High-resolution compound-specific mapping in works of art via data fusion of MA-XRPD with hyperspectral data (part 1: Method evaluation).

BACKGROUND: Hyperspectral imaging techniques have emerged as powerful tools for non-invasive investigation of artworks. This paper employs either reflectance imaging spectroscopy (RIS) or macroscopic X-ray fluorescence (MA-XRF) imaging in combination with macroscopic X-ray powder diffraction (MA-XRPD) for state-of-the-art chemical imaging of painted cultural heritage artefacts. While RIS can provide molecular information and MA-XRF can offer elemental distribution maps of paintings of high lateral resolution, the unique advantage of MA-XRPD lies in its ability to visualize the distributions of specific pigments and estimate in a quantitative manner the relative concentrations of the crystalline phases at the surface of artworks. However, MA-XRPD is more time-consuming and offers a lower lateral resolution than RIS and MA-XRF. RESULTS: This study introduces a machine learning (ML) approach to obtain the distribution of specific compounds on the surface of artworks with a resolution that is comparable to that of RIS and MA-XRF data but with the compound specificity of MA-XRPD. The general aim is to expedite non-destructive artwork imaging analysis by fusing data from different imaging modalities via machine learning models. The effect of preprocessing techniques to enhance the predictive accuracy of the models is explored. The paper demonstrates the method's efficacy on a 16th-century illuminated manuscript, showcasing the feasibility of predicting compound-specific distribution maps. Three evaluation methods-visual examination of the predicted distribution, root mean square errors (RMSE), and feature permutation importance (FPI)-are employed to assess model performance. Fusing MA-XRF with MA-XRPD led to the best RMSE scores overall. However, fusing the RIS and MA-XRPD data blocks also yield very satisfactory and easily interpretable high-resolution compound maps. SIGNIFICANCE: While MA-XRPD allows for highly specific imaging of artworks, its time-consuming nature and limited resolution presents a bottleneck during non-invasive imaging of painted works of art. By integrating data from more time-efficient hyperspectral techniques such as MA-XRF and RIS, and employing machine learning, we expedite the process without compromising accuracy. The fusion process can also denoise the distribution maps, improving their readability for heritage professionals and art historical scholars.

Correlated x-ray fluorescence and ptychographic nano-tomography on Rembrandt's The Night Watch reveals unknown lead "layer".

The Night Watch, one of the most famous masterpieces by Rembrandt, is the subject of a large research and conservation project. For the conservation treatment, it is of great importance to understand its current condition. Correlated nano-tomography using x-ray fluorescence and ptychography revealed a-so far unknown-lead-containing "layer", which likely acts as a protective impregnation layer applied on the canvas before the quartz-clay ground was applied. This layer might explain the presence of lead soap protrusions in areas where no other lead components are present. In addition to the three-dimensional elemental mapping, ptychography visualizes and quantifies components not detectable by hard x-ray fluorescence such as the organic fraction and quartz. The first-time use of this combination of synchrotron-based techniques on a historic paint micro-sample shows it to be an important tool to better interpret the results of noninvasive imaging techniques operating on the macroscale.

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).

Lead(II) Formate in Rembrandt's Night Watch: Detection and Distribution from the Macro- to the Micro-scale.

The Night Watch, painted in 1642 and on view in the Rijksmuseum in Amsterdam, is considered Rembrandt's most famous work. X-ray powder diffraction (XRPD) mapping at multiple length scales revealed the unusual presence of lead(II) formate, Pb(HCOO)2 , in several areas of the painting. Until now, this compound was never reported in historical oil paints. In order to get insights into this phenomenon, one possible chemical pathway was explored thanks to the preparation and micro-analysis of model oil paint media prepared by heating linseed oil and lead(II) oxide (PbO) drier as described in 17th century recipes. Synchrotron radiation based micro-XRPD (SR-µ-XRPD) and infrared microscopy were combined to identify and map at the micro-scale various neo-formed lead-based compounds in these model samples. Both lead(II) formate and lead(II) formate hydroxide Pb(HCOO)(OH) were detected and mapped, providing new clues regarding the reactivity of lead driers in oil matrices in historical paintings.

Reviving degraded colors of yellow flowers in 17th century still life paintings with macro- and microscale chemical imaging.

Over time, artist pigments are prone to degradation, which can decrease the readability of the artwork or notably change the artist's intention. In this article, the visual implication of secondary degradation products in a degraded yellow rose in a still life painting by A. Mignon is discussed as a case study. A multimodal combination of chemical and optical imaging techniques, including noninvasive macroscopic x-ray powder diffraction (MA-XRPD) and macroscopic x-ray fluorescence imaging, allowed us to gain a 3D understanding of the transformation of the original intended appearance of the rose into its current degraded state. MA-XRPD enabled us to precisely correlate in situ formed products with what is optically visible on the surface and demonstrated that the precipitated lead arsenates and arsenolite from the yellow pigment orpiment and the light-induced fading of an organic yellow lake irreversibly changed the artist's intentional light-shadow modeling.

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.

Insights into the composition of ancient Egyptian red and black inks on papyri achieved by synchrotron-based microanalyses.

A hitherto unknown composition is highlighted in the red and black inks preserved on ancient Egyptian papyri from the Roman period (circa 100 to 200 CE). Synchrotron-based macro-X-ray fluorescence (XRF) mapping brings to light the presence of iron (Fe) and lead (Pb) compounds in the majority of the red inks inscribed on 12 papyrus fragments from the Tebtunis temple library. The iron-based compounds in the inks can be assigned to ocher, notably due to the colocalization of Fe with aluminum, and the detection of hematite (Fe2O3) by micro-X-ray diffraction. Using the same techniques together with micro-Fourier transform infrared spectroscopy, Pb is shown to be associated with fatty acid phosphate, sulfate, chloride, and carboxylate ions. Moreover, micro-XRF maps reveal a peculiar distribution and colocalization of Pb, phosphorus (P), and sulfur (S), which are present at the micrometric scale resembling diffused "coffee rings" surrounding the ocher particles imbedded in the red letters, and at the submicrometric scale concentrated in the papyrus cell walls. A similar Pb, P, and S composition was found in three black inks, suggesting that the same lead components were employed in the manufacture of carbon-based inks. Bearing in mind that pigments such as red lead (Pb3O4) and lead white (hydrocerussite [Pb3(CO3)2(OH)2] and/or cerussite [PbCO3]) were not detected, the results presented here suggest that the lead compound in the ink was used as a drier rather than as a pigment. Accordingly, the study calls for a reassessment of the composition of lead-based components in ancient Mediterranean pigments.

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.

Micro-analytical characterization of thorium-rich aggregates from Norwegian NORM sites (Fen Complex, Telemark).

In this study we performed microscopic characterization of mineral particles that were collected in the thorium-rich Fen Complex in Norway and identified and isolated based on autoradiography in function of their radioactivity. For this we combined information obtained with X-ray absorption µ-CT, µ-XRF and µ-XRD, both in bi- and in three-dimensional (tomographic) mode. We demonstrate that radionuclides and metals are heterogeneously distributed both within soil samples and within individual Th-enriched aggregates, which are characterised as low-density mineral bulk particles with high density material inclusions, where Th as well as several metals are highly concentrated. For these sites, it is important to take into account how these inhomogeneous distributions could affect the overall environmental behaviour of Th and progeny upon weathering due to human or environmental factors. Moreover, the estimated size of the Th-containing inclusions as determined in this work represents information of importance for the characterization of radionuclides and toxic metals exposure, as well as for assessing the viability of mining for Th and rare-earth metals in the Fen Complex and the associated environmental impact.

X-ray Diffraction Mapping for Cultural Heritage Science: a Review of Experimental Configurations and Applications.

X-ray diffraction (XRD) mapping consists in the acquisition of XRD patterns at each pixel (or voxel) of an area (or volume). The spatial resolution ranges from the micrometer (µXRD) to the millimeter (MA-XRD) scale, making the technique relevant for tiny samples up to large objects. Although XRD is primarily used for the identification of different materials in (complex) mixtures, additional information regarding the crystallite size, their orientation, and their in-depth distribution can also be obtained. Through mapping, these different types of information can be located on the studied sample/object. Cultural heritage objects are usually highly heterogeneous, and contain both original and later (degradation, conservation) materials. Their structural characterization is required both to determine ancient manufacturing processes and to evaluate their conservation state. Together with other mapping techniques, XRD mapping is increasingly used for these purposes. Here, the authors review applications as well as the various configurations for XRD mapping (synchrotron/laboratory X-ray source, poly-/monochromatic beam, micro/macro beam, 2D/3D, transmission/reflection mode). On-going hardware and software developments will further establish the technique as a key tool in heritage science.

Transmission and Reflection Mode Macroscopic X-ray Powder Diffraction Imaging for the Noninvasive Visualization of Paint Degradation in Still Life Paintings by Jan Davidsz. de Heem.

The use of noninvasive chemical imaging techniques is becoming more widespread for the study of cultural heritage artifacts. Recently a mobile instrument for macroscopic X-ray powder diffraction (MA-XRPD) scanning was developed, which is capable of visualizing the distribution of crystalline (pigment) phases in quasi-flat-painted artifacts. In this study, MA-XRPD is used in both transmission and reflection mode for the analysis of three 17th century still life paintings, two paintings by Jan Davidsz. de Heem (1606-1684) and one copy painting after De Heem by an unknown artist. MA-XRPD allowed to reveal and map the presence of in situ-formed alteration products. In the works examined, two rare lead arsenate minerals, schultenite (PbHAsO4) and mimetite (Pb5(AsO4)3Cl), were encountered, both at and below the paint surface; they are considered to be degradation products of the pigments realgar (α-As4S4) and orpiment (As2S3). In transmission mode, the depletion of lead white, present in the (second) ground layer, could be seen, illustrating the intrusive nature of this degradation process. In reflection mode, several sulfate salts, palmierite (K2Pb(SO4)2), syngenite (K2Ca(SO4)2·H2O), and gypsum (CaSO4.2H2O), could be detected, in particular, at the (top) surface of the copy painting. Estimates for the information depth and sensitivity of both transmission and reflection mode MA-XRPD for various pigments have been made. The possibility of MA-XRPD to allow for noninvasive identification and visualization of alteration products is considered a significant advantage and unique feature of this method. MA-XRPD can thus provide highly relevant information for assessing the conservation state of artworks and could guide possible future restoration treatments.

Macroscopic X-ray Powder Diffraction Scanning: Possibilities for Quantitative and Depth-Selective Parchment Analysis.

At or below the surface of painted works of art, valuable information is present that provides insights into an object's past, such as the artist's technique and the creative process that was followed or its conservation history but also on its current state of preservation. Various noninvasive techniques have been developed over the past 2 decades that can probe this information either locally (via point analysis) or on a macroscopic scale (e.g., full-field imaging and raster scanning). Recently macroscopic X-ray powder diffraction (MA-XRPD) mapping using laboratory X-ray sources was developed. This method can visualize highly specific chemical distributions at the macroscale (dm2). In this work we demonstrate the synergy between the quantitative aspects of powder diffraction and the noninvasive scanning capability of MA-XRPD highlighting the potential of the method to reveal new types of information. Quantitative data derived from a 15th/16th century illuminated sheet of parchment revealed three lead white pigments with different hydrocerussite-cerussite compositions in specific pictorial elements, while quantification analysis of impurities in the blue azurite pigment revealed two distinct azurite types: one rich in barite and one in quartz. Furthermore, on the same artifact, the depth-selective possibilities of the method that stem from an exploitation of the shift of the measured diffraction peaks with respect to reference data are highlighted. The influence of different experimental parameters on the depth-selective analysis results is briefly discussed. Promising stratigraphic information could be obtained, even though the analysis is hampered by not completely understood variations in the unit cell dimensions of the crystalline pigment phases.

Macroscopic X-ray Powder Diffraction Scanning, a New Method for Highly Selective Chemical Imaging of Works of Art: Instrument Optimization.

In the past decade macroscopic X-ray fluorescence imaging (MA-XRF) has become established as a method for the noninvasive investigation of flat painted surfaces, yielding large scale elemental maps. MA-XRF is limited by a lack of specificity, only allowing for indirect pigment identification based on the simultaneous presence of chemical elements. The high specificity of X-ray powder diffraction (XRPD) mapping is already being exploited at synchrotron facilities for investigations at the (sub)microscopic scale, but the technique has not yet been employed using lab sources. In this paper we present the development of a novel MA-XRPD/XRF instrument based on a laboratory X-ray source. Several combinations of X-ray sources and area detectors are evaluated in terms of their spatial and angular resolution and their sensitivity. The highly specific imaging capability of the combined MA-XRPD/XRF instrument is demonstrated on a 15th/16th century illuminated manuscript directly revealing the distribution of a large number of inorganic pigments, including the uncommon yellow pigment massicot ( o-PbO). The case study illustrates the wealth of new mapping information that can be obtained in a noninvasive manner using the laboratory MA-XRPD/XRF instrument.

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.

Combined Computed Nanotomography and Nanoscopic X-ray Fluorescence Imaging of Cobalt Nanoparticles in Caenorhabditis elegans.

Synchrotron radiation phase-contrast computed nanotomography (nano-CT) and two- and three-dimensional (2D and 3D) nanoscopic X-ray fluorescence (nano-XRF) were used to investigate the internal distribution of engineered cobalt nanoparticles (Co NPs) in exposed individuals of the nematode Caenorhabditis elegans. Whole nematodes and selected tissues and organs were 3D-rendered: anatomical 3D renderings with 50 nm voxel size enabled the visualization of spherical nanoparticle aggregates with size up to 200 nm within intact C. elegans. A 20 × 37 nm2 high-brilliance beam was employed to obtain XRF elemental distribution maps of entire nematodes or anatomical details such as embryos, which could be compared with the CT data. These maps showed Co NPs to be predominantly present within the intestine and the epithelium, and they were not colocalized with Zn granules found in the lysosome-containing vesicles or Fe agglomerates in the intestine. Iterated XRF scanning of a specimen at 0° and 90° angles suggested that NP aggregates were translocated into tissues outside of the intestinal lumen. Virtual slicing by means of 2D XRF tomography, combined with holotomography, indicated presumable presence of individual NP aggregates inside the uterus and within embryos.

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.

Plumbonacrite identified by X-ray powder diffraction tomography as a missing link during degradation of red lead in a Van Gogh painting.

Red lead, a semiconductor pigment used by artists since antiquity, is known to undergo several discoloration phenomena. These transformations are either described as darkening of the pigment caused by the formation of either plattnerite (ß-PbO2) or galena (PbS) or as whitening by which red lead is converted into anglesite (PbSO4) or (hydro)cerussite (2 PbCO3⋅Pb(OH)2; PbCO3). X-ray powder diffraction tomography, a powerful analytical method that allows visualization of the internal distribution of different crystalline compounds in complex samples, was used to investigate a microscopic paint sample from a Van Gogh painting. A very rare lead mineral, plumbonacrite (3 PbCO3⋅Pb(OH)2⋅PbO), was revealed to be present. This is the first reported occurrence of this compound in a painting dating from before the mid 20th century. It constitutes the missing link between on the one hand the photoinduced reduction of red lead and on the other hand (hydro)cerussite, and thus sheds new light on the whitening of red lead.

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.