Alessia Daveri

On the use of overtone and combination bands for the analysis of the CaSO4-H2O system by mid-infrared reflection spectroscopy.

With the aim of characterizing ground preparations of paintings by infrared reflection spectroscopy, the CaSO4–H2O system (gypsum/bassanite/anhydrite) has been re-investigated, evaluating and assigning the SO42- and OH overtone and combination bands, respectively, in the ranges 1900–2700 cm−1 and 5000–6000 cm−1 resulting from reflection and high concentration transmission spectra. The second-order modes have been proven to be highly specific, reliable, and less affected by overlap with bands of organic binders and can hence be exploited for the identification of the sulfate hydration phase using infrared (IR) reflection spectroscopy. Subsequently, the characterization and identification of hydration phases in unknown sulfate-based ground preparations on authentic artworks have been carried out noninvasively by fiber-optic reflection IR spectroscopy and on cross-sections by infrared reflection micro-spectroscopy. The spectroscopic data collected both on standards and artworks have been cross-validated by X-ray diffraction.

Non-invasive identification of metal-oxalate complexes on polychrome artwork surfaces by reflection mid-infrared spectroscopy

In this work a reflection mid-infrared spectroscopy study of twelve metal-oxalate complexes, of interest in art conservation science as alteration compounds, was performed. Spectra of the reference materials highlighted the presence of derivative-like and/or inverted features for the fundamental vibrational modes as result of the main contribution from the surface component of the reflected light. In order to provide insights in the interpretation of theses spectral distortions, reflection spectra were compared with conventional transmission ones. The Kramers-Kronig (KK) algorithm, employed to correct for the surface reflection distortions, worked properly only for the derivative-like bands. Therefore, to pay attention to the use of this algorithm when interpreting the reflection spectra is recommended. The outcome of this investigation was exploited to discriminate among different oxalates on thirteen polychrome artworks analyzed in situ by reflection mid-infrared spectroscopy. The visualization of the νs(CO) modes (1400-1200 cm(-1)) and low wavenumber bands (below 900 cm(-1)) in the raw reflection profiles allowed Ca, Cu and Zn oxalates to be identified. Further information about the speciation of different hydration forms of calcium oxalates were obtained by using the KK transform. The work proves reflection mid-infrared spectroscopy to be a reliable and sensitive spectro-analytical method for identifying and mapping different metal-oxalate alteration compounds on the surface of artworks, thus providing conservation scientists with a non-invasive tool to obtain information on the state of conservation and causes of alteration of artworks.

In situ non-invasive investigation on the painting techniques of early Meissen Stoneware.

In situ, non-invasive investigations by means of portable X-ray fluorescence and fibre optic reflectance mid-infrared (mid-FTIR) spectroscopy of painted Böttger Stoneware objects have been carried out through the MOLAB transnational access to the Porcelain Collection of the Staatliche Kunstsammlungen in Dresden. It has been possible to gather information regarding the composition of the black glaze by applying a principal component analysis to the elemental analysis to distinguish between the variations of lead, iron and manganese compositions of each glaze. It has been furthermore feasible to combine molecular spectroscopy for characterization of the constituent painting materials, namely lead white as cerusite and hydrocerusite, the use of cinnabar, azurite and Prussian blue leading to a better knowledge of the state of conservation and utility of certain pigments that may give rise to chronology of the decorative artwork. The identification of oxalates namely whedellite and moolooite are assigned as degradation products relative to the decorative areas.

The application of in situ mid-FTIR fibre-optic reflectance spectroscopy and GC―MS analysis to monitor and evaluate painting cleaning

The development of non-invasive methodologies and portable instrumentation for in situ studies has been subject to great research and development in recent years in the field of conservation science. Despite such interest, very few reported studies employ these versatile techniques in the monitoring of cleaning treatments. This paper describes the application of mid-FTIR fibre-optic reflectance spectroscopy to monitor and evaluate the cleaning treatment of an oil painting using the chelating agent, triammonium citrate, a task undertaken in close collaboration with the painting conservator. Results obtained on site verify the removal of calcium oxalate and an organic component from the surface of the painting, later identified as a terpenic varnish. The subsequent, in laboratory FTIR and GC-MS analysis of the cotton swabs employed during the cleaning treatment acts as an additional non-invasive manner to support the results obtained in situ by mid-FTIR spectroscopy and to better understand the mechanism of the chosen cleaning agent.

The Book of Kells: a non-invasive MOLAB investigation by complementary spectroscopic techniques.

This paper highlights the efficacy of non-invasive portable spectroscopy for assessing the execution technique and constituent materials in one of the most important medieval manuscripts, the Book of Kells. An aimed campaign of in situ measurements by the MObile LABoratory (MOLAB) has analyzed its elemental composition and vibrational and electronic molecular properties. The ample analytical toolbox has afforded complementary diagnostic information of the pigment palette permitting the characterization of both inorganic and organic materials as pigments and dyes in the white, purple, blue, red, orange, green and black areas. In particular, the novel widespread use of calcinated gypsum (anhydrite) as both a white pigment and in correlation to the organic dyes in this manuscript has been noted. The non-invasive identification of the organic dye orchil is significant considering its rare non invasive detection in medieval manuscripts. Finally the occurrence of particular alterations of the organic black areas giving rise to calcium carboxylate and calcium oxalate has been specifically highlighted. Importantly, this work elaborates complex aspects of the employed painting materials which have given rise to numerous significant points of interest for a more elaborate understanding of this Irish treasure.

An uncovered XIII century icon: Particular use of organic pigments and gilding techniques highlighted by analytical methods

The restoration of a panel painting depicting a Madonna and Child listed as an unknown Tuscan artist of the nineteenth century, permitted the hidden original version, a XIII century Medieval icon to be uncovered. It is discovery provided the opportunity for an extensive in situ campaign of non-invasive analytical investigations by portable imaging and spectroscopic techniques (infrared, X-ray fluorescence and diffraction, UV-Vis absorption and emission), followed by aimed micro-destructive investigations (Raman and SEM-EDS). This approach permitted characterization of the original ground and paint layers by complementary techniques. Furthermore, this protocol allowed supplementary particularities of great interest to be highlighted. Namely, numerous original gilding techniques have been accentuated in diverse areas and include the use of surrogate gold (disulphur tin), orpiment as a further false gold and an area with an original silver rich layer. Moreover, pigments including azurite mixed with indigo have been non-invasively identified. Micro-invasive analyses also allowed the diagnosis of organic colorants, namely, an animal anthraquinone lake, kermes and an unusual vegetal chalcone pigment, possibly safflower. The identification of the latter is extremely rare as a painting pigment and has been identified using an innovative adaption to surface enhanced Raman techniques on a cross-section. The resulting data contributes new hypotheses to the historic and artistic knowledge of materials and techniques utilized in XIII century icon paintings and ultimately provides scientific technical support of the recent restoration.

Non-invasive identification of organic materials in historical stringed musical instruments by reflection infrared spectroscopy: a methodological approach

The analysis of historical musical instruments is becoming more relevant and the interest is increasingly moving toward the non-invasive reflection FTIR spectroscopy, especially for the analysis of varnishes. In this work, a specific infrared reflectance spectral library of organic compounds was created with the aim of identifying musical instrument materials in a totally non-invasive way. The analyses were carried out on pure organic compounds, as bulk samples and laboratory wooden models, to evaluate the diagnostic reflection mid-infrared (MIR) bands of proteins, polysaccharides, lipids, and resins by comparing reflection spectra before and after the KK correction. This methodological approach was applied to real case studies represented by four Stradivari violins and a Neapolitan mandolin.

The Bone Black Pigment Identification by Noninvasive, In Situ Infrared Reflection Spectroscopy

Two real case studies, an oil painting on woven paper and a cycle of mural paintings, have been presented to validate the use of infrared reflection spectroscopy as suitable technique for the identification of bone black pigment. By the use of the sharp weak band at 2013 cm−1, it has been possible to distinguish animal carbon-based blacks by a noninvasive method. Finally, an attempt for an eventual assignment for the widely used sharp band at 2013 cm−1 is discussed.

Mid-infrared hyperspectral imaging of painting materials

A novel hyperspectral imaging system (HI90, Bruker Optics), working in the mid-infrared range and recently developed for the remote identification and mapping of hazardous compounds, has here been optimized for investigating painting surfaces. The painting Sestante 10 (1982) by Alberto Burri has been spectrally and spatially investigated with the HI90 system revealing the distribution of inorganic materials constituting the artworks. In order to validate the results obtainable by the imager for the pigment identification previous tests on laboratory models were performed. Yellow, white and blue pigments painted with different binders (namely egg, alkyd, acrylic and vinyl) were investigated by the HI90. Afterwards, the polychrome painting Sestante 10 was investigated focusing the attention on the inorganic material distribution revealing the presence of different extenders (kaolin, BaSO4, CaSO4) mixed with the various silica-based pigments present in the painting. The brightness temperature spectra collected by HI90 have also been compared to single point reflection spectra acquired by a conventional portable FTIR spectrometer (Alpha-R by Bruker Optics) highlighting the good spectral quality of the imaging system. This comparison permitted also to evaluate the spectral response and the diagnostic strengths of the spectral range available by the HI90 imaging (1300-860 cm-1), validating the reliability of the obtained chemical images. This study clearly highlights the high potential of the new hyperspectral imaging system and opens up new perspectives in the current scientific interest devoted to the application of mapping and imaging methods for the study of painting surfaces.