Advanced Microspatially Offset Raman Spectroscopy for Noninvasive Imaging of Concealed Texts and Figures Using Raman Signal, Fluorescence Emission, and Overall Spectral Intensity.

This study explores the possibility of using microspatially offset Raman spectroscopy (micro-SORS) imaging to reconstruct noninvasively letters and figures hidden by opaque layers. Micro-SORS experiments were conducted on mockup samples that mimic real situations encountered in the cultural heritage field, such as sealed letters with inaccessible text and original documents. Subsurface images were obtained using both the characteristic Raman bands of the hidden compounds and their different optical properties from the remaining matrix. In the latter case, contrast obtained through observing a difference in the overall spectral intensity and fluorescence profile rather than any specific Raman bands were used to track the images within the hidden layer. This approach opens new prospects for the use of micro-SORS in heritage science, with applications in the field that include the study of objects covered by opaque overlayers not only through their Raman signatures but also through differences in their optical properties (e.g., fluorescence emission, absorption).

Time and spatially resolved VIS-NIR hyperspectral imaging as a novel monitoring tool for laser-based spectroscopy to mitigate radiation damage on paintings.

The increased adoption of non-invasive laser-based techniques for analysis of cultural assets has recently called into question the non-invasiveness of the techniques in practical operation. The methods to assess the occurrence of radiation-induced alteration on paintings are very limited and none of them can predict damage. Here we present a novel multimodal imaging approach to understand the time and spatial evolution and types of laser-induced surface alterations, through simultaneous monitoring using visible and near infrared (VIS-NIR) reflectance hyperspectral imaging (HSI) and thermal imaging during Raman spectroscopy. The resultant physical and chemical changes were examined in detail by optical coherence tomography and synchrotron based micro-X-ray powder diffraction. HSI was found to be the most sensitive in detecting laser induced alternations compared with conventional methods. It is orders of magnitude more sensitive than Raman spectroscopy and even synchrotron-based micro-X-ray powder diffraction. In cases of thermally driven alterations, transient and reversible reflectance changes were found to be the first indications of laser-induced modifications and can therefore be used as precursors to prevent damage. VIS-NIR reflectance spectroscopy should be used to monitor laser-based analysis and potentially other radiation-based techniques in situ to mitigate laser induced alteration.

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).

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.

Single-sided NMR: a non-invasive diagnostic tool for monitoring swelling effects in paint films subjected to solvent cleaning.

During solvent cleaning of a painted surface, the control of solvent diffusion into the painting matrix is a primary concern for conservators. In this work, a comparative systematic study of solvent ingress and of the ensuing swelling phenomenon in paint films due to cleaning treatments was tackled using single-sided NMR. Specifically, the effects of a TAC aqueous solution (triammonium citrate in deionized water) applied in both free and gelled forms (by Klucel® G) on acrylic emulsion and vinyl-based model paints were evaluated. Notably, the NMR measurements (proton spin density depth profiles and transverse relaxation decays) collected before, during, and after these wet-cleaning tests proved that the use of the aqueous gel did not significantly minimize the penetration and the swelling action of water compared with the free solution. Furthermore, swelling effects associated with the use of an organic solvent (ligroin) were evaluated by NMR profilometry on varnished oil and egg-tempera paints. In this case, by comparing the depth profiles collected before and after the solvent treatments, a moderate paint swelling was observed followed by a width reduction of the paint films ascribable to the removed varnish layer.Overall, the reported NMR results reveal the analytical potentialities of the technique for a non-invasive assessment of the swelling effect of paint films subjected to cleaning (by water or an organic solvent), thereby providing an analytical method in support to the conservators' practice.

Molecular Fluorescence Imaging Spectroscopy for Mapping Low Concentrations of Red Lake Pigments: Van†Gogh's Painting The Olive Orchard.

Vincent van Gogh used fugitive red lake pigments that have faded in some paintings. Mapping their distribution is key to understanding how his paintings have changed with time. While red lake pigments can be identified from microsamples, in situ identification and mapping remain challenging. This paper explores the ability of molecular fluorescence imaging spectroscopy to identify and, more importantly, map residual non-degraded red lakes. The high sensitivity of this method enabled identification of the emission spectra of eosin (tetrabromine fluorescein) lake mixed with lead or zinc white at lower concentrations than elemental X-ray fluorescence (XRF) spectroscopy used on account of bromine. The molecular fluorescence mapping of residual eosin and two carmine red lakes in van Gogh's The Olive Orchard is demonstrated and compared with XRF imaging spectroscopy. The red lakes are consistent with the composition of paint tubes known to have been used by van Gogh.

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.

Revealing the Nature and Distribution of Metal Carboxylates in Jackson Pollock's Alchemy (1947) by Micro-Attenuated Total Reflection FT-IR Spectroscopic Imaging.

Protrusions, efflorescence, delamination, and opacity decreasing are severe degradation phenomena affecting oil paints with zinc oxide, one of the most common white pigments of the 20th century. Responsible for these dramatic alterations are the Zn carboxylates (also known as Zn soaps) originated by the interaction of the pigment and the fatty acids resulting from the hydrolysis of glycerides in the oil binding medium. Despite their widespread occurrence in paintings and the growing interest of the scientific community, the process of formation and evolution of Zn soaps is not yet fully understood. In this study micro-attenuated total reflection (ATR)-FT-IR spectroscopic imaging was required for the investigation at the microscale level of the nature and distribution of Zn soaps in the painting Alchemy by J. Pollock (1947, Peggy Guggenheim Collection, Venice) and for comparison with artificially aged model samples. For both actual samples and models, the role of AlSt(OH)2, a jellifying agent commonly added in 20th century paint tube formulations, proved decisive for the formation of zinc stearate-like (ZnSt2) soaps. It was observed that ZnSt2-like soaps first form around the added AlSt(OH)2 particles and then eventually grow within the whole painting stratigraphy as irregularly shaped particles. In some of the Alchemy samples, and diversely from the models, a peculiar distribution of ZnSt2 aggregates arranged as rounded and larger particles was also documented. Notably, in one of these samples, larger agglomerates of ZnSt2 expanding toward the support of the painting were observed and interpreted as the early stage of the formation of internal protrusions. Micro-ATR-FT-IR spectroscopic imaging, thanks to a very high chemical specificity combined with high spatial resolution, was proved to give valuable information for assessing the conservation state of irreplaceable 20th century oil paintings, revealing the chemical distribution of Zn soaps within the paint stratigraphy before their effect becomes disruptive.

Micro transflection on a metallic stick: an innovative approach of reflection infrared spectroscopy for minimally invasive investigation of painting varnishes.

A new analytical approach, based on micro-transflection measurements from a diamond-coated metal sampling stick, is presented for the analysis of painting varnishes. Minimally invasive sampling is performed from the varnished surface using the stick, which is directly used as a transflection substrate for micro Fourier transform infrared (FTIR) measurements. With use of a series of varnished model paints, the micro-transflection method has been proved to be a valuable tool for the identification of surface components thanks to the selectivity of the sampling, the enhancement of the absorbance signal, and the easier spectral interpretation because the profiles are similar to transmission mode ones. Driven by these positive outcomes, the method was then tested as tool supporting noninvasive reflection FTIR spectroscopy during the assessment of varnish removal by solvent cleaning on paint models. Finally, the integrated analytical approach based on the two reflection methods was successfully applied for the monitoring of the cleaning of the sixteenth century painting Presentation in the Temple by Vittore Carpaccio. Graphical Abstract Micro-transflection FTIR on a metallic stick for the identification of varnishes during painting cleanings.

DFT/TDDFT investigation on the UV-vis absorption and fluorescence properties of alizarin dye.

The photophysical and photochemical properties of alizarin, a fluorescent organic red dye of the family of the anthraquinones, have been theoretically investigated by focusing our attention on its emission properties in relation to an excited-state internal proton transfers from the phenolic hydroxyl group to the carbonyl oxygen. The potential energy curve of the proton transfer in the first excited state has been computed in solvents of different polarity and the emission spectra of both tautomers simulated, including the vibronic effects, using the Franck-Condon approximation. Calculations performed by equilibrating the solvent with the excited-state geometry and electron density using a self-consistent procedure have led to interesting differences with respect to their linear response counterpart. The results obtained point out that, while the emission energy of alizarin is sensitive to solvent polarity, that of the proton-transfer tautomer is computed at similar wavelengths independently of the solvent. Comparison between computed and experimental data has allowed us to rationalize the alizarin double emission measured in non-polar solvents.

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.

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 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).

Mapping of egg yolk and animal skin glue paint binders in Early Renaissance paintings using near infrared reflectance imaging spectroscopy.

In situ chemical imaging techniques are being developed to provide information on the spatial distribution of artists' pigments used in polychrome works of art such as paintings. The new methods include reflectance imaging spectroscopy and X-ray fluorescence mapping. Results from these new methods have extended the knowledge obtained from site-specific chemical analyses widely in use. While these mapping methods have aided in determining the distribution of pigments, there is a growing interest to develop methods capable of identifying and mapping organic paint binders as well. Near infrared (NIR) reflectance spectroscopy has been extensively used in the remote sensing field as well as in the chemical industry to detect organic compounds. NIR spectroscopy provides a rapid method to assay organics by utilizing vibrational overtones and combination bands of fundamental absorptions that occur in the mid-IR. Here we explore the utility of NIR reflectance imaging spectroscopy to map organic binders in situ by examining a series of panel paintings known to have been painted using distemper (animal skin glue) and tempera (egg yolk) binders as determined by amino acid analysis of samples taken from multiple sites on the panels. In this report we demonstrate the success in identifying and mapping these binders by NIR reflectance imaging spectroscopy in situ. Three of the four panel paintings from Cosimo Tura's The Annunciation with Saint Francis and Saint Louis of Toulouse (ca. 1475) are imaged using a highly sensitive, line-scanning hyperspectral imaging camera. The results show an animal skin glue binder was used for the blue skies and blue robe of the Virgin Mary, and egg yolk tempera was used for the red robes and brown landscape. The mapping results show evidence for the use of both egg yolk and animal skin glue in the faces of the figures. The strongest absorption associated with lipidic egg yolk features visually correlates with areas that appear to have white highlights. The results are in agreement with prior site-specific amino acid analysis, underscoring the synergy of both methods. The work here demonstrates that NIR reflectance imaging spectroscopy is a useful technique that can identify and map paint binding media based on differences in chemical composition.

Layout of ancient Greek papyri through lead-drawn ruling lines revealed by Macro X-Ray Fluorescence Imaging.

The use of lead-drawn ruling lines by ancient scribes for the layout of Greek papyrus rolls was known to us only from classical authors and was postulated by a few scholars in modern times. In situ application of noninvasive Macro X-Ray Fluorescence Imaging Spectroscopy (MA-XRF) to unrolled papyri from Herculaneum, dating from about 200 BC to the 1st century AD, has provided the first direct evidence of such practice in ancient book production. The key experimental proof of periodic lines drawn in lead was gathered by a highly sensitive MA-XRF mobile instrument, which allowed detection of ultra-low trace residues of metals with detection limits that rival synchrotron light instruments. Elemental distribution maps of Pb have revealed three different systems of textual layout in ancient papyrus rolls and have resolved the dispute around so-called Maas' Law, by delivering experimental proof that slanted text columns were a deliberate aesthetic choice of scribes.

Microscale mechanochemical characterization of drying oil films by in situ correlative Brillouin and Raman spectroscopy.

Correlative Brillouin and Raman microspectroscopy (BRaMS) is applied for the in situ monitoring of the chemical and physical changes of linseed oil during polymerization. The viscoelastic properties of the drying oil throughout the phase transition were determined by Brillouin light scattering (BLS) and joined to the Raman spectroscopic information about the chemical process responsible for the oil hardening. A comparative study was then performed on an oil mock-up containing ZnO, one of the most common white pigments used in cultural heritage. The intriguing outcomes open new research perspectives for a deeper comprehension of the processes leading to the conversion of a fluid binder into a dry adhering film. The description of both chemical and structural properties of the polymeric network and their evolution are the basis for a better understanding of oil painting degradation. Last, as a feasibility test, BRaMS was applied to study a precious microfragment from J. Pollock's masterpiece Alchemy.

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.