Imaging and micro-invasive analyses of black stains on the passepartout of Codex Atlanticus Folio 843 by Leonardo da Vinci

: This paper accounts for the diagnostic campaign aimed at understanding the phenomenon of black stains appeared on the passepartout close to the margins of Folio 843 of Leonardo da Vinci's Codex Atlanticus. Previous studies excluded microbiological deterioration processes. The study is based on a multi-analytical approach, including non-invasive imaging measurements of the folio, micro-imaging and synchrotron spectroscopy investigations of passepartout fragments at different magnifications and spectral ranges. Photoluminescence hyperspectral and lifetime imaging highlighted that black stains are not composed of fluorescent materials. μATR-FTIR imaging of fragments from the passepartout revealed the presence of a mixture of starch and PVAc glues localized only in the stained areas close to the margin of the folio. FE-SEM observations showed that the dark stains are localized inside cavities formed among cellulose fibers, where an accumulation of inorganic roundish particles (∅100-200 nm in diameter size), composed of Hg and S, was detected. Finally, by employing synchrotron μXRF, μXANES and HR-XRD analyses it was possible to identify these particles as metacinnabar (β-HgS). Further research is needed to assess the chemical process leading to the metacinnabar formation in the controlled conservation condition of Leonardo's Codex

Changsha ware glaze color: Composition, nanostructure, and copper and iron speciation

The opacity/transparency, color, and production of designs in Changsha ware, a Tang dynasty Chinese stoneware renowned for its polychromy and pioneering high‐temperature red glaze, are studied by analyzing the composition, micro/nanostructure, and copper/iron speciation. The results shed new light on some of the most debated questions about Changsha ware. In particular, the role of glaze thickness, composition, and firing conditions on the coexistence of transparent and opaque glazes and of oxidized green and reduced red copper designs on the same object, and on the reason for the development of either green or turquoise colors. New data obtained by reproducing a copper red overglaze and underglaze painting with a similar glaze composition and thickness have provided new insights into the origin of the first high‐temperature copper reds and, in the absence of essential knowledge, their discontinuity. This study also contributes to the long debate regarding the use of overglaze versus underglaze painting techniques

The “Historical Materials BAG”: A new facilitated access to synchrotron X-ray diffraction analyses for cultural heritage materials at the European Synchrotron Radiation Facility

(This article belongs to the Special Issue Advances in Analytical Strategies to Study Cultural Heritage Samples)The European Synchrotron Radiation Facility (ESRF) has recently commissioned the new Extremely Brilliant Source (EBS). The gain in brightness as well as the continuous development of beamline instruments boosts the beamline performances, in particular in terms of accelerated data acquisition. This has motivated the development of new access modes as an alternative to standard proposals for access to beamtime, in particular via the “block allocation group” (BAG) mode. Here, we present the recently implemented “historical materials BAG”: a community proposal giving to 10 European institutes the opportunity for guaranteed beamtime at two X-ray powder diffraction (XRPD) beamlines—ID13, for 2D high lateral resolution XRPD mapping, and ID22 for high angular resolution XRPD bulk analyses—with a particular focus on applications to cultural heritage. The capabilities offered by these instruments, the specific hardware and software developments to facilitate and speed-up data acquisition and data processing are detailed, and the first results from this new access are illustrated with recent applications to pigments, paintings, ceramics and wood.The Historical materials BAG has been implemented with support from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 870313, Streamline, which also supports APC. L. H. is funded via the PANOSC project (European Union’s Horizon 2020 Research and Innovation programme under Grant Agreement No. 823852). I. F. is funded by a grant from the Marie Skłodowska-Curie COFUND Programme “InnovaXN” (contract number 847439 with the European Commission). The ESRF beamtime was granted through the peer-review BAG proposal HG-172 at ID13 and ID22 and in-house beamtime at ID21. The project on wood vessels received financial support from MINECO (Spain), Ref. PID2019-105823RB-I00. The project on cadmium red pigments was financially supported from the Horizon 2020 project IPERION-HS (H2020-INFRAIA-2019-1, GA No. 871034) and the Italian project AMIS (Dipartimenti di Eccellenza 2018–2022, funded by MIUR and Perugia University). V.G. has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 945298-ParisRegionFP. E.A.C. and K.J. would like to acknowledge the project Smart*Light funded by the Interreg V Flanders-Netherlands program with financial support from the European Regional Development Fund (ERDF) for funding in assessing the damage caused by X-rays to model paints. K.J. acknowledges FWO (Brussels) for financial support through grants G054719N and I001919N. F.V. and K.J. acknowledge BELSPO (Brussels) for funding of the FEDtWIN mandate Macro-Imaging. C.C. (Christelle Chauffeton) is grateful to the Fondation Bettencourt-Schueller and the Cité de la Céramique Sèvres-Limoges, France for founding her work in the frame of her PhD thesis. A part of this study has been funded by the Grant-in-Aid for Scientific Research [18700680], JSPS Grant-in-Aid for Young Scientists (B) from the Ministry of Education, Culture, Sports, Science and Technology of Japan.Peer ReviewedArticle signat per 28 autors/es: Marine Cotte, Victor Gonzalez, Frederik Vanmeert, Letizia Monico, Catherine Dejoie, Manfred Burghammer, Loïc Huder, Wout de Nolf, Stuart Fisher, Ida Fazlic, Christelle Chauffeton, Gilles Wallez, Núria Jiménez, Francesc Albert-Tortosa, Nati Salvadó, Elena Possenti, Chiara Colombo, Marta Ghirardello, Daniela Comelli, Ermanno Avranovich Clerici, Riccardo Vivani, Aldo Romani, Claudio Costantino, Koen Janssens, Yoko Taniguchi, Joanne McCarthy, Harald Reichert and Jean Susini.Postprint (published version

Unravelling the role of iron and manganese oxides in colouring Late Antique glass by micro-XANES and micro-XRF spectroscopies

This research aims to understand colouring technologies in 5th–7th centuries glass imported to Atlantic Britain by correlating the iron (Fe) and manganese (Mn) ratios and oxidation states with colour. Despite having a similar matrix chemical composition and concentrations of Fe and Mn oxides, these vessels display different colours (from green to yellow/amber, sometimes with purple streaks). Colour changes can be induced by controlling the reduction-oxidation reactions that occur during glass production, which are influenced by the raw materials, furnace and melt atmosphere, and recycling. To evaluate these parameters, reference glasses were prepared, following the composition of Late Antique archaeological glass recovered from Tintagel (UK) and Whithorn (UK). A corpus of archaeological and experimental glass samples was analysed using bulk Fe and Mn K-edge x-ray absorption near edge structure (XANES) spectroscopy, micro-XANES and micro x-ray fluorescence (μ-XRF) at beamline ID21, at the European Synchrotron Radiation Facility. Fe and Mn XANES spectra of the archaeological glass indicate that Fe and Mn are in a similar oxidation state in all the yellow samples, predominantly Fe3+ and Mn2+. No detectable difference in Mn and Fe oxidation state occurs in the purple streaks compared to the yellow glass bulk but μ-XRF maps of the distribution of Fe and Mn show that Mn is more concentrated in the purple streaks. This indicates that the purple colour of the streaks is mainly due to a higher Mn/Fe ratio and persistence of more oxidised manganese in the purple areas, even though it is difficult to detect. Many archaeological fragments appear pale green in transmitted light but amber in reflected light. XANES studies detected the presence of surface layers where manganese is more oxidised. This layer is believed to scatter transmitted and reflected light differently and might be responsible for the optical features of the archaeological glass

Synchrotron-based nu-XRF mapping and mu-FTIR microscopy enable to look into the fate and effects of tattoo pigments in human skin

The increasing prevalence of tattoos provoked safety concerns with respect to particle distribution and effects inside the human body. We used skin and lymphatic tissues from human corpses to address local biokinetics by means of synchrotron X-ray fluorescence (XRF) techniques at both the micro (mu) and nano (nu) scale. Additional advanced mass spectrometry-based methodology enabled to demonstrate simultaneous transport of organic pigments, heavy metals and titanium dioxide from skin to regional lymph nodes. Among these compounds, organic pigments displayed the broadest size range with smallest species preferentially reaching the lymph nodes. Using synchrotron mu-FTIR analysis we were also able to detect ultrastructural changes of the tissue adjacent to tattoo particles through altered amide I alpha-helix to beta-sheet protein ratios and elevated lipid contents. Altogether we report strong evidence for both migration and long-term deposition of toxic elements and tattoo pigments as well as for conformational alterations of biomolecules that likely contribute to cutaneous inflammation and other adversities upon tattooing

Infrared Spectroscopy as a Tool to Study the Antioxidant Activity of Polyphenolic Compounds in Isolated Rat Enterocytes

The protective effect of different polyphenols, catechin (Cat), quercetin (Qc) (flavonoids), gallic acid (GA), caffeic acid (CfA), chlorogenic acid (ChA) (phenolic acids), and capsaicin (Cap), against H2O2-induced oxidative stress was evaluated in rat enterocytes using Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) Spectroscopy and Fourier Transform Infrared Microspectroscopy (FTIRM), and results were compared to standard lipid peroxidation techniques: conjugated dienes (CD) and Thiobarbituric Acid Reactive Substances (TBARS). Analysis of ATR-FTIR and FTIRM spectral data allowed the simultaneous evaluation of the effects of H2O2 and polyphenols on lipid and protein oxidation. All polyphenols showed a protective effect against H2O2-induced oxidative stress in enterocytes, when administered before or after H2O2. Cat and capsaicin showed the highest protective effect, while phenolic acids had weaker effects and Qc presented a mild prooxidative effect (IR spectral profile of biomolecules between control and H2O2-treated cells) according to FTIR analyses. These results demonstrated the viability to use infrared spectroscopy to evaluate the oxidant and antioxidant effect of molecules in cell systems assays

Probing the chemistry of CdS paints in The Scream by in situ noninvasive spectroscopies and synchrotron radiation x-ray techniques

The degradation of cadmium sulfide (CdS)-based oil paints is a phenomenon potentially threatening the iconic painting The Scream (ca. 1910) by Edvard Munch (Munch Museum, Oslo) that is still poorly understood. Here, we provide evidence for the presence of cadmium sulfate and sulfites as alteration products of the original CdS-based paint and explore the external circumstances and internal factors causing this transformation. Macroscale in situ noninvasive spectroscopy studies of the painting in combination with synchrotron-radiation x-ray microspectroscopy investigations of a microsample and artificially aged mock-ups show that moisture and mobile chlorine compounds are key factors for promoting the oxidation of CdS, while light (photodegradation) plays a less important role. Furthermore, under exposure to humidity, parallel/secondary reactions involving dissolution, migration through the paint, and recrystallization of water-soluble phases of the paint are associated with the formation of cadmium sulfates