ATR-FT-IR spectral collection of conservation materials in the extended region of 4000-80 cm–1

This review covers the analytical developments, instrumentation and methodologies applied to the characterisation of cultural heritage materials published up until 2014. This review covers past and present developments of analytical chemistry in the field of Cultural Heritage (CH), from the methods of characterization of materials to the procedures aiming at diagnosing the state of conservation of CH assets. A large number of analytical methodologies and tools (molecular and elemental spectroscopic techniques, chemometrics, chemical reactivity and modeling, etc. ) are now available to define: (a) the impacts of environmental stressors (natural and anthropogenic), (b) the decaying (chemical reactions) pathways of such materials in the surrounding environment, (c) the development of new remediation (cleaning, consolidation, rehabilitation, etc. ) processes based on the chemical knowledge and (d) the transfer of such knowledge to conservation departments in museums and companies working in the field of CH. Two important issues are highlighted in this review. One is the important role of analytical chemistry in this field, although its role was forgotten until a few decades ago; nowadays there are hundreds of papers demonstrating the important role of analytical chemistry practitioners in many kinds of CH actions. The other is the societal impact of the issues related to the study of heritage ( i.e. , rock art paintings, Pompeii, paintings in medieval churches, famous artists, etc. ) where analytical chemists are key professionals especially if portable instruments are used in field work. Finally a special consideration will be paid to future developments and how analytical chemistry can give added value to the research in CH.

Fourier transform infrared (FTIR) spectroscopy is one of the most widely applied techniques for the investigation of cultural heritage materials. FTIR microscopy is well established as an essential tool in the microdestructive analysis of small samples, and the recent introduction of mapping and imaging equipment allows the collection of a large number of FTIR spectra on a surface, providing a distribution map of identified compounds. In this Account, we report recent advances in FTIR spectroscopy and microscopy in our research group. Our laboratory develops, tests, and refines new and less-studied IR spectroscopy and microscopy methods, with the goal of their adoption as routine analytical techniques in conservation laboratories. We discuss (i) the analysis of inorganic materials inactive in the mid-IR region by means of far-IR spectroscopy, (ii) the development of new methods for preparing cross sections, (iii) the characterization and spatial location of thin layers and small particles, and (iv) the evaluation of protective treatments. FTIR spectroscopy and microscopy have been mostly used in the mid-IR region of 4000-600 cm(-1). Some inorganic pigments, however, are inactive in this region, so other spectroscopic techniques have been applied, such as Raman spectroscopy. We suggest an alternative: harnessing the far-IR (600-50 cm(-1)). Our initial results show that far-IR spectroscopy is exceptionally useful with mural paintings or with corrosion products from which larger sample quantities can generally be collected. Moreover, the inorganic composition of a sample can be characterized by the presence of several compounds that are inactive in the mid-IR range (such as sulfides, oxides, and so forth). Stratigraphical analyses by FTIR microscopy can be hindered by the process of cross section preparation, which often involves an embedding organic polymer penetrating the sample's porous structure. Here, the polymer bands may completely cover the bands of organic compounds in the sample. However, a correct methodological approach can prevent such limitations. For example, it is always advisable to analyze the sample surface before preparing the cross section in order to characterize the preparation layers and the varnish layers, which are generally applied to the surface of a painting both to protect it and improve the color saturation. Furthermore, the innovative use of IR-transparent salts as embedding material for cross sections can prevent contamination of the embedding resin and improve detection of organic substances. Another key point in the use of FTIR microscopy in artwork analysis is spatial resolution. The high-energy output of a new integrated FTIR microscope enhances the ability to characterize and spatially locate small particles and thin layers. Moreover, the new configuration proves extremely useful in the evaluation of protective treatments, because larger areas may be analyzed in less time in comparison to traditional systems, allowing the collection of more statistical data.

Since the first reported analytical studies and technical examinations of art and archaeological objects conducted in the late 18th century, analytical techniques and methods applied to the study of artworks have constantly grown. Among the materials composing the art object, organic compounds used as binding media or protective coatings have attracted the attention of the conservation profession given their noticeable ability for undergoing morphological and chemical changes on ageing. Thus, the aim of this paper is to review the most recent advances in the identification and determination of organic compounds present in art and art conservation materials. Immunofluorescence techniques have been proposed in recent decades as an alternative to the classical and simpler microchemical tests. Besides, a variety of instrumental techniques have also been improved in an attempt to enhance the sensitivity, repeatability and accuracy of the analytical results. Spectroscopic techniques, such as UV-vis, FTIR and Raman spectroscopy, have been coupled with light microscopes for these purposes. Synchrotron radiation FTIR microspectroscopy has also been successfully applied to the analysis of artworks. Mass spectrometry has also been increasingly used as a detector system coupled with a chromatographic device. Chromatographic methods have also improved in recent years. Paper and thin layer chromatographic techniques have been progressively replaced with gas chromatography (GC), pyrolysis-GC, high performance liquid chromatography and capillary electrophoresis. More complex proteomics hyphenated techniques, such as nano-liquid chromatography-nano-electrospray ionisation/collision quadrupole time-of-flight tandem mass spectrometry, have been recently applied to the identification and determination of proteinaceous binders. Microbeam analytical techniques have also been incorporated into the list of advanced instrumental techniques for art conservation purposes. Finally, a number of new instrumental techniques have been proposed as a suitable alternative to the conventional microscopy techniques for morphological studies.