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“2θ-resolution obtainable during – XRPD experiments at Beamline L”. de Nolf W, Jaroszewicz J, Janssens K, Falkenberg G page 1655 (2008).
Keywords: H3 Book chapter; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
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“Assessing the origin and fate of Cr, Ni, Cu, Zn, Pb, and V in an industrial polluted soil by combined micro-spectroscopic techniques and bulk extraction methods”. Terzano R, Spagnuolo M, Vekemans B, de Nolf W, Janssens K, Falkenberg G, Fiore S, Ruggiero P (2008).
Keywords: H3 Book chapter; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
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“Characterization of Yenisey River U-particles using a combination of μ-XRF, μ-XRD and U-LIII μ-XANES”. Lind OC, Claussen-Kjerre L, de Nolf W, Falkenberg G, Jaroszewicz J, Janssens K, Salbu B page 1279 (2008).
Keywords: H3 Book chapter; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
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“Combined use of μ-XRF and μ-XRD for characterization of radioactive particle clusters released during the Chernobyl reactor incident”. Jaroszewicz J, de Nolf W, Janssens K, Claussen-Kjerre L, Lind OC, Salbu B, Falkenberg G (2007).
Keywords: H3 Book chapter; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
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“Combined use of μ-XRF and μ-XRD to determine the heterogeneity, the chemical and phase composition of Ti-B-C ceramics prepared by the pulse plasma sintering (PPS) method”. Jaroszewicz J, de Nolf W, Janssens K, Michalski A, Falkenberg G (2007).
Keywords: H3 Book chapter; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
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“Confocal μ-XRF and μ-XAFS studies of fractured granite following a radiotracer migration experiment”. Denecke MA, Janssens K, Brendebach B, Falkenberg G, de Nolf W, Römer J (2007).
Keywords: H3 Book chapter; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
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“Confocal μ-XRF and μ-XAFS studies on fractured granite following a radiotracer migration experiment”. Denecke MA, Janssens K, Brendebach B, Falkenberg G, Römer J, Simon R, Vekemans B, (2007)
Keywords: P3 Proceeding; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
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“Depth profiling of multilayered systems by means of confocal μ-XRF in the laboratory an at HASYLAB BL L: a comparison”. Alfeld M, Vekemans B, Janssens K, Falkenberg G, Broekaert JAC, Gao N, Gibson D (2007).
Keywords: H3 Book chapter; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
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“Feasibility of (trace-level) micro-XANES at Beamline L”. Janssens K, Vincze L, Wei F, Proost K, Vekemans B, Vittiglio G, Yan Y, Falkenberg G (1999).
Keywords: H3 Book chapter; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
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“High-E scanning m-XRF experiment on test paintings”. Dik J, Janssens K, van der Snickt G, Wallert A, Rickers K, Falkenberg G page 1589 (2008).
Keywords: H3 Book chapter; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
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“Identification of the geochemical forms of CR, Zn, Ni, Pb, V, and Cu in an industrial polluted soil by combined μ-XRF/μ-XRD and μ-XANES”. Terzano R, Spagnuolo M, Ruggiero P, Vekemans B, de Nolf W, Janssens K, Fiore S, Falkenberg G (2008).
Keywords: H3 Book chapter; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
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“Micro-XANES determination of ferric iron and its application in thermobarometry”. Schmid R, Wilke M, Ober R, Dong S, Janssens K, Falkenberg G, Franz L, Gaab A, Lithos 70, 381 (2003). http://doi.org/10.1016/S0024-4937(03)00107-5
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
DOI: 10.1016/S0024-4937(03)00107-5
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“Pigment identification by scanning μ-XRF/μ-XRD”. de Nolf W, Vekemans B, Janssens K, van der Snickt G, Falkenberg G (2007).
Keywords: H3 Book chapter; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
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“Quantitative Fe determination inside tomato roots by confocal μ-XRF”. Terzano R, Spagnuolo M, Ruggiero P, Vekemans B, Scoonjans T, Vincze L, Janssens K, Tomasi N, Cesco S, Falkenberg G page 1513 (2008).
Keywords: H3 Book chapter; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
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“Reexamination of U and Pu in particles from Thule and Palomares by μ-XRD”. Lind O-C, Salbu B, de Nolf W, Jaroszewicz J, Janssens K, Falkenberg G page 1297 (2008).
Keywords: H3 Book chapter; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
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“Study of the degradation on historical documents induced by iron gall ink by means of scanning μ-XRF/μ-XRD”. de Nolf W, Janssens K, Rouchon V, Falkenberg G (2007).
Keywords: H3 Book chapter; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
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“Trace-level micro-XANES by means of bending magnets radiation focused with a polycapillary lens”. Vincze L, Janssens K, Wei F, Proost K, Vekemans B, Vittiglio G, Yan Y, Falkenberg G (1999).
Keywords: H3 Book chapter; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
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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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“Synchrotron XRF analysis identifies cerium accumulation colocalized with pharyngeal deformities in CeO₂, NP-exposed caenorhabditis elegans”. Rossbach LM, Brede DA, Nuyts G, Cagno S, Olsson RMS, Oughton DH, Falkenberg G, Janssens K, Lind OC, Environmental science and technology 56, 5081 (2022). http://doi.org/10.1021/ACS.EST.1C08509
Abstract: A combination of synchrotron radiation-based elementalimaging, in vivo redox status analysis, histology, and toxic responses was usedto investigate the uptake, biodistribution, and adverse effects of Cenanoparticles (CeO2NP; 10 nm; 0.5-34.96 mg Ce L-1) or Ce(NO3)3(2.3-26 mg Ce L-1)inCaenorhabditis elegans. Elemental mapping of theexposed nematodes revealed Ce uptake in the alimentary canal prior todepuration. Retention of CeO2NPs was low compared to that of Ce(NO3)3in depurated individuals. X-rayfluorescence (XRF) mapping showed that Cetranslocation was confined to the pharyngeal valve and foregut. Ce(NO3)3exposure significantly decreased growth, fertility, and reproduction, causedslightly reduced fecundity. XRF mapping and histological analysis revealedsevere tissue deformities colocalized with retained Ce surrounding thepharyngeal valve. Both forms of Ce activated the sod-1 antioxidant defense,particularly in the pharynx, whereas no significant effects on the cellular redox balance were identified. The CeO2NP-induceddeformities did not appear to impair the pharyngeal function or feeding ability as growth effects were restricted to Ce(NO3)3exposure. The results demonstrate the utility of integrated submicron-resolution SR-based XRF elemental mapping of tissue-specificdistribution and adverse effect analysis to obtain robust toxicological evaluations of metal-containing contaminants.
Keywords: A1 Journal article; Antwerp X-ray Imaging and Spectroscopy (AXIS)
Impact Factor: 11.4
DOI: 10.1021/ACS.EST.1C08509
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“Comparison of sediment pollution in the rivers of the Hungarian Upper Tisza Region using non-destructive analytical techniques”. Osán J, Török S, Alföldy B, Alsecz A, Falkenberg G, Baik SY, Van Grieken R, Spectrochimica acta: part B : atomic spectroscopy 62, 123 (2007). http://doi.org/10.1016/J.SAB.2007.02.005
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
DOI: 10.1016/J.SAB.2007.02.005
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“Damages induced by synchrotron radiation-based X-ray microanalysis in chrome yellow paints and related Cr-compounds : assessment, quantification, and mitigation strategies”. Monico L, Cotte M, Vanmeert F, Amidani L, Janssens K, Nuyts G, Garrevoet J, Falkenberg G, Glatzel P, Romani A, Miliani C, Analytical Chemistry 92, 14164 (2020). http://doi.org/10.1021/ACS.ANALCHEM.0C03251
Abstract: 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-K-beta 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.
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Impact Factor: 7.4
DOI: 10.1021/ACS.ANALCHEM.0C03251
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“Examination of Vincent van Gogh's paintings and pigments by means of state-of-the-art analytical methods”. Janssens K, Alfeld M, Van der Snickt G, De Nolf W, Vanmeert F, Monico L, Legrand S, Dik J, Cotte M, Falkenberg G, van der Loeff L, Leeuwestein M, Hendriks E page 373 (2014).
Abstract: Recent studies in which X-ray beams of macroscopic to (sub) microscopic dimensions were used for non-destructive analysis and characterization of pigments, paint micro samples and/or entire paintings by Vincent van Gogh are concisely reviewed. 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 and macroscopic XRF are variants of the method that are well suited to visualize the elemental distribution of key elements, mostly metals, present in paint multi layers, either on the length scale from 1–100 μm inside micro samples taken from paintings or on the 1–100 cm length scale when the (subsurface) distribution of specific pigments in entire paintings is concerned. In the context of the characterization of van Gogh's pigments subject 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 (μ-FTIR) spectroscopy since this method delivers complementary information at more or less the same length scale as the X-ray microprobe techniques. Also in the context of macroscopic imaging of works of art, the complementary use of X-ray based and infra-red based imaging appears very promising; some recent developments are discussed.
Keywords: H2 Book chapter; Art; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
DOI: 10.1039/9781839161957-00373
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“Three-dimensional trace element analysis by confocal X-ray microfluorescence imaging”. Vincze L, Vekemans B, Brenker FE, Falkenberg G, Rickers K, Somogyi A, Kersten M, Adams F, Analytical chemistry 76, 6786 (2004). http://doi.org/10.1021/AC049274L
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
DOI: 10.1021/AC049274L
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“X-ray fluorescence microtomography and polycapillary based confocal imaging using synchrotron radiation”. Vincze L, Vekemans B, Szaloki I, Brenker FE, Falkenberg G, Rickers K, Aerts K, Van Grieken R, Adams F, , 220 (2004). http://doi.org/10.1117/12.560416
Abstract: Ibis work illustrates the development of X-ray fluorescence tomography and polycapillary based confocal imaging towards a three-dimensional (313), quantitative analytical method with lateral resolution levels down to the 2-20 mum scale. Detailed analytical characterization is given for polycapillary based confocal XRF imaging, which is a new variant of the 3D micro-XRF technique. Applications for 2D/3D micro-XR-F are illustrated for the analysis of biological (zooplankton) and geological samples (microscopic inclusions in natural diamonds and fluid inclusions in quartz). Based on confocal imaging, fully three-dimensional distributions of trace elements could be obtained, representing a significant generalization of the regular 2D scanning technique for micro-XRF spectroscopy. The experimental work described in this paper has been carried out at the ESRF ID18F microfluorescence end-station and at HASYLAB Beam Line L.
Keywords: P1 Proceeding; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
DOI: 10.1117/12.560416
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“Confocal mu-XRF, mu-XAFS, and mu-XRD studies of sediment from a nuclear waste disposal natural analogue site and fractured granite following a radiotracer migration experiment”. Denecke MA, Janssens K, Brendebach B, de Nolf W, Falkenberg G, Rothe J, Simon R, Somogyi A, Vekemans B, Noseck U, AIP conference proceedings 882, 187 (2007)
Abstract: Combined mu-XRF, mu-XAFS, and mu-XRD investigations of a uranium-rich tertiary sediment, from a nuclear repository natural analogue site, and a fractured granite bore core section after a column tracer experiment using a Np(V) containing cocktail have been performed. Most mu-XRF/mu-XAFS measurements are recorded in a confocal geometry to provide added depth information. The U-rich sediment results show uranium to be present as a tetravalent phosphate and that U(IV) is associated with As(V). Arsenic present is either As(V) or As(0). The As(0) form thin coatings on the surface of pyrite nodules. A hypothesis for the mechanism of uranium immobilization is proposed, where arsenopyrite acted as reductant of ground water dissolved U(VI) leading to precipitation of less soluble U(IV) and thereby forming As(V). Results for the granite sample show the immobilized Np to be tetravalent and associated with facture material.
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
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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)
DOI: 10.1021/ACS.CHEMMATER.3C01470
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“High resolution micro-XRF maps of iron oxides inside sensory dendrites of putative avian magnetoreceptors”. Falkenberg G, Fleissner GE, Fleissner GUE, Schuchardt K, Kühbacher M, Chalmin E, Janssens K, Journal of physics : conference series 186, 012084 (2009). http://doi.org/10.1088/1742-6596/186/1/012084
Abstract: Iron mineral containing sensory dendrites in the inner lining of the upper beak of homing pigeons [1] and various bird species [2] are the first candidate structures for an avian magnetic field receptor. A new concept of magnetoreception [3, 4] is based on detailed ultra-structural optical and electron microscopy analyses in combination with synchrotron radiation microscopic X-ray fluorescence analysis (micro-XRF) and microscopic X-ray absorption near edge structures (micro-XANES). Several behavioral experiments [5, 6] and first mathematical simulations [6] affirm our avian magnetoreceptor model. The iron minerals inside the dendrites are housed in three different subcellular compartments (bullets, platelets, vesicles), which could be clearly resolved and identified by electron microscopy on ultrathin sections [1, 3]. Micro-XRF and micro-XANES data obtained at HASYLAB beamline L added information about the elemental distribution and Fe speciation [3], but are averaged over the complete dendrite due to limited spatial resolution. Here we present recently performed micro-XRF maps with sub-micrometer resolution (ESRF ID21), which reveal for the first time subcellular structural information from almost bulk-like dendrite sample material. Due to the thickness of 30 μm the microarchitecture of the dendrites can be considered as undisturbed and artefacts introduced by sectioning might be widely reduced.
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Times cited: 2
DOI: 10.1088/1742-6596/186/1/012084
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“Recent advances in analysis of trace elements in environmental samples by X-ray based techniques (IUPAC Technical Report)”. Terzano R, Denecke MA, Falkenberg G, Miller B, Paterson D, Janssens K, Pure and applied chemistry 91, 1029 (2019). http://doi.org/10.1515/PAC-2018-0605
Abstract: Trace elements analysis is a fundamental challenge in environmental sciences. Scientists measure trace elements in environmental media in order to assess the quality and safety of ecosystems and to quantify the burden of anthropogenic pollution. Among the available analytical techniques, X-ray based methods are particularly powerful, as they can quantify trace elements in situ. Chemical extraction is not required, as is the case for many other analytical techniques. In the last few years, the potential for X-ray techniques to be applied in the environmental sciences has dramatically increased due to developments in laboratory instruments and synchrotron radiation facilities with improved sensitivity and spatial resolution. In this report, we summarize the principles of the X-ray based analytical techniques most frequently employed to study trace elements in environmental samples. We report on the most recent developments in laboratory and synchrotron techniques, as well as advances in instrumentation, with a special attention on X-ray sources, detectors, and optics. Lastly, we inform readers on recent applications of X-ray based analysis to different environmental matrices, such as soil, sediments, waters, wastes, living organisms, geological samples, and atmospheric particulate, and we report examples of sample preparation.
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Impact Factor: 2.626
Times cited: 3
DOI: 10.1515/PAC-2018-0605
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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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“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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