Advances in multi-elementary analysis of fluid or solid micro-crystalline inclusions (12

International audienceX-Ray-based analytical methods can be applied in an absolute fashion, provided that matrix effects are calculated and that parameters related to instrumental factors are controlled (Newbury, 1986). When EPMA (Electron Probe Micro Analysis) was conceived at the end of the 60's, this potentiality was abandoned, as the instrument works in a relative fashion, by comparison with standards. At the end of the 70's and in the 80's, PIXE (Proton Induced X-Ray Emission) by contrast was applied in a way that preserved the possibility of an absolute application: the computer programs developed to interpret PIXE spectra calculate matrix effects and also integrate instrumental factors (e.g., Maxwell et al., 1989). In spite of this advantage, and also despite the fact that PIXE application extends to trace element analysis, the development of PIXE in the scientific community was sluggish, in deep contrast with the widespread applications of EPMA. In the field of Earth Sciences particularly, EPMA was recognized by the Mineralogical Society of America to have had 'a revolutionary, profound impact on mineralogy and petrology'. In the same time, PIXE applications remained mainly restricted to trace element analysis, and the potential accuracy of the method was never clearly realized. A first aim of this presentation is to show that, using a simple standardization procedure, the multi-elementary absolute capability of PIXE can be revealed. This in turn changes PIXE into a tool of quantitative mineralogy and trace element geochemistry. We then show that, by coupling PIXE to PIGE (Proton Induced Gamma Ray Emission) and RBS (Rutherford Back Scattering) spectrometries, the Nuclear Microprobe becomes a tool for quantitative mineralogy s.l. and geochemistry, i.e., an instrument to analyze all major to trace elements from Li to U in minerals and their inclusions. In the second part of the presentation, we illustrate the capability of µ-PIXE to analyze in situ individual fluid inclusions that have been carefully localized in space and time. The Hercynian French Massif Central and its sedimentary eastern margin are part of a large European Carbonic Province, which hosts numerous deep CO2 reservoirs and carbonic springs (Blavoux, Dazy, 1990). Carbonic fluids are present at all stages of the long-lived evolution of this crustal segment, from deep metamorphic fluids involved in a thrusting event at 340 M.a to mantle-derived volcanic CO2 related to Neogene volcanism. In order to characterize the main aquo-carbonic fluid reservoirs through time in this crustal segment, we present preliminary data on the trace element content of aquo-carbonic inclusions trapped in the schists at peak and retrograde metamorphic conditions, and compare them to contemporaneous granite-related fluid inclusion

Ancient Restoration in Roman Polychromy: Detecting Aesthetic Changes?

peer reviewedFew instances of material evidence for ancient colour restorations have been documented over the last 20 years, during which time the scientific approach to the study of polychromy has been defined. This article presents eight new cases of ancient restoration of colour from the Roman Imperial Age. By combining observations in visible and UV light and video microscopy with a microstratigraphic approach, MA-X-ray fluorescence spectroscopy, and contextual archaeological data, we have observed evidence which could suggest an aesthetic change in the use of colour between the 2nd and 4th centuries CE: from polychrome and multitone effects to the use of monochromatic, flat, and uniform colour finishes

Towards portable X-ray spectroscopic imaging of Palaeolithic cave art. Insights into used pigments and wall taphonomy at three Palaeolithic key cave sites

Palaeolithic cave art has taken a more and more important place in our cultural heritage. Its preservation is one of the major issues and involves necessarily a better understanding of the cave environments and of their evolution over time. However, the on-site geo-physico- chemical study of archaeological record stays dif cult and the conservation of its integrity imposes restrictions. Taking bene t of recent analytical developments in the X-ray eld, new perspectives of acquiring statistically relevant data for archaeological interpretation directly in the eld are provided by the implementation of portable and non-invasive characterization methods. It allows the improvement of archaeological and physico-chemical knowledge about the pigments used, the evaluation of the state of wall decorated surfaces over time and a better assessment of the relationship between pigment and wall support. For these purposes, complementary self-built portable spectrometers (X-ray uorescence in one and two dimensional mode, X-ray diffraction) are combined to perform qualitative and quantitative characterization of the pigments and cave walls as well as for chemical imaging on a decimetre scale. By using this combination of portable instruments the feasibility of analysis under very dif cult conditions speci c to the cave environments (humidity, temperature, dif cult access to the caves and to the decorated panels) was shown. Special spectrum evaluation procedures have been developed to take into account the heterogeneity of the cave walls in order to gain reliable data for chemical characterisation. The ef ciency of the analytical procedure has been demonstrated for three major cave sites featuring Palaeolithic art: Font-de-Gaume and Rouf gnac cave in Dordogne (France) and La Garma in Cantabria (Spain). A large assortment of colours can be observed in these caves (red, black, yellow and purple), associated to different mineral phases (iron and/or manganese oxides, charcoal and mixtures). Their detailed characterization provides an improved comprehension of the pictorial techniques used. Furthermore, it allows a better comparison between representations in a same cave, giving more detailed insights into its pictorial homogeneity and the different execution phases of its gures. As an example, the results obtained at Rouf gnac cave showed that heterogeneous mixtures of manganese oxides have been employed to design the 65 Great Ceiling gures whereas a unique pigment mixture has been used for the drawing of the Ten Mammoths Frieze. Further information has been obtained on the taphonomic wall processes. The spectroscopic study of these cave art illustrate the strong potential of such combined in situ and non-invasive analyses to better characterize the prehistoric gures in their cave environment and in a wider perspective to better understand the symbolic practices of past societies, appreciate possible cultural changes and relationships within the Franco-Cantabrian region

Analyses non invasives in situ des œuvres préhistoriques de la grotte de Font-de-Gaume pour une meilleure connaissance du décor pariétal polychrome et de son organisation

Dans cet article est présenté un premier bilan des résultats récents d’analyses chimiques du décor de la grotte de Font-de-Gaume. Ces données ont été obtenues lors de quatre missions de terrain entre 2013 et 2017. Un peu plus de deux cents représentations se répartissent entre un art animalier et des signes (tectiformes), dans des proportions d’environ deux tiers un tiers. L'animal le plus représenté est le bison, d'où le nom la "Caverne des bisons". Les figures ont été réalisées avec différentes techniques. On retrouve la peinture polychrome, le dessin et les gravures. L’état de conservation de la grotte étant le reflet de sa grande fragilité, les parois sont très hétérogènes, ce qui représente un réel défi analytique pour l’analyse chimique des figures dans la mesure où les analyses doivent se limiter à des approches non invasives sans contact. Ainsi, nous avons réalisé environ deux cents analyses par fluorescence X portable pour caractériser les matières colorantes. Elles ont été effectuées dans le but d'obtenir de nouveaux éléments de réponse quant à la composition chimique de la matière colorante utilisée et les techniques de réalisation de ces œuvres du Paléolithique supérieur. Nous présentons ici l'approche utilisée en se focalisant particulièrement sur les traitements des mesures effectuées. Ces premières évaluations des données ont permis d'identifier différentes matières colorantes utilisées dans la grotte de Font-de-Gaume. L'approche développée a ainsi montré son potentiel lorsqu'elle est utilisée sur un plus grand nombre de figures et en intégrant des informations complémentaires. Elle devrait permettre, à terme, d’améliorer la connaissance de ces œuvres et de leur réalisation successive dans le cas de superpositions des figures, ce qui paraît très important en l’absence d’une datation directe des œuvres pariétales de Font-de-Gaume.In this article we present a first assessment of recent results of chemical analysis of the decor of the Font-de Gaume cave. These data were obtained during four field missions between 2013 and 2017. Slightly more than two hundred representations are divided between animal art and signs (tectiforms), in proportions of about two thirds to one third. Most represented is the bison, hence the name "Bison Cave". The figures were made with different techniques. We find polychrome paintings, drawings and engravings. The state of conservation of the cave is a reflection of its great fragility. The walls are very heterogeneous, which represents a real analytical challenge for the chemical analysis of figures since the analyzes must be limited to non-invasive approaches without contact. Thus, we carried out around two hundred analyzes by portable X-ray fluorescence to characterize the coloring matters. These analyzes were carried out in order to obtain new elements of answer as for the chemical composition of the coloring matter used and the techniques of realization of these works of the Upper Paleolithic. Here we present the approach used, focusing particularly on the processing of the measurements carried out. These first evaluations of the data made it possible to identify different coloring materials used in the Font-de-Gaume cave. The approach developed has thus shown its potential, when applying on a larger number of figures and by integrating additional information. In the long term this enables improving knowledge of these works and their successive realization in the case of superimposed figures which seems very important, in the absence of a direct dating of the parietal works of Font-de-Gaume

Determination of the natural radioactivity, elemental composition and geological provenance of sands from Douala in the littoral region of Cameroon using X-ray and γ-ray spectrometry

peer reviewedThis study aimed to determine the concentration of natural radionuclides, the chemical composition, and the geological provenance of sand samples from seven large quarries within the Douala Basin and surrounding locations within the Littoral Region of Cameroon along the Gulf of Guinea. The analyses were undertaken on a total of 24 samples, using both gamma- and X-ray spectrometry techniques. Gamma spectrometric results indicated that the samples from the study area contained amounts of natural radioactivity that are less than the globally agreed safe limits. X-ray fluorescence spectrometry yielded quantitative major, minor, and trace element concentrations that were used in tectonic discrimination diagrams, indicating that these sediments were deposited in a passive margin environment. These concentration and natural radionuclide radioactivity level data provide a reference database for this region of Cameroon as well as for the wider Gulf of Guinea

Les méthodes d'analyse en archéométrie

peer reviewe

Searching for the meanings of the lost colours in Roman statues through materiality: some examples

peer reviewedPolycrom