“Combined Micro- and Macro scale X-ray powder diffraction mapping of degraded Orpiment paint in a 17th century still life painting by Martinus Nellius”. Simoen J, De Meyer S, Vanmeert F, De Keyser N, Avranovich E, van der Snickt G, Van Loon A, Keune K, Janssens K, Heritage science 7, 83 (2019). http://doi.org/10.1186/S40494-019-0324-4
Abstract: The spontaneous chemical alteration of artists' pigment materials may be caused by several degradation processes. Some of these are well known while others are still in need of more detailed investigation and documentation. These changes often become apparent as color modifications, either caused by a change in the oxidation state in the original material or the formation of degradation products or salts, via simple or more complex, multistep reactions. Arsenic-based pigments such as orpiment (As2S3) or realgar (alpha-As4S4) are prone to such alterations and are often described as easily oxidizing upon exposure to light. Macroscopic X-ray powder diffraction (MA-XRPD) imaging on a sub area of a still life painting by the 17th century Dutch painter Martinus Nellius was employed in combination with microscopic (mu-) XRPD imaging of a paint cross section taken in the area imaged by MA-XRPD. In this way, the in situ formation of secondary metal arsenate and sulfate species and their migration through the paint layer stack they originate from could be visualized. In the areas originally painted with orpiment, it could be shown that several secondary minerals such as schultenite (PbHAsO4), mimetite (Pb-5(AsO4)(3)Cl), palmierite (K2Pb(SO4)(2)) and syngenite (K2Ca(SO4)(2)center dot H2O) have formed. Closer inspection of the cross-sectioned paint layer stack with mu-XRPD illustrates that the arsenate minerals schultenite and mimetite have precipitated at the interface between the orpiment layer and the layer below that is rich in lead white, i.e. close to the depth of formation of the arsenate ions. The sulfate palmierite has mostly precipitated at the surface and upper layers of the painting.
Keywords: A1 Journal article; Art; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation); Antwerp Cultural Heritage Sciences (ARCHES)
Times cited: 2
DOI: 10.1186/S40494-019-0324-4
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“Imaging secondary reaction products at the surface of Vermeer's Girl with the Pearl Earring by means of macroscopic X-ray powder diffraction scanning”. De Meyer S, Vanmeert F, Vertongen R, van Loon A, Gonzalez V, van der Snickt G, Vandivere A, Janssens K, Heritage science 7, 67 (2019). http://doi.org/10.1186/S40494-019-0309-3
Abstract: The use of non-invasive macroscopic imaging techniques is becoming more prevalent in the field of cultural heritage, especially to avoid invasive procedures that damage valuable artworks. For this purpose, an X-ray powder diffraction scanner (MA-XRPD) capable of visualising crystalline compounds in a highly specific manner was recently developed. Many inorganic pigments present in paintings fall into this category of materials. In this study, the 17th century oil painting Girl with a Pearl Earring (c. 1665) by Johannes Vermeer was analysed with a combination of transmission and reflection mode MA-XRPD. By employing this scanner in reflection mode, the relative sensitivity for compounds that are present at the paint surface could be increased, establishing it as a highly relevant technique for investigating the degradation processes that are ongoing at paint surfaces. Many of the original pigments employed by Vermeer could be identified, along with four secondary alteration products: gypsum (CaSO4 center dot 2H(2)O), anglesite (PbSO4), palmierite (K2Pb(SO4)(2)) and weddellite (CaC2O4 center dot 2H(2)O). The formation of gypsum was linked to the presence of chalk in the upper glaze layer while the formation of palmierite and weddellite is driven by the presence of lake pigments (and their substrates). In this manner, MA-XRPD can also be used to pinpoint locations relevant for sampling and synchrotron mu-XRPD analysis, which provides information on the microscopic make-up of the paint. A paint cross-section taken from an area rich in palmierite was analysed with synchrotron mu-XRPD, which confirmed the presence of this secondary compound at the interface of the upper paint layer with the ground layer as well as the presence of anglesite in the ground layer. The capacity of MA-XRPD to identify and chart secondary alteration products in a non-invasive manner has only very recently been demonstrated and makes it a highly relevant technique for the assessment of the chemical condition of works of art.
Keywords: A1 Journal article; Art; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation); Antwerp Cultural Heritage Sciences (ARCHES)
Times cited: 5
DOI: 10.1186/S40494-019-0309-3
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“Macroscopic x-ray powder diffraction imaging reveals Vermeer's discriminating use of lead white pigments in Girl with a Pearl Earring”. De Meyer S, Vanmeert F, Vertongen R, Van Loon A, Gonzalez V, Delaney J, Dooley K, Dik J, van der Snickt G, Vandivere A, Janssens K, Science Advances 5, eaax1975 (2019). http://doi.org/10.1126/SCIADV.AAX1975
Abstract: Until the 19th century, lead white was the most important white pigment used in oil paintings. Lead white is typically composed of two crystalline lead carbonates: hydrocerussite [2PbCO(3)center dot Pb(OH)(2)] and cerussite (PbCO3). Depending on the ratio between hydrocerussite and cerussite, lead white can be classified into different subtypes, each with different optical properties. Current methods to investigate and differentiate between lead white subtypes involve invasive sampling on a microscopic scale, introducing problems of paint damage and representativeness. In this study, a 17th century painting Girl with a Pearl Earring (by Johannes Vermeer, c. 1665, collection of the Mauritshuis, NL) was analyzed with a recently developed mobile and noninvasive macroscopic x-ray powder diffraction (MA-XRPD) scanner within the project Girl in the Spotlight. Four different subtypes of lead white were identified using XRPD imaging at the macroscopic and microscopic scale, implying that Vermeer was highly discriminatory in his use of lead white.
Keywords: A1 Journal article; Engineering sciences. Technology; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation); Antwerp Cultural Heritage Sciences (ARCHES)
Times cited: 3
DOI: 10.1126/SCIADV.AAX1975
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“Synchroton X-ray powder diffraction study of lead white oxidation by sodium hypochloride”. Clerici EA, De Meyer S, van der Snickt G, Janssens K, , 13 (2017)
Keywords: P1 Proceeding; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
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“Non-invasive and non-destructive examination of artists’ pigments, paints and paintings by means of X-ray imaging methods”. Vanmeert F, De Meyer S, Gestels A, Clerici EA, Deleu N, Legrand S, Van Espen P, Van der Snickt G, Alfeld M, Dik J, Monico L, De Nolf W, Cotte M, Gonzalez V, Saverwyns S, Depuydt-Elbaum L, Janssens K page 317 (2022).
Abstract: Recent studies 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 fifteenth to twentieth century artists are discussed. 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 with X-ray diffraction (XRD). Microscopic XRF (μ-XRF) is a variant of the XRF method able to visualize the elemental distribution of key elements, mostly metals, on the scale from 1 μm to 100 μm present inside multi-layered micro samples taken from paintings. In the context of the characterization of artists’ pigments subjected to natural degradation, in many cases the use of methods limited to elemental analysis or imaging does not suffice to elucidate the chemical transformations that have taken place. However, at synchrotron facilities, combinations of μ-XRF with related methods such as μ-XAS (microscopic X-ray absorption spectroscopy) and μ-XRD have proven themselves to be very suitable for such studies. Since microscopic investigation of a relatively limited number of minute paint samples may not yield representative information about the complete artefact they were taken from, several methods for macroscopic, non-invasive imaging have recently been developed. Combined macroscopic XRF/XRD scanning is able to provide a fairly complete overview of the inorganic pigments employed to create a work of art, to answer questions about ongoing degradation phenomena and about its authenticity. As such these newly developed non-invasive and highly specific imaging methods are of interest for many cultural heritage stakeholders.
Keywords: H1 Book chapter; Art; Antwerp Cultural Heritage Sciences (ARCHES); Antwerp X-ray Imaging and Spectroscopy (AXIS)
DOI: 10.1007/978-3-030-86865-9_11
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“A mobile scanner for xrpd-imaging of paintings in transmission and reflection geometry”. De Meyer S, Vanmeert F, Janssens K, Storme P, ACTA ARTIS ACADEMICA 2017: PAINTING AS A STORY
T2 –, 6th Interdisciplinary ALMA Conference, JUN 01-03, 2017, Brno, CZECH REPUBLIC , 29 (2017)
Abstract: In this paper the possibilities and limitations of a non-invasive prototype of macroscopic X-ray powder diffraction scanning device employed in transmission and reflection mode are demonstrated. Contrarily to e.g. macroscopic X-ray fluorescence scanners, which gather information on the elemental level, the prototype instrument allows to obtain information on the crystallographic structure of the components. When applied to cultural heritage artefacts, it becomes possible to identify and localize crystalline pigments. Furthermore, it became clear that different information can be available depending on the geometry of the scanner components. In transmission mode information over the entire stratigraphy of the painting is gathered, which is useful to e.g. identify background substrates and major pigments. On the other hand, reflection-XRPD is a surface-sensitive technique and allows the identification of pigments and degradation products located on the surface. The data acquired during both experiments can be presented as two-dimensional distribution maps which show the spatial distribution of every identified pigment. The complementary nature of transmission and reflectionmode makes it possible to gain more insight into the stratigraphy of the painting which is valuable information for conservation and restoration scientists.
Keywords: P1 Proceeding; Art; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation); Antwerp Cultural Heritage Sciences (ARCHES)
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“Beauty is skin deep : the skin tones of Vermeer's Girl with a Pearl Earring”. van Loon A, Vandivere A, Delaney JK, Dooley KA, De Meyer S, Vanmeert F, Gonzalez V, Janssens K, Leonhardt E, Haswell R, de Groot S, D'Imporzano P, Davies GR, Heritage science 7, 102 (2019). http://doi.org/10.1186/S40494-019-0344-0
Abstract: The soft modelling of the skin tones in Vermeer's Girl with a Pearl Earring (Mauritshuis) has been remarked upon by art historians, and is their main argument to date this painting to c. 1665. This paper describes the materials and techniques Vermeer used to accomplish the smooth flesh tones and facial features of the Girl, which were investigated as part of the 2018 Girl in the Spotlight research project. It combines macroscopic X-ray fluorescence imaging (MA-XRF), reflectance imaging spectroscopy (RIS), and 3D digital microscopy. Vermeer built up the face, beginning with distinct areas of light and dark. He then smoothly blended the final layers to create almost seamless transitions. The combination of advanced imaging techniques highlighted that Vermeer built the soft contour around her face by leaving a 'gap' between the background and the skin. It also revealed details that were otherwise not visible with the naked eye, such as the eyelashes. Macroscopic imaging was complemented by the study of paint cross-sections using: light microscopy, SEM-EDX, FIB-STEM, synchrotron radiation mu-XRPD and FTIR-ATR. Vermeer intentionally used different qualities or grades of lead white in the flesh paints, showing different hydrocerussite/cerussite ratios and particle sizes. Lead isotope analysis showed that the geographic source of lead, from which the different types of lead white were manufactured, was the same: the region of Peak District of Derbyshire, UK. Finally, cross-section analysis identified the formation of new lead species in the paints: lead soaps and palmierite (K2Pb(SO4)(2)), associated with the red lake.
Keywords: A1 Journal article; Art; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
DOI: 10.1186/S40494-019-0344-0
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De Meyer S (2023) Macroscopic X-ray powder diffraction in reflection mode : a new technique for chemical imaging of artworks. 285 p
Abstract: Scientific research into cultural heritage has significantly grown in importance over the past decades. The growing popularity of macroscopic imaging techniques such as X-ray fluorescence or Fourier transform infrared now means that conservators and restorers have access to highly objective information on the chemical composition of a painting without the necessity for destructive sampling. As many works of art are heterogeneous on the macroscopic scale, it is clear that solely relying on microscopic samples does not provide sufficiently representative information on the condition of a painting and that macroscopic imaging techniques should be considered a crucial part of the analytical toolkit for conservation science. The goal of this research has been to investigate the added value of reflection-mode macroscopic X-ray powder diffraction (MA-XRPD) for scientific and art historical investigations of cultural heritage artefacts. A prototype scanner was developed after careful consideration of the individual components. This mobile instrument allows for the analysis of flat objects such as oil paintings with reflection MA-XRPD. In this manner images can be obtained that show the distribution of crystalline components present at the surface of the stratigraphy. These crystalline materials can originate from different sources and include original pigments and non-original pigments. MA-XRPD offers novel insights into original pigments such as ultramarine, copper sulfates and lead white. In Girl with a Pearl Earring by Vermeer the MA-XRPD instrument was used to prove that Vermeer used multiple subtypes of lead white to achieve subtle optical effects while in the painting The Night Watch by Rembrandt the lead white composition was studied in detail; multiple rare lead-based compounds were identified that could be linked to the usage of specific driers in the oil paint. By investigating the presence of degradation products, MA-XRPD can be used to assess the conservation state of an artwork. Secondary alteration products were identified in paintings by Nellius and Mignon, explaining why the paintings had visually deteriorated over time. MA-XRPD registered the presence of lead arsenates which were formed from the original yellow arsenic-based orpiment. By combining microscopic and macroscopic analysis, a chemical degradation pathway for the conversion of the unstable orpiment pigment was proposed. In this manner, MA-XRPD can also be used to provide highly valuable information for conservators and restorers by pinpointing areas that have undergone degradation and to guide sampling campaigns.
Keywords: Doctoral thesis; Engineering sciences. Technology; Art; Antwerp X-ray Imaging and Spectroscopy (AXIS)
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“A Roman Egyptian Painting Workshop : technical investigation of the portraits from Tebtunis, Egypt”. Salvant J, Williams J, Ganio M, Casadio F, Daher C, Sutherland K, Monico L, Vanmeert F, De Meyer S, Janssens K, Cartwright C, Walton M, Archaeometry 60, 815 (2018). http://doi.org/10.1111/ARCM.12351
Abstract: Roman-period mummy portraits are considered to be ancient antecedents of modern portraiture. However, the techniques and materials used in their manufacture are not thoroughly understood. Analytical study of the pigments as well as the binding materials helps to address questions on what aspects of the painting practices originate from Pharaonic and/or Graeco-Roman traditions, and can aid in determining the provenance of the raw materials from potential locations across the ancient Mediterranean and European worlds. Here, one of the largest assemblages of mummy portraits to remain intact since their excavation from the site of Tebtunis in Egypt was examined using multiple analytical techniques to address how they were made. The archaeological evidence suggests that these portraits were products of a single workshop and, correspondingly, they are found to be made using similar techniques and materials: wax-based and lead white-rich paint combined with a variety of iron-based pigments (including hematite, goethite and jarosite), as well as Egyptian blue, minium, indigo and madder lake to create subtle variations and tones.
Keywords: A1 Journal article; History; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Impact Factor: 1.47
Times cited: 6
DOI: 10.1111/ARCM.12351
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“Removal of a past varnish treatment from a 19th-century Belgian wall painting by means of a solvent-loaded double network hydrogel”. Al-Emam E, Beltran V, De Meyer S, Nuyts G, Wetemans V, De Wael K, Caen J, Janssens K, Polymers 13, 2651 (2021). http://doi.org/10.3390/POLYM13162651
Abstract: Polymeric materials have been used by painting conservator-restorers as consolidants and/or varnishes for wall paintings. The application of these materials is carried out when confronting loose paint layers or as a protective coating. However, these materials deteriorate and cause physiochemical alterations to the treated surface. In the past, the monumental neo-gothic wall painting 'The Last Judgment' in the chapel of Sint-Jan Berchmanscollege in Antwerp, Belgium was treated with a synthetic polymeric material. This varnish deteriorated significantly and turned brown, obscuring the paint layers. Given also that the varnish was applied to some parts of the wall painting and did not cover the entire surface, it was necessary to remove it in order to restore the original appearance of the wall painting. Previous attempts carried out by conservator-restorers made use of traditional cleaning methods, which led to damage of the fragile paint layers. Therefore, gel cleaning was proposed as a less invasive and more controllable method for gently softening and removing the varnish. The work started by identifying the paint stratigraphy and the deteriorated varnish via optical microscopy (OM), scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDX), X-ray diffraction (XRD), and Fourier-transform infrared (FTIR) spectroscopy. A polyvinyl alcohol-borax/agarose (PVA-B/AG) hydrogel loaded with a number of solvents/solvent mixtures was employed in a series of tests to select the most suitable hydrogel composite. By means of the hydrogel composite loaded with 10% propylene carbonate, it was possible to safely remove the brown varnish layer. The results were verified by visual examinations (under visible light 'VIS' and ultraviolet light 'UV') as well as OM and FTIR spectroscopy.
Keywords: A1 Journal article; Art; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation); Antwerp Cultural Heritage Sciences (ARCHES); Antwerp Electrochemical and Analytical Sciences Lab (A-Sense Lab); Antwerp X-ray Imaging and Spectroscopy (AXIS)
Impact Factor: 3.364
DOI: 10.3390/POLYM13162651
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“The darkening of copper- or lead-based pigments explained by a structural modification of natural orpiment : a spectroscopic and electrochemical study”. Vermeulen M, Sanyova J, Janssens K, Nuyts G, De Meyer S, De Wael K, Journal of analytical atomic spectrometry 32, 1331 (2017). http://doi.org/10.1039/C7JA00047B
Abstract: A combined Raman and electrochemical study of natural orpiment (As2S3), an arsenic sulfide pigment, was used to assess the quick formation of oxidized species such as arsenic oxide (As2O3) upon exposing the pigment to 405 nm or 532 nm monochromatic light while simultaneously recording the Raman spectra of the exposed sample. During this process, a distortion of the main band at 355 cm−1, associated with the stretching of the AsS3/2 pyramids of natural orpiment, was observed as well as an increased intensity of the 359 cm−1 band, corresponding to covalent AsAs bonds in natural orpiment. The distortion was accompanied by an overall decrease of the global Raman signal for natural orpiment, which could be explained by a loss in the crystal structure. The same phenomena were recorded in reference natural orpiment model paint samples stored for a long time together with verdigris (Cu(OH)2·(CH3COO)2·5H2O) and minium (Pb3O4) paints, the latter two appearing darkened on their sides closest to the orpiment sample as well as in several historical samples containing natural orpiment mixed with various blue pigments. By SEM-EDX and XRPD analysis, respectively on loose material and cast thin-sections of model paint samples, the darkening was identified as dark sulfide species such as chalcocite (Cu2S) and galena (PbS), suggesting the release of volatile sulfide or related species by the natural orpiment paint. XANES analyses of paint samples presenting AsAs bond increase indicated the presence of sulfur species most likely identified as organosulfur compounds formed upon the AsAs bond formation and explained the darkening of the Cu- and Pb-based pigments. To the best of our knowledge, this article reports for the first time the light-induced formation of AsAs bonds in natural orpiment used as an artists' pigment and objectively demonstrates the incompatibility between orpiment and (arsenic) sulfide-sensitive pigments.
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Impact Factor: 3.379
Times cited: 10
DOI: 10.1039/C7JA00047B
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“Development of a multi-method analytical approach based on the combination of synchrotron radiation X-ray micro-analytical techniques and vibrational micro-spectroscopy methods to unveil the causes and mechanism of darkening of “fake-gilded&rdquo, decorations in a Cimabue painting”. Monico L, Prati S, Sciutto G, Catelli E, Romani A, Balbas DQ, Li Z, De Meyer S, Nuyts G, Janssens K, Cotte M, Garrevoet J, Falkenberg G, Tardillo Suarez VI, Tucoulou R, Mazzeo R, Journal of analytical atomic spectrometry 37, 114 (2022). http://doi.org/10.1039/D1JA00271F
Abstract: Redox processes activated by environmental factors have been identified as the main cause of the chromatic alterations of a number of artists' pigments, including the yellow pigment orpiment (As2S3). Although a general comprehension of the mechanisms has been provided through characterization of degradation compounds of As2S3, experimental evidences to prove how other paint components and how different environmental agents influence the formation pathways of specific secondary compounds are still lacking. Thus, it becomes fundamental to develop a methodological strategy which enable achieving a discrimination among the causes affecting the chemical stability of more heterogenous As2S3-based paints and defining the mechanism through which the alteration establishes and evolves, with the ultimate goal of optimizing the preventive conservation measures of unique masterpieces. In this paper, we propose a comprehensive multi-material and multi-method approach based on the combination of synchrotron radiation X-ray micro-analytical techniques (i.e., X-ray diffraction, X-ray fluorescence and X-ray absorption near edge structure spectroscopy at S K-/Ag L-3-/As K-edges) and vibrational micro-spectroscopy methods to unveil the causes and mechanism of darkening of “fake-gilded” decorations in tempera paintings, originally consisting of an unusual mixture of As2S3 and metallic silver (Ag-0). Such degradation process is a not yet understood phenomenon threatening a series of Old Master paintings, including those by the Italian painters Cimabue and Pietro Lorenzetti. The high specificity, sensitivity and lateral resolution of the employed analytical methods allowed providing first-time evidence for the presence of black acanthite (alpha-Ag2S), mimetite [Pb-5(AsO4)(3)Cl] and syngenite [K2Ca(SO4)(2)center dot H2O] as degradation products of the “fake-gilded” decorations in the Maesta by Cimabue (Church of Santa Maria dei Servi, Bologna, Italy). Furthermore, the study of the painting combined with that of tempera paint mock-ups permitted to explore and define the environmental agents and internal factors causing the darkening, by proving that: (i) Ag-0 and moisture are key-factors for triggering the transformation of As2S3 to alpha-Ag2S and As-oxides; (ii) S2--ions arising from the degradation of As2S3 are the main responsible for the formation of alpha-Ag2S; (iii) light exposure strengthens the tendency of the paint components towards alteration. Based on our findings, we finally propose a degradation mechanism of As2S3/Ag-0-based tempera paints.
Keywords: A1 Journal article; Antwerp X-ray Imaging and Spectroscopy (AXIS)
Impact Factor: 3.4
DOI: 10.1039/D1JA00271F
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“Geranium lake pigments : the role of the synthesis on the structure and composition”. Beltran V, Marchetti A, De Meyer S, Nuyts G, De Wael K, Dyes And Pigments 189, 109260 (2021). http://doi.org/10.1016/J.DYEPIG.2021.109260
Abstract: Eosin Y has an extraordinary capacity to form complexes with metallic elements, that have applications in many different fields, from photovoltaics and photocatalysis to historical artists? pigments. To unravel the complexes reactivity, it is essential to have a precise knowledge of their structure and composition, as well as how these can be affected by the synthesis protocol, an often underestimated factor. This manuscript presents a thorough investigation of the structure and composition of eosin Y complexes based on Al and Pb, by FTIR, XRPD and Raman spectroscopy, with a particular focus on the effect of the synthesis conditions. Results clearly show the change of the coordination mode in Pb complexes depending on the protocol, while the structure of Al complexes remains stable. In both cases, the formation of by-products was observed. Additionally, a detailed band assignment of the FTIR and Raman spectra of eosin Y and Pb and Al complexes is described, providing interesting details such as the interaction between the metallic ion and the xanthene moiety (chromophore). This is extremely important for the analysis of historical paintings where eosin Y is bonded to metallic ions, as well as for other materials in dye-sensitized solar cells, wastewater treatment or photocatalysis.
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Impact Factor: 3.473
DOI: 10.1016/J.DYEPIG.2021.109260
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“Multi-scale X-ray imaging of the pigment discoloration processes triggered by chlorine compounds in the Upper Basilica of Saint Francis of Assisi”. Avranovich Clerici E, De Meyer S, Vanmeert F, Legrand S, Monico L, Miliani C, Janssens K, Molecules: a journal of synthetic chemistry and natural product chemistry 28, 6106 (2023). http://doi.org/10.3390/MOLECULES28166106
Abstract: 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 (2PbCO(3)center dot 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 (21PbCl(2)center dot 20Cu(OH) (2) center dot 6H(2)O).
Keywords: A1 Journal article; Antwerp X-ray Imaging and Spectroscopy (AXIS)
Impact Factor: 4.6
DOI: 10.3390/MOLECULES28166106
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“Role of the relative humidity and the Cd/Zn stoichiometry in the photooxidation process of cadmium yellows (CdS/Cd1-xZnxS) in oil paintings”. Monico L, Chieli A, De Meyer S, Cotte M, de Nolf W, Falkenberg G, Janssens K, Romani A, Miliani C, Chemistry: a European journal 24, 11584 (2018). http://doi.org/10.1002/CHEM.201801503
Abstract: 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 center dot nH(2)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/Cd0.76Zn0.24S) 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) Cd0.76Zn0.24S is more susceptible to photooxidation than CdS; both compounds can act as photocatalysts for the oil oxidation. 2) The photooxidation of CdS/Cd0.76Zn0.24S to CdSO4 center dot nH(2)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.
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Impact Factor: 5.317
Times cited: 5
DOI: 10.1002/CHEM.201801503
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“Macroscopic X-ray powder diffraction scanning, a new method for highly selective chemical imaging of works of art : instrument optimization”. Vanmeert F, de Nolf W, De Meyer S, Dik J, Janssens K, Analytical chemistry 90, 6436 (2018). http://doi.org/10.1021/ACS.ANALCHEM.8B00240
Abstract: 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.
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Impact Factor: 6.32
Times cited: 11
DOI: 10.1021/ACS.ANALCHEM.8B00240
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“Unraveling the Role of Lattice Substitutions on the Stabilization of the Intrinsically Unstable Pb2Sb2O7Pyrochlore: Explaining the Lightfastness of Lead Pyroantimonate Artists&rsquo, Pigments”. Marchetti A, Saniz R, Krishnan D, Rabbachin L, Nuyts G, De Meyer S, Verbeeck J, Janssens K, Pelosi C, Lamoen D, Partoens B, De Wael K, Chemistry Of Materials 32, 2863 (2020). http://doi.org/10.1021/acs.chemmater.9b04821
Abstract: The pyroantimonate pigments Naples yellow and lead tin antimonate yellow are recognized as some of the most stable synthetic yellow pigments in the history of art. However, this exceptional lightfastness is in contrast with experimental evidence suggesting that this class of mixed oxides is of semiconducting nature. In this study the electronic structure and light-induced behavior of the lead pyroantimonate pigments were determined by means of a combined multifaceted analytical and computational approach (photoelectrochemical measurements, UV-vis diffuse reflectance spectroscopy, STEM-EDS, STEM-HAADF, and density functional theory calculations). The results demonstrate both the semiconducting nature and the lightfastness of these pigments. Poor optical absorption and minority carrier mobility are the main properties responsible for the observed stability. In addition, novel fundamental insights into the role played by Na atoms in the stabilization of the otherwise intrinsically unstable Pb2Sb2O7 pyrochlore were obtained.
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation); Electron microscopy for materials research (EMAT); Condensed Matter Theory (CMT)
Impact Factor: 8.6
Times cited: 8
DOI: 10.1021/acs.chemmater.9b04821
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“A combined experimental and computational approach to understanding CdS pigment oxidation in a renowned early 20th century painting”. Mayda S, Monico L, Krishnan D, De Meyer S, Cotte M, Garrevoet J, Falkenberg G, Sandu ICA, Partoens B, Lamoen D, Romani A, Miliani C, Verbeeck J, Janssens K, Chemistry of materials 35, 10403 (2023). http://doi.org/10.1021/ACS.CHEMMATER.3C01470
Abstract: Cadmium sulfide (CdS)-based yellow pigments have been used in a number of early 20th century artworks, including The Scream series painted by Edvard Munch. Some of these unique paintings are threatened by the discoloration of these CdS-based yellow oil paints because of the oxidation of the original sulfides to sulfates. The experimental data obtained here prove that moisture and cadmium chloride compounds play a key role in promoting such oxidation. To clarify how these two factors effectively prompt the process, we studied the band alignment between CdS, CdCl2, and Cd-(OH)Cl as well as the radicals center dot OH and H3O center dot by density functional theory (DFT) methods. Our results show that a stack of several layers of Cd-(OH)Cl creates a pocket of positive holes at the Cl-terminated surface and a pocket of electrons at the OH-terminated surface by leading in a difference in ionization energy at both surfaces. The resulting band alignment indicates that Cd-(OH)Cl can indeed play the role of an oxidative catalyst for CdS in a moist environment, thus providing an explanation for the experimental evidence.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT); Condensed Matter Theory (CMT); Antwerp X-ray Imaging and Spectroscopy (AXIS)
Impact Factor: 8.6
DOI: 10.1021/ACS.CHEMMATER.3C01470
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“Insights into the composition of ancient Egyptian red and black inks on papyri achieved by synchrotron-based microanalyses”. Christiansen T, Cotte M, de Nolf W, Mouro E, Reyes-Herrera J, De Meyer S, Vanmeert F, Salvado N, Gonzalez V, Lindelof PE, Mortensen K, Ryholt K, Janssens K, Larsen S, Proceedings Of The National Academy Of Sciences Of The United States Of America 117, 27825 (2020). http://doi.org/10.1073/PNAS.2004534117
Abstract: 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 fluo-rescence (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, microXRF 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 [Pb-3(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.
Keywords: A1 Journal article; Engineering sciences. Technology; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Impact Factor: 11.1
DOI: 10.1073/PNAS.2004534117
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“Probing the chemistry of CdS paints in The Scream by in situ noninvasive spectroscopies and synchrotron radiation x-ray techniques”. Monico L, Cartechini L, Rosi F, Chieli A, Grazia C, De Meyer S, Nuyts G, Vanmeert F, Janssens K, Cotte M, De Nolf W, Falkenberg G, Sandu ICA, Tveit ES, Mass J, De Freitas RP, Romani A, Miliani C, Science Advances 6, eaay3514 (2020). http://doi.org/10.1126/SCIADV.AAY3514
Abstract: 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.
Keywords: A1 Journal article; Engineering sciences. Technology; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Impact Factor: 13.6
Times cited: 4
DOI: 10.1126/SCIADV.AAY3514
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“Novel optical photothermal infrared (O-PTIR) spectroscopy for the noninvasive characterization of heritage glass-metal objects”. Marchetti A, Beltran V, Nuyts G, Borondics F, De Meyer S, Van Bos M, Jaroszewicz J, Otten E, Debulpaep M, De Wael K, Science Advances 8, eabl6769 (2022). http://doi.org/10.1126/SCIADV.ABL6769
Abstract: Optical photothermal infrared (O-PTIR) is a recently developed molecular spectroscopy technique that allows to noninvasively obtain chemical information on organic and inorganic samples at a submicrometric scale. The high spatial resolution (approximate to 450 nm), lack of sample preparation, and comparability of the spectral results to traditional Fourier transform infrared spectroscopy make it a promising candidate for the analysis of cultural heritage. In this work, the potential of O-PTIR for the noninvasive characterization of small heritage objects (few cubic centimeters) is demonstrated on a series of degraded 16th century brass and glass decorative elements. These small and challenging samples, typically encountering limitations with existing noninvasive methods such as macroscopic x-ray powder diffraction and mu Raman, were successfully characterized by O-PTIR, ultimately identifying the markers of glass-induced metal corrosion processes. The results clearly demonstrate how O-PTIR can be easily implemented in a noninvasive multianalytical strategy for the study of heritage materials, making it a fundamental tool for cultural heritage analyses.
Keywords: A1 Journal article; Engineering sciences. Technology; Antwerp Electrochemical and Analytical Sciences Lab (A-Sense Lab); Antwerp X-ray Imaging and Spectroscopy (AXIS)
Impact Factor: 13.6
DOI: 10.1126/SCIADV.ABL6769
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“Reviving degraded colors of yellow flowers in 17th century still life paintings with macro- and microscale chemical imaging”. De Keyser N, Broers F, Vanmeert F, De Meyer S, Gabrieli F, Hermens E, van der Snickt G, Janssens K, Keune K, Science Advances 8, 1 (2022). http://doi.org/10.1126/SCIADV.ABN6344
Abstract: 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.
Keywords: A1 Journal article; Engineering sciences. Technology; Art; Antwerp Cultural Heritage Sciences (ARCHES); Antwerp X-ray Imaging and Spectroscopy (AXIS)
Impact Factor: 13.6
DOI: 10.1126/SCIADV.ABN6344
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“Lead(II) formate in Rembrandt's Night Watch : detection and distribution from the macro- to the micro-scale”. Gonzalez V, Fazlic I, Cotte M, Vanmeert F, Gestels A, De Meyer S, Broers F, Hermans J, van Loon A, Janssens K, Noble P, Keune K, Angewandte Chemie: international edition in English , 1 (2023). http://doi.org/10.1002/ANIE.202216478
Abstract: 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 17(th) century recipes. Synchrotron radiation based micro-XRPD (SR-mu-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.
Keywords: A1 Journal article; Art; Antwerp X-ray Imaging and Spectroscopy (AXIS)
Impact Factor: 16.6
DOI: 10.1002/ANIE.202216478
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