典型硫酸盐环境中砖质文物的脱盐与加固材料

中国保存有众多砖质文物建筑,目前这些文物多处于户外环境中,面临严重盐害导致的掏蚀损毁问题。因而,研究兼具脱盐功能的加固材料成为砖质文物等保护的一种创新思路,加固材料的研制和工艺技术的开发是其重点和难点,具有重大的社会需求和急迫性。为此,本工作从可溶性盐的破坏机制出发,研究出一种双组分无机加固材料,加固方法是Ba(OH)_2甲醇溶液与H_2C_2O_4、H_3PO_4乙醇溶液交替滴加,并模拟可溶性盐(NaCl、KCl、Na_2SO_4)分布的典型环境,进行加固、除盐,借助X射线衍射仪(XRD)、X射线荧光光谱仪(XRF)和无线阻尼抗钻仪等现代科学仪器,追踪盐的流出与转化过程。结果表明,本材料不仅能够加固模拟样品,同时能对最具破坏性的盐Na_2SO_4实现不可逆转化,生成重晶石的主要成分BaSO_4,加固与脱盐一次完成,是一种具有实际应用潜力的新材料。     

Stable isotope palaeodietary study of humans and fauna from the multi-period (Iron Age,Viking and Late Medieval) site of Newark Bay,Orkney

We report here on stable carbon and nitrogen isotope measurements of human and faunal bone collagen from the Iron Age, Viking Age, and Late Medieval site of Newark Bay, Orkney, Scotland. We found a wide range of results for humans in both δ¹³C (−15.4‰ to −20.3‰) and δ¹⁵N (8.6‰–15.6‰) values. The enriched carbon and nitrogen values indicate the consumption of significant amounts of marine protein, which is very unusual for post-Mesolithic (e.g. 4000 cal BC) UK and European populations. Also of interest is a statistically significant difference in δ¹³C (t = −2.48, p = 0.011) and δ¹⁵N (t = −2.44, p = 0.011) values, and therefore diets, between adult males and females at this site, with males (δ¹³C = −17.8 ± 1.2‰, δ¹⁵N = 13.2 ± 1.6‰) having, on average, a higher proportion of marine protein than females (δ¹³C = −18.9 ± 1.1‰, δ¹⁵N = 11.8 ± 1.8‰). The weaning age of the sub-adults was difficult to interpret due to the large isotopic variation in the adult females, but nearly all individuals between birth and 1.25 years have elevated δ¹⁵N values indicating that they were breastfed to some extent.     

Guanaco (Lama guanicoe) isotopic ecology in southern South America: spatial and temporal tendencies, and archaeological implications

We synthesize and discuss available isotopic data on Holocene guanaco samples from southern South America, extending from Tierra del Fuego Island to northern Patagonia and the Pampean region. We evaluate temporal and spatial tendencies on the basis of 91 samples (mainly based on δ¹³C_collagen values), presenting implications for paleodietary research in archaeology. We conclude that there are no strong correlations with latitude in the macro-spatial scale, while there is a set of interesting patterns at smaller regional scales. These patterns lead us to evaluate the role of ecologic and topographic variables (e.g. canopy effect, variations in altitude, ecotones) in structuring isotopic variability. Finally, on the basis of the present analysis we suggest a number of hypotheses and perspectives for the use of stable isotopes as geographic tracers of guanaco distribution in the past, and specific implications for the paleodietary study of human samples.     

Sr/Sr variability in Puerto Rico: geological complexity and the study of paleomobility

The temptation to use biogeochemical techniques to resolve issues of paleomigration is evident and well intentioned. Knowledge of radiogenic strontium isotope baselines in a region of interest is a sine qua non of such archaeological studies of paleomobility. Here, we present the first detailed study of baseline ⁸⁷Sr/⁸⁶Sr values for the island of Puerto Rico. The high degree of ⁸⁷Sr/⁸⁶Sr variability present in this corpus of modern Puerto Rican bedrock and terrestrial malacological samples (0.70406–0.70909) is a testament to the complex geology of that island. This diversity of ⁸⁷Sr/⁸⁶Sr values makes parsing issues of origin a difficult and highly contingent task. Given these complexities, regional studies seeking to assess paleomigration by such isotopic means should proceed with a great deal of caution.     

Correlation BetweenC Ages and Aspartic Acid Racemization at the Upper Palaeolithic Site of the Abri Pataud (Dordogne, France)

The Upper Palaeolithic site of the Abri Pataud (Dordogne, France) has been the subject of numerous¹⁴C age determinations which cover the period from 20,400±450 years (OXA-373) to 34,250±675 years (Grn-4507). The racemization ratios of aspartic acid have been determined in 26 fossil bones. The bones are present in two different sedimentary surroundings: levels (fine deposits with numerous artefacts and fossil bones) and “éboulis” (coarse deposits derived from the neighbouring limestone cliff). Racemization ratios for total aspartic acid have a poor correlation with¹⁴C ages (respectivelyr²=0·59 and 0·82 for the two environments) but apparent racemization rates are clearly dependent on the type of deposits (levels: K=4·4×10⁻⁶year⁻¹; éboulis: K=9×10⁻⁶year⁻¹).Racemization ratios of aspartic acid in a high molecular weight protein fraction (>10,000 Da) correlate much better with¹⁴C ages (r²=0·999) for the samples from the levels (k=2·1×10⁻⁵year⁻¹). From this regression line we estimate ages for two Aurignacian levels: level 6≈29,560 years and level 9≈30,440 years .It is noteworthy that none of the regression lines intercepts the origin. Racemization of aspartic acid appears to occur only after a delay of many thousands of years. This phenomenon could be the result of a coupling between the degradation of proteins and the racemization of amino acids.     

Possible isotopic fractionation of argon in source obsidians and archeological artifacts from Kulkuletti, Ethiopia

Despite uniform geochemistry ⁴⁰Ar/³⁹Ar ages of 0.6, 1.25, and 1.3 Ma on obsidians from a source flow (Worja) and from archeological artifacts at the sites of Kulkuletti (near Gademotta, Ethiopia) have been interpreted to suggest that they derive from different source flows of different ages. A further suggestion is that the magmatic source of the obsidian flows was chemically homogeneous between 1.3 Ma and 0.6 Ma. Chemical analysis of these obsidians indeed suggests that they derive from a single flow. Reexamination of the argon isotopic data reveals that argon isotopes may have been fractionated within the flow, so that the assumption of an atmospheric ⁴⁰Ar/³⁶Ar ratio of 295.5 is inappropriate to use for computing ages. Three groups of data are apparent, and internally all yield ages near 1.3 Ma if the intercept value for ⁴⁰Ar/³⁶Ar from an isotope correlation plot is used for computation instead of using the atmospheric ratio. The Soret thermal diffusion effect provides a possible mechanism of fractionation of argon within the obsidian flow that is of approximately the right magnitude to explain the observations by in-diffusion of already fractionated atmospheric argon.     

Patterns of Resource Use and Isotopic Niche Overlap Among Guanaco (Lama guanicoe), Pampas Deer (Ozotoceros bezoarticus) and Marsh Deer (Blastocerus dichotomus) in the Pampas. Ecological,Paleoenvironmental and Archaeological Implications

ABSTRACT

In this paper, we analyze the isotopic niche and resource use of the guanaco (Lama guanicoe), pampas deer (Ozotoceros bezoarticus) and marsh deer (Blastocerus dichotomus) on the temperate plain of the northern Pampa region in the southeast of South America. The measured stable isotope compositions in bone tissue are δ¹³C, δ¹⁵N and δ¹⁸O. All the analyzed samples were recovered from different archaeological sites from the late Holocene. According to the results, the guanaco was strictly confined to the Pampa plain environment, developing a broad niche based on C₃ plants and a variable contribution of C₄ grasses within a grazing trend. The pampas deer preferentially used the Pampa plain, but also the prairies on the borders of the wetland, showing eurioic characteristics and a narrower niche based on C₃ plants. In turn, the marsh deer was strictly confined to wetland environments, developing a C₃ diet–base, within a narrow isotopic niche and stenoic characteristics. The three mammals showed a wide range of intraspecific variability, which was a key factor in their adaptability to spatial and temporal changes in the vegetation coverage. In fact, the temporal trends of their isotopic values were concurrent with the major climatic variations of the Holocene. Differences in the correlations between the values of both carbon sources in both deer species compared with the guanaco suggest a distinct chemical composition of their diet and/or differences in the allocation of nutrients. The isotopic values of nitrogen and spacing of the carbon sources in guanaco (pseudoruminant) and both deer species (ruminants) show no significant differences between them, thus establishing the values for local large herbivores. Significant correlations between δ¹³C and δ¹⁵N were found in the guanaco and marsh deer. The regional and extra–regional variability in the guanaco's δ¹³C_collagen and δ¹⁵N probably reflect the clinal variations in the vegetation coverage and the amount of rainfall. The collagen isotope values in the guanaco throughout the entire Holocene show that the humid Pampa would have shifted between being a more recurrent mesic and temperate plain with minor phases of dry–mesic conditions like during the Little Ice Age, and a humid and warm one at the peaks of the Holocene Thermal Maximum and the Medieval Climatic Anomaly. The guanaco and the pampas deer adapted to all the climatic changes that happened on the humid Pampa until the biological invasions of large European mammals changed the herbivores’ guild composition of this vast plain, pushing them into peripheral habitats due to competition. The within–species variability in isotopic signals through time and space make it necessary to carry out adequate sampling before reconstructing the diets of local past populations.     

Strontium isotope analysis of Neolithic and Copper Age populations on the Great Hungarian Plain

The strontium isotope ratio (⁸⁷Sr/⁸⁶Sr) is used in archaeological studies to identify major events of population movement in prehistory such as migration, conquest, and inter-marriage. This study shows that the strontium isotope method can be expanded to identify more subtle shifts in prehistoric human mobility. ⁸⁷Sr/⁸⁶Sr isotope ratios were analyzed in dental enamel from human and faunal specimens from the Late Neolithic and Copper Age on the Great Hungarian Plain. The archaeological record indicates that several aspects of life changed during the transition from the Late Neolithic to the Copper Age (ca. 4500 BC) in Hungary; evidence for increased interaction over a wide geographical area, less resource pooling and the use of secondary products has been used to support the idea that local populations became more mobile, perhaps due to the adoption of an agro-pastoral economy. Results from this study identify a change in the range of strontium isotope values from the Late Neolithic to the Copper Age from a very narrow range of values to a much broader range of values, which suggests that changes in how land and resources were utilized on the Great Hungarian Plain affected incorporation of strontium into the skeletal system. This study indicates that the strontium isotope ratio is a valuable tool for identifying more subtle changes in prehistoric behavior such as a shift to a more pastoral economy.     

Diversity in foddering strategy and herd management in late Bronze Age Britain: An isotopic investigation of pigs and other fauna from two midden sites

Abstract

Middens of the southern British late Bronze and Iron Age are vast accumulations of cultural debris that can be explained as refuse dumps linked with large periodic feasting events. A distinctive feature of these sites is that their faunal assemblages invariably comprise a considerably higher proportion of pig remains than contemporaneous settlement sites. This paper presents results from a programme of stable carbon (δ¹³C) and nitrogen (δ¹⁵N) isotope analysis of fauna from two major midden sites, Llanmaes in South Wales and Potterne in Wiltshire. The research aim is to reconstruct husbandry strategies and foddering regimes, particularly concerning pigs, to better understand how the challenges of raising large herds were met. Analysis produced exceptionally wide-ranging results for pigs and other domesticates at both sites, particularly in terms of δ¹⁵N values, demonstrating that diverse foddering strategies were employed. Diversity in the late Bronze Age pig foddering regimes indicates that the Neolithic husbandry practices (focusing on woodland fodder) had not been abandoned, but that new husbandry methods (consumption of household waste) were also being practised, which subsequently became more widely established in the Iron Age. The heterogeneity of signatures suggests that animals may have been husbanded in a piecemeal fashion at a local, household level. This in turn hints that fauna may have been brought to these sites from households across the surrounding landscape, rather than being husbanded by specialist producers in the vicinity of the middens.     

An investigation of diet in early Anglo-Saxon England using carbon and nitrogen stable isotope analysis of human bone collagen

The principal aim of this work is to investigate whether protein sources in human diets in early Anglo-Saxon (5th-7th century AD) England varied with geographic location, or with respect to age or sex. The methodology used was analysis of δ¹⁵N and δ¹³C in human bone collagen from 76 adult skeletons from a total of 18 different cemeteries located in inland, riverine and coastal environments. In order to control for the possible effects of socio-economic status on diet, only high status individuals, as identified by grave goods, were studied. Data were analysed using statistical manipulation of the raw results and using IsoSource (Phillips and Gregg, 2003), a mathematical treatment which models the composition of the protein part of human diets using bone stable isotope ratios when the isotopic values for potential protein sources are known or can reasonably be inferred. The results suggest that protein sources varied little according to geographic location and that terrestrial foods dominated at all locations. However there were some subtle patterns. Slightly elevated δ¹³C in skeletons from coastal locations, and δ¹⁵N in those from riverine sites may indicate that communities in these locations made greater use of marine and freshwater resources respectively. If this is correct then it demonstrates that 5th-7th century communities made some use of wild resources even within a predominantly agrarian economy. In general the analysis of the raw data and the IsoSource results were mutually supportive, and this work demonstrates the value of this twin-pronged approach to analysis of human bone stable isotope data.     

Seasonality of human site occupation based on stable oxygen isotope ratios of cod otoliths

Oxygen isotope ratios (δ¹⁸O) were measured in micromilled samples of cod otoliths recovered from two Stone Age sites, one from Skoklefald, southeastern Norway and five from Skipshelleren, southwestern Norway. Discrete samples of otolith material were milled from the edge of the otolith towards the centre, each sample representing 3–4 weeks of growth. The δ¹⁸O values showed seasonal signals, covering a period 1–2 years prior to the time of capture. Isotope ratios at the edge of the otoliths, which is the material deposited at the time of fish capture, corresponded to the coldest seasonal water temperatures, in late winter or early spring. These data provide independent evidence for the season of use of the Skoklefald and Skipshelleren sites.     

Forensic Ar/Ar dating: a provenance study of Middle Stone Age obsidian artifacts from Ethiopia

Obsidian sourcing based on geochemistry is widely applied to reconstruct commerce patterns and dissemination of early hominid groups. Due to problems concerning potential intra-source variability or homogeneity of a geological source over large areas, parameters additional to this classical approach are desirable. Here we present the first ⁴⁰Ar/³⁹Ar investigation of Middle Stone Age (MSA) obsidian artifacts (i.e. debitage pieces) for this purpose, as well as of potential geological obsidian sources from Ethiopia. With the present pilot study we demonstrate that ⁴⁰Ar/³⁹Ar geochronology represents a reliable and powerful tool for archaeological provenance studies complementary to the geochemical approach and more recently applied techniques like fission track counting or Mössbauer spectroscopy. Two independent sets of debitage and potential source rock samples were dated by the ⁴⁰Ar/³⁹Ar method. Debitage pieces from the Kulkuletti excavation site and obsidian samples from the nearby obsidian outcrop Worja (central Ethiopia) exhibit basically identical age ranges as well as similar Ca/K and Cl/K ratios, supporting the debitage/source rock relationship previously inferred on geochemical grounds. A second small set of geochemically characterized debitage samples from the Porc Epic cave and potential source rocks from an obsidian outcrop at Kone (Eastern Ethiopia) however have different ⁴⁰Ar/³⁹Ar ages and Ca/K and Cl/K ratios. These results contradict the previous conclusion about a debitage/source rock relationship of the Porc Epic and Kone samples made on the basis of geochemistry [A. Negash, M.S. Shackley, Archaeometry 48 (2006) 1]. Additional sampling at the Kone outcrop as well as of other obsidian occurrences in the greater area is needed to unambiguously pinpoint the origin of these obsidian tools.     

Stable isotope analysis of dog,fox, and human diets at a Late Holocene Chumash village (CA-SRI-2) on Santa Rosa Island,California

Stable carbon (δ¹³C) and nitrogen (δ¹⁵N) isotope analyses of dog (Canis familiaris), island fox (Urocyon littoralis), and human bone collagen from CA-SRI-2 (AD 130–1830) on Santa Rosa Island, California provide a proxy of diet and the relationships between humans and these animals. Carbon isotopic signatures indicate that Native Americans and their dogs at CA-SRI-2 subsisted almost exclusively on marine resources, while the island fox ate primarily terrestrial foods. Nitrogen isotopes and archaeofaunal remains indicate that humans and dogs also ate higher trophic level foods, including finfishes, marine mammals, and seabirds with smaller amounts of shellfish. The CA-SRI-2 island foxes appear to have eaten higher amounts of terrestrial foods, similar to the diets observed in modern fox populations. These data generally confirm the commensal relationship assumed to exist between domesticated dogs and people, but the carbon isotopic composition of dogs is enriched ∼2‰ compared to humans. We hypothesize that the difference in carbon isotopes between dogs and humans may have resulted from a higher consumption of C3 plants with lower δ¹³C values by humans, or less likely from the ingestion by dogs of significant amounts of bone collagen, which is enriched by ∼4‰ over associated muscle.     

Tracing population mobility in the Aegean using isotope geochemistry: a first map of local biologically available Sr/Sr signatures

Strontium isotope ratio (⁸⁷Sr/⁸⁶Sr) analysis of archaeological human skeletal remains is an efficient method of investigating past population movement and residential mobility by determining probable geographical origins for the individuals examined. For this to be achieved, however, a map of biologically available ⁸⁷Sr/⁸⁶Sr signatures across the region investigated is needed. This paper presents a first such map for the Aegean, based on ⁸⁷Sr/⁸⁶Sr values recovered mainly from archaeological animal dental enamel and modern snail shells from sites largely distributed in the southern part of this region. Although not exhaustive, this comprehensive dataset of local biologically available ⁸⁷Sr/⁸⁶Sr signatures shows a marked difference between Mainland sites of the Pindos and Parnassos zones and the islands of south-eastern Aegean crossed by the Sub-Pelagonian zone (0.70808–0.70869), and sites in the central Cyclades and the north-eastern Aegean islands falling into the Attic-Cycladic metamorphic belt and the Vardar zone, respectively (0.70926–0.71187). Biologically available ⁸⁷Sr/⁸⁶Sr values from sites on central Euboea in the Pelagonian zone, south-eastern Attica and the western Cyclades in the Attic-Cycladic metamorphic belt, and on Crete in the Gavrovo zone are also relatively high (0.70853–0.70931), but lower than those recorded for the central Cyclades and the north-eastern Aegean.     

Stable isotope analysis of 14 individuals from the Mesolithic cemetery of Vasilyevka II,Dnieper Rapids region,Ukraine

Bone collagen extracted from 14 humans from the Mesolithic cemetery of Vasilyevka II was analysed for their δ¹³C and δ¹⁵N ratios. This cemetery is one of only two later Mesolithic cemeteries from the Dnieper Rapids region, being dated to 7300–6220 cal BC on the basis of three radiocarbon determinations. This analysis provides insights into the nature of the diet of the Dnieper populations at the very end of the Mesolithic period, prior to the adoption of pottery in the region, and the assumed shift towards the exploitation of domesticates in the economies of the populations of the Dnieper region, and considers these in relation to broader temporal indicators of diet in the region.     

深圳铁仔山古墓群出土铜器腐蚀情况研究

受深圳地区海洋气候及土壤环境影响,铁仔山古墓群出土铜器锈蚀情况严重。为了给后续的保护修复处理提供科学依据,需研究出土铜器锈蚀情况。为此,通过硝酸银定性分析、X射线荧光能谱分析、拉曼光谱分析等手段,对其表面锈蚀物进行综合分析。结果表明,该批铜器矿化严重,其锈蚀成分以孔雀石为主。其中一件铜器表面锈蚀物中含有氯磷钠铜矿,这在潮湿地区土壤环境出土的铜器中较为少见。此外,在另一件铜器表面锈蚀物中还发现疑似纳米SnO2成分。实验结果可对该批铜器的保护修复处理提供有力的理论依据和数据支持,并为深圳地区出土的其他青铜类文物的保护提供参考。     

Human subsistence strategy at Liuzhuang site,Henan, China during the proto-Shang culture (∼2000–1600 BC) by stable isotopic analysis

Since the discovery of the proto-Shang culture, created mostly by ancestors of the Shang clan from the late Neolithic Age to the early Shang period (∼2000–1600 BC), the subsistence strategy and lifestyle of humans in China during their movement southwards have been a great focus. Chinese literature and archaeological findings suggest that the proto-Shang societies were composed of different cultural groups and had various subsistence strategies. For example, at the Liuzhuang site, three types of burials, i.e., stone coffin, wooden coffin and earthen shaft-pit, are found. The wooden coffin and earthen shaft-pit burials had been adopted locally in the Central Plains since the Neolithic Age while the stone coffin burials were usually used by people living in Northeast China and had never been found in the Central Plains before. In this study, stable carbon and nitrogen isotopic analyses were performed on human bones from the Liuzhuang site and animal bones from Zhangdeng site in Henan province, China to determine whether different social groups had various accesses to food resources and whether their dietary difference was related to inequality in social status. Humans have mean δ¹³C and δ¹⁵N values of −7.6 ± 0.6‰ and 9.6 ± 1.0‰ (n = 19) respectively, which strongly indicates that humans rely primarily on C₄-based food. The main contribution of C₄-based food in their diet is from millet agriculture or animals that consume millet by-products. The isotopic spacing of carbon and nitrogen isotopic values between pigs and humans, between dogs and humans, and between cattle and humans, all imply that these animals were the main meat resources for humans. Surprisingly, the δ¹³C values and δ¹⁵N values of humans with different types of burials are quite close, indicating that they had equal access to food resources. This result suggests that the proto-Shang humans had adapted to the local subsistence strategy, and the local cultural factors in the Central Plains were very well integrated into proto-Shang culture.     

Palaeolithic radiocarbon chronology: quantifying our confidence beyond two half-lives

It is now three decades since Waterbolk introduced evaluation criteria to ¹⁴C chronology. Despite this, and other subsequent attempts to introduce quality control in the use of ¹⁴C data, no systematic procedure has been adopted by the archaeological community. As a result, our databases may be significantly weakened by questionable dates and/or questionable associations between dated samples and the archaeological phenomena they are intended to represent. As the use of chronometric data in general becomes more ambitious, we must pause and assess how reliable these data are. Here, we forward a set of evaluation criteria which take into account archaeological (e.g. associational, stratigraphic) and chronometric (e.g. pre-treatment and measurement) criteria. We intend to use such criteria to evaluate a large ¹⁴C dataset we have assembled to investigate Late Glacial settlement in Europe, the Near East and North Africa, supported by the Leverhulme Trust. We suggest that the procedure presented here may at least form the basis of the development of more rigorous, scientific use of ¹⁴C dates.     

Oxygen isotopic composition of limpet shells from the Beagle Channel: implications for seasonal studies in shell middens of Tierra del Fuego

Shell middens distributed along the coastal areas of the Beagle Channel (Tierra del Fuego) testify the primary role of marine resources in the successful social dynamic of hunter–gatherer–fisher societies (HGF) in extreme high latitude environmental conditions. Intertidal and subtidal limpet species are frequently identified taxa of these archaeological deposits. We investigated whether shell δ¹⁸O of the limpet species Nacella deaurata is a valuable record of local sea surface temperature (SST) and ambient water δ¹⁸O (δ¹⁸Ow) fluctuations, and in turn can be used to estimate the season of its exploitation by Holocene HGF. Sequential shell δ¹⁸O of modern species track seasonal changes of SST and δ¹⁸Ow. The comparison of shell δ¹⁸O profiles of N. deaurata and Nacella magellanica (a coexisting species) suggests the occurrence of distinct growth rate and physiological adaptations between species. Shell δ¹⁸O of zooarchaeological specimens of N. deaurata from Lanashuaia II suggests that animals were exploited predominantly in winter and that experienced similar environmental conditions of present day at ∼1320 years BP. Results also indicate that N. deaurata is a valuable candidate for studying past seasonal changes in SST and δ¹⁸Ow in this southernmost part of South America.     

“The Good,the Bad,and the Ugly”: evaluating the radiocarbon chronology of the middle and late Upper Paleolithic in the Enisei River valley,south-central Siberia

The ¹⁴C record for the Upper Paleolithic in Siberia has remained largely unevaluated and includes good, bad, and ugly dates. Too often researchers accept either all published dates or only those dates that tend to support proposed chronological hypotheses, regardless of sample quality and association. This article systematically evaluates all published ¹⁴C dates (including several newly obtained AMS dates) from middle and late Upper Paleolithic sites in the Enisei River valley of south-central Siberia to establish a reliable chronology for the region and address the tempo of modern human dispersals in Siberia during late Pleistocene times. The revised chronology indicates humans were present before and after the Last Glacial Maximum, but absent during this climatic event. Results also suggest that human population in the region may have increased during the Oldest Dryas.