Non-Destructive and Non-Invasive Approaches for the Identification of Hydroxy Lead-Calcium Phosphate Solid Solutions ((PbxCa1-x)5(PO4)3OH) in Cultural Heritage Materials.

Lead-calcium phosphates are unusual compounds sometimes found in different kinds of cultural heritage objects. Structural and physicochemical properties of this family of materials, which fall into the hydroxypyromorphite-hydroxyapatite solid solution, or (PbxCa1-x)5(PO4)3OH, have received considerable attention during the last few decades for promising applications in different fields of environmental and material sciences, but their diagnostic implications in the cultural heritage context have been poorly explored. This paper aims to provide a clearer understanding of the relationship between compositional and structural properties of the peculiar series of (PbxCa1-x)5(PO4)3OH solid solutions and to determine key markers for their proper non-destructive and non-invasive identification in cultural heritage samples and objects. For this purpose, a systematic study of powders and paint mock-ups made up of commercial and in-house synthesized (PbxCa1-x)5(PO4)3OH compounds with a different Pb2+/Ca2+ ratio was carried out via a multi-technique approach based on scanning electron microscopy, synchrotron radiation-based X-ray techniques, i.e., X-ray powder diffraction and X-ray absorption near edge structure spectroscopy at the Ca K- and P K-edges, and vibrational spectroscopy methods, i.e., micro-Raman and Fourier transform infrared spectroscopy. The spectral modifications observed in the hydroxypyromorphite-hydroxyapatite solid solution series are discussed, by assessing the advantages and disadvantages of the proposed techniques and by providing reference data and optimized approaches for future non-destructive and non-invasive applications to study cultural heritage objects and samples.

Multi-Scale X-ray Imaging of the Pigment Discoloration Processes Triggered by Chlorine Compounds in the Upper Basilica of Saint Francis of Assisi.

In this paper, the chromatic alteration of various types of paints, present on mural painting fragments derived from the vaults of The Upper Basilica of Saint Francis of Assisi in Italy (12th-13th century), is studied using synchrotron radiation. Six painted mural fragments, several square centimeters in size, were available for analysis, originating from the ceiling paintings attributed to Cimabue and Giotto; they correspond to originally white, blue/green, and brown/yellow/orange areas showing discoloration. As well as collecting macroscopic X-ray fluorescence and diffraction maps from the entire fragments in the laboratory and at the SOLEIL synchrotron, corresponding paint cross-sections were also analyzed using microscopic X-ray fluorescence and powder diffraction mapping at the PETRA-III synchrotron. Numerous secondary products were observed on the painted surfaces, such as (a) copper tri-hydroxychloride in green/blue areas; (b) corderoite and calomel in vermillion red/cinnabar-rich paints; (c) plattnerite and/or scrutinyite assumed to be oxidation products of (hydro)cerussite (2PbCO3·Pb(OH)2) in the white areas, and (d) the calcium oxalates whewellite and weddellite. An extensive presence of chlorinated metal salts points to the central role of chlorine-containing compounds during the degradation of the 800-year-old paint, leading to, among other things, the formation of the rare mineral cumengeite (21PbCl2·20Cu(OH)2·6H2O).

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.

The "Historical Materials BAG": A New Facilitated Access to Synchrotron X-ray Diffraction Analyses for Cultural Heritage Materials at the European Synchrotron Radiation Facility.

The European Synchrotron Radiation Facility (ESRF) has recently commissioned the new Extremely Brilliant Source (EBS). The gain in brightness as well as the continuous development of beamline instruments boosts the beamline performances, in particular in terms of accelerated data acquisition. This has motivated the development of new access modes as an alternative to standard proposals for access to beamtime, in particular via the "block allocation group" (BAG) mode. Here, we present the recently implemented "historical materials BAG": a community proposal giving to 10 European institutes the opportunity for guaranteed beamtime at two X-ray powder diffraction (XRPD) beamlines-ID13, for 2D high lateral resolution XRPD mapping, and ID22 for high angular resolution XRPD bulk analyses-with a particular focus on applications to cultural heritage. The capabilities offered by these instruments, the specific hardware and software developments to facilitate and speed-up data acquisition and data processing are detailed, and the first results from this new access are illustrated with recent applications to pigments, paintings, ceramics and wood.

Synchrotron radiation Ca K-edge 2D-XANES spectroscopy for studying the stratigraphic distribution of calcium-based consolidants applied in limestones.

In Heritage Science, the evaluation of stone consolidation treatments by investigating the nature of in situ newly formed products and their penetration depth within the consolidated matrix is a grand challenge. A number of analytical methods have been proposed, but, currently, most of them are not able to supply a full overview of the spatial, structural and compositional information of the newly formed crystalline and amorphous phases with a submicrometric lateral resolution. Here, we examined, the capabilities of synchrotron radiation (SR)-based two-dimensional X-ray absorption near-edge structure (2D-XANES) spectroscopy at Ca K-edge for determining the structural and compositional properties of the compounds formed after the application of a calcium acetoacetate-based consolidant on a porous carbonatic stone (limestone) and for investigating their stratigraphic distribution at the submicrometric scale length. We evaluated advantages and drawbacks of three Ca K-edge 2D-XANES-based approaches: (i) transmission mode full-field-XANES (FF-XANES) imaging; (ii) micro-X-ray fluorescence (µ-XRF) mapping above the Ca K-edge combined with the acquisition of XRF mode µ-XANES spectra at a limited number of spots; (iii) full-spectral µ-XANES (FS µ-XANES) mapping in XRF mode and its variant called selectively induced X-ray emission spectroscopy (SIXES) mapping. Overall, Ca K-edge 2D-XANES spectroscopy provided accurate qualitative and semi-quantitative information on the newly formed calcium carbonates (i.e., amorphous calcium carbonate, vaterite and calcite) and their stratigraphic distribution at the submicrometric scale, thus opening a new scenario to study the carbonatation process of calcium-based consolidants in limestones.

Damages Induced by Synchrotron Radiation-Based X-ray Microanalysis in Chrome Yellow Paints and Related Cr-Compounds: Assessment, Quantification, and Mitigation Strategies.

Synchrotron radiation (SR)-based X-ray methods are powerful analytical tools for several purposes. They are widely used to probe the degradation mechanisms of inorganic artists' pigments in paintings, including chrome yellows (PbCr1-xSxO4; 0 ≤ x ≤ 0.8), a class of compounds often found in Van Gogh masterpieces. However, the high intensity and brightness of SR beams raise important issues regarding the potential damage inflicted on the analyzed samples. A thorough knowledge of the SR X-ray sensitivity of each class of pigment in the painting matrix is therefore required to find analytical strategies that seek to minimize the damage for preserving the integrity of the analyzed samples and to avoid data misinterpretation. Here, we employ a combination of Cr K-edge X-ray absorption near-edge structure spectroscopy, Cr-Kß X-ray emission spectroscopy, and X-ray diffraction to monitor and quantify the effects of SR X-rays on the stability of chrome yellows and related Cr compounds and to define mitigation strategies. We found that the SR X-ray beam exposure induces changes in the oxidation state and local coordination environment of Cr ions and leads to a loss of the compound's crystalline structure. The extent of X-ray damage depends on some intrinsic properties of the samples (chemical composition of the pigment and the presence/absence and nature of the binder). It can be minimized by optimizing the overall fluence/dose released to the samples and by working in vacuum and under cryogenic conditions.

Probing the chemistry of CdS paints in The Scream by in situ noninvasive spectroscopies and synchrotron radiation x-ray techniques.

The degradation of cadmium sulfide (CdS)-based oil paints is a phenomenon potentially threatening the iconic painting The Scream (ca. 1910) by Edvard Munch (Munch Museum, Oslo) that is still poorly understood. Here, we provide evidence for the presence of cadmium sulfate and sulfites as alteration products of the original CdS-based paint and explore the external circumstances and internal factors causing this transformation. Macroscale in situ noninvasive spectroscopy studies of the painting in combination with synchrotron-radiation x-ray microspectroscopy investigations of a microsample and artificially aged mock-ups show that moisture and mobile chlorine compounds are key factors for promoting the oxidation of CdS, while light (photodegradation) plays a less important role. Furthermore, under exposure to humidity, parallel/secondary reactions involving dissolution, migration through the paint, and recrystallization of water-soluble phases of the paint are associated with the formation of cadmium sulfates.

Role of the Relative Humidity and the Cd/Zn Stoichiometry in the Photooxidation Process of Cadmium Yellows (CdS/Cd1-x Znx S) in Oil Paintings.

Cadmium yellows (CdYs) refer to a family of cadmium sulfide pigments, which have been widely used by artists since the late 19th century. Despite being considered stable, they are suffering from discoloration in iconic paintings, such as Joy of Life by Matisse, Flowers in a blue vase by Van Gogh, and The Scream by Munch, most likely due to the formation of CdSO4 ⋅n H2 O. The driving factors of the CdYs degradation and how these affect the overall process are still unknown. Here, we study a series of oil mock-up paints made of CdYs of different stoichiometry (CdS/Cd0.76 Zn0.24 S) and crystalline structure (hexagonal/cubic) before and after aging at variable relative humidity under exposure to light and in darkness. Synchrotron radiation-based X-ray methods combined with UV-Vis and FTIR spectroscopy show that: 1) Cd0.76 Zn0.24 S is more susceptible to photooxidation than CdS; both compounds can act as photocatalysts for the oil oxidation. 2) The photooxidation of CdS/Cd0.76 Zn0.24 S to CdSO4 ⋅n H2 O is triggered by moisture. 3) The nature of alteration products depends on the aging conditions and the Cd/Zn stoichiometry. Based on our findings, we propose a scheme for the mechanism of the photocorrosion process and the photocatalytic activity of CdY pigments in the oil binder. Overall, our results form a reliable basis for understanding the degradation of CdS-based paints in artworks and contribute towards developing better ways of preserving them for future generations.

Photochemistry of Artists' Dyes and Pigments: Towards Better Understanding and Prevention of Colour Change in Works of Art.

The absorption of light gives a pigment its colour and its reason for being, but it also creates excited states, that is, new molecules with an energy excess that can be dissipated through degradation pathways. Photodegradation processes provoke long-term, cumulative and irreversible colour changes (fading, darkening, blanching) of which the prediction and prevention are challenging tasks. Of all the environmental risks that affect heritage materials, light exposure is the only one that cannot be controlled without any impact on the optimal display of the exhibit. Light-induced alterations are not only associated with the pigment itself but also with its interactions with support/binder and, in turn, are further complicated by the nature of the environmental conditions. In this Minireview we investigate how chemistry, encompassing multi-scale analytical investigations of works of art, computational modelling and physical and chemical studies contributes to improve our prediction of artwork appearance before degradation and to establish effective preventive conservation strategies.

Chemical Mapping by Macroscopic X-ray Powder Diffraction (MA-XRPD) of Van Gogh's Sunflowers: Identification of Areas with Higher Degradation Risk.

The discoloration rate of chrome yellow (CY), a class of synthetic inorganic pigments (PbCr1-x Sx O4 ) frequently used by Van Gogh and his contemporaries, strongly depends on its sulfate content and on its crystalline structure (either monoclinic or orthorhombic). Macroscopic X-Ray powder diffraction imaging of selected areas on Van Gogh's Sunflowers (Van Gogh Museum, Amsterdam) revealed the presence of two subtypes of CY: the light-fast monoclinic PbCrO4 (LF-CY) and the light-sensitive monoclinic PbCr1-x Sx O4 (x≈0.5; LS-CY). The latter was encountered in large parts of the painting (e.g., in the pale-yellow background and the bright-yellow petals, but also in the green stems and flower hearts), thus indicating their higher risk for past or future darkening. Overall, it is present in more than 50 % of the CY regions. Preferred orientation of LS-CY allows observation of a significant ordering of the elongated crystallites along the direction of Van Gogh's brush strokes.

Non-Invasive and Non-Destructive Examination of Artistic Pigments, Paints, and Paintings by Means of X-Ray Methods.

Recent studies are concisely reviewed, in which X-ray beams of (sub)micrometre to millimetre dimensions have been used for non-destructive analysis and characterization of pigments, minute paint samples, and/or entire paintings from the seventeenth to the early twentieth century painters. The overview presented encompasses the use of laboratory and synchrotron radiation-based instrumentation and deals with the use of several variants of X-ray fluorescence (XRF) as a method of elemental analysis and imaging, as well as with the combined use of X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Microscopic XRF is a variant of the method that is well suited to visualize the elemental distribution of key elements, mostly metals, present in paint multi-layers, on the length scale from 1 to 100 µm inside micro-samples taken from paintings. In the context of the characterization of artists' pigments subjected to natural degradation, the use of methods limited to elemental analysis or imaging usually is not sufficient to elucidate the chemical transformations that have taken place. However, at synchrotron facilities, combinations of µ-XRF with related methods such as µ-XAS and µ-XRD have proven themselves to be very suitable for such studies. Their use is often combined with microscopic Fourier transform infra-red spectroscopy and/or Raman microscopy since these methods deliver complementary information of high molecular specificity at more or less the same length scale as the X-ray microprobe techniques. Since microscopic investigation of a relatively limited number of minute paint samples, taken from a given work of art, may not yield representative information about the entire artefact, several methods for macroscopic, non-invasive imaging have recently been developed. Those based on XRF scanning and full-field hyperspectral imaging appear very promising; some recent published results are discussed.

Evidence for Degradation of the Chrome Yellows in Van Gogh's Sunflowers: A Study Using Noninvasive In Situ Methods and Synchrotron-Radiation-Based X-ray Techniques.

This paper presents firm evidence for the chemical alteration of chrome yellow pigments in Van Gogh's Sunflowers (Van Gogh Museum, Amsterdam). Noninvasive in situ spectroscopic analysis at several spots on the painting, combined with synchrotron-radiation-based X-ray investigations of two microsamples, revealed the presence of different types of chrome yellow used by Van Gogh, including the lightfast PbCrO4 and the sulfur-rich PbCr1-x Sx O4 (x≈0.5) variety that is known for its high propensity to undergo photoinduced reduction. The products of this degradation process, i.e., Cr(III) compounds, were found at the interface between the paint and the varnish. Selected locations of the painting with the highest risk of color modification by chemical deterioration of chrome yellow are identified, thus calling for careful monitoring in the future.

Degradation process of lead chromate in paintings by Vincent van Gogh studied by means of spectromicroscopic methods. Part 5. Effects of nonoriginal surface coatings into the nature and distribution of chromium and sulfur species in chrome yellow paints.

The darkening of lead chromate yellow pigments, caused by a reduction of the chromate ions to Cr(III) compounds, is known to affect the appearance of several paintings by Vincent van Gogh. In previous papers of this series, we demonstrated that the darkening is activated by light and depends on the chemical composition and crystalline structure of the pigments. In this work, the results of Part 2 are extended and complemented with a new study aimed at deepening the knowledge of the nature and distribution of Cr and S species at the interface between the chrome yellow paint and the nonoriginal coating layer. For this purpose, three microsamples from two varnished paintings by Van Gogh and a waxed low relief by Gauguin (all originally uncoated) have been examined. Because nonoriginal coatings are often present in artwork by Van Gogh and contemporaries, the understanding of whether or not their application has influenced the morphological and/or physicochemical properties of the chrome yellow paint underneath is relevant in view of the conservation of these masterpieces. In all the samples studied, microscopic X-ray fluorescence (µ-XRF) and X-ray absorption near edge structure (µ-XANES) investigations showed that Cr(III)-based alteration products are present in the form of grains inside the coating (generally enriched of S species) and also homogeneously widespread at the paint surface. The distribution of Cr(III) species may be explained by the mechanical friction caused by the coating application by brush that picked up and redistributed the superficial Cr compounds, likely already present in the reduced state as result of the photodegradation process. The analysis of the XANES profiles allowed us to obtain new insights into the nature of the Cr(III) alteration products, that were identified as sulfate-, oxide-, organo-metal-, and chloride-based compounds. Building upon the knowledge acquired through the examination of original paint samples and from the investigation of aged model paints in the last Part 4 paper, in this study we aim to characterize a possible relation between the chemical composition of the coating and the chrome yellow degradation pathways by studying photochemically aged model samples covered with a dammar varnish contaminated with sulfide and sulfate salts. Cr speciation results did not show any evidence of the active role of the varnish and added S species on the reduction process of chrome yellows.

Nanoscale investigation of the degradation mechanism of a historical chrome yellow paint by quantitative electron energy loss spectroscopy mapping of chromium species.

Getting the picture: The investigation of 100 year old chrome yellow paint by transmission electron microscopy and spectroscopy has led to the identification of four types of core-shell particles. This nanoscale investigation has allowed a mechanism to be proposed for the darkening of some bright yellow colors in Van Gogh's paintings (e.g. in Falling leaves (Les Alyscamps), 1888).

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.

The use of synchrotron radiation for the characterization of artists' pigments and paintings.

We review methods and recent studies in which macroscopic to (sub)microscopic X-ray beams were used for nondestructive analysis and characterization of pigments, paint microsamples, and/or entire paintings. We discuss the use of portable laboratory- and synchrotron-based instrumentation and describe several variants of X-ray fluorescence (XRF) analysis used for elemental analysis and imaging and combined with X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Macroscopic and microscopic (µ-)XRF variants of this method are suitable for visualizing the elemental distribution of key elements in paint multilayers. Technical innovations such as multielement, large-area XRF detectors have enabled such developments. The use of methods limited to elemental analysis or imaging usually is not sufficient to elucidate the chemical transformations that take place during natural pigment alteration processes. However, synchrotron-based combinations of µ-XRF, µ-XAS, and µ-XRD are suitable for such studies.

Degradation process of lead chromate in paintings by Vincent van Gogh studied by means of spectromicroscopic methods. 3. Synthesis, characterization, and detection of different crystal forms of the chrome yellow pigment.

The painter, Vincent van Gogh, and some of his contemporaries frequently made use of the pigment chrome yellow that is known to show a tendency toward darkening. This pigment may correspond to various chemical compounds such as PbCrO(4) and PbCr(1-x)S(x)O(4), that may each be present in various crystallographic forms with different tendencies toward degradation. Investigations by X-ray diffraction (XRD), mid-Fourier Transform infrared (FTIR), and Raman instruments (benchtop and portable) and synchrotron radiation-based micro-XRD and X-ray absorption near edge structure spectroscopy performed on oil-paint models, prepared with in-house synthesized PbCrO(4) and PbCr(1-x)S(x)O(4), permitted us to characterize the spectroscopic features of the various forms. On the basis of these results, an extended study has been carried out on historic paint tubes and on embedded paint microsamples taken from yellow-orange/pale yellow areas of 12 Van Gogh paintings, demonstrating that Van Gogh effectively made use of different chrome yellow types. This conclusion was also confirmed by in situ mid-FTIR investigations on Van Gogh's Portrait of Gauguin (Van Gogh Museum, Amsterdam).

Degradation process of lead chromate in paintings by Vincent van Gogh studied by means of spectromicroscopic methods. 4. Artificial aging of model samples of co-precipitates of lead chromate and lead sulfate.

Previous investigations about the darkening of chrome yellow pigments revealed that this form of alteration is attributable to a reduction of the original Cr(VI) to Cr(III), and that the presence of sulfur-containing compounds, most often sulfates, plays a key role during this process. We recently demonstrated that different crystal forms of chrome yellow pigments (PbCrO(4) and PbCr(1-x)S(x)O(4)) are present in paintings by Vincent van Gogh. In the present work, we show how both the chemical composition and the crystalline structure of lead chromate-based pigments influence their stability. For this purpose, oil model samples made with in-house synthesized powders of PbCrO(4) and PbCr(1-x)S(x)O(4) were artificially aged and characterized. We observed a profound darkening only for those paint models made with PbCr(1-x)S(x)O(4), rich in SO(4)(2-) (x ≥ 0.4), and orthorhombic phases (>30 wt %). Cr and S K-edge micro X-ray absorption near edge structure investigations revealed in an unequivocal manner the formation of up to about 60% of Cr(III)-species in the outer layer of the most altered samples; conversely, independent of the paint models' chemical composition, no change in the S-oxidation state was observed. Analyses employing UV-visible diffuse reflectance and Fourier transform infrared spectroscopy were performed on unaged and aged model samples in order to obtain additional information on the physicochemical changes induced by the aging treatment.

Degradation process of lead chromate in paintings by Vincent van Gogh studied by means of synchrotron X-ray spectromicroscopy and related methods. 1. Artificially aged model samples.

On several paintings by artists of the end of the 19th century and the beginning of the 20th Century a darkening of the original yellow areas, painted with the chrome yellow pigment (PbCrO(4), PbCrO(4)·xPbSO(4), or PbCrO(4)·xPbO) is observed. The most famous of these are the various Sunflowers paintings Vincent van Gogh made during his career. In the first part of this work, we attempt to elucidate the degradation process of chrome yellow by studying artificially aged model samples. In view of the very thin (1-3 µm) alteration layers that are formed, high lateral resolution spectroscopic methods such as microscopic X-ray absorption near edge (µ-XANES), X-ray fluorescence spectrometry (µ-XRF), and electron energy loss spectrometry (EELS) were employed. Some of these use synchrotron radiation (SR). Additionally, microscopic SR X-ray diffraction (SR µ-XRD), µ-Raman, and mid-FTIR spectroscopy were employed to completely characterize the samples. The formation of Cr(III) compounds at the surface of the chrome yellow paint layers is particularly observed in one aged model sample taken from a historic paint tube (ca. 1914). About two-thirds of the chromium that is present at the surface has reduced from the hexavalent to the trivalent state. The EELS and µ-XANES spectra are consistent with the presence of Cr(2)O(3)·2H(2)O (viridian). Moreover, as demonstrated by µ-XANES, the presence of another Cr(III) compound, such as either Cr(2)(SO(4))(3)·H(2)O or (CH(3)CO(2))(7)Cr(3)(OH)(2) [chromium(III) acetate hydroxide], is likely.

Degradation process of lead chromate in paintings by Vincent van Gogh studied by means of synchrotron X-ray spectromicroscopy and related methods. 2. Original paint layer samples.

The darkening of the original yellow areas painted with the chrome yellow pigment (PbCrO(4), PbCrO(4)·xPbSO(4), or PbCrO(4)·xPbO) is a phenomenon widely observed on several paintings by Vincent van Gogh, such as the famous different versions of Sunflowers. During our previous investigations on artificially aged model samples of lead chromate, we established for the first time that darkening of chrome yellow is caused by reduction of PbCrO(4) to Cr(2)O(3)·2H(2)O (viridian green), likely accompanied by the presence of another Cr(III) compound, such as either Cr(2)(SO(4))(3)·H(2)O or (CH(3)CO(2))(7)Cr(3)(OH)(2) [chromium(III) acetate hydroxide]. In the second part of this work, in order to demonstrate that this reduction phenomenon effectively takes place in real paintings, we study original paint samples from two paintings of V. van Gogh. As with the model samples, in view of the thin superficial alteration layers that are present, high lateral resolution spectroscopic methods that make use of synchrotron radiation (SR), such as microscopic X-ray absorption near edge (µ-XANES) and X-ray fluorescence spectrometry (µ-XRF) were employed. Additionally, µ-Raman and mid-FTIR analyses were carried out to completely characterize the samples. On both paint microsamples, the local presence of reduced Cr was demonstrated by means of µ-XANES point measurements. The presence of Cr(III) was revealed in specific areas, in some cases correlated to the presence of Ba(sulfate) and/or to that of aluminum silicate compounds.