Raw materials for medieval to post-medieval Tuscan glassmaking: new insight from LA-ICP-MS analyses

LA-ICP-MS analyses were performed on a set of Tuscan (post) medieval archaeological glass finds dated to the 13–16th century in order to quantitatively determine the trace element contents. The results are used for defining and distinguishing several compositional groups. The trace element data are consistent with the distinctions obtained by considering the major element data determined via quantitative SEM-EDX, but allow to obtain new insights into the nature and quality of the silica sources employed and the presumed method of ash purification.     

ICP–MS ANALYSIS OF GLASS FRAGMENTS OF PARTHIAN AND SASANIAN EPOCH FROM SELEUCIA AND VEH ARDAŠ?R (CENTRAL IRAQ)*

Forty‐one glass fragments were analysed by inductively coupled plasma – mass spectrometry, determining 40 major, minor and trace elements, including rare earth elements. The fragments came from excavations carried out at the archaeological sites of Seleucia and Veh Arda??r in modern Iraq, and were dated to the Parthian and Sasanian epochs. Analytical data indicate that all the samples are silica–soda–lime glasses. Magnesium and potassium oxide contents below 1% suggest that eight out of nine glasses from Seleucia, dating from between the first and the third century ad , could have been obtained by use of an evaporite as a flux; the same conclusion can be drawn for some of the Sasanian glasses dating from the fourth and fifth centuries ad . The other glasses from Veh Arda??r, as well as the remaining sample from Seleucia, are characterized by higher contents of magnesium and potassium, which suggests recourse to plant ash; different magnesium and phosphorus contents allow one to separate these samples into two main groups, pointing to the use of different kinds of plant ash. Aluminium and calcium contents, together with trace element data, may indicate that different sands were used for preparing glasses of different composition. Samples from Seleucia and Veh Arda??r are mainly blue–green and green to yellow–green, respectively; iron and manganese contents suggest that the furnace atmosphere was mainly responsible for the development of these hues.     

Characterisation of Chinese Tang sancai from Gongxian and Yaozhou kilns using ICP-MS trace element and TIMS Sr–Nd isotopic analysis

Tang sancai is one of the most important types of Chinese ceramics. To determine the provenance of Tang sancai is important to study ancient trade and other issues. In this paper we compare ICP-MS trace elements and TIMS Sr–Nd isotopes of visibly similar Tang sancai from two major production centres Gongxian and Yaozhou. The variation in contents/ratios of many of >40 trace elements is small for samples from Gongxian, yet is considerably bigger for that from Yaozhou. However, the variation in ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd isotopic ratios is very small for samples from both places. Gongxian and Yaozhou samples have distinctive Sr–Nd isotopic and trace element features despite their similarity in major elements, and these analysis data can be interpreted with geochemistry, indicating that Sr and Nd isotopes have great potential in ceramic provenance studies. The distinct characterisation of these samples provides valuable criteria for identifying provenance of Tang sancai of uncertain origin. Two modern fakes are also analysed, and they can as well be distinguished from antique Tang sancai using above criteria.     

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.     

THE USE OF NON-DESTRUCTIVE ACTIVATION ANALYSIS AND PATTERN RECOGNITION IN THE STUDY OF FLINT ARTEFACTS

A method is described for the identification of the origin of flint artefacts. The method is based on the variation in the trace element concentrations for different origins. The trace element concentrations were determined by non-destructive neutron activation analysis. The identification was obtained from a pattern recognition analysis.     

Migration and mobility at the Late Lapita site of Reber–Rakival (SAC), Watom Island using isotope and trace element analysis: a new insight into Lapita interaction in the Bismarck Archipelago

This paper uses strontium isotope (⁸⁷Sr/⁸⁶Sr), oxygen isotope (δ¹⁸O) and Ba/Sr trace element data in archaeological tooth enamel samples to investigate migration and mobility at the Late Lapita site of SAC, Watom Island in the Bismarck Archipelago. Previous archaeological models have identified Lapita mobility at a community level using obsidian distribution patterns and changes in ceramic design, whereas isotope and trace element data can potentially reconstruct prehistoric mobility on an individual level. Human and pig teeth were sampled from SAC and a selection of human teeth were included from the Late–Post Lapita site of Lifafaesing, Tanga Islands as a geographic/geological comparison.The results indicate that there is a large amount of isotopic variation in the Bismarck Archipelago which is useful for identifying non-local individuals and possibly determining their origins. One human individual and several pigs were suggested as coming from elsewhere in the region. Three potentially separate locations were identified for the non-local pigs. It is argued, using the data from SAC, that Late Lapita communities in the Bismarck Archipelago were more mobile than previously assumed. The potential for identifying individual migrants in a Lapita context are discussed in terms of assessing the more subtle aspects of Lapita society in the Southwest Pacific Islands.     

三峡出土宋元青白瓷产地的判别

为研究重庆地区三峡工程抢救性发掘出土了一批宋元时期青白瓷的产地,采用中子活化方法,分析了28枚三峡出土宋元时期的青白瓷残片和20枚时期相近、窑口已知的青白瓷残片,利用SPSS软件对上述样品胎体的微量元素数据进行统计分析.结果发现:江西产青白瓷的稀土元素含量与福建、安徽、湖北等地差异显著,而Rb、Cs、Hf、Th等微量元素含量也明显不同;三峡出土的青白瓷样品中,除编号为荣阳5和涂山窑5这两枚残片外,其余残片的元素特征与景德镇所产青白瓷颇为一致,拟断定这些青白瓷源自景德镇.     

Sasanian glass from Veh Ardašīr: new evidences by ICP-MS analysis

Forty-seven glass fragments excavated at Veh Ardašīr, in central Iraq, were analysed by ICP-MS, determining 38 chemical elements; the samples represented finished objects as well as waste and raw glass. The obtained data point to the use of sodic plant ash for the production of glass in the entire Sasanian period (third–seventh century AD), strengthening previous results from another set of fragments from the same site. Magnesium and phosphorus contents give further evidence of the possible use of different kinds of plant ash, while trace element levels and some element correlations suggest the recourse to different silica sources. As a whole, the obtained results allow one to recognize three main glass compositions, related to the use of different silica sources combined with different kinds of plant ash. The occurrence of waste and raw glass in all groups of composition confirms that at least glass working took place in Veh Ardašīr.     

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.     

A study of the glazing techniques and provenances of Tang sancai glazes using elemental and lead isotope analyses

This study discusses the elemental compositions and lead isotope ratios of Tang sancai glazes unearthed from the Huangpu kiln, Huangye kiln and two Tang sancai tomb sites. The various glazes feature distinct lead isotope ratios and trace element characteristics, which can be interpreted as evidence for the use of different lead ore deposits and siliceous raw materials in the glazes. This is a strong indication that lead isotopes combined with trace element analysis could be used as a viable approach for identifying the provenance of Tang sancai of unknown origin by linking them to kiln sites, This provenance technique could be significant in the interpretation of ancient ceramic trade and communication patterns. In this study, the provenance of several Tang sancai glazes of uncertain origin were determined using this method: some Tang sancai wares unearthed in Xi'an City were produced in the kiln near Luoyang City and then traded to Xi'an City, providing an idea of ancient Tang sancai ceramic trade routes.     

DEEPLY COLOURED AND BLACK GLASS IN THE NORTHERN PROVINCES OF THE ROMAN EMPIRE: DIFFERENCES AND SIMILARITIES IN CHEMICAL COMPOSITION BEFORE AND AFTER ad 150*

In this work we attempt to elucidate the chronological and geographical origin of deeply coloured and black glass dating between 100 bc and ad 300 on the basis of their major and trace element compositions. Samples from the western and eastern parts of the Roman Empire were analysed. Analytical data were obtained by means of a scanning electron microscope – energy‐dispersive system (SEM–EDS, 63 samples analysed) and laser ablation – inductively coupled plasma – mass spectrometry (LA–ICP–MS, 41 samples analysed). Among the glass fragments analysed, dark brown, dark purple and dark green hues could be distinguished. Only among the dark green fragments could a clear compositional distinction be observed between fragments dated to the periods before and after ad 150. In the early samples (first century bc to first century ad ), iron, responsible for the green hue, was introduced by using impure sand containing relatively high amounts of Ti. In contrast, a Ti‐poor source of iron was employed, containing Sb, Co and Pb in trace quantities, in order to obtain the dark green colour in the later glass samples. The analytical results obtained by combining SEM–EDS and LA–ICP–MS are therefore consistent with a differentiation of glassmaking recipes, detectable in glass composition, occurring in the period around ad 150.     

Geochemical sourcing of rock specimens and stone artifacts from Nihoa and Necker Islands,Hawai'i

We report geochemical analysis of seven rock specimens and six stone artifacts from Nihoa and Necker Islands, Hawai'i. The analyzed rock specimens exhibit chemistry consistent with published data sets and establish a major element distinction between Nihoa and Necker. Their trace element data indicate that the analyzed rocks and artifacts are local in origin and they reliably discriminate from sources on Kaua'i. These preliminary results support Emory's thesis that early (archaic) Hawaiian colonists on Nihoa and Necker relied on their local basaltic stone to manufacture stone tools, containers, and other portable objects.     

AN EVALUATION OF ANALYTICAL AND INTERPRETATIVE METHODOLOGIES FOR THE EXTRACTION AND IDENTIFICATION OF LIPIDS ASSOCIATED WITH POTTERY SHERDS FROM THE SITE OF SAGALASSOS,TURKEY*

Three lipid analysis methods were applied to extracts of archaeological potsherds from the ancient city of Sagalassos, south‐west Turkey. In the fatty acid methyl ester fraction, obtained by selective transesterification of acylglycerols, the ratio of methyl palmitate to methyl stearate was determined. Secondly, by means of gas chromatography– combustion–isotope ratio mass spectrometry (GC–C–IRMS), stable carbon isotope ratios were measured for the same methyl esters. Finally, triglyceride composition was determined via high‐performance liquid chromatography–mass spectrometry (HPLC–MS). All three methods can be used to trace the origin of animal fat. Agreement between them is reasonable, especially in recognizing ruminant adipose fat. One sample was found to be of dairy origin using both GC–C–IRMS and HPLC–MS. The advantages of the various methods are discussed. Variations in lipid composition were observed between samples from different periods and excavated in diverse areas within the city of Sagalassos.     

DISCRIMINATING SOURCES OF MEDITERRANEAN MARBLES: A PATTERN RECOGNITION APPROACH

A computer-based pattern recognition procedure has been applied to trace element data obtained from marble samples of different Mediterranean quarries. Nineteen elements, mostly hydromagmatic and rare earth elements were first determined by neutron activation analysis. These elemental concentrations are then used as the data for further multivariate analysis. The results indicate significant differences in chemical patterns of the marble sources.     

PROVENANCE STUDIES OF KOREAN CELADONS OF THE KORYǑ PERIOD BY NEUTRON ACTIVATION ANALYSIS*

Neutron activation analyses of the body fabric of celadons from the main production sites of the Koryǒ period have shown differences in composition between kilns. Comparison of over 50 celadon objects in the collections of the British Museum with this data base from the production sites has permitted the assignment of over 40 of the pieces to their kiln of origin The majority show the trace element pattern of the Sadangri kilns, a smaller proportion are assigned to Yuchǒnri, while others are assigned to the kilns at Chinsanri (underglaze iron) and Kyǒngsǒ-dong (unglazed). A representative group of Chinese Yue wares arc clearly different from Koryǒ celadons in trace element composition.     

中国古墨与现代墨元素成分研究

对中国古墨（汉墨、明墨与清墨）与不同产地的现代墨元素成分作了对比分析。用离子背散射测定墨中常量元素C、N、O的含量,用质子激发X荧光法测定微量元素K、Ca、Ti、Cu、Fe等10种元素的含量。实验结果表明,古墨中微量元素K、Ca的含量比现代徽墨、沪墨高10倍以上,而现代徽墨与沪墨中元素N和An的含量也有明显的差别。     

High‐boron and High‐alumina Middle Byzantine (10th–12th Century ce) Glass Bracelets: A Western Anatolian Glass Industry

The trace element boron is present in most ancient glasses as an impurity, and high boron (≥ 300 ppm) marks raw material sources that are geologically specific and relatively uncommon. Recent analyses of Byzantine glass with high boron contents suggest that glass‐making was not limited to the traditional regions of the Levant and Egypt, and a production origin in or near western Anatolia is proposed. Glass bracelets from ?i?n al‐Tīnāt in southern Turkey give fresh evidence for the production and circulation of high‐boron glasses that closely correlates with object typology. The patterning of findspots suggests that high‐boron glass was closely connected to the Byzantine world.     

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.     

Enhancing Understanding of the Emergence of Global Trade: Analysis of 17th‐ to 19th‐Century Spanish Coins Recovered from Western Australian Shipwrecks Using Laser Ablation – Inductively Coupled Plasma – Mass Spectrometry (LA–ICP–MS)

This research uses legacy data from shipwrecks to further our understanding of global silver movement in the 17th to 19th centuries by analysing a collection of silver coins held by the Western Australian Museum. Three hundred and eighty‐nine silver coins were analysed for their trace element fingerprint in order to identify provenance. The coins are a selection from the ships Batavia, Vergulde Draeck, Zuytdorp, Rapid and Correio da Azia, all wrecked off the coast of Western Australia between 1629 and 1816. Analysis was undertaken using laser ablation – inductively coupled plasma – mass spectrometry (LA–ICP–MS), a relatively non‐destructive technique with a sensitivity of parts per million to parts per billion. Data were interpreted using linear discriminant analysis (LDA), which allowed the coins of known provenance to be sorted into identifiable subgroups on the basis of their trace and minor elemental fingerprints, while 27 unidentified coins were compared with this database and their mint of origin predicted. These results have implications for the provenance determination of archaeological artefacts of many materials.     

ON THE COMPOSITION AND PROVENANCE OF METAL ARTEFACTS FROM POLIOCHNI ON LEMNOS

Summary. The majority of the well-stratified Early Bronze Age metal objects from Poliochni, with the exclusion of one hoard find, was analyzed for their chemical and lead isotope composition. The results show that a major change occurred in the metal used at Poliochni during periods contemporary with Troy I and Troy II. Unalloyed or arsenical copper with relatively high lead contents during the earliest two periods 'azzurro' and 'verde' is gradually replaced and supplemented by tin bronze which, during period 'giallo', i.e., by the end of Troy II, becomes the dominant metal type. Lead isotope abundance ratios in the earlier artefacts are consistent with a derivation of the metal from regional ore sources but the trace element abundance pattern is not. Concurrent with the appearance of tin bronzes is an increase in the diversity of ore deposits exploited; for about one third of the artefacts from period 'giallo' there is as yet no matching ore source in all Anatolia and the Eastern Mediterranean. It is argued that the tin bronzes have been imported as such but that the lead isotope signature does not provide any direct clues to the origin of the tin.