Deterioration and discoloration of historical protective treatments on marble.

This study integrates the complex research conducted on the sources of brown discolorations that occur on marble statues (fifteenth century) of the Church of Orsanmichele in Florence (Italy). They underwent conservative interventions in the past and the brownish discolorations on their surfaces strongly altered the clear tone of the marble. In this study, Carrara marble model specimens were treated with organic and inorganic substances (non-pasteurised milk; linseed oil; walnut oil; ammonium oxalate; microcrystalline wax; beeswax; milk + linseed oil; and milk + ammonium oxalate + linseed oil) to simulate their effects on the stone. Some of the substances were commonly used in the past (as on the Orsanmichele statues) but most of them are still used in many countries. The treated specimens were exposed to natural and artificial ageing. The main results of the research were (i) the specimens treated with linseed oil, milk + linseed oil, and milk + linseed oil + ammonium oxalate showed a severe change of colour after either artificial or natural ageing; (ii) an extensive polymerisation of the organic substances occurred; (iii) calcium oxalate and several oxidised diacylglycerols (DAGs) and triacylglycerols (TAGs) were the last chemical products of the oxidation processes induced by ageing; (iv) Maillard reaction, producing brownish coloration, likely occurred in specimens containing milk as a result of the interaction between sugars and proteins.

Enriching the knowledge of Ostia Antica painted fragments: a multi-methodological approach.

This paper presents the study of selected painted fragments from different contexts of Ostia Antica city, dating between 2nd century BCE and the end of the 1st century CE. The aim is to identify the raw materials used and to understand the execution techniques through a non-invasive protocol including techniques based either on multiband imaging (Visible-VIS, Ultraviolet induced Luminescence - UVL and Visible Induced Luminescence - VIL) and single spot analyses (Fiber Optic Reflectance Spectroscopy- FORS and portable X-Ray Fluorescence spectrometry - XRF). The most representative and interesting fragments were sampled for further studies with laboratory techniques such as optical microscopy (OM) and electron microscopy (SEM), Fourier Transform Infrared and micro-Raman Spectroscopies (FT-IR and µRaman). The extensive use of non-invasive techniques, even working on fragments, is proved to be the most robust and effective approach enabling the analysis of a high number of areas, dramatically increasing the statistical meaning of the collected data. The elaboration of such a huge number of data allows highlighting differences and similarities, thus achieving a more realistic overview of the materials composition and addressing the sampling to the more significant and complex areas.

Non-invasive techniques applied to the alchemical codex of the State Archive of Florence.

This paper focuses on the application of non-invasive techniques to study a peculiar object, an alchemical codex completely made of lead stored at the State Archive of Florence.1 The sheets of the codex appeared entirely covered by thick and heterogeneous corrosion patinas for which a restoration was planned for their removal. This activity was supported by analytical investigations to characterise the materials that made up the patinas using non-invasive techniques. The codex pages were initially documented with imaging techniques. Subsequently, spectroscopic data were acquired on each sheet using spot analytical techniques: Total Reflectance Fourier Transform Infrared Spectroscopy (TR FT-IR), Fibre Optics Reflectance Spectroscopy (FORS), X-Ray Fluorescence (XRF), Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD). The identification of deterioration compounds has been extremely useful for the conservator to deal with the removal of dangerous and disfiguring patinas.

The Tomb of the Diver and the frescoed tombs in Paestum (southern Italy): New insights from a comparative archaeometric study.

The Tomb of the Diver has been subject for many decades of fierce debate among archaeologists and classicists. Since its discovery in 1968, some scholars have considered it a unique example of the lost tradition of Greek painting, others have emphasized Etruscan or Italic parallels. More recently, a possible local production has been suggested. With the aim of trying to solve the archaeological question, an archaeometric comparison among this well-known artwork and several frescoed tombs coming from Hellenistic and Lucan necropolis was carried out. The multi-analytical study was focused on the identification of peculiar features of executive techniques and raw materials since the first period of the archaeological site. The analytical investigation has been preliminary based on a non-destructive approach, performed in-situ by portable equipment including imaging diagnostics and compositional spectroscopic techniques for identifying pigments and the conservation state of original painted surface; subsequently, a further deepening by using destructive techniques was performed in-lab for the mortar-based supports characterization. Archaeometric study suggested that technological choices slightly changed in a time span of about two centuries, highlighting important markers that allow clustering the contemporary artistic productions. Moreover, a comparison with mortars from temples decorations was provided to better understand the whole artistic context. The archaeometric data showed that the Tomb of the Diver could be traced back to a local artisanal tradition and therefore is neither Etruscan nor Greek, but the first and foremost an expression of the local elite culture of Paestum.

The role of different network modifying cations on the speciation of the Co2+ complex in silicates and implication in the investigation of historical glasses.

In the last decades the speciation of the cobalt complex in a glass matrix has been extensively studied. Bivalent cobalt ions in glasses of different composition commonly adopt a tetrahedral coordination, though hexa- or penta-coordinated species are also possible. Changes in the absorbance spectrum of Co-doped glasses were attested in previous studies according to the introduction of different modifying cations. A shifting of the first sub-band characterizing the typical triplets of tetrahedral Co2+ ions in both the visible and near infrared regions was observed, but discrepancies in literature suggested a relevant role of glass composition on the definition of the optical signature of cobalt. Co-doped glasses with different composition (soda-lime, potash-lime, mixed alkali and ZnO-Na2O-CaO-SiO2) were studied via Fiber Optic Reflectance Spectroscopy (FORS). Pseudo-Voigt functions were used for the deconvolution of the absorbance spectra and the features of the bands characteristic of each cobalt complex were investigated. The structural role played by each modifying cation and the fundamental implications of glass basicity on the speciation of different Co-complexes were stressed. Changes in glass structure resulted in different equilibria between the three absorbing species whose specific optical signatures in the 480-530nm region interact to determine the resulting absorbance spectrum.

A multi-analytical approach for the characterization of wall painting materials on contemporary buildings.

Samples from Keith Haring's wall painting of the Necker Children Hospital in Paris were studied by a multi-analytical protocol. X-ray fluorescence (XRF), powder X-ray diffraction (XRDP), Electron microscope (SEM-EDS), Infrared and Raman spectroscopy (µ-FT-IR and µ-Raman) measurements were performed in order to characterize the materials and to identify the art technique used to produce this contemporary work. Materials from the mural suffered from severe detachments of materials and several fragments were found on the ground beneath. Some of these fragments, which were representative of the whole palette and stratigraphic sequence, were collected and studied. The fragments were sufficiently large to enable non-invasive measurements to be performed in order to characterize the materials. A comparison of the data of the techniques applied revealed that Haring's palette was composed of organic pigments such as Naphtol red, phthalocyanine blue and green and Hansa yellow, in accordance with those used previously by the artist in other painted murals.

Cross-section and staining-based techniques for investigating organic materials in painted and polychrome works of art: a review.

The article presents a review of the use of cross-section and staining techniques for investigating natural organic materials (mainly proteinaceous and oil-based binders/varnishes) in painted and polychrome artworks, considering the requirements of conservation practice and routine diagnostics. The reviewed literature calls attention to the importance of using cross sections to prepare samples for optical microscopy and to different properties of embedding resins; the most appropriate instrumental conditions for optical microscopy; and the advantages and disadvantages of the most common staining techniques. A few case studies were selected to illustrate the use of autofluorescence (intrinsic fluorescence) and induced fluorescence (using specific staining tests and fluorophore-labeled antibodies) for mapping and identifying organic paint materials in cross sections. New directions of research in cross-section analyses and fluorescence-based techniques for the identification and mapping of artistic materials are presented. The complementary use of different stains on the same cross section, further exploration of intrinsic and induced fluorescence of aged versus fresh materials, and applicability of cross-section observation and staining as complementary methods for assessing the effectiveness of restoration treatments, such as cleaning and consolidation, are discussed in the last section of the article.

Library of UV-Vis-NIR reflectance spectra of modern organic dyes from historic pattern-card coloured papers.

An accurate characterisation of the organic dyes used in artworks, especially those made of paper, is an important factor in designing safe conservation treatments. In the case of synthetic organic dyes used in modern works of art, for example, one frequently encountered difficulty is that some of these dyes are not still commercially available. Recognizing this problem, the authors of this paper present the results of an analysis of UV-Vis-NIR fibre optic reflectance spectra of 82 samples of dyed paper prepared with 41 dyes. The samples come from a historic book, The Dyeing of Paper in the Pulp, which was published by Interessen-Gemeinschaft (I.G.) Farbenindustrie in 1925. The dyes used in the paper pulp belong to the azo compounds, acridine, anthraquinone, azine, diphenylmethane, indigoid, methine, nitro, quinoline, thiazine, triphenylmethane, sulphur and xanthene classes.

Integrated methodology for the evaluation of cleaning effectiveness in two Russian icons (16th-17th centuries).

This article covers a methodology for evaluating the effectiveness of cleaning two Russian icons. The icons belong to a group of five from the same iconographic school, dating from the 16th to 17th centuries. An integrated and complementary approach to varnish and overpaint removal involved microscopic techniques (optical and scanning electron microscopy) and colorimetry (CIE L*a*b* system). The materials and techniques used in these icons have been characterized previously. Cleaning revealed extensive overpainting that had not only dramatically changed the original appearance, but also the meaning and attribution of one of the two icons. The analyses carried out were useful in determining the extent of the overpainting and led to a better assessment of the results and effectiveness of the restoration.

Integrated analytical study for the authentication of five Russian icons (XVI-XVII centuries).

This article presents an integrated approach for the authentication of five Russian icons through the study of their paint materials (elemental composition and stratigraphic mapping), state of conservation and artistic technique. The results of the applied analytical protocol, involving optical and scanning electron microscopy coupled with energy-dispersive X-ray spectrometry and Fourier transformed infrared spectroscopy/microspectroscopy, led to the conclusion that the five icons belong to the same group and iconographic school (from Northern Russia) and date from the end of the 16th century to the beginning of 17th century. Because of massive overpainting, the icons "suffered" a change in iconographic style and significance, and restoration treatment brought to light the original painting and its attribution. Identification of the composition of the original chromatic palette used by the iconographer, the stratigraphic mapping and the conservation state of the painting materials, along with the features of the original artistic technique, furnished key elements for the icons' authentication. Here, we present the first experimental data concerning the identification of the authentication characteristics, being part of a large project that has as its final aim the evaluation of the effectiveness and effects of the cleaning agent on the paint layers.