X-ray and Infrared Microanalyses of Mona Lisa's Ground Layer and Significance Regarding Leonardo da Vinci's Palette.

An exceptional microsample from the ground layer of Leonardo da Vinci's Mona Lisa was analyzed by high-angular resolution synchrotron X-ray diffraction and micro Fourier transform infrared spectroscopy, revealing a singular mixture of strongly saponified oil with high lead content and a cerussite (PbCO3)-depleted lead white pigment. The most remarkable signature in the sample is the presence of plumbonacrite (Pb5(CO3)3O(OH)2), a rare compound that is stable only in an alkaline environment. Leonardo probably endeavored to prepare a thick paint suitable for covering the wooden panel of the Mona Lisa by treating the oil with a high load of lead II oxide, PbO. The review of Leonardo's manuscripts (original and latter translation) to track the mention of PbO gives ambiguous information. Conversely, the analysis of fragments from the Last Supper confirms that not only PbO was part of Leonardo's palette, through the detection of both litharge (α-PbO) and massicot (ß-PbO) but also plumbonacrite and shannonite (Pb2OCO3), the latter phase being detected for the first time in a historical painting.

Application of Synchrotron Radiation-Based Micro-Analysis on Cadmium Yellows in Pablo Picasso's Femme.

The cultural heritage community is increasingly exploring synchrotron radiation (SR) based techniques for the study of art and archaeological objects. When considering heterogeneous and complex micro-samples, such as those from paintings, the combination of different SR X-ray techniques is often exploited to overcome the intrinsic limitations and sensitivity of the single technique. Less frequently, SR X-ray analyses are combined with SR micro-photoluminescence or micro-Fourier Transform Infrared spectroscopy, which provide complementary information on the molecular composition, offering a unique integrated analysis approach. Although the spatial correlation between the maps obtained with different techniques is not straightforward due to the different volumes probed by each method, the combination of the information provides a greater understanding and insight into the paint chemistry. In this work, we discuss the advantages and disadvantages of the combination of X-ray techniques and SR-based photoluminescence through the study of two paint micro-samples taken from Pablo Picasso's Femme (1907). The painting contains two cadmium yellow paints (based on CdS): one relatively intact and one visibly degraded. SR micro-analyses demonstrated that the two Cd-yellow paints differ in terms of structure, chemical composition, and photoluminescence properties. In particular, on the basis of the combination of different SR measurements, we hypothesize that the degraded yellow is based on nanocrystalline CdS with high presence of Cd(OH)Cl. These two characteristics have enhanced the reactivity of the paint and strongly influenced its stability.

Degradation of Cadmium Yellow Paint: New Evidence from Photoluminescence Studies of Trap States in Picasso's Femme ( Époque des "Demoiselles d'Avignon").

Paints based on cadmium sulfide (CdS) were popular among artists beginning in the mid-19th century. Some paint formulations are prone to degrade, discoloring and disfiguring paintings where they have been used. Pablo Picasso's Femme (Époque des "Demoiselles d'Avignon") (1907) includes two commercial formulations of CdS: one is visibly degraded and now appears brownish yellow, while the other appears relatively intact and is vibrant yellow. This observation inspired the study reported here of the photoluminescence emission from trap states of the two CdS paints, complemented by data from multispectral imaging, X-ray fluorescence spectroscopy, micro-FTIR, and SEM-EDS. The two paints exhibit trap state emissions that differ in terms of spectrum, intensity, and decay kinetics. In the now-brownish yellow paint, trap state emission is highly favored with respect to near band edge optical recombination. This observation suggests a higher density of surface defects in the now-brownish yellow paint that promotes the surface reactivity of CdS particles and their subsequent paint degradation. CdS is a semiconductor, and surface defects in semiconductors can trap free charge carriers; this interaction becomes stronger at reduced particle size or, equivalently, with increased surface to volume ratio. Here, we speculate that the strong trap state emission in the now-brownish cadmium yellow paint is linked to the presence of CdS particles with a nanocrystalline phase, possibly resulting from a low degree of calcination during pigment synthesis. Taken together, the results presented here demonstrate how photoluminescence studies can probe surface defects in CdS paints and lead to an improved understanding of their complex degradation mechanisms.

Time-Resolved Photoluminescence Microscopy Combined with X-ray Analyses and Raman Spectroscopy Sheds Light on the Imperfect Synthesis of Historical Cadmium Pigments.

Recent studies have shown that modern pigments produced after the Second Industrial Revolution are complex systems characterized by a high level of heterogeneities. Therefore, it is fundamental to adopt a multianalytical approach and highly sensitive methods to characterize the impurities present within pigments. In this work we propose time-resolved and spectrally resolved photoluminescence (PL) microscopy for the mapping of luminescent crystal defects and impurities in historical cadmium-based pigments. PL analysis is complemented by X-ray diffraction, X-ray fluorescence and Raman spectroscopies, and by scanning electron microscopy to determine the chemical composition and crystal structure of samples. The study highlights the heterogeneous and complex nature of historical samples that can be associated with the imperfect manufacturing processes tested during the period between the 1850s and 1950s. The results also allow us to speculate on a range of synthesis processes. Since it is recognized that the stability of paints can be related to pigments synthesis, this research paves the way to a wider study on the relationship between synthesis methods and deterioration of cadmium pigments and paints. This rapid and immediate approach using PL can be applied to other semiconductor pigments and real case studies.

Evolved Gas Analysis-Mass Spectrometry to Identify the Earliest Organic Binder in Aegean Style Wall Paintings.

An organic binder was identified in the painted fragments from the Canaanite palace of Tel Kabri, Israel. Recently dated to the late 18th century B.C.E. by 14 C, Tel Kabri is the most ancient of the Eastern Mediterranean sites in which Aegean style paintings have been found. The application of pigments was suspected to be using an organic binding medium, particularly for the Egyptian Blue pigment. Samples of blue paint were examined using evolved gas analysis-mass spectrometry (EGA-MS) in order to overcome the analytical challenges imposed by highly degraded aged proteinaceous materials. Egg was identified as the binder based on the presence of hexadecanonitrile and octadecanonitrile, confirming the use of a secco painting technique. Lysozyme C from Gallus gallus was detected by proteomics analysis, confirming the presence of egg. To our knowledge, this is the earliest use of egg as a binder in Aegean style wall paintings.

Multianalytical Study of Historical Luminescent Lithopone for the Detection of Impurities and Trace Metal Ions.

We have explored the performance of an integrated multianalytical approach to the analysis of a series of microsamples of historical lithopone (a coprecipitate of ZnS + BaSO4) produced at the beginning of the 20th century, based on the combination of spectrally- and lifetime-resolved photoluminescence (PL) microscopy imaging and electron paramagnetic resonance (EPR) spectroscopy. Multispectral imaging of the PL emission from microsamples revealed the presence of different luminescence centers emitting in the visible spectrum, which we have hypothesized as trace Cu and Mn impurities unintentionally introduced into the ZnS crystal lattice during synthesis, which act as deep traps for electrons. Time-resolved PL imaging analyses highlighted the microsecond decay-kinetic behavior of the emission, confirming the trap state nature of the luminescence centers. EPR confirmed the presence of Cu and Mn, further providing information on the microenvironment of defects in the ZnS crystalline lattice related to specific paramagnetic ions. The multianalytical approach provides important insights into the historical synthesis of lithophone and will be useful for the rapid screening and mapping of impurities in complex semiconductor pigments and other artists' materials.

Nondestructive optical detection of monomer uptake in wood polymer composites.

A noninvasive method to assess the local monomer concentration within a wooden matrix, post monomer impregnation, by time-resolved diffuse optical spectroscopy is demonstrated. A data analysis technique for improving accuracy, which takes account of changes in the refractive index during the monomer uptake, has been employed. This technique can be potentially applied in the wood industry for the study of polymer composites as well as in cultural heritage science for noninvasively monitoring the penetration of chemical compounds used for consolidation or conservation purposes.

Time-resolved photoluminescence spectroscopy and imaging: new approaches to the analysis of cultural heritage and its degradation.

Applications of time-resolved photoluminescence spectroscopy (TRPL) and fluorescence lifetime imaging (FLIM) to the analysis of cultural heritage are presented. Examples range from historic wall paintings and stone sculptures to 20th century iconic design objects. A detailed description of the instrumentation developed and employed for analysis in the laboratory or in situ is given. Both instruments rely on a pulsed laser source coupled to a gated detection system, but differ in the type of information they provide. Applications of FLIM to the analysis of model samples and for the in-situ monitoring of works of art range from the analysis of organic materials and pigments in wall paintings, the detection of trace organic substances on stone sculptures, to the mapping of luminescence in late 19th century paintings. TRPL and FLIM are employed as sensors for the detection of the degradation of design objects made in plastic. Applications and avenues for future research are suggested.

Detection of organic colorants in historical painting layers using UV laser ablation surface-enhanced Raman microspectroscopy.

Surface-enhanced Raman spectroscopy (SERS) has been increasingly used in the study of works of art to identify organic pigments and dyes in paintings, which (depending on the material) are difficult or not possible to detect by other current methods. The application of SERS to the study of paintings has been limited, however, by the lack of a sampling approach with sufficient sensitivity and spatial resolution. We show that ultraviolet laser ablation (LA) sampling coupled with SERS detection can be successfully used to study paint layers. LA-SERS permitted the isolation of signals from colorants in individual thin paint layers in sample cross-sections, avoiding contamination from adjacent layers. These results expand the range of analytical applications of SERS demonstrating how the technique can be used to sensitively detect minor organic components in complex matrices. While this is fundamental for the study of cultural heritage, it is also relevant in other fields such as forensic analysis, food science, and pharmacology.

Synchrotron UV-visible multispectral luminescence microimaging of historical samples.

UV-visible luminescence techniques are fre-quently used for the study of cultural heritage materials, despite their limitations for identification and discrimination in the case of complex heterogeneous materials. In contrast to tabletop setups, two methods based on the vacuum ultraviolet (VUV)-UV-visible emission generated at a bending magnet of a synchrotron source are described. The main advantages of the source are the extended wavelength range attained, the continuous tunability of the source, and its brightness, leading to a submicrometer lateral resolution. Raster-scanning microspectroscopy and full-field microimaging were implemented and tested at the DISCO beamline (synchrotron SOLEIL, France). Investigative measurements were performed on a sample from a varnished musical instrument and a paint sample containing the pigment zinc white (ZnO) in order to illustrate some of the challenges analyzing heterogeneous cultural heritage cross-section samples with the novel imaging approach. The data sets obtained proved useful for mapping organic materials at the submicrometer scale and visualizing heterogeneities of the semiconductor pigment material. We propose and discuss the combined use of raster-scanning microspectroscopy and full-field microimaging in an integrated analytical methodology. Synchrotron UV luminescence appears as a novel tool for identification of craftsmen's and artists' materials and techniques and to assess the condition of artifacts, from the precise identification and localization of luminescent materials.

Fluorescence and Fourier-transform infrared spectroscopy for the analysis of iconic Italian design lamps made of polymeric materials.

The preservation of design object collections requires an understanding of their constituent materials which are often polymeric blends. Challenges associated with aging of complex polymers from objects with an unknown physical history may compromise the interpretation of data from analytical techniques, and therefore complicate the assessment of the condition of polymers in indoor museum environments. This study focuses on the analysis of polymeric materials from three well-known Italian design lamps from the 1960s. To assess the degree of chemical modifications in the polymers, non-destructive molecular spectroscopic techniques, Fourier-transform infrared (FTIR) and fluorescence spectroscopy, have been applied directly on the object surfaces using an optical fiber probe and through examination of micro samples. FTIR spectra of the different polymers, polyvinylacetate (PVAc) for the lamps Taraxacum and Fantasma, and both acrylonitrile-butadiene-styrene polymer (ABS) and cellulose acetate (CA) for the lamp Nesso, allowed the detection of ongoing deterioration processes. Fluorescence spectroscopy proved particularly sensitive for the detection of molecular changes in the polymeric objects, as the spectra obtained from the examined lamps differ significantly from those of the unaged reference materials. Differences in fluorescence spectra are also detected between different points on the same object further indicating the presence of different chemical species on the surfaces. With the aid of complementary data from FTIR spectroscopy, an interpretation of the emission spectra of the studied polymeric objects is here proposed, further suggesting that fluorescence spectroscopy may be useful for following the degradation of historical polymeric objects.

A Critical Review on the Analysis of Metal Soaps in Oil Paintings.

Up to 70 % of the oil paintings conserved in collections present metal soaps, which result from the chemical reaction between metal ions present in the painted layers and free fatty acids from the lipidic binders. In recent decades, conservators and conservation scientists have been systematically identifying various and frequent conservation problems that can be linked to the formation of metal soaps. It is also increasingly recognized that metal soap formation may not compromise the integrity of paint so there is a need for careful assessment of the implications of metal soaps for conservation. This review aims to critically assess scientific literature related to commonly adopted analytical techniques for the analysis of metal soaps in oil paintings. A comparison of different analytical methods is provided, highlighting advantages associated with each, as well as limitations identified through the analysis of reference materials and applications to the analysis of samples from historical paintings.

Total synchronous fluorescence spectroscopy combined with multivariate analysis: method for the classification of selected resins, oils, and protein-based media used in paintings.

Recent interest in the fluorescence of binding media and varnishes (proteins, oils, and resins) commonly used in paintings is based on the potential for discriminating these organic materials. A useful way of studying the presence of the broad-band fluorescence emissions found in these complex organic materials is fluorescence excitation emission spectroscopy. However, due to the presence of Raman and Rayleigh scattering which may necessitate correction or preprocessing for statistical analysis and visualization, an alternative approach has been adopted for the analysis of different samples of artist materials based on total synchronous fluorescence spectroscopy. Films of selected drying oils, glue, egg, and casein and the resins mastic, dammar, copal, and shellac were analyzed using total synchronous fluorescence spectroscopy, and an interpretation of the differences between spectra is given. A data reduction method based on the transformation of fluorescence contours extracted from total synchronous fluorescence from Cartesian to polar coordinates is presented and is followed by the comparison of data using multivariate analysis and hierarchical cluster analysis. Results suggest that the new method can be used to classify samples on the basis of their fluorescence spectra, clearly differentiating oils, resins, and protein-based media into groups.

Assessment of the ageing of triterpenoid paint varnishes using fluorescence, Raman and FTIR spectroscopy.

The assessment of the influence of natural and artificial ageing on the spectrofluorescence of triterpenoid varnishes dammar and mastic is the focus of this work. Both Fourier transform infrared (FTIR) microscopy using attenuated total reflectance and Raman spectroscopy have been employed for complementary molecular analysis of samples. Synchronous fluorescence spectroscopy, excitation emission spectroscopy, and statistical analysis of data have been used to monitor changes in the optical properties of varnish samples. Assessment of naturally and artificially aged samples using excitation emission spectroscopy suggests that extensive exposure to visible light does not lead to easily appreciable differences in the fluorescence of mastic and dammar; cluster analysis has been used to assess changes, which occur with artificial ageing under visible light, indicating that differences in the fluorescence spectra of aged triterpenoids may be insufficient for their discrimination. The results highlight significant differences between the initial fluorescence of films of dammar and mastic and the fluorescence, which develops with ageing and oxidation, and specific markers, which change with ageing in FTIR and Raman spectra, have been identified.

Assessment of variations in moisture content of wood using time-resolved diffuse optical spectroscopy.

Time-resolved spectroscopy using a pulsed supercontinuum source was employed for the assessment of moisture content (MC) in dry wood. The MC of wood at different relative humidities between 94% and 12% has been monitored. Following curve fitting, absorption spectra between 700 and 1100 nm of samples suggest that differences in the MC of wood are appreciable at around 970 nm. Further, dynamic changes in MC were simulated following a change in relative humidity. Differences in absorption spectra with changes in MC of around 1% can be detected. Various applications of the technique are suggested.

Red lakes from Leonardo's Last Supper and other Old Master Paintings: Micro-Raman spectroscopy of anthraquinone pigments in paint cross-sections.

The analysis of red particles in paint cross-sections from Leonardo da Vinci's Last Supper, Masolino da Panicale's wall painting Beheading of St. John the Baptist in Castiglione Olona, Tintoretto's The Discovery of the Body of Saint Mark and Paolo Veronese's Supper in the House of Simon has been carried out with micro-Raman measurements. Subtracted shifted Raman spectroscopy methods have been employed to resolve the signals in the presence of fluorescence. Taking advantage of the vibrational assignments based on recent ab initio calculations of aluminum-complexes of anthraquinones, the approach allowed the discriminate between anthraquinone dyes and lakes based on kermesic and carminic acids present in the studied samples for the first time without heavy sample treatment.

Stratigraphic analysis of organic materials in wall painting samples using micro-FTIR attenuated total reflectance and a novel sample preparation technique.

Wall paintings typically contain low concentrations of organic materials within a largely inorganic matrix and are characterised by their high porosity and long-term exposure to severe environmental conditions. The identification of organic materials within specific paint or plaster layers is challenging and the inherent characteristics of wall painting samples present further complications. Embedding materials (such as epoxy, polyester and acrylic-based resins) used to produce cross-sections often infiltrate porous and leanly bound samples, and compromise the interpretation of Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectra and the qualitative identification of natural organic materials. An alternative method for the preparation of cross-sections of wall painting samples was developed using cyclododecane (C(12)H(24)) as a temporary consolidant and barrier coating to encapsulate the sample, and to provide necessary support to produce a cross-section through microtoming. Impacts of traditional and novel sample preparation techniques on the identification of organic materials with micro-FTIR-ATR were examined for both replica and real wall painting samples.

Analysis of protein-based media commonly found in paintings using synchronous fluorescence spectroscopy combined with multivariate statistical analysis.

The spectrofluorimetric analysis of protein-based binding media, which are commonly found as painting materials, is based on the detection of emissions from amino acids, as well as fluorescent degradation products that develop with aging. Laser-induced fluorescence spectroscopy, fluorescence excitation emission spectroscopy, and time-resolved fluorescence spectroscopy have all been employed in efforts to discriminate between commonly found proteinaceous binding media, including egg white, egg yolk, milk, and casein, as well as collagen-based glues from rabbit skin, ox bone, parchment, and fish. However, synchronous fluorescence spectroscopy (SFS), a rapid means of recording fluorescence properties of samples, has not been reported for the differentiation between binding media. This work focuses on the analysis of a large set of naturally aged films of different protein-based binding media using SFS with a range of different offsets between excitation and emission monochromators between 30-60 nm. An interpretation of synchronous fluorescence spectra of binding media is presented and is followed by an assessment and classification of a database of recorded spectra using multivariate analysis. Importantly, following SFS analysis of films of binding media, principal component analysis is used to differentiate among all the proteinaceous media considered on the basis of clustering of data. This application is thus a novel and nondestructive means for differentiation between protein-based binding media.

Fully-Non-Contact Masking-Based Holography Inspection on Dimensionally Responsive Artwork Materials.

Environmental control in galleries and museums is a necessity and is informed by the knowledge of ongoing processes of deterioration which can threaten the integrity and stability of artworks. Invisible dimensional changes in many works of art occur following environmental fluctuations as materials respond to the changes in humidity and temperature. The constant influence of dimensional changes usually remains invisible until displacement generates visible deterioration and irreversible damage. This paper exploits fully non contact coherent interferometry in a sequential masking procedure for visualising and studying surface deformation which is the direct effect of dimensional alterations induced by humidity changes. Surface deformation during dimensional displacements of constituent materials may occur on any artwork within an unstable environment. In this context, the presented research study explores the diagnostic potential of fully non contact sensors for the direct structural assessment of environmental effects as they occur in real time on works of art. The method is employed to characterise material responses, complementing and improving understanding of material behaviour in unstable environments.

A Photoluminescence Study of the Changes Induced in the Zinc White Pigment by Formation of Zinc Complexes.

It is known that oil paintings containing zinc white are subject to rapid degradation. This is caused by the interaction between the active groups of binder and the metal ions of the pigment, which gives rise to the formation of new zinc complexes (metal soaps). Ongoing studies on zinc white paints have been limited to the chemical mechanisms that lead to the formation of zinc complexes. On the contrary, little is known of the photo-physical changes induced in the zinc oxide crystal structure following this interaction. Time-resolved photoluminescence spectroscopy has been applied to follow modifications in the luminescent zinc white pigment when mixed with binder. Significant changes in trap state photoluminescence emissions have been detected: the enhancement of a blue emission combined with a change of the decay kinetic of the well-known green emission. Complementary data from molecular analysis of paints using Fourier transform infrared spectroscopy confirms the formation of zinc carboxylates and corroborates the mechanism for zinc complexes formation. We support the hypothesis that zinc ions migrate into binder creating novel vacancies, affecting the photoluminescence intensity and lifetime properties of zinc oxide. Here, we further demonstrate the advantages of a time-resolved photoluminescence approach for studying defects in semiconductor pigments.