Virgin Eleusa; Polish-Lithuanian Commonwealth; Art materials study; SERS; Inorganic pigments; Micro-FTIR; Layer-by-layer LIBS;INDUCED BREAKDOWN SPECTROSCOPY; RAMAN-SCATTERING; CRETAN SCHOOL; IDENTIFICATION; PIGMENTS; SERS; ENHANCEMENT; ICONOGRAPHY; SURFACE; CANVAS

Here the results are reported on the multi-analytical study of the Belarusian icon ""Virgin Eleusa"" . The X-ray and luminescence studies revealed some interventions performed in different time periods. The materials of original painting as well as the materials of interventions were successfully characterized by spectroscopic techniques. Layer-by-layer Laser induced breakdown spectroscopy was used for elemental composition study of art materials. Fourier-transform infrared microspectroscopy was used to indicate the types of binding media in the grounds and paint layers as well as to identify the art pigments. A low concentration of cerulean and cadmium yellow in the upper paint layers were identified by Surface enhanced Raman scattering . Since cerulean and cadmium yellow are known to come into use in XIX cent., the SERS results played the crucial role for dating of some intervention.

LIBS; Diffuse reflectance; Portable instrument; Hybrid spectrometer; Pigments;IN-SITU; CULTURAL-HERITAGE; MULTITECHNIQUE APPROACH; WALL PAINTINGS; RAMAN ANALYSIS; LIBS; FIBER; ART; IDENTIFICATION; FLUORESCENCE

A novel, portable spectrometer, combining two analytical techniques, laser-induced breakdown spectroscopy (LIBS) and diffuse reflectance spectroscopy, was developed with the aim to provide an enhanced instrumental and methodological approach with regard to the analysis of pigments in objects of cultural heritage. Technical details about the hybrid spectrometer and its operation are presented and examples are given relevant to the analysis of paint materials. Both LIBS and diffuse reflectance spectra in the visible and part of the near infrared, corresponding to several neat mineral pigment samples, were recorded and the complementary information was used to effectively distinguish different types of pigments even if they had similar colour or elemental composition. The spectrometer was also employed in the analysis of different paints on the surface of an ancient pottery sherd demonstrating the capabilities of the proposed hybrid diagnostic approach. Despite its instrumental simplicity and compact size, the spectrometer is capable of supporting analytical campaigns relevant to archaeological, historical or art historical investigations, particularly when quick data acquisition is required in the context of surveys of large numbers of objects and samples. (C) 2017 Elsevier B.V. All rights reserved.

Cultural heritage; Laser scanners; Fiber Bragg grating sensor; Laser-induced fluorescence; Laser-induced breakdown spectroscopy;INDUCED BREAKDOWN SPECTROSCOPY; PLASMA PARAMETERS; FLUORESCENCE

The recent development of laser scanners in environmental diagnostics made possible to implement their prototypes for remote characterization of cultural heritage (CH) surfaces. Specific data analysis algorithms have been developed to handle large data set acquired in high resolution operation. Non-invasive, or at least micro-invasive methodologies applied on real CH targets have shown the possibility to obtain information on surface appearance, morphology and composition. The added value of optical and spectroscopic integrated sensors is discussed for some significant case studies addressed both to a deep knowledge of the artifacts (materials and methods of realization) and to their structural characterization.

INDUCED BREAKDOWN SPECTROSCOPY; PIGMENTS

France is one of the countries involved in the future E-RIHS - European Research Infrastructure for Heritage Science. The research infrastructure dedicated to the study of materials of cultural and natural heritage will provide transnational access to state-of-the-art technologies (synchrotron, ion beams, lasers, portable methods, etc.) and scientific archives. E-RIHS addresses the experimental problems of knowledge and conservation of heritage materials (collections of art and natural museums, monuments, archaeological sites, archives, libraries, etc.). The cultural artefacts are characterized by complementary methods at multi-scales. The variety and the hybrid are specific of these artefacts and induce complex problems that are not expected in traditional Natural Science: paints, ceramics and glasses, metals, palaeontological specimens, lithic materials, graphic documents, etc. E-RIHS develops in that purpose transnational access to distributed platforms in many European countries. Five complementary accesses are in this way available: FIXLAB (access to fixed platforms for synchrotron, neutrons, ion beams, lasers, etc.), MOLAB (access to mobile examination and analytical methods to study the works in situ), ARCHLAB (access to scientific archives kept in the cultural institutions), DIGILAB (access to a digital infrastructure for the processing of quantitative data, implementing a policy on (re) use of data, choice of data formats, etc.) and finally EXPERTLAB (panels of experts for the implementation of collaborative and multidisciplinary projects for the study, the analysis and the conservation of heritage works). Thus E-RIHS is specifically involved in complex studies for the development of advanced high-resolution analytical and imaging tools. The privileged field of intervention of the infrastructure is that of the study of large corpora, collections and architectural ensembles. Based on previous I3 European program, and especially IPERION-CH program that support the creation of new mobile instrumentation, the French institutions are involved in the development of LIBS/LIF/RAMAN portable instrumentation. After a presentation of the challenge and the multiple advantages in building the European Infrastructure and of the French E-RIHS hub, the major interests of associating the three lasers based on analytical methods for a more global and precise characterization of the heritage objects taking into account their precious characters and their specific constraints. Lastly some preliminary results will be presented in order to give a first idea of the power of this analytical tool.

LIBS; prehistorical pigments; caves; calcite layer; climatic conditions;INDUCED BREAKDOWN SPECTROSCOPY

Painted caves are a specific environment which preservation needs multidisciplinary studies carried out within the different actors. The actions set-up must follow national and European ethics and treaties and be as less invasive as possible to preserve the integrity of the site. Studying colorants in caves should meet these expectations and take into account on-field conditions: high humidity rate, reduced access to electricity, etc. Therefore, non-invasive analyses should be preferred. However, their limits restrict the field of application and sometimes sampling and laboratory analyses must be used to answer the problematic. It is especially true when the pigment is covered by calcite. For this purpose, the Laser-Induced Breakdown Spectroscopy (LIBS) has been assessed to identify the composition with stratigraphic analyses. This study carries out in-depth profile on laboratory samples in conditions close to the ones meet in caves. Samples were prepared on a calcareous substrate using three pigments: red ochre, manganese black and carbon black and two binding media: water and saliva. All samples have been covered by calcite. Four sets of measurements have then been done using the LIBS instrument. The in-depth profiles were obtained using the Standard Normal Variate (SNV) normalization. For all the samples, the pigment layer was identified in the second or third shot, the calcite layer being quite thin. However, the results remain promising with the carbon black pigment but not really conclusive, the carbon being generally quite difficult to quantify.

ON-SITE ANALYSIS; CLOISONNE ENAMELS; 19TH CENTURIES

The focus of this paper is on analysis, comparison and research on the colorful lowtemperature, lead-containing overglazes on glazed porcelain body and on the enamel glazes on the metal body of the Qing Dynasty by adopting several analytical methods. Analysis and tests on the element, boron in overglaze on glazed porcelain body and enamel glaze on metal body, were performed using laser induced breakdown spectroscopy (LIBS), and the results showed that Cloisonn enamel, painted enamel and Falangcai samples contained boron, while Famille Rose (Fencai) samples did not contain boron. Meanwhile, such analysis methods as laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), energy dispersive X-ray spectroscopy (EDXRF), Micro-Raman, stereomicroscope and Confocal laser scanning microscopy (CLSM) were used to test and observe the element composition, crystal composition and microstructure of the samples. The results illustrated that matrix glaze of Cloisonn enamel, painted enamel and Falangcai was the same. The yellow glaze was a lead-alkali glass and other color glazes were boron-lead-alkali glass, while all color glazes of Famille Rose were lead-alkali glass. Colorful low-temperature overglaze on glazed porcelain body and enamel glaze on metal body had a common practice and technology in the use of opacifiers and colorants. Compared to painted enamel, the painting technique of Famille Rose was more complicated, and effect was apparently praised as being superior.

Archeological objects; ceramics; laser-induced breakdown spectroscopy; LIBS; pottery;PIGMENT IDENTIFICATION; RAMAN MICROSCOPY; PAINTED ARTWORKS; LIBS

In recent decades, numerous analytical techniques have been used for the analysis of archeological samples. Laser-induced breakdown spectroscopy (LIBS) is a promising technique due to its practically nondestructive nature and minimal sample preparation. In this work, LIBS was used for the qualitative and quantitative elemental analyses of pottery manufactured in ancient settlements of Rome. The qualitative study showed that the ceramics were composed of Fe, Ca, and Mg. For quantitative analysis, calibration curves of Fe, Ca, and Mg were constructed with reference samples of each element in a KBr matrix with zinc as an internal standard. The results obtained by LIBS were compared with values obtained by atomic absorption.

SNV; Cultural heritage; Stratigraphy; Raman; Libs; Luminescence background;INDUCED BREAKDOWN SPECTROSCOPY; RAMAN-SPECTROSCOPY; WAVELET TRANSFORM; SPECTRA; FLUORESCENCE; COPPER; ART; SUBTRACTION; ARCHAEOLOGY; MICROSCOPY

The investigation of cultural heritage materials is always complex and specific because unique. Materials are most often heterogeneous and organized in several layers such as mural paintings or corrosion products. The characterization of a complete artwork's stratigraphy is actually one of the questions of science conservation. Indeed, the knowledge of these layers allows completing the history of the work of art and a better understanding of alteration processes in order to set up an appropriate conservation action. The LIBS technique has been employed to study the stratigraphy of an artwork thanks to the ablation laser. However, as we know, atomic information could be insufficient to characterize two materials composed by the same based elements. Therefore, an additional molecular analysis, like Raman spectroscopy; is sometimes necessary for a better identification of the material in particular for organic coatings in cultural heritage. We suggest in this study to use Standard Normal Variate (SNV) as a common normalization for different kinds of spectra (LIBS and Raman spectroscopy) combined with a 3D colour representation for stratigraphic identification of the different layers composing the complex material from artwork. So in this investigation, the SNV method will be applied on LIBS and Raman spectra but also on baseline Raman spectra often considering as nuisance. The aim of this study is to demonstrate the versatility of SNV applied on varied spectra like LIBS, Raman spectra as well as the luminescence background. This original work considers the SNV with a 3D colour representation as a probable new perspective for an easy recognition of a structure layered with a direct overview of the depth profile of the artwork. (C) 2016 Elsevier B.V. All rights reserved.