X-RAY FLUORESCENCE ANALYSIS WITH SYNCHROTRON RADIATION ON THE INKS AND PAPERS OF INCUNABULA

Non-destructive X-ray fluorescence analyses induced by white synchrotron radiation (SYXRF) have been performed on a page of the Gutenberg Bible and 21 other different single leaves printed in the years 1470 to 1500. Absolute elemental areal densities for the papers and the inks are reported. The known high Cu and Pb content in Gutenberg's ink is confirmed. The elemental compositions of the other inks, if measurable by XRF at all, are in general very low, governed only by a few additional elements and found to be not distinctive for a known printer. This will render an identification of the printer or printing offices by ink composition analysis in the period after 1470 difficult.     

ENERGY DISPERSIVE X-RAY FLUORESCENCE ANALYSIS OF ANCIENT COPPER ALLOYS: EMPIRICAL VALUES FOR PRECISION AND ACCURACY

Energy dispersive X-ray fluorescence (EDXRF) analyses are compared with neutron activation as well as atomic absorption analyses of ancient copper-based alloys in order to examine their accuracy and to estimate realistic values for precision and sensitivity of EDXRF. The results show that it is possible to obtain reliable data of the surface composition of objects non-destructively. Better results for bulk composition are usually obtained with drill samples where the sensitivity of the method is at least competitive with atomic absorption spectroscopy with flame atomization.     

Obsidian from the Epipalaeolithic and Neolithic eastern Maghreb. A view from the Hergla context (Tunisia)

In the present paper, it is shown that in the Hergla area (eastern Tunisia), obsidian was present from the early to at least the late sixth millennium cal BC. The presence of cores indicates that obsidian knapping was at least partly carried out in situ. The origin of these obsidians was determined from their elemental composition, by comparison with those originating from western Mediterranean potential sources, including analyses of new samples from the nearby Pantelleria Island. All obsidians were measured following the same protocol, by particle induced X-ray emission or by scanning electron microscopy/energy dispersion spectrometry. All the Hergla obsidians were found to originate from the Balata dei Turchi sources of Pantelleria. A review of the present body of knowledge on eastern Maghreb suggests, in spite of the still very preliminary data available, that Pantelleria was almost its unique provider of obsidians from the Epipalaeolithic to and during the Neolithic. However, the relative importance of the two main Pantellerian sources of Balata dei Turchi and Lago di Venere as providers of obsidian to eastern Maghreb remains to be investigated.     

印尼“黑石号”沉船及其文物综合研究

"黑石号"沉船出水了大量中国唐代中晚期的瓷器和一些金属器等,为海上丝绸之路的重要物证。通过对长沙窑瓷器、越窑青瓷、白瓷、绿彩瓷器、金银器、铜镜的造型、装饰及图案等的解读,阐述了中国唐中晚期外销瓷器的总体情况和所包含的文化交流内涵,分析了外销对中国部分窑口瓷业生产的影响。对采集到的两件白瓷标本进行了X射线荧光光谱元素组成分析,探讨了外销白瓷可能的产地。论文也就沉船可能的出发港和目的港进行了讨论。     

On the provenance and manufacture of red-slipped fine ware from ancient Cassope (NW Greece): evidence by X-ray analytical methods

Energy-dispersive X-ray fluorescence spectroscopy was used to characterize red-slipped pottery (2nd–1st century BC) from ancient Cassope, north-western Greece. The compositional data were statistically treated by principal component analysis and chemical groups were established, representing locally produced and imported items. Mineralogical investigation by X-ray diffraction indicated firing temperatures in the range from 850 to 1000 °C for most of the sherds, while one group consisted of over-fired items, possibly in excess of 1050 °C. The morphology and elemental composition of the ceramic bodies and surface slips were examined through scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. The analyses revealed that different pottery groups exhibit surface slips of different nature, in terms of thickness, degree of vitrification and elemental composition. Overall, the diversity in technological characteristics of the examined sherds is indicative of the socio-economic conditions prevailing in Cassopaea during the late Hellenistic period.     

Metallurgical study on some Sasanian silver coins in Sistan Museum

Elemental analyses and microstructural studies of historical metal artifacts provide researchers with invaluable and priceless information about metal extraction technology and the procedure of creating artifacts. In addition, the information is helpful for knowing about the metallurgical processes of the artifacts. This study was conducted by a microscopic examination and elemental analyses of seven Sasanian silver coins preserved in the Sistan Anthropology Museum, Iran. For the purpose of this study, three methods were employed: first, the proton induced X-ray emission microanalysis (micro-PIXE), to determine the main and trace elements of the coins; second, scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS), to perform elemental analysis to identify impurities of the metal; and third, microstructural analysis of the coins which was carried out with an optical microscope (OM). The elemental analyses identified Ca, Cu, Ag, Au, and Pb in the coins. The high quantity of Ag in samples validated the application of advanced and accurate cupellation technology for refining silver and separating impurities from raw ore. The gold concentration in the coins indicated the use of non-galena ore for silver extraction. Additionally, the microstructural analyses of samples pointed to the application of thermo-mechanical processes on coins.     

RIETVELD X-RAY DIFFRACTION AND X-RAY FLUORESCENCE ANALYSIS OF AUSTRALIAN ABORIGINAL OCHRES*

Rietveld phase analysis of X-ray powder diffraction patterns and chemical analysis by X-ray fluorescence spectroscopy have been used to characterize a series of red and yellow ochre samples from Aboriginal ochre deposits in South and Western Australia. The ochres were found to have diverse mineralogy, being mixtures of up to seven minerals, and also to have complex trace element signatures. The mineralogical characteristics and geochemistry of the ochres can be used to identify the source quarries. Using this combination of analytieal techniques it may be possible to trace the source of ochres in burial sites and on objects back to the original quarries.     

WHITE LUMPS IN FIFTH- TO SEVENTEENTH-CENTURY AD MORTARS FROM NORTHERN ITALY

Ancient mortars from northern Italy, dating from the fifth to the seventeenth century AD, were examined in order to formulate an hypothesis regarding the origin of the white lumps often observed in these mortars and in other samples of the same geographical provenance. Various characterization techniques were employed, including scanning electron microscopy, X-ray powder diffraction and Fourier transform infrared (FTIR) and micro-FTIR spectroscopy.     

Comparative microstructural and elemental analysis of iron artefacts from Kaveri valley archaeological sites

Iron has been one of the most critical technotraditions that had lasting impact on social formation throughout the Iron Age and historical period. Iron was used in warfare and subsistence economy. Our knowledge on ancient iron smelting and working have generally been derived from ethnography and ethnohistory, which is by all means, time, region, and raw material specific. Scientific analyses of ancient iron have contributed in understanding this heritage to a respectable extent, yet a comprehensive knowledge about the evolution of iron making through time and space in India eludes us. In this work, a comparative study of iron artefacts from two Iron Age/Megalithic-Early Historic sites of Tamil Nadu, south India, that is, Mangadu (burial site) and Ambal (habitation-cum-burial site) is carried out to understand the iron thermal-processing capabilities. The retrieved artefacts were examined using X-ray fluorescence (XRF) for elemental composition. The imaging of the artefacts was done using Scanning Electron Microscopy (SEM), Electron Backscatter Diffraction (EBSD), and Optical Microscopy (OM). In addition, phase identification was performed using X-ray diffraction (XRD) and Energy Dispersive X-ray Spectroscopy (EDS). Combination of these analyses illustrates that inhabitants of Mangadu and Ambal were aware of the iron alloy manufacturing/processing techniques such as forging and hammering.     

New evidence of early use of artificial pozzolanic material in mortars

Hydraulic building composites, such as mortars and plasters, produced with artificial pozzolanic materials, became widely popular thanks to the Romans. Reports on earlier uses of such composites can also be found, mainly in archaeological and historic documents. These date back as far as the time of Minoan and Mycenaean civilizations. Here, we present a holistic analytical investigation of Late Bronze Age mortars from various archaeological sites of Cyprus. We focus on petrographic observations of thin sections, scanning electron microscopy and energy dispersive X-ray microanalyses and we investigate the microstructure and texture of the samples and the chemical composition and interface of their binders. Results of powder X-ray diffraction analyses are also presented, alongside a series of measurements using mercury intrusion porosimetry and vacuum saturation, aiming to estimate the pore size distribution and the physical properties (i.e. open porosity and bulk density) of the specimens under investigation. We also report on tests carried out to assess the drilling resistance of the mortars using a novel, portable system. The results thoroughly confirm, for the first time, the earliest intentional use of crushed brick as an artificial hydraulic additive in lime mortars in Cyprus, in order to enhance their performance and longevity in the absence of natural pozzolanas.     

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.     

Technological Features of Roman Terra Sigillata from Gallic and Italian Centres of Production

Technological features of sherds of Roman terra sigillata were studied. The sherds analysed represented products of workshops which were most probably located in Gaul, central Italy, north-west Italy and the plain of the river Po. Equivalent firing temperatures were estimated by colour measurement, X-ray diffraction and thermal expansion measurement; in addition, the chemical and morphological features of the red sintered slips were investigated using scanning electron microscopy coupled with energy dispersive X-ray microanalysis. The combined results suggest that, relative to northern Italian products,terra sigillata from Gaul and central Italy was made by potters who were more successful in modifying slip composition and controlling firing temperature to obtain highly sintered slips. Northern Italian potters seem to have worked their clays less successfully and fired them at temperatures which were too low to overcome the limited presence of fluxes in the slip.     

重庆钓鱼城遗址悬空卧佛彩绘颜料初步分析

钓鱼城悬空卧佛造像系创作于晚唐时期的一尊巨型石刻,具有极高的历史、艺术、科学、宗教价值,但造像保存现状较差,存在颜料脱落、酥碱粉化、起甲等病害,亟待保护修复。为了解悬空卧佛彩绘颜料层的成分与结构,采用金相显微镜、拉曼光谱、X射线荧光(XRF)、X射线衍射(XRD)、扫描电镜-能谱仪(SEM-EDS)等多种现代方法与技术对彩绘样品进行了分析。结果表明:所用红色颜料为铁红、铅丹;蓝色颜料为群青;绿色颜料为碱式氯化铜;青色颜料为墨绿砷铜矿;白色颜料为硫酸铅;局部有贴金。结果还表明,该造像历史上曾多次重绘。本研究成果以期填补钓鱼城悬空卧佛研究的空白,同时为修复工作的开展提供科学依据。     

四川广汉龙居寺中殿壁画制作材料与工艺研究

广汉龙居寺中殿壁画为四川地区明代建筑壁画中精品。为了解该壁画制作材料与工艺,采用显微观察、激光粒度仪分析、X射线衍射、拉曼光谱、酶联免疫等方法,对样品结构形态和材料组成进行了分析。结果表明:该壁画载体为编竹夹泥墙结构。地仗层泥土颗粒矿物成分主要为石英、钠长石,颗粒组成墙体壁画以粉粒为主、砂粒次之,垫拱板壁画粗泥层比细泥层砂粒含量偏低、粉粒含量偏高;加筋材料粗泥层为稻草秸秆、谷壳等,细泥层为棉或麻纤维。颜料层显色成分为古代壁画常见矿物颜料,红色为朱砂、铅丹,绿色为氯铜矿、副氯铜矿,白色为方解石、滑石,黑色为炭黑,蓝色为石青,黄色为针铁矿,胶料为动物胶或蛋清。该壁画在四川地区明代建筑壁画制作材料与工艺上具有典型性,主要体现在载体结构类型、地仗层材料组成、颜料层显色成分等方面。研究成果不仅可为该壁画后期保护修复提供依据,而且丰富了对四川地区明代建筑壁画的认识。     

Obsidian provenance studies in Colombia and Ecuador: obsidian sources revisited

The field occurrences, elemental compositions and formation ages of Colombian and Ecuadorian obsidians are revisited. It is shown that the regional sources of this raw material are linked to two major volcanic structures: the Chacana and the Paletara calderas, localised on the eastern cordillera of Ecuador and on the central Andean cordillera of south Colombia respectively. Seventy-two samples were analysed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES), inductively coupled plasma-mass spectrometry (ICP-MS) and/or particle induced X-ray emission (PIXE). The same 10 types of elemental compositions were identified independently from ICP and PIXE. Four of these types were previously unknown. The formation ages of these obsidians previously determined by fission tracks dating are in the range 0.17–1.58 Ma at Chacana and 3.46–4.27 Ma at Paletara. Most Colombian and Ecuadorian pre-Hispanic artefacts present elemental compositions compatible with a Chacana- or Paletara-derived origin of the raw material. However, some of them present fission track ages discordant with the present-day known obsidian occurrences, which implies that the regional source inventory is not yet exhaustive.     

CHEMICAL AND MINERALOGICAL ANALYSES OF GALLO-ROMAN WALL PAINTING FROM DIETIKON,SWITZERLAND

Around 90 samples of Roman wall painting dating from the first to the third century AD were analysed using different analytical techniques: X-ray diffraction, X-ray fluorescence, infrared spectrometry, scanning electron microscopy, energy dispersive spectrometry, optical microscopy and physico-chemical tests. The identified pigments are: ash, calcite, carbon black, celadonite, cinnabar, Egyptian Blue, glauconite, goethite, hematite and red lead. Pigment mixtures were used to get other colours such as brown, pink or purple. Three types of plaster were used: a first, and most dominant, with river sand, a second with crushed tile for damp places and a third, to which cinnabar was exclusively applied, was prepared with crushed calcite crystals.     

X-RAY FLUORESCENCE AND DENSITY MEASUREMENTS ON SURFACE-TREATED ROMAN SILVER COINS*

Some 630 Roman silver coins excavated at Augusta Raurica (Switzerland) have been analysed by non-destructive X-ray fluorescence and X-ray diffraction. Furthermore, the density and the weight have been determined. The measured average density of plated and massive depletion-silvered coins is lower than the density calculated from the chemical composition, whereas massive coins display equal values for both of the densities. Based on experimental X-ray investigations of modern silver (tempering, acid treatment, production of corrosion layers), the nature of corrosion products on silver, their impact on surface analysis, and aspects of wearing-off by circulation are briefly discussed.     

Transitions in Islamic plant-ash glass vessels: on-site chemical analyses conducted at the Raya/al-Tur area on the Sinai Peninsula in Egypt

This study focuses on the chemical composition of Islamic plant-ash glass (dated from the 9th to 11th centuries) excavated from the Raya/al-Tur area on the South Sinai in Egypt. Plant-ash glass objects from the Raya site were classified into three compositional types based on on-site chemical analyses with a portable X-ray fluorescence spectrometer. Based on typological characteristics and chemical composition comparisons with contemporary glass objects from other Islamic sites, one hypothesis holds that plant-ash glass objects produced in the Syria–Palestine or Mesopotamian regions could have been imported to Raya during the 9th to 10th centuries. In particular, some colorless glass vessels with a high magnesium/calcium ratio were noted to exhibit post-Sassanian cut decorations. Conversely, most of the bluish-green plant-ash glass objects from the Monastery of Wadi al-Tur near the Raya site exhibited relatively high levels of aluminum, titanium, iron, and lead. These pieces were likely produced during the Fatimid period (late 10th to 12th centuries), and based on their elemental composition, possibly originated in Egypt. The present work provides a greater understanding of chronological changes in post-9th century Islamic plant-ash glasses and the development of social and commercial networks within the Middle Eastern area.     

A STUDY OF GLASS TESSERAE FROM MOSAICS IN THE MONASTERIES OF DAPHNI AND HOSIOS LOUKAS (GREECE)

In this work 51 glass mosaic tesserae from decorations of the two Greek monasteries of Daphni and Hosios Loukas were analysed by inductively coupled plasma optical emission spectroscopy, electron microprobe analysis and X‐ray powder diffraction. On the basis of the chemical analyses, after discrimination between the tesserae of the original decorations and those from other periods, it was possible to outline the distinctive traits of Byzantine mosaic tesserae. In both the monasteries, the original mosaics were decorated with tesserae produced with plant ash based glass, either of the typical composition or a mixture with natron type glass. The samples from the Hosios Loukas decorations show a more homogeneous composition compared with those from Daphni. The major differences among the original samples are due to the presence of opacifiers and colourants.     

NON ISATIS SED VITRUM OR, THE COLOUR OF LINDOW MAN

Summary. As part of the examination of the fragments of a further human body recovered from Lindow Bog, Cheshire, samples of skin were examined using electron probe X-ray micro-analysis. The ionic composition showed an excess of aluminium, silica and copper, with traces of titanium and zinc. These are interpreted as the residues of clay-based copper and other pigments applied to the body. The literary evidence of the use of body paint amongst the Britons is reviewed in the light of these analyses and the interpretation of Classical references in terms of woad-painted Britons is questioned.