Article

Die Kunst der antiken Glasmacher — mit mikroanalytischen Methoden auf der Suche nach den Details römischer Mosaikgläser

Authors:
To read the full-text of this research, you can request a copy directly from the authors.

Abstract

Mikroanalytische Untersuchungen gewinnen in der Archäometrie aus verschiedenen Gründen immer mehr an Bedeutung. Zum einen hat sich die Zahl der unterschiedlichen Methoden in den vergangenen zehn bis fünfzehn Jahren deutlich vergrößert. Neben der traditionell weit verbreiteten Elektronenstrahl-Mikrosonde stehen heute unterschiedliche Typen von Lasersonden, Mikro-Röntgenfluoreszenzanlagen, Mikro-Röntgendiffraktometern, Raman-Mikrospektrometern, Ionensonden oder Protonensonden zur Verfügung. Zum anderen können die Messungen an kleineren Objekten in-situ oft zerstörungsfrei oder wenigstens zerstörungsarm durchgeführt werden. Das ermöglicht die Untersuchung auch wertvoller Funde wie z.B. der prunkvollen, großzügig mit geschliffenem Granat verzierten Gold- oder Silberfibeln der Merowinger (Quast und Schüssler 2000). Für die Analyse größerer Objekte, die nicht als Ganzes in die Probenkammern einiger Instrumente passen, genügt meist die Entnahme winziger Proben für die Messung. Ein typisches Beispiel dafür ist die berühmte Portlandvase im Britischen Museum, eine römische Vase aus Kameoglas, bei deren Restaurierung kleinste Glassplitterchen anfielen, die dann eingebettet und mikroanalytisch untersucht wurden, um die Glasrezeptur zu ermitteln (Bimson und Freestone 1983). Einige Methoden sind allerdings auch geeignet, um größere Objekte in-situ zu analysieren, manche Messgeräte sind sogar portabel und erlauben Messungen unmittelbar vor Ort, z.B. in Museen, Gemäldegalerien oder an Baudenkmälern.

No full-text available

Request Full-text Paper PDF

To read the full-text of this research,
you can request a copy directly from the authors.

Article
En este artículo se han seleccionado y clasificado una serie de camafeos como representativos retratos de Augusto y de personajes masculinos y femeninos, pertenecientes a la Gens Julio Claudia, en un período cronológico comprendido, aproximadamente, entre el 31 a.C. y el 68 d.C., de los que se realiza un estudio desde la perspectiva iconográfica, considerando que sus imágenes trasmiten una valiosa documentación histórica.
Article
In dieser Arbeit werden Pigmente in verschiedenen archäologischen Materialien mittels Mikro-Raman-Spektroskopie archäometrisch untersucht. Zusätzlich werden Analysen mittels Elektronenstrahl-Mikrosonde und Röntgenpulverdiffraktometrie durchgeführt, um einerseits die Ergebnisse der spektroskopischen Untersuchungen zu stützen und andererseits die Vor- und Nachteile der Mikro-Raman-Spektrokopie gegenüber diesen Methoden aufzuzeigen. Im ersten Teil werden Pigmentanalysen römischer Fresken in den Provinzen Noricum, Raetien und Obergermanien vorgestellt, um daraus Informationen über Umfang und Variationsbreite der Farbpalette antiker Maler abzuleiten sowie Rückschlüsse auf die Herkunft der Rohstoffe und eventuelle Handelsrouten zu ziehen. Die Möglichkeit der zeitlichen Einordnung von Fresken anhand der verwendeten Pigmente wird ebenfalls diskutiert. Im zweiten Teil wird die chemische Zusammensetzung antiker Gläser am Beispiel einer Sammlung von Mosaikgläsern aus dem Martin-von-Wagner-Museum Würzburg und verschiedener bunter Glasperlen aus Sri Lanka und Oman untersucht, um Informationen über die verwendeten Rohmaterialien und die Technologie der antiken Glasproduktion zu gewinnen. Insbesondere wird auf die Pigmente eingegangen, die die Farbigkeit der Gläser verursachen. Anhand der Differenzen in den Glasrezepturen und Pigmenten der Gläser wird eine zeitliche Einordnung erörtert.
Article
Full-text available
Beads from graves of the Samad Culture. Sultanate of Oman, and from an ancient craftsmen quarter of the old kingdom of Ruhuna. excavated in Sri Lanka, were investigated using electron microprobe analysis and X-ray powder diffraction. Both experimental methods were optimized towards a non-destructive analysis of archaeo­ logical finds. Based on their analysis, the beads from Oman can be divided into those made from natural rocks or minerals, metal, glass, Egyptian Blue and synthetic enstatite. Preferred natural rock types are serpentinite, chloritite and massive chlorite amphibolite which occur in the Samail Ophiolite of Oman and indicate a local production of these beads. Garnet beads are almandine-pyrope-rich and are interpreted as imports from the Sri Lanka/India area. Metal beads are made from pure Ag. ± pure Au or from Ag-Au-Cu alloys. Reddish-brown glass beads from Oman are Na-rich and coloured by Cu present in the glass matrix. Opaque red glass beads from Sri Lanka are commonly K-rich and coloured by tiny cuprite droplets which recrystallized from the melt and which are intensively disseminated within the glass matrix. Blue-while-blue and brown-white-brown sandwich beads from Oman and Sri Lanka are stylistically similar, but differ in composition of the white glass. Parts of the glass beads from Oman is partially or completely altered to form smectite. A cogged wheel bead from Oman was cut from steatite and then hardened by transformation of the steatite lo synthetic enstatite during firing at about 1000'C. Large amounts of microbeads from a Samad grave also consist of synthetic enstatite and most probably were produced from Mg-rich clay by firing. Comparable beads have been recovered from excavations in the Indus area, especially Harappa. but also in the Arabian Emirates.
Article
Full-text available
Die Antikenabteilung des Martin von Wagner Museums in Würzburg besitzt etwa 200 Fragmente von Mosaikgläsern, die aus dem Kunsthandel stammen und von denen jetzt 100 archäologisch bearbeitet wurden [1]. Bei diesen Gläsern handelt es sich um Gefäße, Einlagen und Verkleidungs-platten, die aus einzelnen kleinen Scheibchen von vorgefer-tigten Mosaikglasstäben zusammengesetzt sind. Stilistisch kann man die untersuchten Fragmenten in drei Gruppen unterteilen, eine hellenistische, eine ptolemäisch-frühkaiserzeitliche und eine frühkaiserzeitliche. Zwölf reprä-sentative Fragmente wurden mit folgenden Fragestellungen materialkundlich analysiert: -Sind alle Gläser der römischen Glasrezeptur zuzuordnen? -Gibt es Stücke, die nicht antik sind? -Sind die Stilgruppen in der Glasrezeptur unterscheidbar? -Auf welcher Basis beruht die Färbung der Gläser? Untersuchungsmethoden Die Grundzusammensetzung der ein-zelnen Farbgläser wurde mit einer Elektronenstrahl-Mikrosonde analysiert, da die Fragmente klein genug sind und weil jeweils eine Seite der korrodierten Gläser im 19. Jh. durch vorbesitzende Kunsthändler aufpoliert worden war. Pauschalchemische Unterschiede zwi-schen den einzelnen Farbgläsern sowie die zur Färbung und Trübung benutzten Pigmente wurden im Rück-streuelektronenbild sichtbar gemacht. Die verschiedenen Farbpigmente wur-den mit Hilfe der Raman-Mikrospek-troskopie identifiziert [2,3].
Article
Full-text available
For geological studies, interest in mass spectrometry with an inductively coupled plasma as an ion source and its association with laser ablation as a sample introduction technique (LA-ICP-MS) has steadily increased during the past few years and is now being developed in other fields such as archaeology. After a description of the analytical procedure and the calculation method, we show the potential of this technique to characterize, almost non-destructively, archaeological artefacts. Among the 70 elements that could be routinely analysed by LA-ICP-MS with detection limits below the ppm level, we choose to determine the more critical ones in order to evaluate the geochemical models of the magmatic process (major elements, rare earths and some transition elements). A detailed survey of Cappadocian obsidian flows is given, and includes the characterization of nine different sources. Evidence of complex trade activities is clearly shown by the obsidian tools found at different prehistoric sites (from Neolithic to Bronze Age levels) in the Mediterranean and the Near East. New results obtained on some archaeological sites located in Turkey, Syria and Cyprus are presented. They show the importance of Cappadocian sources in obsidian trade. Our results show that LA-ICP-MS allows a non-destructive analysis of archaeological objects and that it combines the advantage of the different classical methods used to characterize obsidian sources (mainly XRF and INAA) with high sensitivity and rapidity. Thus LA-ICP-MS appears to be a very powerful analytical tool and, at this time, this technique is the only one which can non-destructively determine such an important number of elements with such low detection limits.
Book
Full-text available
X-Ray Fluorescence analysis (XRF) is a reliable multi-elemental and nondestructive analytical method widely used in research and industrial applications. This practical handbook provides self-contained modules featuring XRF instrumentation, quantification methods, and most of the current applications. The broad spectrum of topics is due to the efforts of a large number of authors from a variety of different types of institutions such as universities, research institutes, and companies. The book gives a survey of the theoretical fundamentals, analytical instrumentation, software for data processing, various excitation regimes including gracing incidents and microfocus measurements, quantitative analysis, applications in routine and micro analysis, mineralogy, biology, medicine, criminal investigations, archeology, metallurgy, abrasion, microelectronics, environmental air and water analysis. It gives the basic knowledge on this technique, information on analytical equipment and guides the reader to the various applications. This practical handbook is intended as a resource for graduate students, research scientists, and industrial users.
Article
Full-text available
The elemental composition of 14 Roman cameo glass fragments was measured quantitatively by X-ray fluorescence analysis induced by synchrotron radiation. The study was intended to learn more about the possible manufacturing techniques of these glasses. In the white cameo decor of nine fragments all belonging to vessels a higher lead oxide concentration was detected compared to the colored body. In contrast, lead oxide is not enhanced in the remaining five fragments from cameo disks or plates. The higher concentrations may be interpreted as flux added to lower the melting temperature of the white cameo layers of the vessels, thus supporting the recent hypothesis that these cameo vessels were manufactured with the help of a mold on a turning wheel, which had not to be used for the production of cameo plates.
Article
Full-text available
This paper gives a short overview of the Special Issue on Raman Spectroscopy in Art and Archaeology, with the papers collected after the '3rd International Conference on the Application of Raman Spectroscopy in Art and Archaeology' held at the University Pierre et Marie Curie-Paris 6, Paris, France, from 31 August to 3 September, 2005. The contributions present an extended view of the work in the field, from technical developments and special analytical procedures to various applications. Copyright (C) 2006 John Wiley & Sons, Ltd.
Book
The application of X-rays to archaeological objects with the goal of gaining insight into both their construction and chemical composition, in a non-destructive manner, dates back to the discovery of radiation. Nowadays, X-ray techniques, such as X-ray fluorescense and diffraction are standard tools. This book offers physicists, art historians, archaeologists, curators, and conservators a detailed overview via contributions written by leading scientists in the field. The book contains scientific data, i.e. in situ measurement data taken with portable XRF and XRD, and fine data taken with accelerating ion beams and synchrotron radiations, together with their explanations. Results obtained by traditional scientific methods are also reviewed. The broad data collection spans experimental data taken both from monuments in the field and exhibits in museums, for example: ancient Egyptian wall-painting pigments ancient Egyptian wooden statues and mummies ancient Greek funerary monuments Cypriot ceramics medieval, Lyubliana and Venetian glass Romanian ceramics ancient Near-Eastern clay old Japanese porcelain pre-Hispanic items from America ancient Chinese underglaze-red blue and white porcelain Chinese celadon Phoenician cosmetics Also included are data from glazes, ancient gold and silver coins, gold jewelleries, gold alloys, corroded metals, gemstones (ruby, emerald and garnet), painting pigments, pottery, bronze, obsidian, stucco, turquoise, and so on. The discussion fostered here between natural scientists and archaeologists anticipates the future direction of archaeology.
Chapter
Raman spectroscopic techniques have some special advantages for application in art and archaeological analysis; the provision of spectral data from microscopic specimens typically in the nanogram to picogram range, the ability to examine samples with minimal or no chemical and mechanical pretreatment, the versatility of selection of a range of laser excitation wavelengths to interrogate colored specimens, the acceptance of specimens of a size range from milligram to kilogram, and, because of the low Raman scattering cross-section for water, the accessibility of data from hydrated archaeological specimens all contribute to the unique niche position that is occupied by Raman spectroscopy in this field today. The major advantages of the adoption of Raman spectroscopy for the analysis of artifacts and works of art are twofold: the technique is nondestructive and requires little or no chemical and mechanical pretreatments of the specimen, and the molecular signatures from both the organic and inorganic components are obtained in the same spectrum, hence affording the opportunity for assessing the interactions and relative stabilities to chemical, biological, and environmental changes operating on the specimen. The examination of diverse range of artifacts and specimens using nondestructive laser Raman spectroscopic analysis provides the acquisition of novel historical information about their origins and degradation suffered in a new light. In this chapter, the results of several selected case studies that are undertaken in collaboration with archaeologists, art historians, and conservation scientists is presented to illustrate the use of the analytical data derived from Raman molecular spectroscopic applications.
Chapter
When a monochromatic (i.e. single-frequency) beam of light traverses a medium (gas, liquid or solid) the majority of the scattered light will remain at the incident frequency. However, a small proportion of the scattered light will be at changed frequencies, above and below the incident frequency, and this is referred to as the Raman effect. The Raman effect was first observed by Raman and Krishnan (1928) using focused sunlight and filters and relied on the visual observation of colour changes in the scattered light. However, it was not until the advent of continuous wave visible lasers, during the 1960s, that the importance of Raman spectroscopy as a routine analytical technique was realized. Furthermore, the availability of this highly intense monochromatic light source, which could be focused to a narrow waist, allowed the analysis of small volumes of gas, liquid or solid.
Chapter
X-ray fluorescence analysis (XRFA) is a standard technique that is used routinely for the analysis of rocks and minerals. Potts (1987; Chapter 8) covers the theory and practice. When an X-ray photon interacts with an atom, there is a well-defined probability that the photon energy will drive out (i.e., ionize) an electron from a bound state. The excited atom regains equilibrium by emission of either an X-ray photon or an Auger electron, both with characteristic energy determined by the quantum numbers of the initial and final electronic states and the atomic number of the atom. Measurement of the energy of the emitted X-ray photon identifies the type of atom (except for accidental overlap within the experimental resolution). Determination of the flux of this particular type of photon with respect to the total flux from all X-ray photons from all atoms in a sample provides a measure of the atomic concentration in the bulk sample. There are many details involving the relative probabilities of the various processes, the competition with coherent diffraction and other scattering processes, the perturbation of electronic states of an atom from changes in chemical bonding, and the actual experimental details of the X-ray source, the detectors and the algorithms for the mathematical analysis. Nevertheless, the technique is fundamentally straightforward and potentially accurate to the per cent level of the amount present, when suitable standards are available. Classical X-ray fluorescence analysis is technically easiest for those elements that can be determined from K line fluorescent photons with energies in the 1–20 keV range. The spectrum becomes progressively more complex from the K to the L and M line series. Analytical complications from energy shifts related to chemical bonding and electronic state only become significant at lower energy, but these perturbations can be valuable to a structural crystallographer/geochemist.
Chapter
X-ray fluorescence spectrometry is a technique for the analysis of bulk specimens. Samples are prepared as compressed powder pellets or fused glass discs and excited with x-ray radiation, normally generated by an x-ray tube operated at a potential of between 10 and 100 kV. Interaction of this primary radiation with atoms of the sample causes ionization of discrete orbital electrons. During the subsequent electronic rearrangement by which the atom then de-excites back to the ground state, fluorescence x-rays of energy characteristic of that element are emitted. The emission intensity of this characteristic radiation is measured with a suitable x-ray spectrometer and compared with that from a standard sample. The technique is one of the most widely used routine instrumental methods of analysing rock samples both for the major elements Na, Mg, Al, Si, P, K, Ca, Ti, Mn, Fe and selected trace elements, including Rb, Sr, Y, Nb, Zr, Cr, Ni, Cu, Zn, Ga, Ba, Pb, Th, and U. Detection limits for many of these trace elements lie in the range 1 to 10 ppm rock under routine operating conditions.
Chapter
Der Raman-Effekt wurde im Jahre 1928 von Raman und Krishnan [1] an Flüssigkeiten und fast gleichzeitig von Landsberg und Mandelstam [2] an Festkörpern entdeckt, nachdem ihn Smekal [3] bereits 1923 theoretisch vorhergesagt hatte. Die quantenmechanische Behandlung wurde ebenfalls bereits vor der Entdeckung des Effektes von Kramers und Heisenberg [4] und später von Dirac [5] durchgeführt. In den ersten Jahren nach der experimentellen Verifikation dieses Effektes wurde er vorwiegend zur Strukturaufklärung von organischen und anorganischen Substanzen in flüssiger Phase eingesetzt [6]. Seit der Realisierung des Lasers im Jahre 1960 hat die Raman-Spektroskopie insbesondere im Bereich der Festkörperuntersuchungen eine wahre Renaissance erlebt. Neben der Spektroskopie von Phononen wurde er u. a. auch zum Nachweis einer Reihe von anderen Quasiteilchen in Festkörpern (z. B. Plasmonen, Polaritonen etc.) verwendet [7]. Die hohen, durch Laser erzielbaren Lichtintensitätsdichten führten zudem zu neuen, nichtlinearen Effekten wie dem stimulierten Raman-Effekt [8].
Article
The x-ray production cross-sections for the K lines of heavy elements is large enough at 68 MeV proton energy to detect heavy elements via the K in addition to their L x-rays. The large proton penetration range and the fact that the absorption coefficients for the x-ray K lines are much smaller than for the L lines result in an analytical depth of several millimeters. The intensity ratio between the stimulated x-ray L and K lines yields information about the physical composition (e.g. layered structure, layer sequence, hidden structure elements) of the samples supplementary to their chemical composition. Also, based on the now detectable K lines, spectra with mixtures of heavy elements are easier to evaluate, as the K lines will overlap less than the L lines. The experimental set-up and several examples of measurements on archaeological and art historical objects are presented. Copyright © 2004 John Wiley & Sons, Ltd.
Chapter
For many years it has been possible to measure accurately the small-scale variations in the major and minor element chemistry of minerals by the electron microprobe technique, in which the sample surface is bombarded with an electron beam and the X-ray signal is measured (Chapter 2). Abundances of isotopes, trace and ultra-light elements (e.g. H and Li) which cannot be determined by this method can, however, be measured by secondary ion mass spectrometry (SIMS; Shimizu, Semet and Allègre, 1978; Shimizu and Hart, 1982; Reed, 1989; Zinner, 1989). The ion microprobe is a SIMS instrument with a focused primary ion beam, which permits in situ microanalysis of minerals in samples prepared as standard polished sections. Nearly all elements from H to U can be detected and many can be analysed quantitatively down to part-per-million levels, or below.
Article
In this report, the authors describe the first successful coupling of an atmospheric-pressure He ICP to a commercial ICP-MS system. Minor modifications of the load coil and the plasma impedance matching network were made to sustain the annular He ICP in a low-gas-flow torch at a forward power of 500-900 W and a total gas flow of 8 L/min. The objectives of this work were to investigate the feasibility of using a mass spectrometer for fundamental studies in He ICPs and to explore the analytical capabilities of the He ICP-MS system for the determination of halogens and sulfur. Except for this report on the He ICP and an earlier study with an Ar-N/sub 2/ICP all previous investigations of ICP mass spectrometry have been concerned with Ar discharges.
Article
A nano-high performance liquid chromatography-inductively coupled plasma mass spectrometry (nano-HPLC-ICPMS) method is developed, using a demountable direct injection high efficiency nebulizer (d-DIHEN), to reduce sample and mobile phase consumption, minimize organic waste generation, decrease analysis time, and enhance separation efficiency. A HPLC column (50 mm × 0.3 mm id), packed with 3.5 μm C18 material, is explored for chromatographic separation of five arsenic species naturally present in the environment or introduced as a pollutant: sodium (meta)arsenite [As(III)], arsenic acid [As(V)], dimethylarsenic acid (DMA), disodium methylarsenate (MA), and p-arsanilic acid (p-ASA). A fast chromatographic separation of five arsenic species is achieved in less than 12 min at a solution flow rate of 0.9 μL min−1 using a 50 nL sample injection. The HPLC-ICPMS interface provides well defined flow injection profiles at various concentrations, giving a correlation coefficient of 0.999 for each individual arsenic species calibration curve. Precision values for peak height and area of five arsenic species range from 0.5 to 6.5% RSD and absolute detection limits are within 0.4 to 5.4 pg arsenic, which are comparable to previously reported data at higher solution uptake rates (20 μL min−1 to 1 mL min−1) and larger sample injection volumes (20–100 μL).
Article
An overview of the techniques used in art and archaeology is presented and the applicability of X-ray radiography, X-ray fluorescence (XRF), and X-ray diffraction analysis (XRD) as a tool for nondestructive investigations of objects of art and archaeology is discussed. X-ray radiography, for example, is a standard technique widely used and accepted by art historians, archaeologists, curators, and conservators as this method enables information about the manufacturing process and the condition of an object without “touching” the artifact. XRF and XRD enable a nondestructive determination of the material composition of artifacts and the determination of the crystalline structure of the components too. Air path systems and instruments with the micro-beam of X-ray and synchrotron radiation were applied for the analysis of easel paintings, pigments in paint layers, glass artifacts, and coins.
Article
Lead and copper isotopes of Roman Imperial copper coins (denominations as and quadrans) were analysed by MC–ICP–MS. We concentrated on well-dated coins minted at the official mint of Rome under the Emperors Augustus and Tiberius (between 16 bc and ad 37). The lead isotope results were compared with published lead isotope data of ore bodies from the Aegaean, Cyprus, Italy and Spain, in order to fingerprint the sources of Roman copper. During the Augustan period the main copper supply, as judged from the copper coins, is from Sardinia and south-east Spain, with minor contributions from Tuscany. Except for Tuscany, this continued into the Tiberian period, when Cypriot copper also appears. Augustan quadrantes and late Tiberian asses came solely from the Rio Tinto area in south-west Spain. Copper isotopes were applied here for the first time to systematic archaeometric studies. They are supplementary to lead isotopes and allow further grouping and classification of the copper coins.
Article
Ancient coloured glass beads from Sri Lanka and Oman were analysed by Raman microspectroscopy for non-destructive identification of inorganic pigments in the glass. Calcium phosphate (Ca3(PO4)2), cassiterite (SnO2), cuprite (Cu2O) and a Pb(Sn,Si)O3-type lead tin oxide were found to be used as colouring agents. Moreover, a distinction between lead-based and alkali-based glass matrices could be made. Electron microprobe analysis and X-ray diffractometry were performed to show the capability of Raman microspectroscopy in comparison to these methods for answering archaeometric questions. Copyright © 2006 John Wiley & Sons, Ltd.
Article
Material analysis of Limoges painted enamels was undertaken by using an x-ray fluorescence spectrometer equipped with a low-power x-ray tube, polycapillary x-ray optics and a silicon drift chamber detector. The spectrometer, which includes helium purging for detecting elements down to sodium, can easily be assembled and dismantled within 1 h. A quantification method for enamel and glass objects was developed and verified using standard materials. The layer arrangement and possible influence on the XRF measurements were especially considered in theoretical calculations. Over 160 painted enamels from the late Renaissance and Revival periods in the 19th century in various collections were investigated. Comparison of the quantitative results from objects which are securely dated and attributed by art historians allowed a more reliable attribution of pieces with doubted authenticity. Copyright © 2004 John Wiley & Sons, Ltd.
Article
Raman spectroscopy is becoming increasingly important as an analytical and diagnostic tool for the investigation of precious and brittle objects of art and antiquities. In addition to this introductory paper, this special issue of the Journal of Raman Spectroscopy contains 31 papers dedicated to this subject. This introduction gives an overview and paints a picture of the different approaches in this field. Copyright © 2004 John Wiley & Sons, Ltd.
Article
Accuracy and repeatability of analytical results obtained by laser ablation (LA) inductively coupled plasma mass spectrometry (ICP-MS) critically depends on the availability of calibration standards, which should ideally have a matrix composition very close to the samples being analyzed. The preparation of synthetic obsidian standards (SOS) is described in this work, their minor and trace element composition (>40 elements), determined by solution nebulization ICP-MS and inductively coupled plasma optical emission spectrometry is presented and their performance in the quantitative and semiquantitative analysis of obsidians by LA-ICP-MS is discussed. Due to matrix matching of SOS and natural obsidians, internal standardization of the analyte intensities by 27Al or 29Si had no significant effect on the final results. Good analytical curves (r2>0.995) were obtained with the SOS series, permitting quantitative determination of a large number of trace elements in geological and archaeological samples with repeatabilities typically between 5 and 10% and adequate accuracies, as shown by the generally good agreement between solution nebulization and laser ablation data for the same samples. Results obtained in the fast semiquantitative mode of calibration were in most cases statistically not different from those obtained by the quantitative mode. This, for the routine analysis of a large number of samples attractive feature, was achieved by the use of 47 quantified elements in SOS for updating of the response factors. An example for the application of analytical methodologies introduced in this work is shown in provenance studies of archaeological obsidian artifacts from Ecuador.
Article
Cosmelting experiments to produce copper–arsenic alloys were carried out by Lechtman in 1984. The experiments included crucible and furnace smelting techniques utilizing ores collected in the Peruvian Andes. Smelting charges consisted of mixtures of copper oxide ore with either copper sulpharsenide or iron sulpharsenide ore. The experimental furnaces were constructed to resemble furnaces excavated at Batán Grande, a large ore smelting site on the Peruvian north coast where copper–arsenic alloys were produced during the Middle Horizon and later.The cosmelting experiments yielded coherent copper–arsenic alloy ingots over a wide range of oxide: sulpharsenide ore mixtures. Crucible/furnace charges containing ratios of between 2:1 and 4:1 oxide:sulpharsenide mineral produced clean metal, fully separated from slag or matte byproducts. The sulphide ores were not roasted prior to smelting; no flux was added to the charges.Study of the metal ingots, mattes, and slags helps determine the chemical and thermodynamic reactions and the phase separation mechanisms that took place inside the smelting enclosures. The copper–arsenic alloys found in ancient artefacts could have been made easily, deliberately or accidentally, by cosmelting procedures.
Article
1. Introduction; 2. Essential features of the electron microprobe; 3. Electron gun; 4. The probe-forming system; 5. Scanning; 6. Wavelength-dispersive spectrometers; 7. Proportional counters; 8. Counting electronics; 9. Lithium-drifted silicon detectors; 10. Electronics for energy-dispersive systems; 11. Wavelength-dispersive analysis; 12. Energy-dispersive analysis; 13. X-ray generation and stopping power; 14. Electron backscattering; 15. Absorption corrections; 16. Fluorescence corrections; 17. Matrix corrections in practice; 18. Light element analysis; Appendix: origin of characteristic X-rays.
Article
A newly developed spectrometer for energy-dispersive micro X-ray fluorescence spectrometry has been designed for the demands of archaeometry. ArtTAX combines the advantages of non-destructive and sensitive multi-elemental analysis at sub-mm resolution with the possibility of working outside the laboratory. The spectrometer consists of an air-cooled, low-power molybdenum tube, new generation polycapillary X-ray optics, a silicon drift detector without the need for liquid-nitrogen cooling, a CCD camera, and three light diodes for sample positioning. The motor-driven measurement head is fixed on a x,y,z-flexible tripod support which can be assembled and dismantled within minutes. The spot size of the primary X-ray beam was determined to be 94 microm for the Cu(Kalpha) energy, the detection limits are in a range of a few tens of microg g(-1) for the medium energy-range in glass. Additional open helium purging in the excitation and detection paths enables the determination of elements down to sodium, thus avoiding vacuum conditions or a size-limiting sample chamber. A selection of qualitative and quantitative results on pigment, metal, glass, and enamel analyses are presented to show the potential of ArtTAX in the field of art and archaeology.
The nuclear microprobe
  • Dg-Ixe Fraser
  • Rbs Pige
  • Erda Nra
  • Pj Potts
  • Jfw Bowles
  • Sjb Reed
  • Mr Cave
Farbloses Glas im Wandel der Zeit - Materialanalytische Untersuchungen an farblosen Gläsern des 13. bis 17. Jahrhunderts mit Hilfe der Laser Induced Breakdown Spectroscopy und der Mikro-Röntgenfluoreszenzanalyse
  • K Müller
  • K. Müller
Mineral microanalysis by laserprobe inductively coupled plasma mass spectrometry
  • Wt Perkins
  • Njg Pearce
  • Pj Potts
  • Jfw Bowles
  • Sjb Reed
  • Mr Cave
Laser-Ablation-ICPMS in the Earth Sciences - Principles and Applications
  • P Sylvester
Kameoglasfragmente im Martin von Wagner Museum der Universität Würzburg und im Allard Pierson Museum Amsterdam
  • C Weiß
  • U Schüssler
  • C. Weiß
Glas in Antike und Mittelalter, Geschichte eines Werkstoffs
  • Kh Wedepohl
Ion microprobe analysis in geology
  • Rw Hinton
  • Pj Potts
  • Jfw Bowles
  • Sjb Reed
  • Mr Cave
Synchrotron X-ray microanalysis
  • Jv Smith
  • Ml Rivers
  • Pj Potts
  • Jfw Bowles
  • Sjb Reed
  • Mr Cave
Die mobile Mikro-Röntgenfluoreszenzanalyse-Neue Möglichkeiten der In-situ-Untersuchung
  • H Stege
  • O Hahn
  • J Müller
  • H. Stege
Electron microprobe analysis and X-ray diffraction methods in archaeometry: Investigations on ancient beads from the Sultanate of Oman and from Sri Lanka
  • C Rösch
  • R Hock
  • U Schüssler
  • Yule P Hannibal
  • C. Rösch
Mineral microanalysis by laserprobe inductively coupled plasma mass spectrometry
  • W T Perkins
  • Njg Pearce
Raman Spectroscopy in Archaeology and Art History. Cambridge
  • Hgm Edwards
  • J M Chalmers
  • H.G.M. Edwards