Elena Possenti

Synchrotron radiation micro X-ray diffraction–micro X-ray fluorescence (SR μXRF–μXRF) mapping explores the interaction of ammonium oxalate (AmOx) conservation treatment with the Mg-containing decayed matrix of cultural heritage fresco.

This study focuses on assessing the indoor air quality in a storage room (SR) belonging to Museo Nazionale Scienza e Tecnologia Leonardo da Vinci in Milan (MUST), covering pollutants originating from outdoor sources and emissions from historical plastic objects made from cellulose acetate (CA), cellulose nitrate (CN), and urea–formaldehyde (UF) stored in metal cabinets. The concentrations of SO₂ (sulphur dioxide), NO₂ (nitrogen dioxide), NOx (nitrogen oxides), HONO (nitrous acid), HNO₃ (nitric acid), O₃ (ozone), NH₃ (ammonia), CH₃COOH (acetic acid), and HCOOH (formic acid) were determined. The concentrations of SO₂, O₃, and NOx measured inside the metal cabinets were consistently lower compared to the other sampling sites. This result was expected due to their reactivity and the lack of internal sources. The SR and metal cabinets showed similar concentrations of NO and NO₂, except for CA, where a high NO concentration was detected. The interaction between the CA surfaces and NO₂ altered the distribution of NO and NO₂, leading to a significant increase in NO. The presence of HNO₃ potentially led to the formation of ammonium nitrate, as confirmed by ER-FTIR measurements. High levels of HONO and HNO₃ in CN and NH₃ in the UF indicate object deterioration, while elevated concentrations of CH₃COOH in CA and HCOOH in the SR suggest specific degradation pathways for cellulose acetate and other organic materials, respectively. These results could direct conservators towards the most appropriate practical actions.

In cultural heritage, paint stratigraphies are complex systems typically consisting of various paint layers with fine crystalline phases mixed with coarse pigment and filler grains. This complexity poses significant challenges for X-ray diffraction (XRD) analysis. In this work, we employed synchrotron radiation micro-X-ray diffraction in transmission geometry (SR-µTXRD) with linear mapping to develop a novel approach for studying the crystalline phases (pigments and fillers) in mock-up paint stratigraphies. A targeted approach was followed for qualitative, quantitative, and microstructural analysis, combining signals from micrometric crystallites and coarse single crystals as well as from randomly oriented and iso-oriented crystalline phases. This allows for identifying, localizing, and quantifying these phases even in low fractions and distinguishes the same phases across different layers with varying grain sizes or spatial orientations. Critical analysis of 2D XRD patterns, coupled with full-profile fitting performed by the Rietveld method, provides insights into material preparation (e.g., grinding), painting technique (e.g., color palette, use of fillers, brushing), and crystallo-chemical modifications over time. This analytical approach, integrating spatially resolved investigation with high-quality phase characterization, enhances the potential of specific XRD methodologies for a 2D investigation of multi-phase materials in cultural heritage, even without dedicated micro-mapping techniques.

SR X-ray diffraction computed tomography (XRDCT) was used to non-destructively analyse the effects of sequential inorganic-mineral re-treatments on decayed cultural heritage carbonatic stones. It offers new analytical perspectives for conservation science.

This study is aimed at investigating crystals (calcium and magnesium phosphates) formed due the interaction of an inorganic conservation treatment (diammonium hydrogen phosphate—DAP) with carbonatic (calcitic and dolomitic) stones through micro-Raman Spectroscopy. The addressed questions concern (i) the identification of magnesium and calcium phosphate minerals crystallized within dolomitic stone samples with a different degree of conservation state and treated with two different DAP solution molarities and (ii) the distinction of complex calcium phosphate mixtures (hydroxyapatite—HAP and octa calcium phosphate—OCP) crystallized within a calcarenite stone treated with DAP. A statistically relevant number of Raman spectra have been acquired in sample cross sections and curve fitting analysis has been performed for the in-depth interpretation of data. The outcomes indicate that Raman Spectroscopy is an effective alternative method for the identification of poorly crystalline calcium phosphates (not easily detectable with X-ray diffraction), even when scarcely present in mixture with magnesium phosphates. Evidence of the Raman analytical capability and high potential to distinguish HAP and OCP in calcitic stones are also presented and discussed.

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.