Paint Microsamples Research Articles

Correlated x-ray fluorescence and ptychographic nano-tomography on Rembrandt’s The Night Watch reveals unknown lead “layer”

The Night Watch , one of the most famous masterpieces by Rembrandt, is the subject of a large research and conservation project. For the conservation treatment, it is of great importance to understand its current condition. Correlated nano-tomography using x-ray fluorescence and ptychography revealed a—so far unknown—lead-containing “layer”, which likely acts as a protective impregnation layer applied on the canvas before the quartz-clay ground was applied. This layer might explain the presence of lead soap protrusions in areas where no other lead components are present. In addition to the three-dimensional elemental mapping, ptychography visualizes and quantifies components not detectable by hard x-ray fluorescence such as the organic fraction and quartz. The first-time use of this combination of synchrotron-based techniques on a historic paint micro-sample shows it to be an important tool to better interpret the results of noninvasive imaging techniques operating on the macroscale.

High performance liquid chromatography as a micro-destructive technique for the identification of anthraquinone red dyestuffs in cultural heritage objects

Abstract This article describes two of the most common natural sources of red anthraquinones that have been used since antiquity for textile dyeing and as lake pigments, namely cochineal insect and the roots of Rubia and Relbunium plants. Carminic acid is the main component of carmine, the red colorant obtained from cochineal. Alizarin and purpurin are found in the extracts of Rubia roots, but Relbunium roots contain only purpurin. These red anthraquinones have been identified in a variety of cultural heritage objects. High performance liquid chromatography with diode array detection (HPLC-DAD) is described as the most suitable analytical technique for the identification of these dyestuffs, particularly in micro-samples from textiles or pigment layers in paintings and polychrome sculptures. Finally, application of HPLC-DAD analysis to the identification of lake pigments in micro-samples of mural paintings of two eighteenth century Andean churches in Peru is described.

Application of Synchrotron Radiation-Based Micro-Analysis on Cadmium Yellows in Pablo Picasso's Femme.

The cultural heritage community is increasingly exploring synchrotron radiation (SR) based techniques for the study of art and archaeological objects. When considering heterogeneous and complex micro-samples, such as those from paintings, the combination of different SR X-ray techniques is often exploited to overcome the intrinsic limitations and sensitivity of the single technique. Less frequently, SR X-ray analyses are combined with SR micro-photoluminescence or micro-Fourier Transform Infrared spectroscopy, which provide complementary information on the molecular composition, offering a unique integrated analysis approach. Although the spatial correlation between the maps obtained with different techniques is not straightforward due to the different volumes probed by each method, the combination of the information provides a greater understanding and insight into the paint chemistry. In this work, we discuss the advantages and disadvantages of the combination of X-ray techniques and SR-based photoluminescence through the study of two paint micro-samples taken from Pablo Picasso's Femme (1907). The painting contains two cadmium yellow paints (based on CdS): one relatively intact and one visibly degraded. SR micro-analyses demonstrated that the two Cd-yellow paints differ in terms of structure, chemical composition, and photoluminescence properties. In particular, on the basis of the combination of different SR measurements, we hypothesize that the degraded yellow is based on nanocrystalline CdS with high presence of Cd(OH)Cl. These two characteristics have enhanced the reactivity of the paint and strongly influenced its stability.

Optimization of protein extraction and ELISA immunodetection from protein-based paint models with mesoporous silica nanoparticles and MCM41

Protein-based biological materials such as albumin, casein and collagen are found in various cultural heritage (CH) artefacts. This study focuses on the study of protein binders from easel paintings media. Proteins have complex structures which are difficult to identify with non-invasive spectroscopic methods (FT-IR, Raman, UV). Immunoassays such as ELISA determine the protein’s source of origin which is necessary for art objects. To increase the detection and identification of proteins by immunoassays, the efficiency of micro-extraction of proteins from heritage materials is a crucial step. Extractions mediated by cycles of orbital agitation and ultrasonic radiation give the possibility to extract proteins from easel painting sample. In this work, protein-based paint models coupled with silica nanoparticles were used for micro-extraction. Nanoparticles possess high surface-to-volume ratios that can attach bioactive molecules such as proteins and increase the total protein recovered from microsamples. Protein extracts were quantified with Bradford Assay in the presence of Coomassie blue. The protein recovery results were statistically computed, and the SPSS analysis shows significant (p < 0.05) increase in protein recovery, above 1.3 times for NPSiO2 and above 1.6 times for MCM-41. The statistical data shows evidence that silica nanoparticles intensify the total protein recovered from paint microsamples. Finally, ELISA was realized on the protein extracts to verify and compare the immunodetection of protein from the paint models with and without the use of silica nanoparticles.

Laser ablation inductively coupled plasma mass spectrometry appointed to subserve pigment identification

Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) was used apart from Scanning Electron Microscopy (SEM) equipped with Energy Dispersive Spectroscopy (EDS) and Raman spectroscopy (RS) to support identification of inorganic pigments from historic oil painting. Samples in form of tiny particles were collected from painting layer during conservation processes. Detection of lead white (2PbCO3·Pb(OH)2); Naples yellow (Pb2Sb2O7); lead‑tin‑antimony yellow (Pb2SnSbO6.5); ochre (Fe2O3); ultramarine (Na8–10Al6Si6O24S2–4); smalt (CoO·nSiO2); cadmium yellow (CdS); malachite (2CuCO3·Cu(OH)2); chrome yellow (PbCrO4); ceruleum (CoSnO3), chalk (CaCO3); Schweinfurt green, Cu(C2H3O2)2·3Cu(AsO2)2; vermilion (HgS) and carbon black (C) is documented in this work. The aim of this study was to estimate eventual benefits for using LA-ICP-MS to attain coherent elemental and molecular information of paint micro-samples for cross-checking the reliability of their chemical identification. The use of LA-ICP-MS was helpful to get detailed elemental data for some mixtures of pigments when only microscopic amount of material was available for examinations.

Unravelling the spatial dependency of the complex solid-state chemistry of Pb in a paint micro-sample from Rembrandt's Homer using XRD-CT.

The surface of many Old Master paintings has been affected by the appearance of whitish lead-rich deposits, which are often difficult to fully characterise, thereby hindering conservation. A paint micro-sample from Rembrandt's Homer was imaged using X-ray Diffraction Computed Tomography (XRD-CT) in order to understand the evolving solid-state Pb chemistry from the painting surface and beneath. The surface crust was identified as a complex mixture of lead sulfates. From the S : Pb ratios throughout the paint layer, we can conclude that S is from an external source in the form of SO2, and that the nature of Pb-SO4 product is dependent on the degree of diffusion/absorption of SO2 into the paint layers.

Two-step analytical procedure for the characterization and quantification of metal soaps and resinates in paint samples

Metal soaps and resinates are known to be spontaneously formed in artistic paintings, as a product of the reaction between aliphatic and terpenoid acids released by hydrolysis and oxidation of the organic media and certain cations contained in some inorganic pigments. In this paper we present an optimization and the validation of a GC/MS method for the qualitative and quantitative analysis of mixtures of terpenoid acids and aliphatic mono and dicarboxylic acids and metal carboxylates of terpenoid and aliphatic mono and dicarboxylic acids in the same paint microsample. This is based on a two-step analytical approach entailing the subsequent use of two silylating agents, N,O-bis(trimethylsilyl)trifluoroacetamide for the analysis of free acids and metal carboxylates, and 1,1,1,3,3,3-hexamethyldisilazane for the analysis of free acids. The application of this approach is possible because of the good stability at room temperature of the TMS derivatives of aliphatic and terpenoid species, characterized by high boiling points and relatively low vapour pressures. The method was then applied to the characterization of samples collected from two reference paint layers aged for 20 years, a paint sample taken from a pulpit, and sample of the varnish coating of a wooden writing desk, both from the second half of the seventeenth century.

Examination of 14–15th century Buddhist wall paintings from a cave complex in Saspol, Ladakh

Buddhist wall paintings from a cave complex in Saspol, Ladakh, India, dating to the 14-15th century, were taken up for a study of their painting technology. Paint micro-samples were investigated by scanning electron and optical microscopy, and multi-spectral imaging of the paintings conducted at site. Azurite, vermilion, orpiment, indigo, and madder are the main inorganic and organic pigments identified. Pigments were typically applied in one or more layers on the wall surfaces, depending on the painting scheme and on the colour finish desired. The materials and techniques employed for the Saspol paintings are consistent with those known to exist in the region up to that time, with no indications of any new external influences as made out for their artistic style or iconographic content.

An Enhanced GC/MS Procedure for the Identification of Proteins in Paint Microsamples.

The chemical characterization of materials used in works of art is extremely useful for gaining a better knowledge of the artistic heritage and to guarantee its preservation. A derivatization GC/MS procedure for the identification of proteins in a microsample from painted works of art has been optimized. The amino acid fraction is derivatized using anhydrous dimethylformamide (DMF) as solvent instead of pyridine (Py), commonly used to facilitate the reaction. Although pyridine is often considered a silylation catalyst, there are many instances in which silylation reactions actually are slower in pyridine than other solvents. In addition, pyridine also may have other undesirable effects such as the promotion of secondary products and other chromatographic anomalies. Using DMF, the formation of artifacts is limited and the derivatization yield of hydrophilic amino acids such as proline and hydroxyproline has improved, thus making the identification of organic paint media more straightforward. The method has been validated and successfully applied to identify the binder of the sample taken from the pictorial cycle of the 12th century monastery of Santa Maria delle Cerrate (Lecce, Italy), thus highlighting the use of eggs as a binding medium.

"Paintings Fade Like Flowers": Pigment Analysis and Digital Reconstruction of a Faded Pink Lake Pigment in Vincent van Gogh's Undergrowth with Two Figures.

Color fading in Vincent van Gogh's Undergrowth with Two Figures was studied chemically to facilitate the creation of a digital reconstruction of fugitive colors . The painting contains a field of white, green, orange, and yellow flowers under a canopy of poplar trees with two central figures-a man and a woman, arms entwined. From Van Gogh's letters, however, it is known that he painted the picture with some pink flowers, which appear to have altered, presumably to white. Raman spectroscopy was applied to microsamples of paint to identify the faded pigment as geranium lake, which in this painting consists of the dye, eosin (2',4',5',7'-tetrabromofluorescein). For the first time, lead(II) sulfate has been specifically identified as the likely inorganic substrate for a geranium lake used by Van Gogh in the last months of his life. Microfocus X-ray fluorescence (MXRF) spectroscopy was subsequently used in situ to analyze the white flowers to identify bromine as a proxy for eosin, thus indicating an original pink coloration. Of the 387 white flowers analyzed, 37.7% contained measurable bromine and were, therefore, originally pink. Several cross-sections from these formerly pink areas were assessed using a combination of visual inspection and microcolorimetry to create a colored mask in Adobe Photoshop to digitally reconstruct a suggestion of the original appearance of the painting with regard to the faded flowers. Additionally, microfadeometry was undertaken for the first time on a painting cross-section sample to understand the actual fading kinetics of the underlying bright pink geranium lake used by Van Gogh. A combination of Raman microspectroscopy, MXRF, and scanning electron microscopy energy dispersive spectroscopy (SEM-EDS) were utilized in situ and on paint microsamples to identify the complete palette used to create Undergrowth with Two Figures.

Visualization of As(iii) and As(v) distributions in degraded paint micro-samples from Baroque- and Rococo-era paintings

Orpiment and realgar are two artists' pigments that appear not to be stable upon light exposure, quickly degrading to arsenic trioxide and arsenate. Their identification appears challenging but can be overcome by the use of synchrotron based techniques such as μ-XANES.

Characterisation of metal carboxylates by Raman and infrared spectroscopy in works of art

This work introduces the complementary use of μ‐Raman and μ‐Fourier transform infrared (IR) spectroscopy for the detection of specific carbon chains and cations for the identification of metal carboxylates within oil paint microsamples. Metal carboxylates (metal soaps) form naturally when free fatty acids react with metal cations and may also be found as additives or degradation products. Twenty‐two metal carboxylates were synthesised, and their spectra assembled in a reference database. Metal salts of cations commonly present in oil paintings were used, including lead, zinc, calcium, cadmium, copper and manganese. The fatty acids selected were the saturated acids palmitic (C16 : 0) and stearic (C18 : 0) and the polyunsaturated oleic acid (C18 : 1). Azelaic acid (C9 diacid), a product resulting from autoxidation of polyunsaturated acids, was also included. Metal carboxylates were characterised by Raman and IR spectroscopy, and their structures were confirmed by X‐ray diffraction. Raman and IR spectroscopy proved to be complementary techniques for a full identification of the metal carboxylates in complex aged paint. Raman enables the differentiation of the carbon chain length in the C–C stretching region (1120–1040 cm−1), and IR distinguishes the metal cation in the COO− stretching absorption region (1650–1380 cm−1). Principal component analysis was applied to the spectra in order to facilitate a fast and accurate method to discriminate between the different metal carboxylates and to aide in their identification. Finally, spectra from case studies were successfully projected in the principal component analysis models built, enabling a higher confidence level for the identification of copper palmitate and copper azelate in two 19th‐century Portuguese oil paintings. Copyright © 2014 John Wiley &amp; Sons, Ltd.

Simultaneous identification of historical pigments Prussian blue and indigo in paintings by electrospray mass spectrometry

A new analytical protocol for identification of Prussian blue (PB) and indigo was proposed. Pigments useful for dating of artworks were detected by flow injection analysis/electrospray ionization mass spectrometry after alkalization of their suspensions in water, decomposition of PB to iron (III) hydroxide and hexacyanoferrate (II) and reduction of indigo to soluble leucoindigo using sodium dithionite. Limits of detection (PB 47 pg, indigo 59 pg) complied with requirements for analysis of microsamples of historical paintings. Potential of the developed method was proven in analysis of blue samples of two oil paintings from the 20(th) century. Further, PB was confirmed in a microsample from a painting of 'Crucifixion', St. Sebestian church on St. Hill in Mikulov, Czech Republic.

Characterization of the organic materials used in the painting of the vaulted ceiling at the Saadian Tomb of Mulay Ahmed Al-Mansour (Marrakech)

The Saadian tombs from the era of sultan Ahmed al-Mansour (1574–1603) are beautifully decorated and have always been a major attraction for visitors to Marrakesh. The central mausoleum, named the Hall of Twelve Columns, encloses the tombs of Ahmed al-Mansour and his family. The hall has a huge vaulted ceiling, carved cedar doors, opening windows with wooden marquetry screen (Mashrabiya), and grey Italian marble columns. This paper presents the first attempt to identify the organic materials used by the Moroccan artisans. A GC/MS analytical procedure was used for the characterization of lipids, waxes, resins, pitch, tar, proteinaceous and saccharide materials in the same paint micro-sample. The analytical study identified the organic materials used in the polychrome and gilded decorations of the walls, ceiling and dome of the hall. Data showed that the polychrome decorations were painted using animal glue as a binder, and highlighted the treatment of the wall surface with linseed oil and the retouching of the paintings based on a saccharide binder. The use of a proteinaceous-resinous-oil mixture, applied on a proteinaceous preparation layer, for the gilded decorations revealed a very similar technique to that used at the time in Europe for mural paintings.

The Use of Synchrotron Radiation for the Characterization of Artists' Pigments and Paintings

We review methods and recent studies in which macroscopic to (sub)microscopic X-ray beams were used for nondestructive analysis and characterization of pigments, paint microsamples, and/or entire paintings. We discuss the use of portable laboratory- and synchrotron-based instrumentation and describe several variants of X-ray fluorescence (XRF) analysis used for elemental analysis and imaging and combined with X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Macroscopic and microscopic (μ-)XRF variants of this method are suitable for visualizing the elemental distribution of key elements in paint multilayers. Technical innovations such as multielement, large-area XRF detectors have enabled such developments. The use of methods limited to elemental analysis or imaging usually is not sufficient to elucidate the chemical transformations that take place during natural pigment alteration processes. However, synchrotron-based combinations of μ-XRF, μ-XAS, and μ-XRD are suitable for such studies.

Degradation Process of Lead Chromate in Paintings by Vincent van Gogh Studied by Means of Spectromicroscopic Methods. 3. Synthesis, Characterization, and Detection of Different Crystal Forms of the Chrome Yellow Pigment

The painter, Vincent van Gogh, and some of his contemporaries frequently made use of the pigment chrome yellow that is known to show a tendency toward darkening. This pigment may correspond to various chemical compounds such as PbCrO(4) and PbCr(1-x)S(x)O(4), that may each be present in various crystallographic forms with different tendencies toward degradation. Investigations by X-ray diffraction (XRD), mid-Fourier Transform infrared (FTIR), and Raman instruments (benchtop and portable) and synchrotron radiation-based micro-XRD and X-ray absorption near edge structure spectroscopy performed on oil-paint models, prepared with in-house synthesized PbCrO(4) and PbCr(1-x)S(x)O(4), permitted us to characterize the spectroscopic features of the various forms. On the basis of these results, an extended study has been carried out on historic paint tubes and on embedded paint microsamples taken from yellow-orange/pale yellow areas of 12 Van Gogh paintings, demonstrating that Van Gogh effectively made use of different chrome yellow types. This conclusion was also confirmed by in situ mid-FTIR investigations on Van Gogh's Portrait of Gauguin (Van Gogh Museum, Amsterdam).

A simple protocol for Matrix Assisted Laser Desorption Ionization- time of flight-mass spectrometry (MALDI-TOF-MS) analysis of lipids and proteins in single microsamples of paintings

A simple protocol, based on Bligh–Dyer (BD) extraction followed by MALDI-TOF-MS analysis, for fast identification of paint binders in single microsamples is proposed. For the first time it is demonstrated that the BD method is effective for the simultaneous extraction of lipids and proteins from complex, and atypical matrices, such as pigmented paint layers. The protocol makes use of an alternative denaturing anionic detergent (RapiGest™) in order to improve efficiency of protein digestion and purification step. Detection of various lipid classes, such as triacylglycerols (TAGs) and phospholipids (PLs), and their oxidation by-products was accomplished, whereas proteins could be identified by peptide mass fingerprinting. The effect of pigments on ageing of lipids and proteins was also investigated.Finally, the proposed protocol was successfully applied to the study of a late-15th century Italian panel painting allowing the identification of various proteinaceous and lipid sections in organic binders, such as egg yolk, egg white, animal glue, casein, and drying oil.

Proteinaceous binders identification in the works of art using ion-pairing free reversed-phase liquid chromatography coupled with tandem mass spectrometry

A simple, fast and reliable procedure for the proteinaceous binders identification in the works of art samples is presented. The procedure consisted of ammonia extraction in order to suppress pigment interferences, acidic hydrolysis and quantification of underivatized amino acids using reversed phase liquid chromatography coupled with electrospray tandem mass spectrometry (RP-LC–ESI-MS/MS). Fourteen underivatized amino acids were quantified without the addition of ion-pairing agents (IPA) using the multiple reaction monitoring (MRM) mode. The chromatographic separation was optimized by testing three C18 columns and three different eluent compositions. The optimal chromatographic resolution and the ionization efficiency were achieved with Symmetry C18 column and the eluent consisting of water with methanol. The amino acids composition of the proteins commonly found in the paint binding media, eggs, casein and animal glues, was determined. The procedure was tested using a set of naturally aged samples. Calculated detection and quantification limits indicated that the method is suitable for the analysis of protein binders in the paint micro-samples. Animal glues, casein and eggs were identified in the samples from 18th and 19th century paintings by Jacek Malczewski, while eggs and casein were detected in the mural painting samples from the 13th century UNESCO-listed church of Yemrehanna Krestos. The LC/MS/MS based method of the protein binders identification described here can be used as an alternative for the approach based on the gas chromatography coupled with mass spectrometry (GC/MS).

Degradation Process of Lead Chromate in Paintings by Vincent van Gogh Studied by Means of Synchrotron X-ray Spectromicroscopy and Related Methods. 2. Original Paint Layer Samples

The darkening of the original yellow areas painted with the chrome yellow pigment (PbCrO(4), PbCrO(4)·xPbSO(4), or PbCrO(4)·xPbO) is a phenomenon widely observed on several paintings by Vincent van Gogh, such as the famous different versions of Sunflowers. During our previous investigations on artificially aged model samples of lead chromate, we established for the first time that darkening of chrome yellow is caused by reduction of PbCrO(4) to Cr(2)O(3)·2H(2)O (viridian green), likely accompanied by the presence of another Cr(III) compound, such as either Cr(2)(SO(4))(3)·H(2)O or (CH(3)CO(2))(7)Cr(3)(OH)(2) [chromium(III) acetate hydroxide]. In the second part of this work, in order to demonstrate that this reduction phenomenon effectively takes place in real paintings, we study original paint samples from two paintings of V. van Gogh. As with the model samples, in view of the thin superficial alteration layers that are present, high lateral resolution spectroscopic methods that make use of synchrotron radiation (SR), such as microscopic X-ray absorption near edge (μ-XANES) and X-ray fluorescence spectrometry (μ-XRF) were employed. Additionally, μ-Raman and mid-FTIR analyses were carried out to completely characterize the samples. On both paint microsamples, the local presence of reduced Cr was demonstrated by means of μ-XANES point measurements. The presence of Cr(III) was revealed in specific areas, in some cases correlated to the presence of Ba(sulfate) and/or to that of aluminum silicate compounds.

GC/MS Analytical Procedure for the Characterization of Glycerolipids, Natural Waxes, Terpenoid Resins, Proteinaceous and Polysaccharide Materials in the Same Paint Microsample Avoiding Interferences from Inorganic Media

An innovative GC/MS procedure for the characterization of organic materials in samples from works of art was developed. It is based on a multistep chemical pretreatment of the samples based on the ammonia extraction of proteins and polysaccharide materials, in order to separate them from lipid and resinous materials. The extraction is then followed by the separation and purification of proteinaceous and polysaccharide materials before hydrolysis, based on the use of monolithic sorbent tip technology with a C4 stationary phase. Lipids and resins are saponified/salified separately. Three fractions are generated and analyzed separately by GC/MS, thus enabling a quantitative analysis to be performed on aldoses and uronic acids, amino acids, mono- and dicarboxylic aliphatic acids, to determine polysaccharide, proteinaceous, and glycerolipid materials and molecular pattern recognition for the natural resin and wax components. With this analytical procedure, for the first time, glycerolipids, natural waxes, and proteinaceous, resinous, and polysaccharide materials can be simultaneously characterized in the same microsample from painted works of art. This new analytical approach prevents any analytical difficulties arising when the sample is divided into several different aliquots to be chemically processed separately, in order to characterize the various classes of organic materials. The procedure was successfully applied to samples from paintings from the Bamiyan Buddhas and a panel painting from the 15th century, highlighting the occurrence of glycerolipids, animal and plant resins, proteinaceous and polysaccharide materials.