Koen Janssens

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 womans 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 Goghs 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.

Elemental compositions of comet 81P/Wild 2 samples collected by Stardust

We measured the elemental compositions of material from 23 particles in aerogel and from residue in seven craters in aluminum foil that was collected during passage of the Stardust spacecraft through the coma of comet 81P/Wild 2. These particles are chemically heterogeneous at the largest size scale analyzed (∼180 ng). The mean elemental composition of this Wild 2 material is consistent with the CI meteorite composition, which is thought to represent the bulk composition of the solar system, for the elements Mg, Si, Mn, Fe, and Ni to 35%, and for Ca and Ti to 60%. The elements Cu, Zn, and Ga appear enriched in this Wild 2 material, which suggests that the CI meteorites may not represent the solar system composition for these moderately volatile minor elements.

Use of microscopic XRF for non‐destructive analysis in art and archaeometry

The various application possibilities of microscopic x-ray fluorescence and associated methods for the characterization and provenance analysis of objects and materials of cultural heritage value are discussed by means of a number of case studies. They include the trace analysis of historic glass, the analysis of corroded coins and statues in bronze and silver and the study of inks on historical documents. These studies are conducted by means of micro-XRF instruments installed at synchrotron beamlines and by means of laboratory equipment, some of which is easily transportable to the museum or archaeological site where the objects of interest are located. Copyright

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.

A mobile instrument for in situ scanning macro-XRF investigation of historical paintings

Scanning macro-X-ray fluorescence analysis (MA-XRF) is rapidly being established as a technique for the investigation of historical paintings. The elemental distribution images acquired by this method allow for the visualization of hidden paint layers and thus provide insight into the artists creative process and the paintings conservation history. Due to the lack of a dedicated, commercially available instrument the application of the technique was limited to a few groups that constructed their own instruments. We present the first commercially available XRF scanner for paintings, consisting of an X-ray tube mounted with a Silicon-Drift (SD) detector on a motorized stage to be moved in front of a painting. The scanner is capable of imaging the distribution of the main constituents of surface and sub-surface paint layers in an area of 80 by 60 square centimeters with dwell times below 10 ms and a lateral resolution below 100 μm. The scanner features for a broad range of elements between Ti (Z = 22) and Mo (Z = 42) a count rate of more than 1000 counts per second (cps)/mass percent and detection limits of 100 ppm for measurements of 1 s duration. Next to a presentation of spectrometric figures of merit, the value of the technique is illustrated through a case study of a painting by Rembrandts student Govert Flinck (1615–1660).

Optimization of mobile scanning macro-XRF systems for the in situ investigation of historical paintings

Elemental distribution maps are of great interest in the study of historical paintings, as they allow to investigate the pigment use of the artist, to image changes made in the painting during or after its creation and in some cases to reveal discarded paintings that were later over painted. Yet a method that allows to record such maps of a broad range of elements in a fast, non-destructive and in situ manner is not yet commonly available; a dedicated mobile scanning XRF instrument might fill this gap. In this paper we present three self-built scanning macro-XRF instruments, each based on the experience gained with its precursor. These instruments are compared in terms of sensitivity and limits of detection, which includes a discussion of the use of polycapillary optics and pinhole collimators as beam defining devices. Furthermore, the imaging capabilities of the instruments are demonstrated in three exemplary cases: (parts of) historical paintings from the 15th to the 19th century are examined. These cases illustrate the value of element specific distribution maps in the study of historical paintings and allow in the case of Vincent van Goghs “Patch of Grass” a direct comparison between in situ and synchrotron based scanning macro-XRF.

Microscopic X-ray fluorescence analysis and related methods with laboratory and synchrotron radiation sources

The present status of microprobe versions of XRF analysis with tube excitation and with synchrotron radiation sources is reviewed with respect to analytical parameters such as lateral resolution and imaging capability, and achievable detection limits, precision and accuracy. The main characteristics of the method are contrasted with those of other microanalytical techniques. For laboratory source µ-XRF, results with a rotating anode tube equipped with capillary X-ray optics are discussed in terms of sensitivity and achievable lateral resolution. The possibilities of the new third generation synchrotron radiation storage rings, especially those of the European Synchrotron Radiation Facility (ESRF) and its X-ray micro-fluorescence, imaging and diffraction beamline (ID 22) are discussed and related to second generation storage rings. Some characteristic applications are given to illustrate the recent possibilities of the methodologies, in particular for the characterization of atmospheric particles, and in an analytical problem related to archaeology.

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.

High energy X-ray microscopy for characterisation of fuel particles

Abstract For the first time different high energy microanalysis techniques were combined to characterise individual micrometer sized radioactive particles. It was shown that particle characteristics including weathering rates and mobilisation of associated radionuclides are source specific and release-scenario dependent. Fuel particles released during the explosion are characterised by UO 2 -cores with surrounding layer of reduced U with low weathering rates. In contrast, fuel particles released during the subsequent fire show UO 2 -core with surrounding layers of oxidised U 2 O 5 /U 3 O 8 with high weathering rates

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 objects 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 objects 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.