Multi-scale optical coherence tomography imaging and visualization of Vermeer's Girl with a Pearl Earring.

We demonstrate multi-scale multi-parameter optical coherence tomography (OCT) imaging and visualization of Johannes Vermeer's painting Girl with a Pearl Earring. Through automated acquisition, OCT image segmentation, and 3D volume stitching we realize OCT imaging at the scale of an entire painting. This makes it possible to image, with micrometer axial and lateral resolution, an entire painting over more than 5 orders of length scale. From the multi-scale OCT data we quantify multiple parameters in a fully automated way: the surface height, the scattering strength, and the combined glaze and varnish layer thickness. The multi-parameter OCT data of Girl with a Pearl Earring shows various features: Vermeer's brushstrokes, surface craquelure, paint losses, and restorations. Through an interactive visualization of the Girl, based on the OCT data and the optical properties of historical reconstructions of Vermeer's paint, we can virtually study the effect of the lighting condition, viewing angle, zoom level and presence/absence of glaze layer. The interactive visualization shows various new painting features. It demonstrates that the glaze layer structure and its optical properties were essential to Vermeer to create an extremely strong light to dark contrast between the figure and the background that gives the painting such an iconic aesthetic appeal.

Unraveling the Composition of Rembrandt's Impasto through the Identification of Unusual Plumbonacrite by Multimodal X-ray Diffraction Analysis.

Rembrandt (1606-1669) is renowned for his impasto technique, involving his use of lead white paint with outstanding rheological properties. This paint was obtained by combining lead white pigment (a mixture of cerussite PbCO3 and hydrocerussite Pb3 (CO3 )2 (OH)2 ) with an organic binding medium, but the exact formulation used by Rembrandt remains a mystery. A powerful combination of high-angle and high-lateral resolution x-ray diffraction was used to investigate several microscopic paint samples from four Rembrandt masterpieces. A rare lead compound, plumbonacrite (Pb5 (CO3 )3 O(OH)2 ), was detected in areas of impasto. This can be considered a fingerprint of Rembrandt's recipe and is evidence of the use of an alkaline binding medium, which sheds a new light on Rembrandt's pictorial technique.

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.

Large area imaging of forensic evidence with MA-XRF.

This study introduces the use of macroscopic X-ray fluorescence (MA-XRF) for the detection, classification and imaging of forensic traces over large object areas such as entire pieces of clothing and wall paneling. MA-XRF was sufficiently sensitive and selective to detect human biological traces like blood, semen, saliva, sweat and urine on fabric on the basis of Fe, Zn, K, Cl and Ca elemental signatures. With MA-XRF a new chemical contrast is introduced for human stain detection and this can provide a valuable alternative when the evidence item is challenging for conventional techniques. MA-XRF was also successfully employed for the chemical imaging and classification of gunshot residues (GSR). The full and non-invasive elemental mapping (Pb, Ba, Sr, K and Cl) of intact pieces of clothing allows for a detailed shooting incident reconstruction linking firearms and ammunition to point of impact and providing information on the shooting angle. In high resolution mode MA-XRF can even be used to provide information on the shooting order of different ammunition types. Finally, by using the surface penetration of X-rays we demonstrate that the lead signature of a bullet impact can be easily detected even if covered by multiple layers of wall paint or human blood.

Investigating the Photocatalytic Degradation of Oil Paint using ATR-IR and AFM-IR.

As linseed oil has a longstanding and continuing history of use as a binder in artistic paints, developing an understanding of its degradation mechanism is critical to conservation efforts. At present, little can be done to detect the early stages of oil paint deterioration due to the complex chemical composition of degrading paints. In this work, we use advanced infrared analysis techniques to investigate the UV-induced deterioration of model linseed oil paints in detail. Subdiffraction limit infrared analysis (AFM-IR) is applied to identify and map accelerated degradation in the presence of two different grades of titanium white pigment particles (rutile or anatase TiO2). Differentiation between the degradation of these two formulations demonstrates the sensitivity of this approach. The identification of characteristic peaks and transient species residing at the paint surface allows infrared absorbance peaks related to degradation deeper in the film to be extricated from conventional ATR-FTIR spectra, potentially opening up a new approach to degradation monitoring.

Exploring a Hidden Painting Below the Surface of René Magritte's Le Portrait.

Two state-of-the-art methods for non-invasive visualization of subsurface (or overpainted) pictorial layers present in painted works of art are employed to study Le portrait, painted by Belgian artist René Magritte in 1935. X-ray radiography, a commonly used method for the nondestructive inspection of paintings, had revealed the presence of an underlying figurative composition, part of an earlier Magritte painting entitled La pose enchantée (1927) which originally depicted two full length nude female figures with exaggerated facial features. On the one hand, macroscopic X-ray fluorescence analysis (MA-XRF), a method capable of providing information on the distribution of the key chemical elements present in many artists' pigments, was employed. The ability of the X-rays to penetrate the upper layer of paint enabled the imaging of the facial features of the female figure and provided information on Magritte's palette for both surface and hidden composition. On the other hand, visible and near infrared hyperspectral imaging spectroscopies in transmission mode were also used, especially in the area of the table cloth in order to look through the upper representation and reveal the pictorial layer(s) below. MA-XRF provided elemental information on the pigment distributions in both the final painting and the prior whereas the transmission mode provided information related to preparatory sketches as well as revealing differences between the paints used in both compositions. These results illustrate very well the manner in which the two imaging methods complement each other, both in the sense of providing different types of information on the nature and presence of paint components/pigments and in the sense of being optimally suited to easily penetrate through different types of overpaint.

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.

Combined use of synchrotron radiation based micro-X-ray fluorescence, micro-X-ray diffraction, micro-X-ray absorption near-edge, and micro-fourier transform infrared spectroscopies for revealing an alternative degradation pathway of the pigment cadmium yellow in a painting by Van Gogh.

Over the past years a number of studies have described the instability of the pigment cadmium yellow (CdS). In a previous paper we have shown how cadmium sulfide on paintings by James Ensor oxidizes to CdSO(4)·H(2)O. The degradation process gives rise to the fading of the bright yellow color and the formation of disfiguring white crystals that are present on the paint surface in approximately 50 µm sized globular agglomerations. Here, we study cadmium yellow in the painting "Flowers in a blue vase" by Vincent van Gogh. This painting differs from the Ensor case in the fact that (a) a varnish was superimposed onto the degraded paint surface and (b) the CdS paint area is entirely covered with an opaque crust. The latter obscures the yellow color completely and thus presents a seemingly more advanced state of degradation. Analysis of a cross-sectioned and a crushed sample by combining scanning microscopic X-ray diffraction (µ-XRD), microscopic X-ray absorption near-edge spectroscopy (µ-XANES), microscopic X-ray fluorescence (µ-XRF) based chemical state mapping and scanning microscopic Fourier transform infrared (µ-FT-IR) spectrometry allowed unravelling the complex alteration pathway. Although no crystalline CdSO(4) compounds were identified on the Van Gogh paint samples, we conclude that the observed degradation was initially caused by oxidation of the original CdS pigment, similar as for the previous Ensor case. However, due to the presence of an overlying varnish containing lead-based driers and oxalate ions, secondary reactions took place. In particular, it appears that upon the photoinduced oxidation of its sulfidic counterion, the Cd(2+) ions reprecipitated at the paint/varnish interface after having formed a complex with oxalate ions that themselves are considered to be degradation products of the resin and/or oil in the varnish. The SO(4)(2-) anions, for their part, found a suitable reaction partner in Pb(2+) ions stemming from a dissolved lead-based siccative that was added to the varnish to promote its drying. The resulting opaque anglesite compound in the varnish, in combination with the underlying CdC(2)O(4) layer at the paint/varnish interface, account for the orange-gray crust that is disfiguring the painting on a macroscopic level. In this way, the results presented in this paper demonstrate how, through a judicious combined use of several microanalytical methods with speciation capabilities, many new insights can be obtained from two minute, but highly complex and heterogeneous paint samples.

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.

Synchrotron-based X-ray absorption spectroscopy for art conservation: looking back and looking forward.

A variety of analytical techniques augmented by the use of synchrotron radiation (SR), such as X-ray fluorescence (SR-XRF) and X-ray diffraction (SR-XRD), are now readily available, and they differ little, conceptually, from their common laboratory counterparts. Because of numerous advantages afforded by SR-based techniques over benchtop versions, however, SR methods have become popular with archaeologists, art historians, curators, and other researchers in the field of cultural heritage (CH). Although the CH community now commonly uses both SR-XRF and SR-XRD, the use of synchrotron-based X-ray absorption spectroscopy (SR-XAS) techniques remains marginal, mostly because CH specialists rarely interact with SR physicists. In this Account, we examine the basic principles and capabilities of XAS techniques in art preservation. XAS techniques offer a combination of features particularly well-suited for the chemical analysis of works of art. The methods are noninvasive, have low detection limits, afford high lateral resolution, and provide exceptional chemical sensitivity. These characteristics are highly desirable for the chemical characterization of precious, heterogeneous, and complex materials. In particular, the chemical mapping capability, with high spatial resolution that provides information about local composition and chemical states, even for trace elements, is a unique asset. The chemistry involved in both the object's history (that is, during fabrication) and future (that is, during preservation and restoration treatments) can be addressed by XAS. On the one hand, many studies seek to explain optical effects occurring in historical glasses or ceramics by probing the molecular environment of relevant chromophores. Hence, XAS can provide insight into craft skills that were mastered years, decades, or centuries ago but were lost over the course of time. On the other hand, XAS can also be used to characterize unwanted reactions, which are then considered alteration phenomena and can dramatically alter the object's original visual properties. In such cases, the bulk elemental composition is usually unchanged. Hence, monitoring oxidation state (or, more generally, other chemical modifications) can be of great importance. Recent applications of XAS in art conservation are reviewed and new trends are discussed, highlighting the value (and future possibilities) of XAS, which remains, given its potential, underutilized in the CH community.

TeraHertz imaging of hidden paint layers on canvas.

We show terahertz reflection images of hidden paint layers in a painting on canvas and compare the results with X-ray Radiography and In-frared Reflectography. Our terahertz measurements show strong reflections from both the canvas/paint interface and from the raw umber/lead white interface, indicating sufficient refractive-index contrast. Our results show that X-rays cannot be used to image through the lead white pigment which effectively blocks the X-rays. Although Infrared Reflectography is capable of vaguely observing the hidden paint strokes from the canvas side, we show that only terahertz imaging is capable of providing information on the thickness of the hidden paint layers. Terahertz imaging is thus shown to be a powerful imaging method for art historians, conservators and conservation scientists.

Characterization of a degraded cadmium yellow (CdS) pigment in an oil painting by means of synchrotron radiation based X-ray techniques.

On several paintings of James Ensor (1860-1949), a gradual fading of originally bright yellow areas, painted with the pigment cadmium yellow (CdS), is observed. Additionally, in some areas exposed to light, the formation of small white-colored globules on top of the original paint surface is observed. In this paper the chemical transformation leading to the color change and to the formation of the globules is elucidated. Microscopic X-ray absorption near-edge spectroscopy (mu-XANES) experiments show that sulfur, originally present in sulfidic form (S(2-)), is oxidized during the transformation to the sulfate form (S(6+)). Upon formation (at or immediately below the surface), the highly soluble cadmium sulfate is assumed to be transported to the surface in solution and reprecipitates there, forming the whitish globules. The presence of cadmium sulfate (CdSO(4).2H(2)O) and ammonium cadmium sulfate [(NH(4))(2)Cd(SO(4))(2)] at the surface is confirmed by microscopic X-ray diffraction measurements, where the latter salt is suspected to result from a secondary reaction of cadmium sulfate with ammonia. Measurements performed on cross sections reveal that the oxidation front has penetrated into the yellow paint down to ca. 1-2 microm. The morphology and elemental distribution of the paint and degradation product were examined by means of scanning electron microscopy equipped with an energy-dispersive spectrometer (SEM-EDS) and synchrotron radiation based micro-X-ray fluorescence spectrometry (SR micro-XRF). In addition, ultraviolet-induced visible fluorescence photography (UIVFP) revealed itself to be a straightforward technique for documenting the occurrence of this specific kind of degradation on a macroscale by painting conservators.

A note on medieval microfabrication: the visualization of a prayer nut by synchrotron-based computer X-ray tomography.

One of the most fascinating objects in the Rijksmuseum (Amsterdam, The Netherlands) is an early 16th century prayer nut. This spherical wooden object measures 4 cm in diameter and consists of two hemispheres connected with a small hinge so that it can be opened. The interior of the nut holds wood carvings with scenes from the life of Christ. These miniature reliefs show an incredible degree of finish with carving details well beyond the millimetre scale. In the present paper it is shown how synchrotron-based computer X-ray tomography revealed the structure and fabrication method of the bead. The central part of the relief was cut from a single piece of wood, rather than assembled from multiple components, underlining the extraordinary manual dexterity of its maker. In addition, a piece of fibrous material contained in the inner structure of the bead is revealed. This may have served as a carrier for an odorous compound, which would be in line with the religious function of the prayer nut.

Visualization of a lost painting by Vincent van Gogh using synchrotron radiation based X-ray fluorescence elemental mapping.

Vincent van Gogh (1853-1890), one of the founding fathers of modern painting, is best known for his vivid colors, his vibrant painting style, and his short but highly productive career. His productivity is even higher than generally realized, as many of his known paintings cover a previous composition. This is thought to be the case in one-third of his early period paintings. Van Gogh would often reuse the canvas of an abandoned painting and paint a new or modified composition on top. These hidden paintings offer a unique and intimate insight into the genesis of his works. Yet, current museum-based imaging tools are unable to properly visualize many of these hidden images. We present the first-time use of synchrotron radiation based X-ray fluorescence mapping, applied to visualize a woman's head hidden under the work Patch of Grass by Van Gogh. We recorded decimeter-scale, X-ray fluorescence intensity maps, reflecting the distribution of specific elements in the paint layers. In doing so we succeeded in visualizing the hidden face with unprecedented detail. In particular, the distribution of Hg and Sb in the red and light tones, respectively, enabled an approximate color reconstruction of the flesh tones. This reconstruction proved to be the missing link for the comparison of the hidden face with Van Gogh's known paintings. Our approach literally opens up new vistas in the nondestructive study of hidden paint layers, which applies to the oeuvre of Van Gogh in particular and to old master paintings in general.

Relics in medieval altarpieces? Combining X-ray tomographic, laminographic and phase-contrast imaging to visualize thin organic objects in paintings.

X-ray radiography is a common tool in the study of old master paintings. Transmission imaging can visualize hidden paint layers as well as the structure of the panel or canvas. In some medieval altarpieces, relics seem to have been imbedded in the wooden carrier of paintings. These are most probably thin organic fibrous materials such as paper or textile, which in traditional radiography are shadowed by the more absorbing surrounding material. This paper studies the application potential of synchrotron-based tomographic and laminographic imaging complemented with phase-contrast imaging for detection of such relics. The techniques are applied to a dummy painting. The results demonstrate that by using these imaging methods it is possible to three-dimensionally visualize hidden cavities in panels and detect thin fibrous low-Z materials sandwiched between a high-Z paint layer and a thick wooden panel.