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Analytical Chemistry for Cultural Heritage

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Chapters (11)

Synchrotrons have provided significant methods and instruments to study ancient materials from cultural and natural heritages. New ways to visualise (surfacic or volumic) morphologies are developed on the basis of elemental, density and refraction contrasts. They now apply to a wide range of materials, from historic artefacts to paleontological specimens. The tunability of synchrotron beams owing to the high flux and high spectral resolution of photon sources is at the origin of the main chemical speciation capabilities of synchrotron-based techniques. Although, until recently, photon-based speciation was mainly applicable to inorganic materials, novel developments based, for instance, on STXM and deep UV photoluminescence bring new opportunities to study speciation in organic and hybrid materials, such as soaps and organometallics, at a submicrometric spatial resolution over large fields of view. Structural methods are also continuously improved and increasingly applied to hierarchically structured materials for which organisation results either from biological or manufacturing processes. High-definition (spectral) imaging appears as the main driving force of the current trend for new synchrotron techniques for research on cultural and natural heritage materials.
The in situ non invasive methods have experienced a significant development in the last decade because they meet specific needs of analytical chemistry in the field of cultural heritage where artworks are rarely moved from their locations, sampling is rarely permitted, and analytes are a wide range of inorganic, organic and organometallic substances in complex and precious matrices. MOLAB, a unique collection of integrated mobile instruments, has greatly contributed to demonstrate that it is now possible to obtain satisfactory results in the study of a variety of heritage objects without sampling or moving them to a laboratory. The current chapter describes an account of these results with particular attention to ancient, modern, and contemporary paintings. Several non-invasive methods by portable equipment, including XRF, mid- and near-FTIR, UV–Vis and Raman spectroscopy, as well as XRD, are discussed in detail along with their impact on our understanding of painting materials and execution techniques. Examples of successful applications are given, both for point analyses and hyperspectral imaging approaches. Lines for future perspectives are finally drawn.
Recent studies are concisely reviewed, in which X-ray beams of (sub)micrometre to millimetre dimensions have been used for non-destructive analysis and characterization of pigments, minute paint samples, and/or entire paintings from the seventeenth to the early twentieth century painters. The overview presented encompasses the use of laboratory and synchrotron radiation-based instrumentation and deals with the use of several variants of X-ray fluorescence (XRF) as a method of elemental analysis and imaging, as well as with the combined use of X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Microscopic XRF is a variant of the method that is well suited to visualize the elemental distribution of key elements, mostly metals, present in paint multi-layers, on the length scale from 1 to 100 lm inside micro-samples taken from paintings. In the context of the characterization of artists’ pigments subjected to natural degradation, the use of methods limited to elemental analysis or imaging usually is not sufficient to elucidate the chemical transformations that have taken place. However, at synchrotron facilities, combinations of μ-XRF with related methods such as μ-XAS and μ-XRD have proven themselves to be very suitable for such studies. Their use is often combined with microscopic Fourier transform infra-red spectroscopy and/or Raman microscopy since these methods deliver complementary information of high molecular specificity at more or less the same length scale as the X-ray microprobe techniques. Since microscopic investigation of a relatively limited number of minute paint samples, taken from a given work of art, may not yield representative information about the entire artefact, several methods for macroscopic, non-invasive imaging have recently been developed. Those based on XRF scanning and full-field hyperspectral imaging appear very promising; some recent published results are discussed.
We present an overview of recent advances in the application of Fourier Transform Infrared (FTIR) microscopy for analysis of complex, multicomponent, and multilayer samples such as those typically encountered in the field of heritage materials. This technique is particularly useful since it allows identification and localization of both organic and inorganic (if IR active) compounds. New improvements have been possible thanks to the introduction of ad hoc sample preparation methods to obtain either thin or cross sections that allow both avoidance of contamination from organic embedding resin and improvement of the quality of the acquired spectra. Moreover, integrated use of spectra registered in the nearinfrared (NIR) and mid-infrared (MIR) regions allows better comprehension of cross section composition. Data interpretation has been improved thanks to the development of chemometric methods for elaboration of hyperspectral data. A new and very promising field is the development of enhanced FTIR methods for detection of trace components in microextracts. These systems, allowing detection of extractable organic compounds from about 0.1 mg of sample, will be extremely useful in the future for analysis of natural and synthetic colorants, varnishes extracted, for instance, from cotton swabs used during cleaning of paintings, and organic residues on archeological remains.
Rooted in the long tradition of Raman spectroscopy of cultural heritage materials, in this work we provide a personal perspective on recent applications and new frontiers in sampling modalities, data processing, and instrumentation.
The present review is aimed at reporting on the most advanced and recent applications of immunochemical imaging techniques for the localization of proteins within complex and multilayered paint stratigraphies. Indeed, a paint sample is usually constituted by the superimposition of different layers whose characterization is fundamental in the evaluation of the state of conservation and for addressing proper restoration interventions. Immunochemical methods, which are based on the high selectivity of antigen–antibody reactions, were proposed some years ago in the field of cultural heritage. In addition to enzyme-linked immunosorbent assays for protein identification, immunochemical imaging methods have also been explored in the last decades, thanks to the possibility to localize the target analytes, thus increasing the amount of information obtained and thereby reducing the number of samples and/or analyses needed for a comprehensive characterization of the sample. In this review, chemiluminescent, spectroscopic and electrochemical imaging detection methods are discussed to illustrate potentialities and limits of advanced immunochemical imaging systems for the analysis of paint cross-sections.
Despite the large diffusion of natural organic substances in art-historical materials, their characterization presents many challenges due to the chemical complexity and instability with respect to degradation processes. Among natural products, proteins have been largely used in the past as binders but also as adhesives or additives in coating layers. Nevertheless, biological identification of proteins in art-historical objects is one of the most recent achievements obtained in heritage science thanks to the development of specifically tailored bio-analytical strategies. In the context of this active emerging discipline, immunological methods stand out for sensitivity, specificity and versatility for both protein recognition and localization in micro-samples. Furthermore, the growing use of immunological techniques for advanced diagnostics and clinical applications ensures continuous improvement in their analytical performance. Considering such, this review provides an overview of the most recent applications of enzyme linked immunosorbent assay and immunofluorescence microscopy techniques in the field of heritage materials. Specifically, the main strengths and potentials of the two techniques as well as their limits and drawbacks are presented and discussed herein.
The separation, detection and quantitation of specific species contained in a sample in the field of Cultural Heritage requires selective, sensitive and reliable methods. Procedures based on liquid chromatography fulfil these requirements and offer a wide range of applicability in terms of analyte types and concentration range. The main applications of High Performance Liquid Chromatography in this field are related to the separation and detection of dyestuffs in archaeological materials and paint samples by reversed-phase liquid chromatography with suitable detectors. The relevant literature will be revised, with particular attention to sample treatment strategies and future developments. Reversed phase chromatography has also recently gained increasing importance in the analysis of lipid binders and lipid materials in archaeological residues: the main advantages and disadvantages of the new approaches will be discussed. Finally, the main applications of ion chromatography and size exclusion chromatography in the field of Cultural Heritage will be revised in this chapter.
Gas chromatography/mass spectrometry (GC/MS), after appropriate wet chemical sample pre-treatments or pyrolysis, is one of the most commonly adopted analytical techniques in the study of organic materials from cultural heritage objects. Organic materials in archaeological contexts, in classical art objects, or in modern and contemporary works of art may be the same or belong to the same classes, but can also vary considerably, often presenting different ageing pathways and chemical environments. This paper provides an overview of the literature published in the last 10 years on the research based on the use of GC/MS for the analysis of organic materials in artworks and archaeological objects. The latest progresses in advancing analytical approaches, characterising materials and understanding their degradation, and developing methods for monitoring their stability are discussed. Case studies from the literature are presented to examine how the choice of the working conditions and the analytical approaches is driven by the analytical and technical question to be answered, as well as the nature of the object from which the samples are collected.
During the last three decades, DNA analysis on degraded samples revealed itself as an important research tool in anthropology, archaeozoology, molecular evolution, and population genetics. Application on topics such as determination of species origin of prehistoric and historic objects, individual identification of famous personalities, characterization of particular samples important for historical, archeological, or evolutionary reconstructions, confers to the paleogenetics an important role also for the enhancement of cultural heritage. A really fast improvement in methodologies in recent years led to a revolution that permitted recovering even complete genomes from highly degraded samples with the possibility to go back in time 400,000 years for samples from temperate regions and 700,000 years for permafrozen remains and to analyze even more recent material that has been subjected to hard biochemical treatments. Here we propose a review on the different methodological approaches used so far for the molecular analysis of degraded samples and their application on some case studies.
Although most historians and art historians consider the radiocarbon dating technique not to be very precise by their criteria, the method has gained much importance over the last decades. Radiocarbon dating is increasingly used in the field of textile research and old polychrome statues, but also objects made of ivory, stucco, paper, and parchment are dated with the technique. Especially after the introduction of the AMS technique, a boom of this type of research has been noticed.
... nowadays, the preservation of cultural heritage must consider many different aspects. For example, to operate on a historical building, it is important to choose the analytical methods and tools that allow to obtain the essential information for the conservation purpose [2][3][4][5]. Generally, the possibility to use portable and complementary in situ techniques can be definitely helpful and can provide useful information about cultural heritage [4][5][6][7]. ...
... For example, to operate on a historical building, it is important to choose the analytical methods and tools that allow to obtain the essential information for the conservation purpose [2][3][4][5]. Generally, the possibility to use portable and complementary in situ techniques can be definitely helpful and can provide useful information about cultural heritage [4][5][6][7]. In addition, to realize a correct diagnostic plan, the choice of analytical techniques, in particular before the restoration, should be based on questions and doubts found from restoration staff [8,9]. ...
... In the upper part of the apse of S. Nicola in Carcere, Pasqualoni painted Christ in Glory between the Virgin andS. Nicholas and one of the themes of the New Testament iconography (the episode of the Calming the tempest) handed down by Mark the Evangelist (4,(35)(36)(37)(38)(39)(40)(41), giving it a definite political meaning. The subject alludes to Pius IX himself as figure of the militant Church, in the act of rowing, bringing the clergy and the people of Rome to safety approach the Basilica of St. Peter. ...
Article
An analytical approach applied to Vincenzo Pasqualoni's wall paintings in the apse of S. Nicola in Carcere (Rome) is described in this work. The diagnostic campaign was guided following the indications of the restorers, which were supported over all the phases of the restoration, addressing the multi-analytical approach to identify the original pigments palette used by artist, the conservation state and the presence of consolidants materials, by using spectroscopic techniques supported by chemometric analyses. In particular, reflectance spectroscopy from ultraviolet to short wavelength infrared (UV-VIS-SWIR) combined with chemometric approach, X-Ray Fluorescence spectroscopy (XRF) and Raman spectroscopy are used to characterize the original pigments palette and execution techniques. In addition, original binders and synthetic compounds, used in previous restoration treatments, were detected by using Time Gated Laser Induced Fluorescence spectroscopy (TG-LIF) and Fourier Transform Infrared (FT-IR) spectroscopy. The obtained results onto the case study of S. Nicola in Carcere is a proof of a synergic integration between scientific analytical methods and conservation/restoration approach, subject of high impact and interest in the field of Cultural Heritage. Specifically, through the application of the above-mentioned techniques it was possible to identify the palette used by the artist, mainly composed of inorganic pigments such as ochers, chrome green, cobalt blue, and others. About the binders used by the artist we deduce the use of fresco technique for the upper part of the apse, combined with the use of tempera for retouches. Finally, the presence of acrylic-based compounds used in previous restoration treatments was also documented.
... [2][3][4] Archaeological chemistry is a subset of archaeometry that concerns with identification the original ancient materials, revealing the chemical changes, detection the degradation mechanism, and evaluation the restoration methods. [1][2][3]5,6] The archaeological materials change with time, so the conservation and restoration processes are employed to safeguard the cultural heritage. [1,4] The preventive conservation process is applied to increase the lifespan of archaeological materials through setting the optimum environmental conditions. ...
... [30] Artificial aging of the paintings There was a mitigation test for the aging experiments as the icon models were examined at different time periods of the aging procedures to choose the suitable conditions for the actual aging process. The heat aging was carried out by placing the painting models at temperature 80 C for four-time intervals (5,11,15, and 20 days). [31] An ultraviolet chamber was set up to perform the aging experiment. ...
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The study is composed of three phases to describe the paintings at normal and several aging times: modeling of new icons similar to an ancient one, aging of the icons by heat and ultraviolet irradiation, and characterization of the icons. The results showed a change in the chemical structure of the painting materials, the crystallinity of the wood and canvas materials, and the chromaticity coordinates with darkening in the heat treatment and fading in the UV irradiation treatment. There is a correlation between the exposure time, the chemical properties of the materials, and the optical properties of the paintings.
... Применение современных оптических методов при исследовании произведений искусства имеет огромный потенциал в изучении состава материалов, контроле их состояния и разработке путей реставрации, в том числе красочных слоев [1]. На данный момент в этой области к числу широко используемых оптических методов можно отнести следующие: комбинационное рассеяние света (КРС), ИК поглощение в среднем ИК диапазоне, спектроскопия поглощения/отражения в УФ-БИК диапазонах (в том числе с использованием волоконнооптических зондов), лазерная искровая спектроскопия, а также люминесцентная спектроскопия [2][3][4]. Комбинации этих методов, а также дополнение их другими структурными методами, например рентгеновскими (рентгеновская дифракция, рентгенофлуоресцентный анализ, метод энергодисперсионной рентгеновской спектроскопии и др.), позволяют существенно расширить возможности при исследовании объектов культурного наследия различного состава и размера, от миниатюр и различного рода изображений [5][6][7][8] до стеклянных и керамических предметов [9][10][11][12], а также продуктов коррозии металлических скульптур [13][14][15][16]. Кроме того, использование комплексного подхода позволяет получить информацию о структуре и составе культурных объектов, состояние которых еще в прошлом веке считалось безнадежно утраченным [17]. ...
... Применение современных оптических методов при исследовании произведений искусства имеет огромный потенциал в изучении состава материалов, контроле их состояния и разработке путей реставрации, в том числе красочных слоев [1]. На данный момент, в этой области к числу широко используемых оптических методов можно отнести следующие: комбинационное рассеяние света (КРС), ИК поглощение в среднем ИК диапазоне, спектроскопия поглощения/отражения в УФ-БИК диапазонах (в том числе с использованием волоконнооптических зондов), лазерная искровая спектроскопия, а также люминесцентная спектроскопия [2][3][4]. Комбинации этих методов, а также дополнение их другими структурными методами, например, рентгеновскими (рентгеновская дифракция, рентгенофлуоресцентный анализ, метод энергодисперсионной рентгеновской спектроскопии и др.) позволяют существенно расширить возможности при исследовании объектов культурного наследия различного состава и размера, от миниатюр и различного рода изображений [5][6][7][8] до стеклянных и керамических предметов [9][10][11][12], а также продуктов коррозии металлических скульптур [13][14][15][16]. Кроме того, использование комплексного подхода позволяет получить информацию о структуре и составе культурных объектов, состояние которых еще в прошлом веке считалось безнадежно утраченным [17]. ...
Article
In the present article the pigments palette of a parchment handwritten fragment from the collection of Finnish fragments N 29 (Library of the Russian Academy of Sciences, Finnish fragment 29, old code - 4.9.28), dating from the XIV century, was investigated. This manuscript has not been restored earlier. With the aid of Raman spectroscopy technique it was found the use of cinnabar for red shades, the mixture of indigo and gypsum pigments in various ratios for blue shades and a mixture of sulfur-arsenic pigments (orpiment and pararealgar) for yellow shades. It was performed the study of the characteristic luminescence detection capability of the pigments at the real (non-model) samples, when excited by laser radiation of various wavelengths.
... Spectroscopic and separation techniques such as Raman, FTIR and GC-MS are well established in the investigation of heritage materials [6,7] including in the analysis of panel paintings [8,9], and imaging spectroscopy was recently explored by Delaney et al. [10]. In a study of an Italian early renaissance panel painting, a combination of different molecular and elemental spectroscopic imaging methods was shown to provide insight into artistic materials, pigment distribution and underdrawings [11]. ...
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In this study, a painted beehive panel from the collection of the Slovene Ethnographic Museum was examined with respect to its material composition with the aim to reveal the painting technique. Due to the state of degradation due to outdoor weathering (UV irradiation, rainfall, extreme temperature and humidity fluctuations), as well as past conservation interventions, the object represented a complex analytical challenge. We aimed for non-invasive techniques (FTIR in reflection mode, Raman spectroscopy and hyperspectral imaging in the range of 400–2500 nm); however, in order to explore paint layers, cross-sections were also analysed using Raman spectroscopy. FTIR spectroscopy in transmission mode and gas chromatography coupled to mass spectrometry were also used on sample fragments. Various original materials were identified such as pigments and binders. The surface coating applied during conservation interventions was also characterised. Additionally, organic compounds were found (oxalate, carboxylate), representing transformation products. The potential use of Prussian blue as a background paint layer is discussed.
... The degradation of CH materials can be assessed using several analytical techniques, with spectroscopic techniques being the most commonly used. It was already shown that Raman spectroscopy, infrared spectroscopy and GC-MS can offer detailed information for material characterisation as well as about the degradation and degradation products 18 . Furthermore, colourimetry can support an investigation on the basis of an assessment of the colour change. ...
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Fires can have a negative impact on the environment, human health, property and ultimately also on various objects of cultural heritage (CH). This paper deals with an investigation into the degradation of selected proteinaceous paint layers that were exposed to fire-related effects (i.e., fire effluents and/or high temperatures) in a modified cone-calorimeter system. Paint layers of egg yolk adhesive (E) and lead white tempera (E + LW) were exposed to fire-related impacts on top of a CH stack and in a specially designed CH test chamber. On the CH stack, the proteinaceous paint layers were exposed to fire effluents and high temperatures, while in the CH test chamber, the samples were exposed mainly to fire effluents. The molecular changes to the exposed paint layers were analysed by invasive and non-invasive spectroscopic analyses (i.e., FTIR and Raman spectroscopy) and complimented with pyrolysis-GC–MS, while the colour changes were evaluated using colourimetry. It was concluded that the proteinaceous binder degrades into aromatic amino acids and/or fatty acids after exposure to the overall impacts of the fire. Aromatic amino acids were detected by means of the FTIR and py-GC–MS analyses. In the case of the lead white tempera exposure, partial dissociation of the lead white pigment was confirmed by the detection of alteration products, such as lead oxide and lead carbonate. Moreover, the investigation of the E + LW samples exposed for longer times revealed the presence of lead carboxylates. On the other hand, no significant molecular changes were observed with the CH samples exposed to fire effluents in the CH test chamber. The research offered us an insight into the fire-induced effects on selected paints for the first time.
... In view of the fact that artworks are objects of a unique character presenting great artistic and/or cultural historical value in addition to often adding great monetary value, no significant damage to their integrity should occur. Therefore, having a non-destructive character is an essential requirement for scientific methods that operate in research in the field of cultural heritage [1][2][3][4][5][6][7]. ...
Article
In this work, a painting suspected of counterfeiting was analyzed using the synchrotron-based scanning macro X-ray fluorescence (MA-XRF) technique. The canvas has erasures including a signature erasure; however, some visible numbers indicate that the artwork may be from the 17th century. Through the studies' elemental maps, Cl-K and Ca-K were observed, which allowed us to reconstruct the signature present in the painting. Elemental maps of Ba-K, Ti-K, Fe-K, Zn-K, and Pb-K were also obtained from the painting, which made possible to visualize how the pigments based on these elements were used in the creative composition of the painting. In addition to the signature region, a region of the painting with dimensions of approximately 120 mm × 120 mm was investigated by synchrotron radiation induced MA-XRF, while keeping a high spatial resolution and elemental sensitivity. The measurements were carried out at the D09B micro-XRF beamline of the Brazilian Synchrotron Light Laboratory (LNLS), part of the Brazilian Center of Research in Energy and Materials, in Campinas Brazil. The painting was also investigated by SEM-EDS, and FTIR techniques. Those results, in addition to the supporting elemental maps, allowed additional information to be obtained, such as the binders used on the painting.
... O LD Master paintings precious objects illuminating Europes rich cultural heritage and history are often the subject of detailed technical examination, whether to investigate an artists materials and technique or in support of conservation or restoration treatments in order to preserve them for future generations. These processes have traditionally relied on X-ray radiography (or X-ray imaging) [1], infrared reflectography [2] or micro-sample analysis [3] an invasive and destructive process in order to understand the materials present within specific features of a painting [4], [5]. ...
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X-radiography (X-ray imaging) is a widely used imaging technique in art investigation. It can provide information about the condition of a painting as well as insights into an artist's techniques and working methods, often revealing hidden information invisible to the naked eye. In this paper, we deal with the problem of separating mixed X-ray images originating from the radiography of double-sided paintings. Using the visible color images (RGB images) from each side of the painting, we propose a new Neural Network architecture, based upon 'connected' auto-encoders, designed to separate the mixed X-ray image into two simulated X-ray images corresponding to each side. In this proposed architecture, the convolutional auto encoders extract features from the RGB images. These features are then used to (1) reproduce both of the original RGB images, (2) reconstruct the hypothetical separated X-ray images, and (3) regenerate the mixed X-ray image. The algorithm operates in a totally self-supervised fashion without requiring a sample set that contains both the mixed X-ray images and the separated ones. The methodology was tested on images from the double-sided wing panels of the \textsl{Ghent Altarpiece}, painted in 1432 by the brothers Hubert and Jan van Eyck. These tests show that the proposed approach outperforms other state-of-the-art X-ray image separation methods for art investigation applications.
... Raman and XRF are two complementary techniques, as the first provides molecular information of the studied compound while the second provides its elemental composition, so they are often used [6][7][8][9] to unambiguously identify unknown compounds, as in the case of the present measurements. ...
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Laser-induced fluorescence (LIF), Raman spectroscopy and X-ray (XRF) fluorescence were used to study two frescoes at the S. Alexander catacombs complex, in Rome. LIF analysis has shown the presence of a transparent protective material probably deposited in previous restoration treatments and allowed to clearly distinguish the areas undergoing the current restoration process from the ones which still have to be treated. Raman and XRF analysis allowed to non-destructively characterizing most of the pictorial materials used for the artworks, including calcite (CaCO3), red ochre (Fe2O3), minium (Pb3O4), yellow ochre (α-FeOOH) and others. Therefore, thanks to the complementarity of the above-mentioned techniques, it was possible to obtain a detailed characterization of the studied frescoes. Finally, the whole ensemble of results constituted a valid tool to effectively plan the restoration of the frescoes.
... Small fragments were obtained from each bone sample, while the tooth has been cut in half. The fragments were then embedded in Implex® polyester resin (Remet S.A.S., Bologna, Italy) and polished with abrasive paper Micromesh™ from 120 to 12,000 grit to obtain a smooth surface 76 . Visible images of the smaller cross-sections were acquired with an Olympus BX51M optical microscope (Olympus Corporation, Tokyo, Japan) connected to an Olympus DP70 digital camera and processed through Autopano Giga 4.2 and Adobe Photoshop 2020. ...
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Bones and teeth are biological archives, but their structure and composition are subjected to alteration overtime due to biological and chemical degradation postmortem, influenced by burial environment and conditions. Nevertheless, organic fraction preservation is mandatory for several archeometric analyses and applications. The mutual protection between biomineral and organic fractions in bones and teeth may lead to a limited diagenetic alteration, promoting a better conservation of the organic fraction. However, the correlation between elemental variations and the presence of organic materials (e.g., collagen) in the same specimen is still unclear. To fill this gap, chemiluminescent (CL) immunochemical imaging analysis has been applied for the first time for collagen localization. Then, Laser Ablation–Inductively Coupled Plasma–Mass Spectrometry (LA–ICP–MS) and CL imaging were combined to investigate the correlation between elemental (i.e., REE, U, Sr, Ba) and collagen distribution. Teeth and bones from various archeological contexts, chronological periods, and characterized by different collagen content were analyzed. Immunochemical analysis revealed a heterogeneous distribution of collagen, especially in highly degraded samples. Subsequently, LA–ICP–MS showed a correlation between the presence of uranium and rare earth elements and areas with low amount of collagen. The innovative integration between the two methods permitted to clarify the mutual relation between elemental variation and collagen preservation overtime, thus contributing to unravel the effects of diagenetic alteration in bones and teeth.
... The painting represents a wide spectrum of the world's cultural heritage and needs proper safeguarding procedures. The icon painting consists of hybrid materials (organic and inorganic materials) in multilayers form; support, canvas, ground, paint "pigments and binder" and varnish layer [1][2][3][4]. There are many sources, which can cause slow deterioration or sudden damage for the painting layers such as relative humidity, heat, UV radiation, dust, insects and poor handling. ...
... Considering the uniqueness, the peculiarity, and the vicissitudes of this painting, it was deeply studied by a historical point of view, but, to our knowledge, no scientific investigation about the materials constituting the painting was ever performed. Therefore, we thought that a scientific study could be crucial to reveal invisible details, hidden by the artist or by time [2][3] to give additional information about its conservation state. ...
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The “Trionfo della morte” is a detached fresco painting dated at the half of the XV century. Its history is strictly connected with the history of Palermo and it is considered a symbol of the late Gothic period. Some small areas of the fresco were analyzed using a combination of non-invasive techniques and hand-held instrumentations (multispectral imaging analysis, X-ray fluorescence (XRF), and IR spectroscopy). The characterization of the nature of pigments used in its realization and restoration works was performed and some indications about its conservation state were obtained. More interestingly, some hidden details were revealed on the mysterious painting. They constitute additional evidence of the preciousness of the fresco.
... The aim of this article is to give a call of attention to analytical chemists on the multiple and exciting areas within the research on the cultural heritage where we are required to give analytical information and help to interpret the overall results. An exhaustive description or explanation is not intended, as the scientific literature on this subject is prolific, and includes a recent book [9], general reviews [10], and ...
Article
Professionals belonging to very different areas of expertise are usually involved in research on the cultural heritage. Among the names given to the person in charge of analyses are conservator or material cientist, as the most usual, but never “analytical chemist”, despite analytical equipment, obtainment of analytical data and application of chemometrics approaches to obtain analytical results are always involved in their tasks. This article tries to be a call of attention to analytical chemists by showing the different areas within the research on cultural heritage in which they should be involved to provide the necessary analytical information. Examples of the analytical equipment involved in these studies, the research on pigments, dyes, binders and coatings, dating and cleaning of artworks are given, thus showing that analytical information on chemical aspects related to research on the cultural heritage should be, evidently, conducted in cooperation with analytical chemists.
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Review of the book Analytical Chemistry for Cultural Heritage (2017) that compiles eleven articles reporting the new advances of analytical techniques applied to Cultural Heritage in fields such as Science for the Conservation and Archaeometry. Each article offers a general view of the technique and the newest advances of the recent years, exemplified by research projects from around Europe.
Article
The tools of analytical chemistry, and the expertise and enthusiasm of many of its practitioners, have had a profound influence in the field of cultural heritage [1, 2]. Analytical techniques, especially those involving non-destructive methods of examination, have played a key role in the characterization, restoration, and preservation of an incredible range of works of art and cultural heritage, including ceramics, textiles, paintings, books, drawings, sculptures, jewelry, and a myriad of artifacts made of glass, wood, or metal. In addition, modern analytical instrumentation has been successfully applied to study the techniques used to produce heritage materials, to verify the authorship or estimate the date of pieces of art, and to detect reproductions and forgeries.
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Undertaking the conservation of artworks informed by the results of molecular analyses has gained growing importance over the last decades, and today it can take advantage of state-of-the-art analytical techniques, such as mass spectrometry-based proteomics. Protein-based binders are among the most common organic materials used in artworks, having been used in their production for centuries. However, the applications of proteomics to these materials are still limited. In this work, a palaeoproteomic workflow was successfully tested on paint reconstructions, and subsequently applied to micro-samples from a 15th-century panel painting, attributed to the workshop of Sandro Botticelli. This method allowed the confident identification of the protein-based binders and their biological origin, as well as the discrimination of the binder used in the ground and paint layers of the painting. These results show that the approach is accurate, highly sensitive, and broadly applicable in the cultural heritage field, due to the limited amount of starting material required. Accordingly, a set of guidelines are suggested, covering the main steps of the data analysis and interpretation of protein sequencing results, optimised for artworks.
Article
Pigments and binders include several natural and synthetic materials which have been used since pre‐history to produce a variety of colored artworks and textiles. Binders are used in paintings to disperse pigments. They include inorganic materials (e.g., in frescoes, water is the pigment vehicle; however, plaster is the ultimate binder) and organic materials (natural ones, such as proteins, siccative oils; or synthetic ones, such as acrylic, vinylic, alkydic). Characterizing the binding medium is fundamental in assessing the painting technique and addressing conservation issues, in order to devise the optimal restoration and/or display strategy. In addition, knowledge of an artist's palette facilitates a complete understanding of their work. These materials are usually characterized starting with an array of noninvasive imaging techniques, followed by the application of micro‐invasive (both destructive and not) protocols based on chromatographic and spectroscopic techniques.
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A new portable macro X-ray fluorescence scanner has been specifically designed for in situ, real-time elemental mapping of large painted surfaces. This system allows scanning 80 × 80 × 20 cm 3 along the X, Z, and Y directions, respectively, with adaptive beam size at the energy of the Rh Ka-line. The detection system consists of a 50 mm 2 active area detector coupled to a CUBE pre-amplifier and to the DANTE digital pulse processor (DPP) with adaptive shaping time. The system is controlled with a custom software including a graphical user interface (GUI) programmed in Python for real-time control of the stage, DPP, and camera of the scanner. This system allows considering new ways of sampling the object surface than the usual raster scanning in serpentine as well as a live elaboration of X-ray data; technical details and performances of the scanner are presented in this paper together with an example of its application to investigate painted surface, illustrating the value of the developed instrument.
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Through the paintings of the old masters, we showcase how materials science today provides us with a vision of the processes involved in the creation of a work of art: the choice of materials, the painter's skill in handling these materials, and the perception of the finished work.
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