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Although multiple structural, mechanical, and molecular factors are definitely involved in osteoporosis, the assessment of subregional bone mineral density remains the most commonly used diagnostic index. In this study, we characterized bone quality in the femoral neck of one osteoporotic patients as compared to an age-matched control subject, and so used a multiscale and multimodal approach including X-ray computed microtomography at different spatial resolutions (pixel size: 51.0, 4.95 and 0.9 µm), microindentation and Fourier transform infrared spectroscopy. Our results showed abnormalities in the osteocytes lacunae volume (358.08 ± 165.00 for the osteoporotic sample vs. 287.10 ± 160.00 for the control), whereas a statistical difference was found neither for shape nor for density. The osteoporotic femoral head and great trochanter reported reduced elastic modulus (Es) and hardness (H) compared to the control reference (−48% (p < 0.0001) and −34% (p < 0.0001), respectively for Es and H in the femoral head and −29% (p < 0.01) and −22% (p < 0.05), respectively for Es and H in the great trochanter), whereas the corresponding values in the femoral neck were in the same range. The spectral analysis could distinguish neither subregional differences in the osteoporotic sample nor between the osteoporotic and healthy samples. Although, infrared spectroscopic measurements were comparable among subregions, and so regardless of the bone osteoporotic status, the trabecular mechanical properties were comparable only in the femoral neck. These results illustrate that bone remodeling in osteoporosis is a non-uniform process with different rates in different bone anatomical regions, hence showing the interest of a clear analysis of the bone microarchitecture in the case of patients’ osteoporotic evaluation.

This article tests the suitability of a new method to monitor the degree of substitution of cellulose acetate films, by employing a compact and inexpensive near-infrared miniaturized spectrometer (908.1-1676.2 nm) that can be easily applied in situ. The present study compares the analytical performance of the proposed method against conventional diagnostic strategies based on benchtop micro-attenuated total reflectance Fourier transform Infrared (μATR -FTIR) measurements in the mid-infrared spectral range. The novel calibration function exploits the shifts in the first overtone of the hydroxyl stretching 2νOH band of probe materials and was created using a set of analytical standards with different degrees of substitution. The robustness of the method was assessed by application on a group of sixteen historical cinematographic films. The accurate condition assessment of these films was performed in situ, in a non-invasive manner. The proposed analytical procedure is quick and easy-to-implement, and therefore it constitutes a rapid method to guide conservation strategies regarding film storage and digitalization in cultural institutions, including museums and cinematheques. Potential applications on three-dimensional objects and industrial processes are possible.

Hydrogels and organogels are widely used as cleaning materials, especially when a controlled solvent release is necessary to prevent substrate damage. This situation is often encountered in the personal care and electronic components fields and represents a challenge in restoration, where the removal of a thin layer of aged varnish from a painting may compromise the integrity of the painting itself. There is an urgent need for new and effective cleaning materials capable of controlling and limiting the use of solvents, achieving at the same time high cleaning efficacy. In this paper, new sandwich-like composites that fully address these requirements are developed by using an organogel (poly(3-hydroxybutyrate) + γ-valerolactone) in the core and two external layers of electrospun nonwovens made of continuous submicrometric fibers produced by electrospinning (either poly(vinyl alcohol) or polyamide 6,6). The new composite materials exhibit an extremely efficient cleaning action that results in the complete elimination of the varnish layer with a minimal amount of solvent adsorbed by the painting layer after the treatment. This demonstrates that the combined materials exert a superficial action that is of utmost importance to safeguard the painting. Moreover, we found that the electrospun nonwoven layers act as mechanically reinforcement components, greatly improving the bending resistance of organogels and their handling. The characterization of these innovative cleaning materials allowed us to propose a mechanism to explain their action: electrospun fibers play the leading role by slowing down the diffusion of the solvent and by conferring to the entire composite a microstructured rough superficial morphology, enabling to achieve outstanding cleaning performance.

Removal of old deteriorated varnish layers from an easel painting is one of the most common but also most delicate restoration treatments. Apart from purely mechanical methods various solvents or mixtures of solvents have been used for this task over the last hundred years. Most often these chemicals were applied mechanically by swabbing, but also in a form of gels. However, the resulting formation of secondary and detrimental effects (such as swelling, leaching, solvent retention as well as high toxicity to the user) forced the development of new cleaning methodologies, aimed to overcome these drawbacks, guaranteeing a safe and effective removal of the damaged material. The aim of this paper is to discuss the applicability of optical coherence tomography for a multi-faceted and complementary assessment of different varnish removal processes, including the application of a novel nanogel system, the PHB-GVL. Since some effects, like swelling, may develop in a time span of hours, which is not a typical examination time for OCT, long-lasting stability of the measurement system had been ensured. For this task, a lab-developed high-resolution OCT instrument (3 µm axial resolution in the air) was adopted and the repeatability of surface recognition of 1.5 μm over 17 hours was achieved. This permitted for tracing of swelling effects in a multi-hour scale. The most desirable effect of such a restoration treatment is the removal of varnish without any alteration to the paint layer underneath. With the use of OCT, it was possible to trace this process by a direct comparison of the topography of the paint layer under varnish (before treatment) and after treatment. The results pointing at superior properties of the PHB-GVL nanogel applied with an electrospun polymeric tissue will be presented.

Contamination by microplastics (MP) represents a critical environmental challenge with potential consequences at ecosystem, economic and societal levels. As the marine system is the final sink for MP, there is an urgent need to develop methods for the monitoring of synthetic particles in different marine compartments and sample matrices. Extensive evaluations are hindered by time and costs associated with to conventional MP spectroscopic analyses. The potential of near infrared hyperspectral imaging (NIR-HSI) has been recently evaluated. However, NIR-HSI has been poorly studied so far, limitedly to the detection of large particles (>300 μm), and its capability for direct characterization of MP in real marine matrices has not been considered yet. In the present study, a rapid near infrared hyperspectral imaging (NIR-HSI) method, coupled with a customised normalised difference image (NDI) strategy for data processing, is presented and used to detect MP down to 50 μm in environmental matrices. The proposed method is largely automated, without the need for extensive data processing, and enabled a successful identification of different polymers, both in surface water and mussel soft tissue samples, as well as on real field samples with environmentally occurring MP. NIR-HSI is applied directly on filters, without the need for particles pre-sorting or multiple sample purifications, avoiding time consuming procedures, airborne contaminations, particle degradation and loss. Thanks to the time and cost effectiveness, a large-scale implementation of this method would enable to extensively monitor the MP presence in natural environments for assessing the ecological risk related to MP contamination.

Microplastic (MP) has become ubiquitous in the marine environment. Its threat to marine organisms has been demonstrated under laboratory conditions, yet studies on wild populations still face methodological difficulties. We reviewed the methods used to separate MP from soft animal tissues and highlighted a lack of standardised methodologies, particularly critical for synthetic microfibres. We further compared enzymatic and a potassium hydroxide (KOH)-based alkaline digestion protocols on wild crabs (Carcinus aestuarii) collected from three coastal lagoons in the north Adriatic Sea and on laboratory-prepared synthetic polyester (PES) of different colour and polypropylene (PP). We compared the cost-effectiveness of the two methods, together with the potential for adverse quantitative or qualitative effects on MP that could alter the capability of the polymers to be recognised via microscopic or spectroscopic techniques. Only 5.5% of the 180 examined crabs contained MP in their gastrointestinal tracts, with a notably high quantitative variability between individuals (from 1 to 117 particles per individual). All MP found was exclusively microfibres, mainly PES, with a mean length (±SE) of 0.5 ± 0.03 mm. The two digestion methods provided comparable estimates on wild crabs and did not cause any visible physical or chemical alterations on laboratory-prepared microfibres treated for up to 4 days. KOH solution was faster and cheaper compared to the enzymatic extraction, involving fewer procedural steps and therefore reducing the risk of airborne contamination. With digestion times longer than 4 days, KOH caused morphological alterations of some of the PES microfibres, which did not occur with the enzymatic digestion. This suggests that KOH is effective for the digestion of small marine invertebrates or biological samples for which shorter digestion time is required, while enzymatic extraction should be considered as alternative for larger organisms or sample sizes requiring longer digestion times.

Gels have been recently introduced in conservation to better control the cleaning action. The slow solvent release is of utmost importance to selectively remove varnish layers of a few microns in thickness, applied on paint layers which may have similar chemical properties. To evaluate the interactions of the underlying paint with solvents, diagnostic methods should study the physical and chemical changes that occur during and after the treatment. In this paper, we propose an innovative analytical protocol based on the combination of solid phase microextraction (SPME) and nuclear magnetic resonance (NMR) relaxometry to evaluate solvent entry and retention in the paint layer, as well as the induced microscopic and macroscopic changes to the elasticity of the binder. Moreover, FTIR and optical microscopy are used to evaluate the cleaning efficacy. The proposed analytical protocol can be used to identify solvents or gels which show minimal interaction with the paint. In particular, we have tested the protocol to evaluate the performance of non-toxic and biodegradable green gels on mock-ups and on a painting dated 19th century showing that they perform better than solvents applied with swabs. Five-minute gel treatments were found to be as effective at varnish removal as thirty-second swab treatments following traditional cleaning methods. Cleaning with gels limits the mechanical stress, solvent entry and retention in the paint layer, and reduces the embrittlement due to lower mass transfer. An unusual “sandwich” system was used to avoid the retention of gel residues on the surface with the gels contained in two sheets of Japanese papers – one on top and the other at the bottom.

This paper proposes an analytical protocol for the identification of synthetic dyes in degraded wool fibres using a multi-step micro-extraction protocol coupled with Thin Layer Chromatography (TLC)/Metal-Underlayer Attenuated Total Reflection (MU-ATR) FTIR. TLC/MU-ATR is a new enhanced FTIR method, which enables even very few nanograms of analyte to be detected. The efficacy of the method was tested on synthetic dyes (both acid and base), which were artificially aged at 20 h, 60 h, 140 h and 305 h using UV light (∼365 nm). The method was validated on real samples from a pattern book dated 1893. Coupling chromatographic separation with enhanced spectroscopic detection, the method allows substantial reduction of matrix interference by means of TLC and can identify the dyes even in degraded states.

The selective removal of thin varnish layers from oil and egg tempera paintings is still an open challenge in the conservation field. In this paper, a new cleaning system was developed by using a gel composed of fully green components as deep eutectic solvents (DES) and agar. The gel, prepared admixing choline chloride -urea with an EtOH-H2O agar gel, exhibited good rheological properties in terms of gel stiffness, allowing easy handling and removal of the gel. The new developed cleaning gel was successfully tested for the removal of proteinaceous layers applied over both hydrophobic (linseed oil as binder) and hydrophilic (egg temperas as binder) surfaces. The procedure consists on two steps: first the choline chloride -urea agar gel was applied and let to act then an EtOH-H2O agar gel was applied for few seconds to allow the removal of the DES residues Moreover, an innovative non-destructive approach based on micro-Spatially Offset Raman Spectroscopy (micro-SORS) allowed to demonstrate how the gel impairs the diffusion of the cleaning agents in the paint layers, highlighting the good solvent retention ability of the gel.

In the present study, an innovative and highly efficient near-infrared hyperspectral imaging (NIR-HSI) method is proposed to provide spectral maps able to reveal collagen distribution in large-size bones, also offering semi-quantitative estimations. A recently introduced method for the construction of chemical maps, based on Normalized Difference Images (NDI), is declined in an innovative approach, through the exploitation of the NDI values computed for each pixel of the hyperspectral image to localize collagen and to extract information on its content by a direct comparison with known reference samples. The developed approach addresses an urgent issue of the analytical chemistry applied to bioarcheology researches, which rely on well-preserved collagen in bones to obtain key information on chronology, paleoecology and taxonomy. Indeed, the high demand for large-sample datasets and the consequent application of a wide variety of destructive analytical methods led to the considerable destruction of precious bone samples. NIR-HSI pre-screening allows researchers to properly select the sampling points for subsequent specific analyses, to minimize costs and time and to preserve integrity of archaeological bones (which are available in a very limited amount), providing further opportunities to understand our past.

The paper reports on the development of an analytical method based on the use of a new miniaturised short-wave infrared (SWIR) spectrometer for the analysis of cultural heritage samples. The spectrometer is a prototype characterised by small dimension (45.0 mm in diameter x 47.5 mm in height x 60 g weight), easily handled and transferable out of research laboratories. The prototype enables the acquisition of spectra in the SWIR range of 1200–2200 nm, which is a unique feature for miniaturised spectrometers. The exploitation of this spectral range allows the detection of a high number of combination and overtone bands, which guarantees significant diagnostic power to the instrument. The present study lays a significant foundation to the development of analytical strategies based on miniaturised NIR spectrometers working in the SWIR spectral range for the characterization of complex samples such as cultural heritage specimens. Analytical performances of the new spectrometer were assessed on archaeological bones, cinematographic films and bronze patinas. The selected cases of study present challenging conservation issues not properly addressed, and their analyses usually require to be performed on-site, in places not easily accessible by restorers, archaeologists and/or scientists. The data acquired with the prototype, combined with a multivariate data analysis approach, show the possibility to i) differentiate between the materials used as a support for cinematographic film namely cellulose nitrate (CN), cellulose acetates (CA) and polyethylene terephthalate (PET); ii) sort out archaeological bone fragments according to their collagen content as an initial screening test for bones characterization; iii) differentiate between corrosion products on outdoor bronze sculpture, which is important for assessing the state of conservation of the artwork. The prototype enabled rapid information acquisition to guide restoration strategies, which need to be supported in real time by quick and easy analytical procedures.

This study proposes a non-invasive analytical method to study the molecular diffusion of a chemical agent into a turbid matrix with an emerging analytical technique, micro-Spatially Offset Raman Spectroscopy (micro-SORS). Here, the micro-SORS concept has been extended from the analysis of chemically distinct stratified layers to the studies and monitoring of the absorption and diffusion processes, addressing a key analytical need in a number of areas including polymer, pharmaceutical, forensic and biomedical sciences. In Cultural Heritage the knowledge of the penetration depth of a polymer used to consolidate or to protect an object, or the absorption depth of solvents used during a cleaning procedure is crucial for the performance evaluation of restoration methods and their safety towards the work of art. To date the most common protocol for obtaining this type of information comprises the application of stratigraphical analysis on cross-sections prepared after taking a small amount of sample from the work of art. This approach is destructive and may lack of statistical meaning, since the analytical information is limited to the micro area of sampling. To overcome these drawbacks, in this study micro-SORS was successfully used, for the first time, to non-invasively characterise the penetration of a polymer and of a viscous solvent into a gypsum substrate, permitting the reconstruction of the diffusion trends of the products into the matrix and the evaluation of their performances.

Microplastic (MP) contamination is a critical environmental challenge with a strong impact on the ecosystems, economy and potentially for human health. The smaller the MP size, the greater is the environmental risks as well as the analytical difficulties in detecting and characterising the particles. .We propose a rapid near infrared hyperspectral imaging (NIR-HSI) method that enables the chemical identification and characterisation of small MP (down to 80 μm) in aquatic samples, directly on filters, with no pre-sorting step needed. By considerably reducing the procedural steps, the time of analysis and costs our method addresses the urgent need of cost-effective and robust tools for extensive monitoring of MP in natural systems.

10 pags., 6 figs., 1 tab., Acid Organge 20 is a synthetic monoazo dye, which molecular structure consists of a naphtol unit and a sulfonated benezene ring linked together by an azo chromophore group. As a phenylazonaphthol with the OH group inparaposition respect to the azo group, it undergoes an azo-hydrazone tautomerism. In this work, the study of the preponderance of one tautomer over the other in different pH conditions was carried out by means of UV-Vis, Raman, and surface-enhanced Raman scattering (SERS) spectroscopies. Raman spectra of powder and aqueous solutions of the dye were obtained at different excitation lines at the natural pH of the AO20 solutions. The best results were obtained at 633 nm, and the observed Raman bands suggested the presence of the hydrazone tautomer. The molecular structure and the theoretical Raman spectra of the two tautomers were calculated by density functional theory (DFT) methods. The obtained results were used for the assignment of the Acid Orange 20 vibrational modes. The SERS analysis of the dye solutions were carried out employing Ag nanostars, pH below and above 4.7, and excitation at 442, 532, and 633 nm. The hydrazone tautomer was prevalent in most conditions. The azo tautomer was only detected at pH similar to 5 under excitation with the 532 nm wavelength due to resonant Raman conditions. Finally, the effect of pH on the morphology of metal nanoparticles employed as SERS substrates was evaluated by TEM., This work was supported by Ministerio de Economía, Industria y Competitividad de España (project FIS2017-84318-R) and Comunidad de Madrid/EU (project TOP Heritage).

Compared to western wall paintings, the study, conservation and restoration of Far East Asian wall paintings is a more difficult task, owing not only to the varied supports and painting material constituents they are made of, but also to the particular social environments in which they are located and the consequences this has on the adopted theoretical and practical approaches to conservation. The recent availability of complementary non-invasive and micro-invasive analytical techniques led conservation scientists to have an increased interest in studying painting materials and techniques used in Far East Asian mural paintings. This chapter aims at presenting and discussing some of the most intriguing issues that conservation professionals are still confronted with. To this purpose, the chapter first introduces readers to the understanding of their material constitution and ancient painting techniques adopted with specific reference to plaster, preparation, paint layers and binding media and varnishes. Afterwards, the most advanced analytical approaches suitable for the achievement of a clear understanding of original schemes of polychromy, painting materials and technique are presented and discussed. This is of the outmost importance as the main issue when talking about Far East Asian mural painting conservation is the imminent risk of loss or damage.

10 pags., 7 figs., 2 tabs., Acid Red 26 and Acid Red 18 are two early synthetic dyes belonging to the monazo dye class. The molecular structure of this class of dyes is characterized by the chromophoric azo group (N[dbnd]N) generally attached to benzene or naphthalene derivatives containing electron withdrawing and/or donating groups as substituents. As both red dyes have an OH group in ortho- position respect to the azo group, they undergo an azo-hydrazone tautomerism. In this work, UV–Vis, Raman and SERS spectroscopic analysis of the red dye solutions were carried out at different pH conditions, in order to evaluate the preponderance of one tautomer over the other as a function of the pH. Different experimental conditions were tested in order to find the best ones for the detection of both dyes. Thus, Raman spectra of the powder and aqueous solutions of AR26 and AR18 were obtained at the natural pH of the solutions, and above and below that value. The SERS analysis of the dye solutions were carried out at various pH values between 2 and 10, and with excitation at 442, 532 and 633 nm. The molecular structure and the theoretical Raman spectra of the two tautomers of both red dyes were calculated by DFT methods. The obtained results were used for the assignment of the Acid Red 26 and Acid Red 18 vibrational modes. Finally, a textile sample dyed with AR18 was analyzed by SERS., This work was supported by Ministerio de Economía, Industria y Competitividad de España (project FIS2017-84318-R) and Comunidad de Madrid/EU (project TOP Heritage).

Salt marshes in urban watersheds are prone to microplastics (MP) pollution due to their hydrological characteristics and exposure to urban runoff, but little is known about MP distributions in species from these habitats. In the current study, MP occurrence was determined in six benthic invertebrate species from salt marshes along the North Adriatic lagoons (Italy) and the Schelde estuary (Netherlands). The species represented different feeding modes and sediment localisation. The 96% of the analysed specimens (330) did not contain any MP, which was consistent across different regions and sites. Suspension and facultative deposit-feeding bivalves exhibited a lower MP occurrence (0.5-3%) relative to omnivores (95%) but contained a much more variable distribution of MP sizes, shapes and polymers. The study provides indications that MP physicochemical properties and species' ecological traits could all influence MP exposure, uptake and retention in benthic organisms inhabiting European salt marsh ecosystems.

Organo- and hydrogels have been proposed in the restoration field to treat different types of surfaces. The possibility to retain solvents and to have a controlled and superficial action allowed to use these materials for the removal of very thin layers applied on ancient historical objects, when the under paint layers are particularly delicate and water sensitive. In the last years, an increased attention has been devoted to the proposal of more healthy products to guarantee the safeguard of the operators. Few attention has been devoted to the development of green methods which foresee the use of renewable and biodegradable materials. The aim of this paper is to test a green organo-gel for the cleaning of water sensitive surfaces like varnished egg tempera paintings. The gel has been tested experimented on mock ups varnished with natural and synthetic materials and has been validated on a small portion of a Cimabue painting for the removal of two varnishes applied on two different test areas of the painting.

The photoreduction of aqueous Ag+ to silver nanoparticles (AgNPs) on a substrate was studied aiming at the application of surface-enhanced Raman scattering (SERS) technique to the sensitive analysis of organic colorants directly on artworks. In particular, the presence of the synthetic dyes methyl violet (BV1) and fuchsine (BV14), in both standard and historical wool fibers, was analyzed. Scanning electron microscopy was employed to study the morphology and distribution of the NPs obtained on the fiber. We have carried out an investigation of the influence of several factors on the morphology of NPs: excitation wavelength, substrate, laser power and laser irradiation time. The resulting materials were analyzed at different laser wavelengths in order to evaluate the application range of the probe laser after the NPs formation. SERS spectra of the BV1 and BV14 dyes on the fiber were obtained and compared with those obtained in suspended conventional AgNPs, in order to deduce the possible influence of the wool substrate on the Raman spectra. SERS spectra were analyzed considering the possible resonance Raman processes. Bands attributed to the protein substrate were also identified. The main goal of this work was to assess and optimize a general method of analysis of organic dyes on natural fibers based on the direct preparation of AgNPs by laser SERS technique. Copyright © 2017 John Wiley & Sons, Ltd.

In the field of applied researches in heritage science, the use of multivariate approach is still quite limited and often chemometric results obtained are often underinterpreted. Within this scenario, the present paper is aimed at disseminating the use of suitable multivariate methodologies and proposes a procedural workflow applied on a representative group of case studies, of considerable importance for conservation purposes, as a sort of guideline on the processing and on the interpretation of this FTIR data. Initially, principal component analysis (PCA) is performed and the score values are converted into chemical maps. Successively, the brushing approach is applied, demonstrating its usefulness for a deep understanding of the relationships between the multivariate map and PC score space, as well as for the identification of the spectral bands mainly involved in the definition of each area localised within the score maps.

Macroscopic mapping and hyperspectral imaging in the mid-infrared region (2500-25000 nm/4000-400 cm-1) are promising technologies in the field of analysis of cultural heritage. So far they have been successfully employed to study paintings and illuminated manuscripts, gathering important information on spatial distribution of artists’ materials. The present paper reports on the application of mid-infrared macroscopic mapping and hyperspectral imaging to the study of artworks. For an exhaustive overview, instrumental details, working principles and image processing methods will be also presented and discussed.

In this research, we propose an advanced system for the cleaning of wax-based coatings applied on indoor bronzes. To this aim we developed a new kind of eco-friendly gel based on PHB (poly-3-hydroxybutyrate) used as thickening agent, biodiesel (BD) and dimethyl carbonate (DMC). BD is a mixture of methyl esters obtained from palm oil, which acts as cleaning agent while DMC was added as additional solvent to partially solubilize PHB and forming a gelly phase. For the first time a PHB-based gel obtained by mixing two solvents with different proprieties was proposed, expanding the range of possible formulations, that can be used according to the specific restoration purpose. After the preliminary characterization of chemical and physical properties of the gel, an ad hoc analytical protocol was implemented to evaluate both the cleaning efficiency and the release of residues on the treated surfaces. Standard samples were prepared following ancient recipes and submitted to spectroscopic and chromatographic analysis before and after the cleaning procedures. Finally, the performances of PHB-DMC/BD gel were assessed on a real case of study presenting a wax-based coating: the Pulpito della passione attributed to Donatello and dated back to 1460. In situ analysis demonstrated the high cleaning efficiency of the proposed systems also for the removal of aged coatings.

Metallographic features of ancient bronze artefacts often hide peculiar micro-chemical processes and corrosion behaviours, which are worth to be studied as they can provide conservators and archaeologists with valuable tools and information. It is widely documented that Chinese bronzes were cast and the way to adjust their properties was to change the alloy composition. In particular, addition of lead, which is insoluble in the bronze matrix, results in the formation of inclusions or globules, which undergo oxidation processes leading to their conversion into corrosion products. The mechanisms through which this occurs were still poorly investigated. The present work was conducted to further study the corrosion behaviour of high-leaded bronze, especially focusing on the behaviour of lead globules. To this aim, a collection of Chinese archaeological bronzes, showing intermediate steps of degradation, were selected and investigated. The use of combined microscopy-based, molecular and elemental, analytical techniques allowed the characterization as well as the precise location of corrosion products, thus enabling us to propose a degradation pathway basing on thermodynamic data provided by Pourbaix diagram. The achieved results will be useful for researchers involved in these kinds of studies to better interpret data obtained. Metallographic features of ancient bronze artefacts often hide peculiar micro-chemical processes and corrosion behaviours, which are worth to be studied as they can provide conservators and archaeologists with valuable tools and information. It is widely documented that Chinese bronzes were cast and the way to adjust their properties was to change the alloy composition. In particular, addition of lead, which is insoluble in the bronze matrix, results in the formation of inclusions or globules, which undergo oxidation processes leading to their conversion into corrosion products. The mechanisms through which this occurs were still poorly investigated. The present work was conducted to further study the corrosion behaviour of high-leaded bronze, especially focusing on the behaviour of lead globules. To this aim, a collection of Chinese archaeological bronzes, showing intermediate steps of degradation, were selected and investigated. The use of combined microscopy-based, molecular and elemental, analytical techniques allowed the characterization as well as the precise location of corrosion products, thus enabling us to propose a degradation pathway basing on thermodynamic data provided by Pourbaix diagram. The achieved results will be useful for researchers involved in these kinds of studies to better interpret data obtained. © 2013 Elsevier Masson SAS.

none 9 no Fully biodegradable novel bio-based organogels were developed for removing aged protective films from the surfaces of paintings, aiming at providing effective cleaning tools, easily controllable by reducing the solvent permeation into underlying paint layers and not dangerous for human health and the environment. The gels were based on poly-3-hydroxybutyrate (PHB) as gelling agent, γ-valerolactone (GVL) as solvent and triethyl citrate (TEC) as plasticizer. PHB-gels were able to completely remove protective varnishes on real oil paintings, without affecting the pictorial layer and leaving negligible residues after the application. Moreover, the gels showed good mechanical and handling properties, they were fully composed by non-toxic ingredients and resulted readily biodegradable in water, therefore easily disposable after the use. mixed Samorì, Chiara; Galletti, Paola; Giorgini, Loris; Mazzeo, Rocco; Mazzocchetti, Laura; Prati, Silvia; Sciutto, Giorgia; Volpi, Francesca; Tagliavini, Emilio Samorì, Chiara; Galletti, Paola; Giorgini, Loris; Mazzeo, Rocco; Mazzocchetti, Laura; Prati, Silvia; Sciutto, Giorgia; Volpi, Francesca; Tagliavini, Emilio

The development of user-friendly devices for on site analysis and characterization of painting materials is one of the most challenging objectives in the diagnostics for cultural heritage. Thanks to the specificity of antigen–antibody reactions, immunological methods have been already successfully applied for the detection of proteins and for their localization within painting stratigraphies. Moreover, by combining the advantages of the immunological techniques with the high detectability offered by chemiluminescence detection, it has been possible to achieve good analytical performance and very low detection limits. This work was aimed at developing a portable analytical device for the detection of chicken ovalbumin (a protein found in egg tempera and in egg-based protective varnishes) in painting samples employing ready-to-use analytical cartridges and a thermoelectrically-cooled CCD camera as a chemiluminescence detector. The protein was extracted from using a simple procedure and revealed by a non-competitive immunoassay with chemiluminescence contact imaging detection. The assay was simple, fast and suitable for the detection of ovalbumin in small samples. This analytical system provided positive identification of ovalbumin in samples obtained from both fresh or artificially aged paint reconstructions and historical paintings. It might be easily employed in different contexts (such as small museums, restoration laboratories or even on site) by restorers to obtain prompt information during restoration actions, such as cleaning operations. In perspective this device could be also employed for the detection of other proteinaceous and organic painting components.

The present study describes a multivariate strategy that can be used for automatic on-site processing of reflection mode macro FTIR mapping (MA-rFTIR) data obtained during investigation of artworks. The chemometric strategy is based on the integration of principal component analysis (PCA) with a clustering approach in the space subtended by the three lowest-order principal components and allows to automatically identify the regions of interest (ROIs) of the area scanned and to extract the average FTIR spectra related to each ROI. Thanks to the automatic data management, in-field HSI (hyperspectral imaging)-based analyses may be performed even by staff lacking specific advanced chemometric expertise, as it is sometimes the case for conservation scientists or conservators with a scientific background. MA-rFTIR was only recently introduced in the conservation field and, in this work the technique was employed to characterize the surface of metallic artefacts. The analytical protocol was employed as part of a rapid procedure to evaluate the conservation state and the performance of cleaning methods on bronze objects. Both activities are commonly part of restoration campaigns of bronzes and require an on-site analytical procedure for efficient and effective diagnosis. The performance of the method was first evaluated on aged standard samples (bronzes with a layer of green basic copper hydroxysulphate, treated with different organic coatings) and then scrutinized in situ on areas of the 16th century Neptune fountain statue (Piazza del Nettuno, Bologna, Italy) by Gianbologna.

In the recent years, an increasing interest has been devoted to the development of compact macro X-ray fluorescence (MA-XRF) systems, establishing the technique as one of the most powerful non-invasive method for the characterization of artworks. Nevertheless, important information may be lost due to the poor signal-to-noise ratio, which characterises spectra collected with a limited acquisition time. Moreover, well-known drawbacks of the XRF analysis, such as the matrix effect and the penetration depth of X-rays, have to be also considered. In the attempt to overcome such limitations, without compromising the potentialities of a MA-XRF imaging analysis in terms of dimension of investigated surface and time of analysis, a specific methodological strategy is proposed. In particular, high signal-to-noise ratio maps were acquired on regions of interest selected after preliminary fast scans on the entire painting. Subsequently, the elaboration of the dataset was supported by the use of ad hoc analytical tools, such as correlation diagrams, averaged extracted spectra and line emission maps for each element. The correct interpretation of the non-invasive results allowed to define a proper sampling strategy. The proposed experimental workflow has been applied to a masterpiece panel painting by Cimabue (1240–1302) depicting “Madonna Enthroned with the Child and Two Angels”, disclosing new knowledge on the adopted execution technique, about which little is known. Thus, for the first time a painting created by Cimabue was investigated under a material and technical point of view. Due to the relevance of the information obtained by MA-XRF analyses, micro-destructive investigations were carried out. Thus, the joint evaluation of elemental distribution and the stratigraphic composition of the selected samples allowed to obtain information about Cimabue painting technique. Particular attention was devoted to the characterization of the throne decorations, pointing out new questions on a non-conventional middle-age gilding technique that need still to be investigated.

The point-of-care testing concept has been exploited to design and develop portable and cheap bioanalytical systems that can be used on-site by conservators. These systems employ lateral flow immunoassays to simultaneously detect two proteins (ovalbumin and collagen) in artworks. For an in-depth study on the application of these portable biosensors, both chemiluminescent and colorimetric detections were developed and compared in terms of sensitivity and feasibility. The chemiluminescent system displayed the best analytical performance (that is, two orders of magnitude lower limits of detection than the colorimetric system). To simplify its use, a disposable cartridge was designed ad hoc for this specific application. These results highlight the enormous potential of these inexpensive, easy-to-use, and minimally invasive diagnostic tools for conservators in the cultural heritage field.

Understanding the original techniques in the creation of an artwork is a prerequisite for the selection of the most appropriate conservation method. This is particularly essential in wall paintings where control of potential agents of deterioration and efficient monitoring are limited due to the scale of the paintings and their exposure to uncontrollable environmental fluctuations. Analytical studies are increasingly focused on the investigation and study of degradation products of organic binders originally added in the paintings on a lime-based plaster ground. In the framework of IPERION-CH (Integrated Platform for the European Research Infrastructure ON Cultural Heritage) project, a collaborative task is dedicated to obtain knowledge about original organic materials used in wall paintings by evaluating and comparing different innovative methodologies and conventional diagnostic techniques used for the investigation of markers related to alteration mechanisms and degradation products. The non-invasive and microsampling methodology is first optimized on well-defined models that have been designed to simulate different painting techniques with limewater and five organic binders in different relative proportions. Future investigations will focus on the application of the optimized methodology on archaeological samples. In the present paper, preliminary results on a selected set of models, submitted in different stages of a well-established artificial ageing protocol, demonstrate the specific complementary input of each analytical technique included in the analytical approach (colour measurements, micro FTIR-ATR analyses in cross-sections, Evolved Gas Analysis-Mass Spectrometry and Gas Chromatography-Mass Spectrometry). The comparative evaluation and interpretation of the results is a step forward in the optimization of the approach and in relating the analytical findings detected on the analysed samples to the original compounds and the possible changes for each group of binders (proteins/gums) due to degradation or interaction depending on the pigment/metal ion present.

open 17 si The composition of the ancient wax-based painting technique known as encaustic has long been the subject of debate. Ancient sources provide few details of the technology, and modern understanding of the medium is restricted to theoretical interpretation and experimental observation. In this multi-analytical collaborative study, a number of analytical approaches were used to investigate the physical and molecular properties of a range of experimentally prepared encaustic paints before and after ageing. Analysis using gas chromatography mass spectrometry, Fourier transform infrared spectroscopy (invasive and non-invasive), X-ray diffraction and thermogravimetric analysis demonstrated how differences in the technology of production alter the properties and composition of the medium and showed how these are modified by the addition of pigment and the effects of ageing. Comparison of results from the different analytical techniques highlights the benefit of an integrated analytical approach to the analysis of ancient encaustic paints and the fundamental importance of insights from invasive study to evaluating the results of non-invasive analysis. open Stacey, R.J.*; Dyer, J.; Mussell, C.; Lluveras-Tenorio, A.; Colombini, M.P.; Duce, Celia; La Nasa, Jacopo; Cantisani, Emma; Prati, S.; Sciutto, G.; Mazzeo, R.; Sotiropoulou, S.; Rosi, F.; Miliani, C.; Cartechini, L.; Mazurek, J.; Schilling, M. Stacey, R.J.*; Dyer, J.; Mussell, C.; Lluveras-Tenorio, A.; Colombini, M.P.; Duce, Celia; La Nasa, Jacopo; Cantisani, Emma; Prati, S.; Sciutto, G.; Mazzeo, R.; Sotiropoulou, S.; Rosi, F.; Miliani, C.; Cartechini, L.; Mazurek, J.; Schilling, M.

Irradiation with γ rays is widely used in the sterilization of a large variety of products and materials in the field of medical supplies, pharmaceuticals, cosmetics, food industry and cultural heritage. It is also applied on wood materials, with the purpose of improving their shelf-life, by lowering the microbial charge and hence the microbial-related deterioration rate. A fundamental issue when applying γ rays is the preservation of the chemico-physical as well as of the structural and mechanical properties of the materials irradiated, since a significant change of properties may jeopardize the use of the materials for the purpose intended. To this end, in this paper, we analyzed the chemico-physical properties of four different types of wood used for the construction of musical instruments namely fir, maple, poplar and durmast oak under increasing doses of γ rays. In detail, the effect of incremental radiation doses was evaluated by comparing the results obtained by acoustic tests with those providing information at molecular level, i.e., cyclic voltammetry, linear square voltammetry and infrared spectroscopy. Moreover, in this work, the glucose released as a result of the degradation of wood cellulose and hemicellulose, has been analyzed for the first time, with an innovative tool, based on the use of a Gellan gel. The integrated approach presented here, based on both traditional and innovative techniques has proven to be highly efficient in providing a complete picture of wood behavior following γ-ray irradiation, at both the macroscopic and the molecular level.

The corrosion products usually found on outdoor bronzes are generated by the interaction between the metal alloy and the atmospheric pollutants. To protect the external surface of bronzes, different organic materials (natural or synthetic) can be applied, creating over time a patina consisting of a complex mixture of inorganic and organic degraded components. The correct chemical characterization of patina constituents is fundamental to define the state of conservation of a metal artwork and address proper restoration actions. In this paper, we evaluated the potentialities of near-infrared (NIR) reflectance microscopy (4000–7500cm−1) as complementary method to mid-infrared (MIR) analyses for the characterization of bronze patinas. Although NIR spectroscopy has been already used in the field of heritage science, its application for the characterization of bronze patinas is almost unexplored. In this paper, several corrosion products usually found on the surface of outdoor bronze sculptures were synthesized, characterized, and submitted to the NIR-MIR total reflection analysis to build up a reference spectral database. We devoted particular attention to the NIR features of copper hydroxychlorides, such as atacamite and paratacamite, which have not been studied in detail up to now. A selection of organic-based formulations, commonly used by restorers to protect the bronze surface against the outdoor aggressive environment, were also considered as references. Successively, NIR-MIR reflectance microscopy was successfully employed for the analysis of patina micro-samples collected from the bronze statues of the Neptune Fountain (sixteenth century) located in Bologna. The obtained results demonstrate the ability of NIR spectroscopy to identify organic and inorganic patina constituents, even in mixtures. In addition, the study can be considered as a proof of concept for the possible future application of the technique for in situ diagnostic campaigns on bronze sculptures.

Off-line pyrolysis coupled with GC-MS through SPME sampling, overcomes some of the limitation of online Py-GC-MS configuration without laborious sample treatment. The introduction of on fiber silylation procedure between SPME sampling and analysis allowed to obtain a complete silylation of polar pyrolysis products with diagnostic relevance. The method was applied to the analysis of pure sugars and carbohydrates, providing a picture of the type of anhydrosugars evolved by pyrolysis of natural gums, namely cellulose and polysaccharide based gums (Arabic, Ghatti, Tragacanth, Guar, Karaya and Xanthan). Characteristic anhydrosugars produced by pyrolysis of hexoses, pentoses and deoxyhexoses were tentatively identified. Despite an unambiguous marker for uronic acids was not identified, the final method allowed to obtain, with minimal work-up, a detailed picture of polar pyrolysis products as those obtainable from carbohydrates, which can be easily used for identification purposes.

InthispapersomecoloredframescomingfromtheverypopularcinematographicfilmSardinianDrummerBoy,datingbacktothebeginning of the XX century, were analyzed. The presence in the emulsion of silver nanoparticles (AgNPs), which are formedthanks to the impression–development mechanism, confers to the cinematographic film the characteristic of being an efficientSurface Enhancement Raman Spectroscopy (SERS) substrate. This peculiarity makes it possible to investigate, in a non-invasiveway, the nature of the film components, such as the dyes used for the coloring process. In particular, Raman analyses allowedthe unambiguous identification of the dyes used in tinted frames, i.e. tartrazine and safranin, in which the colorant is absorbedby the gelatin, and intoned frames, i.e.Rhodamine B, wherethe dyeisfixed thankstothe formationofaninsolublespecies withAgIobtainedbyconversionofmetallicsilver.Thissecondcaseisofparticularinteresttoevaluatethepossibilitytoidentifythedyeeven when it is present as a silver iodide derivative. For this purpose an AgI-colorant derivative has been prepared and its SERSspectrum compared with that obtained on the film sheet. Copyright © 2015 John Wiley & Sons, Ltd.Additional supporting information may be found in the online version of this article at the publisher’s web site.Keywords: cinematographic film; tinting; toning; SERS; dyes

This paper reports the results of several scientific analyses carried out on ten mandolins made in the second half of the eighteenth century by the most important Neapolitan mandolin manufacturers such as the Filano, Fabricatore, Gagliano and Vinaccia families. Various elements of decoration were characterized for each mandolin: the resins of the sound hole decorations, the black wood strips of the purflings, the varnishes and the glues. Thanks to microscopy observations SEM-EDX, µFT-IR and µRaman analysis, a multi-technique approach was used in order to fully characterize and compare some of the decoration-making techniques peculiar of each family of makers. Shellac was the main organic material used both in the sound hole decorations and in the varnishes. Inorganic fillers such as aluminosilicates, particles of iron oxides/hydroxides and microfossils of diatoms were found within the false inlays. Black iron-based dyes were identified as dyes for the black wood strips of the purflings.

The research complements the complex study carried out to understand the source of brown discolourations of ten marble statues in the Church of Orsanmichele in Florence, Italy. Originally located in exterior niches, the statues were restored to reverse the extensive alterations they had undergone throughout the centuries. One of the major alterations was the application of a dark brown patina that dated just after 1789. After the statues were placed indoors, brownish discolourations started to appear on their surfaces. Cross sections were examined using FTIR mapping and immunological methods. In parallel, the pyrolysis-gas chromatography/mass spectrometry (py-GC/MS) data already obtained from the statues' scrapings were compared with data from aged casein films applied to microscope glass slides and aged milk-treated marble. All the statues had been treated with milk-based substances before the time the bronze patina was applied. The values of temperature and illumination of the room were important factors in the ageing of organic substances and in the formation of calcium oxalates. It is likely that products of thermo-oxidation and photo-oxidation of the oils together with the oxalates caused the darkening. The marble samples corresponded to a Lunense provenance.

Analytical investigations were aimed at providing the wall painting conservator with information related to the painting materials’ constitution with particular reference to the identification of binding media, pigments and lime, and cement covering applied on the occasion of previous restoration interventions. Elemental, molecular spectroscopic (μFTIR, μRaman), and immunochemical methods applied directly on the paint cross-sections were used to characterize and spatially locate each paint component.

The present research is focused on the setting up of an advanced analytical system for the detection of synthetic dyes. The system is based on the combination of an innovative thin layer chromatography (TLC) plate coupled with enhanced infrared (MU-ATR, metal underlayer attenuated total reflection) and Surface Enhanced Raman (SERS) spectroscopy. In particular, a TLC plate made of silver iodide (AgI) applied onto a gold coated glass slide (AgI@Au) is proposed as an efficient stationary phase for the separation of dyes mixtures. The separated dyes are then identified by means of both enhanced FTIR and SERS, performed directly on the same eluted spots. The use of a mid-IR transparent inorganic salt as stationary phase coupled with the underneath gold layer avoids spectral interferences, enhancing the signal obtained from ATR analyses. At the same time, SERS spectra can be recorded as the TLC plate may act as a SERS active substrate due to the photoreduction of AgI to metallic Ag caused by the exposure to the laser during the Raman analysis. Different mixtures of synthetic dyes of known composition, widely used in dyeing processes, have been tested and the method resulted to be effective in identifying trace amounts in the order of tens nanograms. Moreover, the method has been further evaluated on a real case study represented by dyes extracted from dyed wool.

The ability to analyse layers within a paint sample is important both for historical studies as well as determining the most suitable method for restoration. The difficulty in physically separating these very thin layers makes detailed analysis difficult, and a combination of destructive and non-destructive techniques are needed. Laser pyrolysis/gas chromatography - mass spectrometry (LaPy/GC–MS) is a technique that has proved successful in the analysis of geological samples which pose the same difficulties for analysis, but it has not yet been tried on paint cross sections. This study presents preliminary results of applying LaPy/GC–MS on standard mock-ups for identification of organic compounds used as varnishes, binders and colourants. The technique was shown to be particularly effective for the identification and localisation of natural resins and synthetic colourants. Moreover, the integration between this technique and other stratigraphical analyses may allow the complete characterisation of the composition of organic substances in paint cross-sections.