Mobile depth profiling and sub-surface imaging techniques for historical paintings—A review

Hidden, sub-surface paint layers and features contain valuable information for the art-historical investigation of a painting's past and for its conservation for coming generations. The number of techniques available for the study of these features has been considerably extended in the last decades and established techniques have been refined.This review focuses on mobile non-destructive subsurface imaging and depth profiling techniques, which allow for the in-situ investigation of easel paintings, i.e. paintings on a portable support.Among the techniques discussed are: X-ray radiography and infrared reflectography, which are long established methods and are in use for several decades. Their capabilities of element/species specific imaging have been extended by the introduction of energy/wavelength resolved measurements.Scanning macro-X-ray fluorescence analysis made it for the first time possible to acquire elemental distribution images in-situ and optical coherence tomography allows for the non-destructive study the surface paint layers in virtual cross-sections.These techniques and their variants are presented next to other techniques, such as Terahertz imaging, Nuclear Magnetic Resonance depth profiling and established techniques for non destructive testing (thermography, ultrasonic imaging and laser based interference methods) applied in the conservation of historical paintings.Next to selected case studies the capabilities and limitations of the techniques are discussed.     

Characterization of polyvinyl resins used as binding media in paintings by pyrolysis–silylation–gas chromatography–mass spectrometry

Polyvinyl resins, in particular poly(vinyl acetate) emulsions (PVA), are widely used in contemporary paintings as binding media, because of the optimum mechanical and optical properties these polymers confer on the paint layers. A study has been carried out to chemically characterize samples of PVA resins prepared as coating films from commercial products currently available from fine arts suppliers. For this purpose, a new method has been based on "on-line" silylation-pyrolysis using hexamethyldisilazane as derivatisation reagent in pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). This proposed procedure leads to unambiguous identification of this type of binder and improves conventional direct Py-GC-MS. PVA media used in three contemporary paintings from a private collection and from the Museum of Fine Arts of Málaga (Spain) have been successfully identified with this procedure. As a second step of this work, a study devoted to the characterization of changes in the chemical composition of the PVA commercial products studied has been carried out. Effects induced in the specimens by three different types of artificial accelerated ageing process--thermal, UV light, and in an SO(2)-polluted chamber--were compared.     

A study of ochres from an Australian aboriginal bark painting using thermal methods

The potential of thermogravimetric analysis (TG) as a tool for the characterisation of ochre paint used in indigenous Australian bark paintings has been investigated. TG has been combined with differential scanning calorimetry (DSC) and mass spectrometry (MS) to identify and quantify the main inorganic and organic components present in the paints. The results obtained were supported by comparison with infrared spectra and XRD data obtained for the same specimens. The potential of thermal methods for the characterisation ochres has been demonstrated, with subtle differences between small samples being able to be identified.     

Surface-enhanced Raman spectroscopy analysis of house paint and wallpaper samples from an 18th century historic property

Conservation efforts for heritage buildings require a substantial knowledge of the chemical makeup of materials that were used throughout the lifetime of the property. In particular, conservators are often concerned with the identification of colorants used in both interior and exterior wall treatments (paint, wallpaper, etc.) in order to gain perspective into how the building may have appeared during a certain time period in its existence. Ideally, such an analysis requires a technique that provides molecular level information as to the identity of the colorant as well as other sample components (binders, fillers, etc.), which is useful for dating purposes. In addition, the technique should be easily applied to paint layer samples which can be extremely thin and fragile. Herein we report the surface-enhanced Raman spectroscopy (SERS) analysis of paint and wallpaper samples taken from exterior and interior surfaces of a historic building. Several pigments were identified in the samples, which ranged from early inorganic pigments (lead white, barium sulfate, calcium carbonate, anhydrous chromium(III) oxide) which have been used in house paints for centuries, to a more modern pigment (phthalocyanine blue), developed in the middle of the 20th century. This analysis highlights the usefulness of SERS in such a conservation effort, and demonstrates for the first time pigment identification in house paints and wallpaper using SERS, which has far-reaching implications not only in the field of conservation, but also in forensics, industrial process control, and environmental health and safety.     

Multivariate chemical mapping of pigments and binders in easel painting cross-sections by micro IR reflection spectroscopy

Paintings are composed of superimposed layers of inorganic and organic materials (pigments and binders). Knowledge of the stratigraphic sequence of these heterogeneous layers is fundamental for understanding the artist’s painting technique and for conservation issues. In this study, micro-IR mapping experiments in reflection mode have been carried out on cross-sections taken from simulations of ancient easel paintings. The objective was to locate both organic binders and inorganic pigments. Chemical maps have been re-constructed using the common approach based on the integration of specific infrared bands. However, owing to the complexity of painting materials, this approach is not always applicable when dealing with broad and superimposed spectral features and with reststrahlen or derivative-like bands resulting from acquisition in reflection mode. To overcome these limitations, principal-component analysis has been successfully used for the re-construction of the image, extracting the relevant information from the complex full spectral data sets and obtaining reliable chemical distributions of the stratigraphy materials. Different pigment–binder combinations have been evaluated in order to understand limitations and strengths of the approach. Finally, the method has been applied for stratigraphic characterization of a cross-section from a 17th century wooden sculpture identifying both the original paint layer and the several overpaintings constituting the complex stratigraphy.     

Detecting art forgeries using LA-ICP-MS incorporating the in situ application of laser-based collection technology

The nature of art lends itself to forgery as a skilled and determined forger can mimic the techniques and styles of an artist to a level where even an expert can be duped. The authentication of paintings is a subjective process, but modern techniques may provide the means to provenance artist pigments based on elemental composition. This study applies laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to the analysis of artist paints from different manufacturers to identify variation between the elemental association patterns of these materials. The technique facilitates comparison of the paints used by an artist with produced works of art to assist provenancing initiatives of questioned materials. The effects of the trace element profiles of the backing substrate and binder on analytical data were also identified. By applying the technique to paint scraped from real paintings, a limited database was created to allow comparison to be made with some of Australian artist, Kathleen O’Connor's artworks and assist in determining production chronology. Data from this study were able to facilitate comparison of blue paints from two different paintings and confirm their co-provenance consequently determining the relative production date of a separate painting of previously unknown age.Preliminary trials of a prototype collection device designed to reduce damage and allow for in situ sampling of artworks were also undertaken. The device, which allows direct laser-based sampling of a complete painting, was tested using a Francis Ryan painting. The prototype allows for the collection of debris directly generated by LA-ICP-MS of a predefined area of a painting prior to subsequent analysis using direct LA-ICP-MS. This collection method significantly minimizes the amount of damage produced by conventional sampling methods. Analyses of the debris collected, using the prototype, were found to be comparable to the scrapings of equivalent paint analysed using direct LA-ICP-MS analysis.     

Study of mural paintings using in situ XRF, confocal synchrotron-μ-XRF, μ-XRD, optical microscopy, and SEM-EDS--the case of the frescoes from Misericordia Church of Odemira

In this work, we present the results of an analytical method developed for detailed pigment identification, stratigraphy, and degradation of the paint layers of mural paintings applied in the study of the 17th century frescoes from the Misericordia Church of Odemira (Southwest Portugal). In situ X-ray fluorescence spectrometry analyses were performed on three panels of the mural paintings and complemented by colorimetric measurements. The different color areas were also sampled as microfragments (approx. 1 mm2) that were studied as taken or mounted in epoxy resin to expose the different paint layers. The microfragments of paint layers and their cross sections were characterized by optical microscopy and scanning electron microscopy coupled with energy dispersive X-ray spectrometry. Furthermore, elemental analysis was obtained with spatially resolved confocal synchrotron radiation μ-X-ray fluorescence spectrometry performed at ANKA synchrotron FLUO beamline. Occasionally, phase analysis by μ-X-ray diffraction was also performed. Results from the different techniques allowed pigment identification and, in some cases, the evaluation of color changes due to degradation processes and, considering the Southern Portugal geology, the identification of their possible provenance. The pigments used were essentially yellow, brown and red ochres, smalt blue, copper green, and black earths, probably from local sources.     

Evolved Gas Analysis‐Mass Spectrometry to Identify the Earliest Organic Binder in Aegean Style Wall Paintings

An organic binder was identified in the painted fragments from the Canaanite palace of Tel Kabri, Israel. Recently dated to the late 18th century B.C.E. by ¹⁴C, Tel Kabri is the most ancient of the Eastern Mediterranean sites in which Aegean style paintings have been found. The application of pigments was suspected to be using an organic binding medium, particularly for the Egyptian Blue pigment. Samples of blue paint were examined using evolved gas analysis‐mass spectrometry (EGA‐MS) in order to overcome the analytical challenges imposed by highly degraded aged proteinaceous materials. Egg was identified as the binder based on the presence of hexadecanonitrile and octadecanonitrile, confirming the use of a secco painting technique. Lysozyme C from Gallus gallus was detected by proteomics analysis, confirming the presence of egg. To our knowledge, this is the earliest use of egg as a binder in Aegean style wall paintings.     

Molecular Fluorescence Imaging Spectroscopy for Mapping Low Concentrations of Red Lake Pigments: Van Gogh's Painting The Olive Orchard

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

Single and multiplexed immunoassays for the chemiluminescent imaging detection of animal glues in historical paint cross-sections

The characterization of the organic components in a complex, multilayered paint structure is fundamental for studying painting techniques and for authentication and restoration purposes. Proteinaceous materials, such as animal glue, are of particular importance since they are widely used as binders, adhesives and for gilding. Even though proteins are usually detected by chromatographic and proteomic techniques, immunological methods represent an alternative powerful approach to protein analysis thanks to the high specificity of antigen–antibody reactions. Our previous studies demonstrated that ovalbumin and casein could be localized in paint cross-sections with high sensitivity and good spatial resolution (i.e. within the single painting layers) by using chemiluminescent (CL) immunochemical microscope imaging. In the present research work, we describe for the first time the immunolocalization of collagen (the main protein of animal glue) in paint cross-sections by CL imaging microscopy. Two different analytical protocols have been developed, allowing either the detection of collagen or the simultaneous detection of collagen and ovalbumin in the same paint sample. The assays were used to detect collagen and ovalbumin in cross-sections from model samples and historical paintings (a wall painting dated to 1773–1774 and a painted wood panel of the Renaissance period) in order to achieve information on paint techniques and past restoration interventions.

Enhancement of the static SIMS secondary ion yields of lipid moieties by ultrathin gold coating of aged oil paint surfaces

Static secondary ion mass spectrometry (SIMS) is a powerful technique for identification and localization of pigments and binding media present in traditional paintings. Coating the surface of a cross‐section with a 20 Å thick gold layer improves the yields of secondary ions from the fatty acids and diacids. A chalk tablet containing 1% stearic acid, which was partially covered during gold deposition, is used as a test system to investigate the increase of the organic secondary ion yields upon gold deposition in SIMS imaging. A comparative study of a native and gold‐coated aged surface of a lead white‐containing linseed oil paint demonstrates the enhancement of the organic ion yields on a sample relevant for painting studies. The yields of oil paint‐derived negative ions increase by a factor of 3 whereas the yields of positive ions increase by a factor of 2–4. The different types of charged functional groups determine the degree of improvement in yield. Gold coating improves the ionization process of the fatty acids and does not influence their fragmentation. The dissociation of the lead white by the primary ion beam is reduced due to the gold coating. Copyright © 2004 John Wiley & Sons, Ltd.     

14C dating of ancient rock art: A new application of plasma chemistry

We have developed a new statically operated oxygen plasma method that allows direct¹⁴C dates to be obtained from ancient rock paintings. The method is applicable even to paintings on limestone (CaCO₃) walls. A sample of a pictograph which had naturally spalled offa shelter wall in the Lower Pecos region of Texas was subjected to a low temperature ( 150°C) oxygen plasma to selectively remove the organic carbon-containing material used in the paint as CO₂, without contamination from the limestone substrate. The Zürich EHT accelerator mass spectrometer was then used to determine the radiocarbon age of this prehistoric rock painting. It was successfully dated at 3865 ± 100 years BP, in good accord with the archaeological context which has set the onset of this Pecos River style of pictograph between 4100 and 3200 years BP. The method appears feasible and is applicable to rock art in which organic materials were used in the paint.     

Surface-enhanced Raman scattering substrates fabricated using electroless plating on polymer-templated nanostructures

Surface-enhanced Raman scattering (SERS) has great potential as an analytical technique based on the unique molecular signatures presented even by structurally similar analyte species and the minimal interference of scattering from water when sampling in aqueous environments. Unfortunately, analytical SERS applications have been restricted on the basis of limitations in substrate design. Herein, we present a simple SERS substrate that exploits electroless deposition onto a nanoparticle-seeded polymer scaffold that can be fabricated quickly and without specialized equipment. The polymer-templated nanostructures have stable enhancement factors that are comparable to the traditional silver film over nanospheres (AgFON) substrate, broad localized surface plasmon resonance spectra that allow various Raman excitation wavelengths to be utilized, and tolerance for both aqueous and organic environments, even after 5 day exposure. These polymer-templated nanostructures have an advantage over the AgFON substrate based on the ease of fabrication; specifically, the ability to generate fresh SERS substrates outside the laboratory environment will facilitate the application of SERS to new analytical spectroscopy applications.     

A Critical Review on the Analysis of Metal Soaps in Oil Paintings

Up to 70 % of the oil paintings conserved in collections present metal soaps, which result from the chemical reaction between metal ions present in the painted layers and free fatty acids from the lipidic binders. In recent decades, conservators and conservation scientists have been systematically identifying various and frequent conservation problems that can be linked to the formation of metal soaps. It is also increasingly recognized that metal soap formation may not compromise the integrity of paint so there is a need for careful assessment of the implications of metal soaps for conservation. This review aims to critically assess scientific literature related to commonly adopted analytical techniques for the analysis of metal soaps in oil paintings. A comparison of different analytical methods is provided, highlighting advantages associated with each, as well as limitations identified through the analysis of reference materials and applications to the analysis of samples from historical paintings.     

A label-free gold-nanoparticle-based SERS assay for direct cyanide detection at the parts-per-trillion level

Cyanide is an extremely toxic lethal poison known to humankind. Developing rapid, highly sensitive, and selective detection of cyanide from water samples is extremely essential for human life safety. Driven by the need, here we report a gold-nanoparticle-based label-free surface-enhanced Raman spectroscopy (SERS) system for highly toxic cyanide ion recognition in parts-per-trillion level and to examine gold-nanoparticle-cyanide interaction. We have shown that the SERS assay can be used to probe the gold nanoparticle dissociation process in the presence of cyanide ions. Our experimental data indicates that gold-nanoparticle-based SERS can detect cyanide from a water sample at the 110 ppt level with excellent discrimination against other common anions and cations. The results also show that the SERS probe can be used to detect cyanide from environmental samples.     

External proton beam analysis of layered objects

Ion-beam analysis for determining the elemental composition and to obtain depth information has been carried out with MeV protons in air by means of simultaneous external PIXE and RBS. Stainless steel products of extended size and a historic painting are analyzed non-destructively. These objects include systems of layers with areal densities up to some ten mg/cm(2). Depth information is obtained by PIXE using energy variation of the primary proton beam and in addition directly from RBS for the outermost near-surface region. Main and secondary elements as well as impurities can be determined together with areal densities. Particularly, the knowledge on the depth distribution of the pigments in paintings provides information on paint techniques.     

Mass Spectrometric and Synchrotron Radiation based techniques for the identification and distribution of painting materials in samples from paints of Josep Maria Sert

ABSTRACT: BACKGROUND: Establishing the distribution of materials in paintings and that of their degradation products by imaging techniques is fundamental to understand the painting technique and can improve our knowledge on the conservation status of the painting. The combined use of chromatographic-mass spectrometric techniques, such as GC/MS or Py/GC/MS, and the chemical mapping of functional groups by imaging SR FTIR in transmission mode on thin sections and SR XRD line scans will be presented as a suitable approach to have a detailed characterisation of the materials in a paint sample, assuring their localisation in the sample build-up. This analytical approach has been used to study samples from Catalan paintings by Josep Maria Sert y Badia (20th century), a muralist achieving international recognition whose canvases adorned international buildings. RESULTS: The pigments used by the painter as well as the organic materials used as binders and varnishes could be identified by means of conventional techniques. The distribution of these materials by means of Synchrotron Radiation based techniques allowed to establish the mixtures used by the painter depending on the purpose. CONCLUSIONS: Results show the suitability of the combined use of SR FTIR and SR XRD mapping and conventional techniques to unequivocally identify all the materials present in the sample and their localization in the sample build-up. This kind of approach becomes indispensable to solve the challenge of micro heterogeneous samples. The complementary interpretation of the data obtained with all the different techniques allowed the characterization of both organic and inorganic materials in the samples layer by layer as well as to establish the painting techniques used by Sert in the works-of-art under study.     

Stratigraphic analysis of organic materials in wall painting samples using micro-FTIR attenuated total reflectance and a novel sample preparation technique

Wall paintings typically contain low concentrations of organic materials within a largely inorganic matrix and are characterised by their high porosity and long-term exposure to severe environmental conditions. The identification of organic materials within specific paint or plaster layers is challenging and the inherent characteristics of wall painting samples present further complications. Embedding materials (such as epoxy, polyester and acrylic-based resins) used to produce cross-sections often infiltrate porous and leanly bound samples, and compromise the interpretation of Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectra and the qualitative identification of natural organic materials. An alternative method for the preparation of cross-sections of wall painting samples was developed using cyclododecane (C(12)H(24)) as a temporary consolidant and barrier coating to encapsulate the sample, and to provide necessary support to produce a cross-section through microtoming. Impacts of traditional and novel sample preparation techniques on the identification of organic materials with micro-FTIR-ATR were examined for both replica and real wall painting samples.     

Non-destructive in situ determination of pigments in 15th century wall paintings by Raman microscopy

Raman microscopy has been applied to the study of 15th century wall paintings in a chapel of St. Orso Priory palace (Aosta, Italy) in view of their restoration. The use of a transportable instrument has made it possible to work non-destructively in situ without sampling. The main inorganic pigments used by the unknown artist, namely mercury sulphide, azurite, white lead, red and yellow ochre, carbon black and lead tin yellow type I have been identified, and the presence of organic substances and of some decay products (calcium sulphate and oxalate) has been observed.     

Characterization of pigments and ligands in a wall painting fragment from Liternum archaeological park (Italy)

Spectroscopic and MS techniques were used to characterize the pigments and the composition of polar and nonpolar binders of a stray wall painting fragment from Liternum (Italy) archaeological excavation. X‐ray fluorescence and diffraction analysis of the decorations indicated mainly the presence of calcite, quartz, hematite, cinnabar, and cuprorivaite. Infrared spectroscopy, GC coupled to flame‐ionization detector, and MS analysis of the polar and nonpolar components extracted from paint layers from three different color regions revealed the presence of free amino acids, sugars, and fatty acids. Interestingly, LC‐MS shotgun analysis of the red painting region showed the presence of αS1‐casein of buffalo origin. Compared to our previous results from Pompeii's wall paintings, even though the Liternum painting mixture contained also binders of animal origin, the data strongly suggest that in both cases a tempera painting technique was utilized.