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

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

Hydrothermal palaeofluid circulation in the fracture network of the Baksa Gneiss Complex of SW Pannonian Basin,Hungary

A well‐developed fracture‐filling network is filled by dominantly Ca‐Al‐silicate minerals that can be found in the polymetamorphic rock body of the Baksa Gneiss Complex (SW Hungary). Detailed investigation of this vein network revealed a characteristic diopside→epidote→sphalerite→albite ± kfeldspar→chlorite1 ± prehnite ± adularia→chlorite2→chlorite3→pyrite→calcite1→calcite2→calcite3 fracture‐filling mineral succession. Thermobarometric calculations (two feldspar: 230–336°C; chlorites: approximately 130–300°C) indicate low‐temperature vein formation conditions. The relative succession of chlorites in the mineral sequence combined with the calculated formation temperatures reveals a cooling trend during precipitation of the different chlorite phases (T_chlorite1: 260 ± 32°C →T_chlorite2: 222 ± 20°C →T_chlorite3: 154 ± 13°C). This cooling trend can be supported by the microthermometry data of primary fluid inclusions in diopside (T_h: 276–362°C) and epidote (T_h: 181–359°C) phases. The identical chemical character (0.2–1.5 eq. wt% NaCl) of these inclusions mean that vein mineralization occurred in a same fluid environment. The high trace element content (e.g. As, Cu, Zn, Mn) and Co/Ni ratio approximately 1–5 of pyrite grains support the postmagmatic hydrothermal origin of the veins. The vein microstructure and identical fluid composition indicate that vein mineralization occurred in an interconnected fracture system where crystals grew in fluid filled cracks. Vein system formed at approximately <200 MPa pressure conditions during cooling from approximately 480°C to around 150°C. The rather different fluid characteristics (T_h: 75–124°C; 17.5–22.6 eq. wt% CaCl₂) of primary inclusions of calcite1 combining with the special δ¹⁸O signature of fluid from which this mineral phase precipitated refer to hydrological connection between the crystalline basement and the sedimentary cover.     

MATHEMATICAL MODELLING OF THE RELATIONSHIP BETWEEN NEOLITHIC SITES AND THE RIVERS IN XI’AN (SHAANXI PROVINCE,CHINA)*

Based on analyses of the ecological environments of the Neolithic sites along the Chan and Ba Rivers in the Xi’an area (Shaanxi Province, China), it was found that the characteristic factors of the sites had a very close relationship with the nearby river. The characteristic factors of Neolithic sites have been analysed and defined as mathematical parameters by statistical methods. A mathematical model of the human–land relationship between Neolithic sites and rivers has been established using the stepwise regression procedure REGRESS in SPSS^®. The mathematical model is Y = 496.153 – 4.833X₁ + 113.692X3 + 725.097X₅ – 27.683X₃X₄. It shows that the distance (Y) from a site to a river has a marked relationship with the site area (X₁), the river flux (X₃), the site location (X₅) and river ratio drop (X₄). The model shows that the relationship between the sites and the river is in accordance with the conclusions of archaeological research. The mathematical model not only offers theoretical guidance for the archaeological excavation of Neolithic sites in Xi’an, but also contributes to the archaeological environmental research of Xi’an Neolithic sites.      

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.     

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.     

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.     

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

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

Retrograde P–T evolution and high temperature–low pressure fluid circulation in relation to late Hercynian intrusions: a mineralogical and fluid inclusion study of the Charroux-Civray plutonic complex (north-western Massif Central, France)

The calc‐alkaline plutonic complex from Charroux‐Civray (north‐western part of the French Massif Central) displays multiphase hydrothermal alteration. Plutonic rocks, as well as early retrograde Ca–Al silicate assemblages, which have crystallized during cooling and uplifting of the plutonic series, are affected by multiphase chlorite–phengite–illite–carbonate alteration linked to intense pervasive fluid circulation through microfractures. The petrographic study of alteration sequences and their associated fluid inclusions in microfissures of the plutonic rocks, as well as in mineral fillings of the veins, yields a reconstruction of the P–T–X evolution of the Hercynian basement after the crystallization of the main calc‐alkaline plutonic bodies. This reconstruction covers the uplift of the basement to its exposure and the subsequent burial by Mesozoic sediments. Cooling of the calc‐alkaline plutonic series started at solidus temperatures (～650°C), at a pressure of about 4 kbar (1 bar = 10⁵ N m^?2), as indicated by magmatic epidote stability, hornblende barometry and fluid inclusion data. Cooling continued under slightly decreasing pressure during uplift down to 2–3 kbar at 200–280°C (prehnite–pumpellyite paragenesis). Then, a hot geothermal circulation of CO₂‐bearing fluids was induced within the calc‐alkaline rocks leading to the formation of greisen‐like mineralizations. During this stage, temperatures around 400–450°C were still high for the inferred depths (～2 kbar). They imply abnormal heat flows and thermal gradients of 60–80°C km^?1. The hypothesis of the existence of one large or a succession of smaller peraluminous plutons at depth, supported by geophysical data, suggests that localized heat flows were linked to concealed leucogranite intrusions. As uplift continued, greisen mineralization was subsequently affected by the chlorite–phengite–dolomite assemblage, correlated with aqueous and nitrogen‐bearing fluid circulations in the temperature range of 400–450°C. In a later stage, a continuous temperature decrease at constant pressure (～0.5 kbar) led to the alteration of the dolomite–illite–chlorite type in the 130–250°C temperature range.     

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.     

Br/Cl signature of hydrothermal fluids: liquid–vapour fractionation of bromine revisited

Br/Cl ratios of hydrothermal fluids are widely used as geochemical tracers in marine hydrothermal systems to prove fluid phase separation processes. However, previous results of the liquid–vapour fractionation of bromine are ambiguous. Here we report new experimental results of the liquid–vapour fractionation of bromine in the system H₂O–NaCl–NaBr at 380–450°C and 22.9–41.7 MPa. Our data indicate that bromine is generally more enriched than chlorine in the liquid phase. Calculated exchange coefficients K_D(Br‐Cl)^{liquid‐vapour} for the reaction Br^vapour + Cl^liquid = Br^liquid + Cl^vapour are between 0.94 ± 0.08 and 1.66 ± 0.14 within the investigated P–T range. They correlate positively with D_Cl^{liquid‐vapour} and suggest increasing bromine–chlorine fractionation with increasing opening of the liquid–vapour solvus, i.e. increasing distance to the critical curve in the H₂O–NaCl system. An empirical fit of the form K_D(Br‐Cl)^{liquid‐vapour} = a*ln[b*(D_Cl^{liquid‐vapour}?1) + e^1/a] yields a = 0.349 and b = 1.697. Based on this empirical fit and the well‐constrained phase relations in the H₂O–NaCl system we calculated the effect of fluid phase separation on the Br/Cl signature of a hydrothermal fluid with initial seawater composition for closed and open adiabatic ascents along the 4.5 and 4.8 J g^?1 K^?1 isentropes. The calculations indicate that fluid phase separation can significantly alter the Br/Cl ratio in hydrothermal fluids. The predicted Br/Cl evolutions are in accord with the Br/Cl signatures in low‐salinity vent fluids from the 9 to 10°N East Pacific Rise.     

Late Holocene Historical Ecology: The Timing of Vertebrate Extirpation on Crooked Island,Commonwealth of The Bahamas

We report eight new accelerator-mass spectrometer (AMS) radiocarbon (¹⁴C) dates performed directly on individual bones of extirpated species from Crooked Island, The Bahamas. Three dates from the hutia (Geocapromys ingrahami), recovered from a culturally derived bone assemblage in McKay's Bluff Cave (site CR-5), all broadly overlap from AD 1450 to 1620, which encompasses the time of first European contact with the Lucayan on Crooked Island (AD 1492). Marine fish and hutia dominate the bone assemblage at McKay's Bluff Cave, shedding light on vertebrate consumption by the Lucayans just before their demise. A fourth AMS ¹⁴C date on a hutia bone, from a non-cultural surface context in Crossbed Cave (site CR-25), is similar (AD 1465 to 1645) to those from McKay's Bluff Cave. From Pittstown Landing (site CR-14), an open coastal archaeological site, a femur of the Cuban crocodile (Crocodylus rhombifer) yielded an AMS ¹⁴C date of AD ～1050–1250, which is early in the Lucayan cultural sequence. From a humerus in a non-cultural surface context in 1702 Cave (site CR-26), we document survival of the Cuban crocodile on Crooked Island until AD ～1300–1400, which is several hundred years later than the well-documented extinction of Cuban crocodiles on Abaco in the northern Bahamas. We lack a clear explanation of why Cuban crocodiles likely survived longer on Crooked Island than on a larger Bahamian island such as Abaco. One AMS ¹⁴C date on Crooked Island's extinct, undescribed species of tortoise (Chelonoidis sp.) from 1702 Cave is BC 790 to 540 (2740 to 2490 cal BP), which is ～1500–1700 years prior to human arrival. A second AMS ¹⁴C date, on a fibula of this tortoise from McKay's Bluff Cave, is AD 1025 to 1165, thereby demonstrating survival of this extinct species into the period of human occupation.     

Raising Practices of Neolithic Livestock Evidenced by Stable Isotope Analysis in the Wei River Valley,North China

Although a patchwork of projects shows a process of agriculture intensification in North China during the Neolithic, the impact of cereal farming on animal husbandry and their mutual interaction remain cloudy. This study reports bone collagen δ¹³C and δ¹⁵N of humans and animals from Wayaogou (ca 6.5–6.0 kyrs bp ) and Dongying (ca 5.9–5.6 kyrs bp , 4.6–4.0 kyrs bp ) to explore temporal trend of livestock raising and particularly the importance of millet fodder to stock raising practices in the Wei River valley, North China. The isotopic evidence overall shows that millet products increased in human and domestic animal diets during the mentioned chronological span. δ¹³C values of pigs and dogs at Dongying are higher than those at Wayaogou, implying that the importance of millet nutrients increased to animal husbandry diachronically. Interestingly, δ¹³C results of domestic cattle of Dongying late phase (−14.1 ± 1.1‰, N = 5) are more enriched than Wayaogou wild Bos (−17.8 ± 0.3‰, N = 3), indicating that millet fodder had taken a significant place in early cattle husbandry. Besides, differences between Bos species of the two periods also imply that δ¹³C values of bone collagen constitute a potential indicator for tracing the origin of cattle husbandry in North China. In addition, domestic sheep at Dongying produced similar isotope data to wild ovicaprid at Wayaogou, suggesting that they possibly had grazed for the most in grassland and therefore experienced a different lifestyle from cattle. Copyright © 2014 John Wiley & Sons, Ltd.     

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

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

New Insights into Mesolithic Human Diet in the Mediterranean from Stable Isotope Analysis: The Sites of Campu Stefanu and Torre d'Aquila,Corsica

Mesolithic human remains are rare in the archaeological record of the French Mediterranean. Only the island of Corsica has so far produced relatively well‐preserved burials, and recent archaeological excavations have brought to light new Mesolithic human remains. The site of Campu Stefanu , located in Sollacaro in the southeast of the island, contained a collective burial of seven to eight individuals in a previously unobserved funerary context. A re‐evaluation of collections in regional museums yielded the remains from another Mesolithic individual from the site of Torre d 'Aquila , excavated at Pietracorbara, in the northern part of the island, at the beginning of the 1990s. These two discoveries presented the rare opportunity to obtain new radiocarbon dates and paleodietary insights from this crucial time period using stable isotope analysis (δ¹³C, δ¹⁵N) on collagen. From Campu Stefanu, one individual had sufficient collagen preserved for radiocarbon dating, revealing that it is the oldest Mesolithic human known on the island, dated to 10216–9920 cal. BP. At Torre d'Aquila, radiocarbon dates indicate that the individual belonged to a younger Mesolithic phase than Campu Stefanu, dated to 9903–9596 cal. BP. δ¹³C and δ¹⁵N isotope ratios are similar between the Campu Stefanu and Torre d'Aquila individuals and indicate a diet dominated by the consumption of terrestrial animal protein and a lack of marine resources. These findings are in contrast with the previous results from two other Mesolithic individuals from Corsica from the sites of Araguina Sennola and Monte Leone , for which about 25–30% of the consumed proteins came from a marine diet. The dietary variability recorded in Corsica is consistent with results obtained from Mesolithic human remains of Sicily and the Iberian Peninsula. We can hypothesise, that despite the nomadic lifestyle, the distance to the sea played a major role in Mesolithic food choices in Corsica. Copyright © 2016 John Wiley & Sons, Ltd.     

Fluid circulation related to post‐Messinian extension,Thassos Island,North Aegean

In the North Aegean Domain, Thassos Island contains a Plio‐Pleistocene basin controlled by a large‐scale flat‐ramp extensional system with a potential décollement located at depth within a marble unit. Numerous mineralizations associated with normal faults of Plio‐Pleistocene age are the sign of fluid circulation during extension. Two main generations of fluid flow are recognized, related to Plio‐Pleistocene extension. A first circulation under high‐temperature conditions (about 100–200°C) resulted in dolomitization of marbles near the base of the Plio‐Pleistocene basin. The dolomites are characterized by low δ¹⁸O values (down to 11‰ versus Standard Mean Ocean Water). Some cataclastic deformation affected the dolomites. Hydrothermal quartz that crystallized in extension veins above a blind ramp also has low δ¹⁸O values (about 13‰). This shows that high‐temperature fluids moved up from the décollement level toward the surface. A second downward circulation of continental waters at near‐surface temperature is documented by calcite veins in fault zones and at the base of the Plio‐Pleistocene basin. These veins have O isotope values relatively constant at about 23–25‰ and C isotope values intermediate between the high δ¹³C value of the carbonate host rock (about 1–3‰ versus Peedee Belemnite) and the low δ¹³C value of soil‐derived carbon (?10‰). The calcites associated with the oxidative remobilization of primary sulphide Zn–Pb mineralization of Thassos carbonates have comparable O and C isotope compositions. Hot fluids, within the 100–200°C temperature range, have likely contributed to the weakening of the lower marble unit of Thassos and, thus, to the process of décollement.     

Solubility of quartz in crustal fluids: experiments and general equations for salt solutions and H2O–CO2 mixtures at 400–800°C and 0.1–0.9 GPa

The solubility of quartz has been measured in a wide range of salt solutions at 800°C and 0.5 GPa, and in NaCl, CaCl₂ and CsCl solutions and H₂O–CO₂ fluids at six additional P–T conditions ranging from 400°C at 0.1 GPa to 800°C at 0.9 GPa. The experiments cover a wide range of compositions along each binary. At P–T conditions where the density of pure water is low (0.43 g cm^?3), addition of most salts produces an enhancement of quartz solubility at low to moderate salt concentrations (salt‐in effect), although quartz solubility falls with further decrease in X_H2O. At higher fluid densities (0.7 g cm^?3 and greater), the salt‐in effect is generally absent, although this depends on both the cation present and the actual P–T conditions. The salt‐in effect is most readily produced by chloride salts of large monovalent cations, while CaCl₂ only produced a salt‐in effect at the most extreme conditions of high‐T and low‐P investigated (800°C at 0.2 GPa). Under most crustal conditions, the addition of common salts to aqueous fluids results in a lowering of quartz solubility relative to that in pure water (salt‐out effect). Comparing quartz solubility in different fluids by calculating X_H2O on the basis that all salts are fully associated under all conditions yields higher quartz solubility in solutions of monovalent salts than in solutions of divalent salts, absolute values are also influenced by cation radius. Quartz solubility measurements have been fitted to a Setchenow‐type equation, modified to take account of the separate effects of both the lowering of X_H2O and the specific effects of different salts, which are treated as arising through distinct patterns of non‐ideal behaviour, rather than the explicit formation of additional silica complexes with salt components. Quartz solubility in H₂O–CO₂ fluids can be treated as ideal, if the solvation number of aqueous silica is taken as 3.5. For this system the solubility (molality) of quartz in the binary fluid, S is related to its solubility in pure water at the same P–T conditions, S^o, by: Quartz solubility in binary salt systems (H₂O–RCl_n) can be fitted to the relationship: where salt concentration mRCl_n is expressed as molality and the exponent b has a value of 1 except under conditions where salting‐in is observed at low salt concentrations, in which case it is <1. Under most crustal conditions, the solubility of quartz in NaCl solutions is given to a good approximation by: We propose that quartz solubility in multicomponent fluids can be estimated from an extended expression, calculating X_H2O based on the total fluid composition (including dissolved gasses), and adding terms for each major salt present. Our experimental results on H₂O–NaCl–CO₂ fluids are satisfactorily predicted on this basis. An important implication of the results presented here is that there are circumstances where the migration of a fluid from one quartz‐bearing host into another, if it is accompanied by re‐equilibration through cation exchange, may lead to dissolution or precipitation of quartz even at constant P and T, with concomitant modification of the permeability structure of the deep crust.     

Petroleum infiltration of high-grade basement, South Norway: Pressure-Temperature-time-composition (P–T–t–X) constraints

Fluid inclusion data provide pressure–temperature–time–composition (P–T–t–X) constraints for an episode of petroleum infiltration of the crystalline basement in South Norway. Petroleum inclusions associated with pyrobitumen occur in postmetamorphic quartz veins in the Modum Complex. Three groups of fluid compositions have been shown, ranging from CH₄ ± CO₂ to condensates with alkanes up to C₁₅. The range in fluid composition is a result of petroleum decomposition at high temperature. Globular and massive pyrobitumen occurs in the quartz veins or in associated vein systems. Reflectance (%Rm) measurements of 3.20–3.35 correspond to a maximum temperature of 207–214°C for the pyrobitumen associated with group II and III inclusions. Geothermometry of chlorites included in the quartz show results of 226–231°C. Pressure conditions of trapping for all three groups of inclusion fluids have been estimated to 520–985 bar at 220°C. The pressure range is probably a result of fluctuations caused by repeated fracture opening and sealing due to seismic activity coupled with mineral growth. A lack of systematic textural relationships between the three groups of inclusions and similar pressure–temperature estimates for all fluid types indicate trapping at similar times and a process of rapid change. Fluid migration in fractures from an overlying, overpressured sedimentary basin into a dry, crystalline basement best explains the observed P–T–t–X constraints.     

Potassium–Calcium Glass: New Data and Experiments*

The chemical composition of potassium–calcium ‘wood‐ash’ glass reflects the elemental pattern of the involved non‐volatile base materials in quartz sand, wood ash and possibly potash. The essential elemental ratio K₂O/CaO of wood ash varies between 0.2 and 0.8, and depends on the habitat and geological substratum of the wood rather than on the tree species; ratios between 1.0 and 3.0 in wood‐ash glass are only possible when potash is added as a third base material. Melting temperatures of wood‐ash glass sensu stricto, termed K–Ca‐2, produced with the two raw materials quartz sand and wood ash, are between 1250°C and 1400°C, while those of three‐component‐glasses, termed K–Ca‐3, are between 900°C and 1250°C, according to the amount of added potash. Experimentally produced glass displays different hues, from colourless to brown, olive‐green and pink, according to the chemical composition of the wood ash. Elevated MnO concentrations between 0.5 and 3 wt% may originate from wood ash and are hence not necessarily an indicator of colour‐inhibiting additives. Phosphate stemming from wood ash is an essential discriminator between wood‐ash glass and potash–lime glass. Because wood ash contains only minor amounts of sodium, wood‐ash glass with equal concentrations of potassium and sodium is a hybrid glass type, where besides quartz sand, wood ash, possibly potash and also soda‐rich cullet have been applied for glass production.     

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

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

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.