Technology of Medieval Mortars: An Investigation into the Use of Organic Additives

This work proposes a multi‐analytical approach to determine the additives in historical mortars, the use of which is widely described in bibliographical sources, but has rarely been reported in the literature. A protocol to thoroughly analyse mortars was created (optical microscopy, X‐ray diffraction, infrared spectroscopy, thermal analyses and gas chromatography – mass spectrometry). These techniques, which had already been carried out on samples from various sites from the Roman to the modern era, determined that additives had only been used in the mortars from the internal masonry at our sampling site: the medieval military shipyard of Amalfi (Italy). The investigations yielded information on the production technology, and FT–IR and GC–MS revealed a saccharide material‐based additive in the mortars, of plant origin. The FT–IR spectra suggested the presence of a natural gum, which has been used since ancient times to strengthen the cohesion properties of mortars and their resistance to tensile stress.     

文物中蜡类材料的热裂解-气相色谱/质谱识别

为识别文物中蜡质原材料,以及文物保护修复工作中常用蜡类材料的类别,研究通过在线甲基化热裂解-气相色谱/质谱联用技术对蜂蜡、棕榈蜡、小烛树蜡、地蜡、石蜡等蜡类材料进行分析检测。研究发现:蜂蜡的主要裂解产物为直链烷烃、直链脂肪酸、直链醇、含羟基脂肪酸;棕榈蜡为直链醇、直链脂肪酸、脂肪酸衍生物;小烛树蜡为直链烷烃、直链脂肪酸、直链醇、羽扇豆醇及其衍生物、计曼尼醇及其衍生物、脂肪酸衍生物;地蜡、石蜡等矿物蜡的主要裂解产物为直链烷烃。不同蜡中裂解产物的种类及其相对含量分布规律均有所区别,因此通过在线甲基化热裂解-气相色谱/质谱联用技术可以实现不同种类蜡的区分。通过所建立的方法及总结的数据,研究推断故宫旧藏清代紫檀木边座嵌玉人鸂鶒木山水图插屏中镶嵌珐琅构件所用棕色蜡为蜂蜡,所用白色蜡为矿物蜡及少量蜂蜡。本研究所建立方法易于推广,适用于文物中蜡类材料的准确、快速识别。     

热脱附-气质联用法无损测定函套中挥发性物质的探索研究

热脱附-气质联用法作为一种无损分析技术,可以用于测定函套中的挥发性物质。为此,用Tenax-TA吸附管对10种目标化合物进行吸附,在优化的色谱条件下,苯、甲苯、乙酸正丁酯、乙苯、间/对二甲苯、苯乙烯、邻二甲苯、正十一烷和糠醛等组分相关性良好。对实际样品进行测定,可以实现函套等装具中挥发性有害物质的分离分析。研究结果对纸质文献的保护有参考作用。     

The multivariate statistical analysis and XRD analysis of pottery at Xigongqiao site

A series of pottery samples excavated from the Xigongqiao site in Tengzhou city of Shandong province was determined using inductively coupled plasma atomic emission spectrometry. Together with excavation data and archaeological analysis, the potential for provenance and technology of unearthed ancient pottery was studied by using multivariate statistical analysis and X-ray powder diffraction pattern (XRD) analysis. In order to characterize and classify these earthenware samples, the major and minor/trace element concentrations were studied with both cluster analysis and principal component analysis. The results showed that there were three different groups in cluster analysis dendrogram in good correlation with their colors. This indicated that the potteries were made from clays of different composition. These results were in agreement with the results of principal component analysis. XRD analysis further assessed the validity of multivariate statistical analysis.     

Comparing the survival of osteocalcin and mtDNA in archaeological bone from four European sites

The small mineral-binding bone protein, osteocalcin, has been applied in a number of studies on ancient bone due to predictions of its long-term stability. However, the intact protein has not been shown to survive in ancient bone devoid of DNA, which is a much more phylogenetically informative biomolecule. In this investigation, the survival of osteocalcin is directly compared to the amplification of mtDNA in a set of 34 archaeological samples from four sites throughout Europe. We also present unpublished osteocalcin sequences of seven mammalian species in addition to the 19 published sequences to highlight phylogenetic limitations of this protein. The results indicate that the intact osteocalcin molecule survives less in archaeological samples than mtDNA and is more subject to the temperature of the archaeological site. Amino acid analyses show the persistence of the dominant protein collagen in samples that failed both osteocalcin and mtDNA analyses. The implications these findings present for biomolecular species identification in archaeological and palaeontological material are that, although proteins do survive beyond ancient DNA, osteocalcin does not appear to be the most ideal target.     

Characterization of dyestuffs in ancient textiles from Xinjiang

Extraordinarily well-preserved organic remains from mortuary and settlement sites, including mummified bodies, are scattered along the outer, oasis-laden rim of the Tarim Basin in Xinjiang Province, China, ranging in date from about 1400 BC to the late first millennium BC. Specimens of textile finds from Chärchän, dated at about 1000 BC were selected for dye analysis using newly developed protocols employing high performance liquid chromatography with spectrophotometric and mass spectrometric detection. A single blue (from an indigo plant), a red (from madder, a Rubia species) and two yellow dyes were detected, although the exact plant source for none of them could be identified with certainty. This research offers new insights in the interpretation of textile finds from prehistoric Xinjiang, and more generally, of early Bronze Age Eurasia.     

MC‐ICP‐MS analyses of tin isotopes in Roman‐era bronze coins reveal temporal and spatial variation

Tin's small mass fractionation and the lack of accepted reference standards have hindered Sn isotopy in archaeology and conservation science. Because of ore field variation and potential fractionation during ore reduction, attempts to determine artefacts’ ore sources have been limited. After norming the fractionations to NIST 3161a (Lot #070330), significant differences in Sn isotope mass fractionation in Judaean bronze ‘Biblical’ coins minted by different rulers during the first centuries bce and ce were discovered. These variations and those in δ ⁶⁵Cu and ²⁰⁶Pb/²⁰⁴Pb are connected to historical events in the Levant.     

Provenance of Early Bronze Age metal artefacts in Western Switzerland using elemental and lead isotopic compositions and their possible relation with copper minerals of the nearby Valais

Ten Early Bronze Age (BzA1, 2200–2000 BC) copper artefacts from the central Valais region from Switzerland were studied for their elemental composition and lead isotope ratios. In order to answer the archaeological question of a local copper supply, a database for copper minerals across the Valais (Switzerland) has been established. This database contains 69 data on lead isotope ratios as well as additional information on the minerals and geochemical associations for copper minerals from 38 locations in the Valais. Comparisons of the artefacts were also made with data pertaining to minerals from various deposits from Europe and Anatolia taken from the literature. The provenance of the materials is very diverse. Some of the data are compatible with the data from the copper mineral deposits of the Valais region. Moreover, three copper lunulae were identified as possibly Tuscan, which suggests contacts between Italy and the Valais region. This pattern also establishes a multiplicity of provenances for the metal and cultural influences in the Alpine environment of the Rhone Valley of Switzerland at the beginning of the Early Bronze Age.     

Chemical evidence for wine production around 4000 BCE in the Late Chalcolithic Near Eastern highlands

Archaeological excavations in the Areni-1 cave complex in southeastern Armenia revealed installations and artifacts dating to around 4000 cal. BCE that are strongly indicative of wine production. Chemical evidence for this hypothesis is presented here using a new method to detect the anthocyanin malvidin that gives grapes and pomegranates their red color. Using solid phase extraction (SPE) and alkaline treatment of the samples, followed by combined liquid chromatography-tandem mass spectrometry (LC-MS/MS), this method was applied to authentic standards and four ancient potsherds from Armenia and Syria. A positive result was observed for two of the samples from the Areni-1 cave complex, adding evidence supporting the hypothesis that wine was produced in the Near Eastern highlands in the Late Chalcolithic Period.     

Mapping prehistoric social fields on the Sepik coast of Papua New Guinea: ceramic compositional analysis using laser ablation-inductively coupled plasma-mass spectrometry

The Sepik coast of northern Papua New Guinea is one of the most linguistically diverse places on earth despite communities there currently being connected into wide-reaching social and economic networks that cross language boundaries. One possible explanation for observed human diversity is that social connections were substantially less intensive prior to colonial pacification. As a proxy for human interaction, we compositionally analyzed 287 ceramic sherds from archaeological contexts using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to determine their place of production. Our results indicate that ceramics produced on Tumleo Island—currently the most important regional ceramic producer—were transported to other places on the Sepik coast after ∼1000 BP, suggesting that linguistic diversity on the coast has been maintained in an interactive environment for at least a millennium.