Multispectroscopic Characterization of Oil on Copper Painting

A small plate of oil on copper painting from the Italian Renaissance period was characterized by means of noninvasive spectroscopic methods. The study was conducted by the use of energy-dispersive X-ray fluorescence, X-ray diffraction, and Raman and diffuse reflectance infrared Fourier transform spectroscopies to determine the technology production process in such kinds of artworks. Results allowed us to characterize the copper alloy of the support media; the preparation layer, which is composed by white lead; and the pictorial layer of variable composition (green copper sulphate compounds, red lead, carbon black, brown earth pigments, gold, vermilion, and white lead). The complementarity of the techniques used in this study has proven to be highly effective.     

Study and characterization of mural paintings from XIX Century in a noble Venetian (Italy) palace

The present paper describes the characterization carried out on the roof of a private palace located in the historical center of Venice (Italy). We focused our attention on the studies of original constituent materials (pigments and binders), in order to identify the pictorial technique of the artist and verify the stylistic attribution to Giuseppe Borsato, a Venetian painter operating between 18th and 19th century. Characterization of collected samples was carried on using both conventional and advanced analytical techniques, such as Optical Microscopy and Scanning Electron Microscopy coupled with Energy Dispersive X-Ray (SEM–EDS) microscopy, Fourier Transform Infrared Spectroscopy (FTIR) and High Performance Liquid Chromatography (HPLC) coupled with photodiode array detection (DAD) and Mass Spectrometry (MS). The finding of dating pigments (such as Cobalt blue and Cu–As based green) and of a complex binding's mixture compatible with the considered supposed period, allowed us to confirm the attribution hypothesis.     

Analysis of pigments from Roman wall paintings found in Vicenza

The analysis of about 60 samples of wall paintings was carried out using different chemicophysical techniques: optical microscopy, scanning electron microscopy (SEM) equipped with an EDS microanalysis detector, X-ray powder diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The identified pigments were cinnabar, hematite, red ochre, celadonite, cuprorivaite (Egyptian blue), yellow ochre, goethite and carbon. Only in one case some lead white was found instead. In general, the mortar preparation did not correspond to the complex structure suggested by Vitruvius (De Architectura), but it generally showed a porous layer, with crushed grains under the pigment layer. In certain cases two superposed pigment layers were found: yellow superimposed on both red and pink, black on pink, green on black.     

An example of the complementarity of laser‐induced breakdown spectroscopy and Raman microscopy for wall painting pigments analysis

Laser‐induced breakdown spectroscopy (LIBS) and Raman microscopy were used for the identification of pigments in wall painting. Raman spectroscopy, which provides the molecular ‘fingerprint’ of the compound, is nowadays widely used by the archaeometry community, especially for pigment analysis. LIBS, which provides the elementary composition of samples, is a rapid noncontact method, enabling layer‐by‐layer analysis through a precise laser ablation of the sample. This work deals with the behavior of pigments after a LIBS analysis, by trying to identify the compounds before and after the laser shot. Six commercial pigments prepared with the fresco technique were investigated: ultramarine blue, red lead, charcoal, a yellow and a red ochre, and a green earth. Raman spectra, acquired on the sample surface and in the crater induced by LIBS analysis, were compared. The results show that these pigments are well recognized after a LIBS measurement. The analysis of green earth illustrates that the combination of these two techniques gives complete information from a sample. Copyright © 2007 John Wiley & Sons, Ltd.     

μ‐Raman spectroscopy of prehistoric paintings from the Abrigo Remacha rock shelter (Villaseca,Segovia, Spain)

The composition of the materials present in prehistoric paintings discovered on the walls of the Abrigo Remacha rock shelter (Villaseca, Segovia, Spain) has been characterised by micro‐Raman spectroscopy. In addition, scanning electron microscopy and energy dispersive X‐ray microanalysis have been used as auxiliary techniques. The results show that haematite (α‐Fe₂O₃) is the main component of the red pigment. Amorphous carbon and paracoquimbite (Fe₂(SO₄)₃.9H₂O) have been detected in the bluish black pigment used in a significant bi‐colour pictograph. This is the first time that this mineral has been discovered in a prehistoric painting. Accretions of whewellite and weddellite form crusts covering most of the painting panel. Different carbonates are the main components of the rocky substrate. The detection of gypsum on the surface of the panel is associated to the flaking process that is affecting the painting panel. Copyright © 2013 John Wiley & Sons, Ltd.     

Microanalysis of clay‐based pigments in painted artworks by the means of Raman spectroscopy

FT Raman spectroscopy and micro‐Raman spectroscopy with lasers of three different wavelengths (1064 nm, 785 nm and 532 nm) were used for analysis of reference samples of natural clay pigments including white clay minerals (kaolinite, illite, montmorillonite), green earths (glauconite and celadonite) and red earths (natural mixtures of white clay minerals with hematite). In addition, eight micro‐samples obtained from historical paintings containing clay pigments in ground and colour layers have been examined. Powder X‐ray diffraction and micro‐diffraction were used as supplementary methods. It was found that laser operating at 1064 nm provided the best quality Raman spectra for distinguishing different white clay minerals, but the spectra of green and red earths were affected by strong fluorescence caused by the presence of iron. Green earth minerals could be easily distinguished by 532 or 785 nm excitation lasers, even in small concentrations in the paint layers. On the other hand, when anatase (TiO₂) or iron oxides (such as hematite) were present as admixtures (both are quite common, particularly in red earths), the collection of characteristic spectra of clay minerals which form the main component of the layer was hindered or even prevented. Another complicating factor was the fluorescence produced by organic binders when analysing the micro‐samples of artworks. In those cases, it is always necessary to use powder X‐ray micro‐diffraction to avoid misleading interpretations of the pigment's composition. Copyright © 2013 John Wiley & Sons, Ltd.     

The nature of black stains in Lascaux Cave,France, as revealed by surface‐enhanced Raman spectroscopy

We used surface‐enhanced Raman spectroscopy to investigate the chemical composition of the black stains threatening the rock‐art paintings of Lascaux Cave, Montignac, France. The stains are mainly composed of melanin from the fungus Ochroconis sp. and the faecal pellets of the collembolan Folsomia candida. Surface‐enhanced Raman spectroscopy is a useful technique for revealing the structure of unknown macromolecules in cultural heritage research. Copyright © 2011 John Wiley & Sons, Ltd.     

In situ energy dispersive X‐ray fluorescence analysis of rock art pigments from the ‘Abrigo dos Gaivões’ and ‘Igreja dos Mouros’ caves (Portugal)

A portable energy dispersive X‐ray fluorescence spectrometer was used to obtain the elemental composition of Neolithic rock art paintings of the ‘Abrigo dos Gaivões’ and ‘Igreja dos Mouros’ caves. These caves, located in the Esperança parish, Arronches' county, in the San Mamede's mountains (Portugal), belong to a group of spread shelters just next to the western Spanish border. Results show the strong presence of iron in bare rock, and this element can be clearly detected as the main component of the red paintings. No evidence of manganese was detected in either the brownish or the black paintings, contrary to other Neolithic paintings in the Mediterranean area. Copyright © 2011 John Wiley & Sons, Ltd.     

Analysis of Roman age wall paintings found in Pordenone, Trieste and Montegrotto

The aim of the present work is the study of many fragments of wall painting from archaeological excavations in three different Roman age sites dating back to the I Century before Common Era: Pordenone (località Torre); Trieste (Crosada) and Padova (Montegrotto). The techniques used were optical microscopy, scanning electron microscopy (SEM), equipped with a EDS microanalysis detector, X-rays powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Fourier transform Raman spectroscopy (FT-Raman) and electron paramagnetic resonance (EPR) spectroscopy. The identified pigments were: cinnabar, hematite, celadonite, glauconite, cuprorivaite (Egyptian blue), yellow and red ochre, calcite, limonite, coal black.In general, the mortar preparation did not correspond to the complex procedure suggested by Vitruvius (De Architectura), but generally showed a porous layer, with crushed grains under the pigment layer. In some cases, two superimposed pigment layers were found: yellow superimposed on both red and pink, black on pink, green on black.The slight differences we found in the use of the pigments in the three studied sites might show that the same technology, culture and taste spread all over the Roman Empire in North Eastern Italy (X^a Regio Venetia et Histria).     

Spectroscopic investigation of a ‘Virgin of Sorrows’ canvas painting: A multi-method approach

The investigation of unmatched ancient objects is an attentive and arduous activity to conservation scientists. An important aspect of art analysis is the question on sampling and avoiding damage on the artefact during the study. A possible way to maximize the information that is extracted from the historical object is using several sensitive micro-analytical techniques on the same micro samples. As an illustration of this multi-method approach, in this work, a canvas painting ‘Virgin of Sorrows’ was studied and its materials were analysed in order to roughly date and to authenticate this object of art. Proton induced X-ray emission (PIXE), neutron activation analysis (NAA), optical microscopy, scanning electron microscopy (SEM), micro-Raman spectroscopy (MRS) and Fourier transform infrared spectroscopy (FT-IR) were used, obtaining successful results. These methods allowed identifying the different inorganic pigments (iron oxide, carbon black, white lead, Prussian blue) as well as indigo. Optical microscopy and SEM revealed the layered structure of the samples, while FT-IR enabled to determine the nature of the varnish used (shellac). By using these complementary techniques, it was possible to identify the materials in the painting, which are indicative for the period of manufacturing the artwork.