COMMENTS ON F. BEGEMANN, E. PERNICKA, S. SCHMITT-STRECKER, 'THERMI ON LESBOS: A CASE STUDY OF CHANGING TRADE PATTERNS', OXFORD JOURNAL OF ARCHAEOLOGY, 14(2) (1995), 123–135.

Summary. A considerable part of the paper on which I comment is devoted to criticisms of the trace element analyses made in Oxford and the authors argue that analytical problems exist at Oxford for at least the elements Co, Pb and Zn. A close examination of 'blind' analyses made in the British Museum, in Heidelberg and in Oxford of a series of ancient copper based alloys circulated by V. Rychner, University of Neuchatel, shows that agreement is in fact excellent between these laboratories. Analyses in Oxford of a series of copper based alloys certified for their content of various trace elements by the U.S. National Institute for Standards and Technology shows excellent agreement with those certified values. There has been a problem with the analyses of very low contents of Co in copper alloys, less than about 10 ppm, which affects the published analyses of Co (at such low levels only) from both Oxford and Heidelberg prior to 1993; this problem has now been recognised and overcome independently by both laboratories.     

Quantitative EDXRF Studies of Obsidian Sources in Northern Hokkaido

Quantitative trace element data from six obsidian sources on the Japanese island of Hokkaido is presented. Previous work by Japanese scholars has utilized neutron activation analysis (NAA) focusing on the rare earth elements, or qualitative energy dispersive X-ray fluorescence (EDXRF). In this study, non-destructive EDXRF is used to generate trace element data for 9 elements. Bivariate plots of the incompatible trace elements (Ba, Rb, Sr, Y, and Zr) can be used to separate the obsidian sources in this study. Source separation was confirmed by using linear discriminant analysis. Stepwise discriminant analysis indicates that Ba, Sr, Rb, Ti, Y, and Zr are the most discriminating elements.     

Element localization in archaeological bone using synchrotron radiation X-ray fluorescence: identification of biogenic uptake

Trace element analysis related to archaeological bone is viewed as one way to determine levels of element exposure in past populations. This area of research is complex because there is the potential for the incorporation of trace elements from the burial environment into archaeological bone. We tested the hypothesis that matching the spatial distribution of trace elements within cortical bone with the biological structures would provide evidence of biogenic uptake. We examined samples from a non-segregated Royal British Naval cemetery (1793–1822) in Antigua, West Indies. A key historical question related to this population was the extent of exposure to lead and the resulting health effects. Images from conventional light microscopy (histological) analysis of the bone samples were matched with elemental maps of calcium, strontium, and lead that were created through the use of synchrotron radiation X-ray fluorescence (SR-XRF). Biogenic uptake of both strontium and lead was indicated based on the localization of these trace elements within discreet microstructural elements. The successful integration of histological information with XRF data is a powerful technique for the interpretation of past biological events through trace elements.     

PRE-COLUMBIAN METALLURGY: TECHNOLOGY,MANUFACTURE, AND MICROPROBE ANALYSES OF COPPER BELLS FROM THE GREATER SOUTHWEST*

Twenty-four cast copper crotals (commonly called bells), one 'spilled bell’, one tinkler bell and a number of minerals from locations throughout the Greater Southwest were analysed for their elemental composition by a PIXE nuclear microprobe at Los Alamos National Laboratory, New Mexico, USA. Sixteen bells contained minor and trace amounts of silver, antimony, arsenic, lead, and in some cases tin, strontium, and selenium. Nine bells contained little or no detectable amounts of these elements. This suggests that several workshops throughout the Greater Southwest and Mexico might have manufactured these bells.     

Can trace elements in fossils provide information about palaeodiet?

The main aim of this study is to try to see if, despite the diagenetic changes undergone by the fossil bones buried in Venta Micena (Orce, Spain), the concentration of trace elements permits the differentiation of particular groups. It is possible that some chemical elements allow us to identify different dietary groups in accord with their archaeological context. Different multivariant methods—correlation, principal component analysis and cluster analysis—were applied to the data, and in all cases the results show that two elements (Ba and Zn) seem able to discriminate between groups with different diets. In this sense, diagenesis cannot explain all the variability found in the concentrations of trace elements in fossils from the Orce region. © 1998 John Wiley & Sons, Ltd.     

THE DESIGN OF EVALUATION OF ASSAYS OF TRACE ELEMENTS IN A FOSSIL BONE*

The flame atomic absorption spectroscopy method of analysis of trace elements (Mn, Sr, and Cu) in a mammoth's bone and the method of estimation of the data using regression analysis are described. The concentration fields of the single elements in a cross-section through the bone are well described by a fourth degree polynomial. The minimum values and their coordinates have been determined. A method of determination of the original concentrations of trace elements in fossil bones is described further. The approximating features of the regression exponential equations and of the diffusion functions of various shapes were determined and a method for calculating the concentrations and diffusion properties of the bones once deposited in the soil is suggested. The original trace element concentration can be estimated by extrapolation of a suitable exponential or diffusion function.     

利用微量元素示踪青铜器矿料来源的实验研究

通过仿古范铸实验和微量元素分析研究,可以初步得出利用微量元素示踪青铜器产地及矿料来源或探索古代矿冶产品输出路线是可行的,但要走新的技术路线的看法。     

Does it come from the Pays de Bray? Examination of an origin hypothesis for the ferrous reinforcements used in French medieval churches using major and trace element analyses

A new methodology based on major and trace element analyses of slag inclusions is proposed to determine (or exclude) the provenance of iron artefacts. It is applied to verify if the Pays de Bray, a French area between Rouen and Beauvais, could have been an important supplier for the ferrous reinforcements used in the Middle Ages for the building of churches and cathedrals in these two towns. To this purpose, the behaviour of trace elements during both direct and indirect operating chains is studied combining experimental smelting and different analytical methods, such as SEM–EDS, ICP–MS, LA–ICP–MS and INAA, performed on archaeological samples. The chemical signature of the Pays de Bray iron ore and slag is determined considering MnO and P₂O₅ contents as a first rough filter and seven couples of trace elements. Then, the major and trace elements are analysed using the same methods in the slag inclusions of 32 artefacts from the Beauvais and Rouen churches, made by the bloomery process. The trace element signature of the inclusions from each artefact is compared with the ore from the Pays de Bray area. The iron used in the Rouen and Beauvais churches seems not to come mainly from the Pays de Bray.     

ICP-MS trace element analysis of Song dynasty porcelains from Ding,Jiexiu and Guantai kilns,north China

Bodies of Ding kiln white porcelains and their imitations from Guantai and Jiexiu kilns of the Chinese Song dynasty (960–1279 AD) were analysed for 40 trace elements by inductively coupled plasma mass spectrometry (ICP-MS). Numerous trace element compositions and ratios allow these visually similar products to be distinguished, and a Ding-style shard of uncertain origin is identified as a likely genuine Ding product. In Jiexiu kiln, Ding-style products have trace element features distinctive from blackwares of an inferior quality intended for the lower end market. Based on geochemical behaviour of these trace elements, we propose that geochemically distinctive raw materials were used for Ding-style products of a higher quality, which possibly also underwent purification by levigation prior to use. Capable of analysing over 40 elements with a typical long term precision of <2%, this high precision ICP-MS method proves to be very powerful for grouping and characterising archaeological ceramics. Combined with geochemical interpretation, it can provide insights into the raw materials and techniques used by ancient potters.     

MICROCHEMICAL CHARACTERIZATION OF BUILDING STONE FROM SEVILLE CATHEDRAL,SPAIN

Enrichment diagrams for trace elements have been proposed as a useful and straightforward procedure to identify ores and stones. The identification of the diverse stone of the exterior of the Cathedral of Seville has been achieved by this means. Fourteen trace elements have been analysed, from both quarry and building material samples, using atomic absorption and flame emission spectrometry in order to apply enrichment diagrams for identification purposes.     

FINGERPRINTING ANCIENT EGYPTIAN QUARRIES: PRELIMINARY RESULTS USING LASER ABLATION MICROPROBE-INDUCTIVELY COUPLED PLASMA-MASS SPECTROMETRY*

Microchemical analysis of minerals present in pottery and stone artefacts may help determine their provenance. Electron microprobe major element analyses of augite suggest that minor elements (Ti0₂,MnO, Aa₂O) are important in fingerprinting basalts. This points to the potential usefulness of trace elements. Augite present in six basalt samples (representing all known/suspected Pharaonic basalt quarries in northern and middle Egypt) and basaltic temper fragments in two New Kingdom pottery sherds was analysed for 28 trace elements (Sr, Ba, Th, U, Zr, Hf, Nb, Ta, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu. Sc, V, Cr, Ni, Ga) by laser ablation microprobe-inductively coupled plasma-mass spectrometry (LAM-ICP-MS, laserprobe). Cluster and discriminant analysis indicate that (1) laserprobe trace element data are more effective at fingerprinting basalts than conventional electron-microprobe data and (2) basaltic temper in the two sherds does not match any of the quarries. Microbeam techniques providing trace element data may represent the future for mineral-based provenance studies.     

微量元素示踪古代青铜器铜矿料来源的可行性

目前,微量元素示踪法在青铜器矿料来源研究中的应用不尽人意。为此,模拟熔铸青铜器,对它们的微量元素作多元统计分析,旨在探讨利用微量元素探索古代青铜器铜矿料来源的可行性。分析表明：若舍弃冶炼后富集亍炉渣中的亲石亲铁元素,而仅选取富集于铜料中的亲铜元素及一些凡具有亲铜性,又具有亲铁性元素的成分数据,则通过多元统计分析,能较好地区别不同产地的铜矿料。     

Partitioning of trace elements between the ores, fluxes, slags and metal during the smelting of copper

This paper gives the results of smelting seven parcels of copper ores from well-known mining areas. The behaviour of the trace elements introduced from the ore, the fuel, and the fluxes has been investigated by analysis of the main products, metallic copper and the slags. Most of the ores were capable of giving copper of relatively high purity and therefore, in order to represent conditions believed to have existed in the Early Bronze Age, two artificial ores were made up and copper high in arsenic and nickel was obtained.The results show that it is relatively easy to smelt a wide range of copper minerals to give copper of high purity apart from iron. This latter element can be removed by careful refining. The remaining elements are present at the parts/10³ level. Wood fuel is thought to contribute little to the trace element pattern. Even if it did, it would merely reinforce the elements already contributed by the ore and flux as the timber is likely to have been grown in the immediate vicinity of the ore and will probably contain the same trace elements.Useful comparison is made between the trace element pattern resulting from these smelting runs and material from archaeological sites in the vicinity of the mining areas.     

PREHISTORIC FLINT MINES AND THEIR IDENTIFICATION AS SOURCES OF RAW MATERIAL

This paper is a statistical and geological study of the results of analysis of flint from British and West European flint mines, carried out by emission and atomic absorption spectroscopy. Groups of flint specimens were studied from each geographically separate flint mining area. Flints were analysed for a group of easily measured trace elements shown by previous work to be generally present. The ratios between the trace elements form a consistent pattern for each flint mine and statistically valid differences of pattern can be recognized between different flint mines. A geological investigation shows that the measured trace elements may be derived from clay minerals and explains geographical and statistical variation in the composition of flint in terms of its mode of origin in the chalk. An advanced statistical technique allows individual flint specimens of unknown origin to be attributed by their composition to one or other of the identified flint sources. The archaeological implications of this study are discussed.     

虢国墓地出土部分青铜器微量元素的分析

将微量元素示踪法与铅同位素比值法结合起来对青铜器矿料的溯源会起到相得益彰的效果。先前对虢国墓地青铜器的铅同位素比值测定表明,其青铜器铅同位素与山西中条山和长江中下游地区都有重合。本次微量元素分析结果显示,虢国墓地青铜器与山西中条山古矿冶遗址微量元素特征不同,而与长江中下游地区的湖北铜绿山古矿冶遗址铜锭的微量元素特征相似,推测长江中下游地区可能为虢国墓地青铜器提供了大量的铜料。此外,微量元素与铅同位素都表明虢国墓地不同墓葬的青铜器基本具有一致的矿料来源。     

Oscillatory zoning and trace element incorporation in hydrothermal minerals: insights from calcite growth experiments

Oscillatory zoning and fine‐scale variations in trace element chemistry are commonly observed in hydrothermal minerals. It has been suggested that fine‐scale chemical variations are caused by extrinsic changes in the parent hydrothermal system, such as varying fluid composition, pressure or temperature, as well as changes in mineral growth rate. In this study, LA–ICP–MS (laser ablation, inductively coupled plasma mass spectrometer) analyses were carried out on calcite crystals grown in Ca–NH₃–Cl solutions doped with rare earth elements (REE). The variety of crystal morphologies observed (euhedral to acicular), likely relate to variations in trace element abundance and calcite supersaturation state. Crystals display oscillatory and sector zoning, with significant variations in REE concentrations among zones. Cyclic variations in REE concentrations (exceeding 10‐fold) occur over distances of <1 mm along the growth direction of acicular calcite crystals. In general, trace element concentrations decrease during progressive crystal growth, implying that the concentration of trace and REEs within crystals reflects the overall composition of the growth solution. However, bulk changes in crystal composition are modulated by fine‐scale (<1 mm) variations, which are inferred to be caused by growth‐rate‐controlled incorporation of trace elements. These results have important implications for using hydrothermal minerals to infer fluctuations in fluid compositions in ancient, exhumed hydrothermal systems.     

Evidence for the trade of Mesopotamian and Egyptian glass to Mycenaean Greece

The origins of raw glass used to fashion Mycenaean beads were explored using trace elements analyzed by laser ablation ICP-TOFMS. The use of this minimally destructive technique for the in-situ analysis of these beads was ideal given that the material is exceedingly rare and thus too sensitive to make use of traditional micro-sampling (e.g., by scalpel). A wide range of trace elements were measured to compare these Greek glasses to other Late Bronze Age glass coming from Egypt and Mesopotamia. Of the eleven beads analyzed, four blue glasses colored with cobalt and two blue/green glasses colored with copper have trace element compositions consistent with an Egyptian origin of manufacture. The other five of the glasses, all colored with copper, were found to conform to the composition of Mesopotamian glass. These data are the first to demonstrate direct and clear evidence for the trade of raw glass to the Mycenaean states.     

郑韩故城出土青铜器的矿料来源初步分析

基于富集在铜料中而保留其母矿信息的元素可以用于示踪青铜器的矿料来源,为了解郑韩故城青铜器的矿料来源,利用ICP-AES方法对郑韩故城出土东周时期青铜器的微量元素进行了检测。结果显示,21个青铜器样品微量元素特征具有相对一致性,推测可能具有相同的原料来源。与小双桥遗址出土青铜器的微量元素特征进行对比,二者存在明显的差异,说明从商代中期到春秋战国时期,这一地区的原料来源发生了改变。研究结果可为研究东周时期这一地区铜业发展状况提供线索。     

COMPOSITIONAL VARIATION IN ROMAN COLOURLESS GLASS OBJECTS FROM THE BOCHOLTZ BURIAL (THE NETHERLANDS)*

We investigated the major and trace element composition and Pb and Sr isotope characteristics of a series of about 20 colourless glass objects from a single high‐status Roman burial from the Netherlands (Bocholtz). The major elements show a relatively homogeneous group, with one outlier. This is corroborated by the Sr isotopes. Based on the Sb and Pb content, three major groups can be discerned, with two other outliers. This grouping is corroborated by the contents of the trace elements Bi, Sn, Ag, As and Mo, and by variations in lead isotopic ratios. On the basis of these results, we conclude that the glass of all objects was probably made with sand and lime from the same source. The variation in trace elements and lead isotope composition is most likely the result of variations in the composition of the sulphidic antimony ore(s) that were used to decolourize the glass. The composition of the Bocholtz glass is compared with that of other Roman glass, and implications for production models, trade and use of colourless glass objects are discussed. On the basis of isotopic and major element variation, we conclude that the antimony ore presumably originated from different mines.     

Trace element concentrations in teeth – a modern Idaho baseline with implications for archeometry,forensics, and palaeontology

Concentrations of 69 minor and trace elements were measured in situ using laser ablation inductively-coupled plasma mass spectrometry in multiple teeth of modern herbivores (Cervus elaphus, Odocoileus hemionus, Odocoileus virginianus; n = 52), omnivores (Ursus americanus; n = 56), and carnivores (Felis concolor; n = 33; Canis lupus; n = 4) from Idaho, USA. On each tooth, two to five analyses were collected on enamel, primary dentine, and secondary dentine with spot diameters of 30–100 μm. Continuous 30-μm-wide line traverses were collected across deer, elk, and wolf teeth. Results confirm trace element concentrations below 1 ppm for many elements, including Li, Be, transition metals (excepting Mn, Fe and Zn), heavy metals (excepting Hg and Pb), the rare earths, and actinides. Strontium and Ba generally biopurify with increasing trophic level, but Ba shows decreasing discrimination with tissue type in the order secondary dentine – primary dentine – enamel. Most elements show strong zoning within tissues and variable trophic level behavior, so concentrations in omnivores rarely fall between herbivores and carnivores. Trace element mass balance suggests that soil and dust, not food, commonly deliver the largest trace element load in terrestrial carnivores and omnivores, even for elements that biopurify, like Ba. Use of trace elements for inferring past diets are likely compromised by unknown rates of dust and soil ingestion rather than indicating the degree of herbivory and carnivory. The low concentrations of many elements provide multiple sensitive markers of post-burial overprinting that can be used to discriminate altered vs. original biogenic compositions. REE and actinide trends do not directly follow bedrock compositions.