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Archaeological pottery are the most numerous objects found during excavations and reflect the culinary practices of the past. However, their functionality for cooking/storing specific foods or drinks cannot be deduced solely from comparing their shapes and sizes. Analysis of protein residues bound to ceramics can reveal the protein/animal type through their amino acid sequence, thus enabling direct identification of food types. Therefore, the aim of our experimental study was to test sixteen aptamers for the analysis of proteinaceous organic residues found within the porous structure of pottery. Traditionally prepared archaeological ceramic replicas were cooked for 5 days in various food/protein suspensions, were UV aged, buried for a year, excavated, and extensively cleaned. Their shards were analysed using immunofluorescence microscopy with aptamers. Results show that eight aptamers (Clone1 and Kirby for egg residuals; seqU5 and BLG14 for milk residuals; HA for blood residuals; Gli4 for gluten residuals; Par1 for fish residuals; and D1 for collagen residuals) produced a successful/specific immunofluorescence microscopy result when they were hybridised to shards containing target protein residuals. Interestingly, on whole egg control samples, when the egg lysozyme-targeting aptamer Kirby was used, fluorescence intensity was 3.1 times greater compared to that observed with anti-ovalbumin antibodies.

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Nantokite (CuCl) locked inside subsurface micro-pits has been recognised as the driving force to the form of corrosion called bronze disease. The use of the traditional corrosion inhibitor benzotriazole is questioned because of toxicity. So there is a need for alternative conservation treatments. This work is focused on the experimental design to test the effectiveness of sodium oxalate followed by treatment with limewater to face bronze disease on outdoor bronzes. A number of foundry bronze coupons were exposed to weathering at Genoa Experimental Marine Station (GEMS) exposure site and sprayed twice a week with a 5% NaCl solution for the first 124 days. After 562 days of natural weathering, the patinas on coupons were characterised with non-destructive techniques (NDT) and the presence of nantokite was verified. We designed a workflow, as similar as possible to conservation treatments on real artworks, to test a 3% w/v sodium oxalate treatment with two different application times, with or without limewater, on the coupons. The effectiveness of the treatments was analysed by comparison of surface properties by several NDT measurements. A statistical approach and XRD measurements directly on the corroded bronze surfaces are suggested as an effective way to characterise and compare the overall behaviour of bronze disease treatments for conservation.

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In the field of engineering, surface metrology is a valuable tool codified by international standards that enables the quantitative study of small-scale surface features. However, it is not recognized as a resource in the field of cultural heritage. Motivated by this fact, in this work, we demonstrate the use and the usefulness of surface metrology based on scanning conoscopic holography for monitoring treatments on the Venetian masterpiece by Tintoretto St. Martial in Glory with the Saints Peter and Paul. We carried out in situ and in-process monitoring of the painting microtexture during an experimental, innovative laser-chemical treatment, and we performed a statistical analysis based on ISO areal field parameters. A wide and in-band roughness analysis through the complementary use of amplitude, spatial, and hybrid parameters confirmed the noninvasive nature of the whole treatment on the painting surface topography, giving us the chance to review and critically discuss the use of these parameters in a real case in heritage science.

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Analytical data of Roman and early Islamic glass established several primary glass production groups linked to glassmaking centres in the Levant and in Egypt. In contrast, the activities of secondary glass workshops are largely invisible in the compositional fingerprint of first millennium glass. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) of 261 glass finds from the Visigothic settlement of Tolmo de Minateda (Spain) revealed a site-specific contamination pattern due to secondary glass processing and recycling, namely the enrichment of the glass batch by a unique combination of rare alkali elements (Li, K, Rb, Cs). With a median of 21 ppm, Li is particularly distinctive. Elevated lithium contents (Li>30 ppm) are also one of the characteristic features of Iberian plant ash glass from the Islamic period. The earliest known examples of this type of glass were found among the ninth-century remains from Tolmo.

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Raman spectroscopy (RS) is a powerful non-invasive tool for the characterization of materials. However, the fluorescence effect often hampers the detectability of the relatively weak vibrational Raman signal. Several approaches were exploited to overcome this limit. This work, in particular, evaluates the performance of an in situ portable sequentially shifted excitation (SSE™) Raman spectrometer applied to the examination of artistic historical pigment powders enclosed in glass vials. The explored handheld spectrometer employs a dual, temperature-shifted, 785 nm and 852 nm laser excitation to optimize both spectral coverage and fluorescence subtraction. The study demonstrates the feasibility of the SSE RS approach for non-invasive identification of art materials, and its applicability in complex situations where the examined material cannot be removed from its container. Laboratory measurements using benchtop dispersive micro-Raman spectroscopy at 785 nm are reported for comparison.

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SignificanceThe exploration of gold-based colorants in glass and glazes led Nobel Laureate Richard Zsigmondy to the study of colloids, and to the development, with Henry Siedentopf, of the earliest microscopes capable of resolving such small length scales. Zsigmondy's studies were preceded by alchemical investigations starting in the 17th century that yielded the gold-based Purple of Cassius, and experiments in the early 18th century resulting in an unusual purple iridescent porcelain overglaze, called Böttger luster, at the Meissen Manufactory. We discuss the first nano-scale characterization of Böttger luster, its successful replication, and propose an explanation for its optical properties based on the physics of scattering and interference of nanoparticle arrays.

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A rare and valuable Palaeolithic wooden point, presumably belonging to a hunting weapon, was found in the Ljubljanica River in Slovenia in 2008. In order to prevent complete decay, the waterlogged wooden artefact had to undergo conservation treatment, which usually involves some expected deformations of structure and shape. To investigate these changes, a series of surface-based 3D models of the artefact were created before, during and after the conservation process. Unfortunately, the surface-based 3D models were not sufficient to understand the internal processes inside the wooden artefact (cracks, cavities, fractures). Since some of the surface-based 3D models were taken with a microtomographic scanner, we decided to create a volumetric 3D model from the available 2D tomographic images. In order to have complete control and greater flexibility in creating the volumetric 3D model than is the case with commercial software, we decided to implement our own algorithm. In fact, two algorithms were implemented for the construction of surface-based 3D models and for the construction of volumetric 3D models, using (1) unsegmented 2D images CT and (2) segmented 2D images CT. The results were positive in comparison with commercial software and new information was obtained about the actual state and causes of the deformation of the artefact. Such models could be a valuable aid in the selection of appropriate conservation and restoration methods and techniques in cultural heritage research.

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The present research exploits the strengths of external reflection FT-IR spectroscopy to non-invasively study heritage plastic objects through inspection, for the first time, of the wide spectral range including the near- and mid-IR (12500-350 cm-1). Unlike most of previous works on historical plastic objects, reflection-mode spectra were not corrected for the unfamiliar surface reflection profiles to the more recognizable absorption-like band shapes. This avoided data misinterpretation due to ill-suited Kramers Krönig correction when volume reflection is also present or when highly absorbing IR compounds generate Reststrahlen bands. The inspection of the enlarged spectral range allowed the detection of fundamental, combination and overtone bands which provided reliable identification and semi-quantitative characterization of different polystyrene-based co-polymers. Furthermore the variation of the plastic optical properties across the explored spectral range allowed us to sample the plastic materials to different depths in the mid- and near-IR regions, so as to probe the chemistry at the surface and in the plastic bulk, respectively, in a non-invasive manner. This proved particularly useful to observe spectral markers of surface degradation occurring in historical ABS-based polymers.

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We discuss a synchronised sensing technique for the analysis of painted surfaces of frescos. Specifically, the performance of Visible-Near Infrared (VIS-NIR) Reflectance Imaging Spectroscopy (RIS) synchronized with three-dimensional (3D) acquisition is demonstrated in the study of a detached mural painting by Alessandro Botticelli. Synchronized sensing generates georeferenced data for simplified data treatment and interpretation. We show how such output data can provide key information to interpret important fresco surface and subsurface features (e.g., painting technique, material composition, pentimenti).

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Determining the nature, evolution, and impact of acid-generating sulfur deposits in the Mary Rose wooden hull is crucial for protecting Henry VIII's famous warship for generations to come. Here, a comprehensive X-ray absorption near-edge spectroscopy (XANES) and X-ray fluorescence (XRF) study sheds vital light on the evolution of complex sulfur-based compounds lodged in Mary Rose timbers as a function of drying time. Combining insights from infrared spectroscopy correlates the presence of oxidized sulfur species with increased wood degradation via the loss of major wood components (holocellulose). Intriguingly, zinc is found to co-exist with iron and sulfur in the most degraded wood regions, indicating its potential contributing role to wood degradation. This study provides crucial information on the degradation processes and resulting products within the wood, which can be used to develop remediation strategies to save the Mary Rose.

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Acrylic emulsion paint is among the most common media employed by 20th century artists. Since early acrylic paintings have begun to require the attention of conservators, scientists are working to characterize the properties of these paints to facilitate conservation efforts. In this study, we report an investigation of the physical and chemical properties of acrylic emulsion paints using single-sided NMR in conjunction with gloss measurements and scanning electron microscopy-energy dispersive spectrometry. Combining the data from these techniques gives insight into pigment-base interactions and the acrylic curing process, showing that as pigment concentration is increased in paints, the amount of acrylic base adsorbed to pigment particles increases, resulting in films with differing relaxation times. This research both emphasizes and contextualizes the utility of NMR relaxometry in studying cultural heritage objects and prompts further study into the effects of pigment concentration on the curing and conservation of paint films.

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Vincent van Gogh used fugitive red lake pigments that have faded in some paintings. Mapping their distribution is key to understanding how his paintings have changed with time. While red lake pigments can be identified from microsamples, in situ identification and mapping remain challenging. This paper explores the ability of molecular fluorescence imaging spectroscopy to identify and, more importantly, map residual non-degraded red lakes. The high sensitivity of this method enabled identification of the emission spectra of eosin (tetrabromine fluorescein) lake mixed with lead or zinc white at lower concentrations than elemental X-ray fluorescence (XRF) spectroscopy used on account of bromine. The molecular fluorescence mapping of residual eosin and two carmine red lakes in van Gogh's The Olive Orchard is demonstrated and compared with XRF imaging spectroscopy. The red lakes are consistent with the composition of paint tubes known to have been used by van Gogh.

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The nature printing technique was designed for the electrotyping reproduction of leaves and other natural products. Authentic impressions could be performed by inserting leaves between two lead plates or pressing leaves into the lead plate by a press. The impression obtained in the soft lead plate could then be further reproduced by copper electroplating. Electrochemically deposited copper is hard-wearing and therefore very suitable for the production of printing plates. However, depending on the technical implementation and the choice of the materials used, decisive differences in the faithfulness of reproductions of original motifs may occur during the electrochemical deposition. A central topic in electroforming of printing plates is the choice of the conductive layer on the mould. In the present study, it has been shown that graphite powder represents a conductive phase on the siloxane mould superior to silver and copper powder. The grain size of the copper electrodeposit depended on the powder grain size. The copper plate deposited on graphite powder showed the lowest grain size (5-20 µm) and the highest homogeneity of the print background. Hand polishing of the printing plate resulted in a much better faithfulness of the motif details than that of the machine polished version. However, the background of the print derived from the machine polished plate was the most homogeneous. Electrochemical investigation showed that remnants of the silver powder could result in local elements that could enhance corrosion and thus impair the durability of the printing plates. This phenomenon was negligible with the conductive layers consisting of graphite and copper.

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A physico-chemical elucidation of the first photographic technology that allowed manifold reproduction is presented. An etched daguerreotype manufactured around 1840 in Vienna, preserved by the Technisches Museum Wien, served as a case study. Surface analysis showed that the photographic process involved the formation of colloidal Ag nanoparticles with sizes of 30-120 nm with shell layers consisting of Ag2 O, Ag2 S, and some AgCl. This breakthrough photographic technique provided a hitherto unachieved high sensitivity because of various halogenide mixtures without the use of Hg. The image development consisted of the reduction of the Ag halides by H2 SO3 created by the hydrolysis of S2 Cl2 leading to the formation of Ag nanoparticles adjacent to the Ag nuclei of the latent image. The fixing of the image was performed either by KCN or by Na2 S2 O3 . The investigated plate exhibits etched areas with Ag2 O conversion layers and no Cl or S. The gum arabic use for etching preferentially wetted the exposed Ag nanoparticle regions so that unexposed areas could be etched by HNO3 .

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This paper provides new insights for the study of polymer degradation through the detection of markers released at the polymer surface using Al-coated SERS active substrates. Combining a nanodestructive sampling procedure with the SERS sensitivity allows achieving detection limits much lower than traditional polymer characterization techniques, opening the way to the use of SERS as part of an innovative strategy to diagnose surface degradation in polymeric museum artefacts. The method was applied to artificially photo-aged model polymers and to museum artworks.

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Nonlinear unmixing of hyperspectral reflectance data is one of the key problems in quantitative imaging of painted works of art. The approach presented is to interrogate a hyperspectral image cube by first decomposing it into a set of reflectance curves representing pure basis pigments and second to estimate the scattering and absorption coefficients of each pigment in a given pixel to produce estimates of the component fractions. This two-step algorithm uses a deep neural network to qualitatively identify the constituent pigments in any unknown spectrum and, based on the pigment(s) present and Kubelka-Munk theory to estimate the pigment concentration on a per-pixel basis. Using hyperspectral data acquired on a set of mock-up paintings and a well-characterized illuminated folio from the 15th century, the performance of the proposed algorithm is demonstrated for pigment recognition and quantitative estimation of concentration.

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This research assesses the precision, repeatability, and accuracy of crowdsourced scientific measurements, and whether their quality is sufficient to provide usable results. Measurements of colour and area were chosen because of the possibility of producing them with smartphone cameras. The quality of the measurements was estimated experimentally by comparing data contributed by anonymous participants in heritage sites with reference measurements of known accuracy and precision. Participants performed the measurements by taking photographs with their smartphones, from which colour and dimensional data could be extracted. The results indicate that smartphone measurements provided by citizen scientists can be used to measure changes in colour, but that the performance is strongly dependent on the measured colour coordinate. The same method can be used to measure areas when the difference in colour with the neighbouring areas is large enough. These results render the method useful in some heritage science contexts, but higher precision would be desirable.

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The molecular characterization of organic materials in samples from artworks and historical objects traditionally entailed qualitative and quantitative analyses by HPLC and GC. Today innovative approaches based on analytical pyrolysis enable samples to be analysed without any chemical pre-treatment. Pyrolysis, which is often considered as a screening technique, shows previously unexplored potential thanks to recent instrumental developments. Organic materials that are macromolecular in nature, or undergo polymerization upon curing and ageing can now be better investigated. Most constituents of paint layers and archaeological organic substances contain major insoluble and chemically non-hydrolysable fractions that are inaccessible to GC or HPLC. To date, molecular scientific investigations of the organic constituents of artworks and historical objects have mostly focused on the minor constituents of the sample. This review presents recent advances in the qualitative and semi-quantitative analyses of organic materials in heritage objects based on analytical pyrolysis coupled with mass spectrometry.

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The use of VOC analysis to diagnose degradation in modern polymeric museum artefacts is reported. Volatile organic compound (VOC) analysis is a successful method for diagnosing medical conditions but to date has found little application in museums. Modern polymers are increasingly found in museum collections but pose serious conservation difficulties owing to unstable and widely varying formulations. Solid-phase microextraction gas chromatography/mass spectrometry and linear discriminant analysis were used to classify samples according to the length of time they had been artificially degraded. Accuracies in classification of 50-83 % were obtained after validation with separate test sets. The method was applied to three artefacts from collections at Tate to detect evidence of degradation. This approach could be used for any material in heritage collections and more widely in the field of polymer degradation.

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Microscale mid-infrared (mid-IR) imaging spectroscopy is used for the mapping of chemical functional groups. The extension to macroscale imaging requires that either the mid-IR radiation reflected off or that emitted by the object be greater than the radiation from the thermal background. Reflectance spectra can be obtained using an active IR source to increase the amount of radiation reflected off the object, but rapid heating of greater than 4 °C can occur, which is a problem for paintings. Rather than using an active source, by placing a highly reflective tube between the painting and camera and introducing a low temperature source, thermal radiation from the room can be reduced, allowing the IR radiation emitted by the painting to dominate. Thus, emissivity spectra of the object can be recovered. Using this technique, mid-IR emissivity image cubes of paintings were collected at high collection rates with a low-noise, line-scanning imaging spectrometer, which allowed pigments and paint binders to be identified and mapped.