvenile, and three infants—recovered from the Hets Mountain Cave site in southern Mongolia, where they had been secondarily deposited. All of the individuals show evidence of violent perimortem trauma, but no skeletal indicators of nutritional or disease-related stress. Multi-isotopic data (δ¹³C, δ¹⁵N, δ¹⁸O, ⁸⁷Sr/⁸⁶Sr, and ²⁰ⁿPb/²⁰⁴Pb) were characterized in multiple tissues from each individual when possible, in order to reconstruct diet composition and residential origin at different points in life. Specifically, δ¹³C and δ¹⁵N in bone carbonate and collagen (N = 8) and hair keratin (N = 4) were coupled with enamel carbonate δ¹⁸O and δ¹³C (N = 3) and enamel ⁸⁷Sr/⁸⁶Sr, and ²⁰ⁿPb/²⁰⁴Pb (N = 3) to assess diet and residential mobility in relation to skeletal indicators of health and trauma. Results are consistent with a persistence of mixed C₃/C₄ pastoral subsistence and general stability of diet composition over the life course, in contrast to contemporary accounts of widespread famine and a dependence on grains imported from China throughout the region. However, results also suggest that at least some individuals may have migrated to this region of southern Mongolia from elsewhere during life, meaning that their dietary isotopic profiles may not represent local subsistence patterns near the Hets Mountain Cave site. Overall, these results speak to the utility of life course oriented multi-isotopic analysis in complementing more top-down historical analyses in understanding variation in subsistence, nutrition, and migration in regions undergoing significant political and economic turmoil.     

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.     

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

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

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.