Analysis of pigments from Roman wall paintings found in Vicenza

The analysis of about 60 samples of wall paintings was carried out using different chemicophysical techniques: optical microscopy, scanning electron microscopy (SEM) equipped with an EDS microanalysis detector, X-ray powder diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The identified pigments were cinnabar, hematite, red ochre, celadonite, cuprorivaite (Egyptian blue), yellow ochre, goethite and carbon. Only in one case some lead white was found instead. In general, the mortar preparation did not correspond to the complex structure suggested by Vitruvius (De Architectura), but it generally showed a porous layer, with crushed grains under the pigment layer. In certain cases two superposed pigment layers were found: yellow superimposed on both red and pink, black on pink, green on black.     

Non-destructive analysis of museum objects by fibre-optic Raman spectroscopy

Raman spectroscopy is a versatile technique that has frequently been applied for the investigation of art objects. By using mobile Raman instrumentation it is possible to investigate the artworks without the need for sampling. This work evaluates the use of a dedicated mobile spectrometer for the investigation of a range of museum objects in museums in Scotland, including antique Egyptian sarcophagi, a panel painting, painted surfaces on paper and textile, and the painted lid and soundboard of an early keyboard instrument. The investigations of these artefacts illustrate some analytical challenges that arise when analysing museum objects, including fluorescing varnish layers, ambient sunlight, large dimensions of artefacts and the need to handle fragile objects with care. Analysis of the musical instrument (the Mar virginals) was undertaken in the exhibition gallery, while on display, which meant that interaction with the public and health and safety issues had to be taken into account. Experimental set-up for the non-destructive Raman spectroscopic investigation of a textile banner in the National Museums of Scotland     

Analysis of bulk and inorganic degradation products of stones,mortars and wall paintings by portable Raman microprobe spectroscopy

This work reports the use of a portable Raman microprobe spectrometer for the analysis of bulk and decaying compounds in carbonaceous materials such as stones, mortars and wall paintings. The analysed stones include limestone, dolomite and carbonaceous sandstone, gypsum and calcium oxalate, both mono- and dihydrated, being the main inorganic degradation products detected. Mortars include bulk phases with pure gypsum, calcite and mixtures of both or with sand, soluble salts being the most important degradation products. The pigments detected in several wall paintings include Prussian blue, iron oxide red, iron oxide yellow, vermilion, carbon black and lead white. Three different decaying processes have been characterised in the mortars of the wall paintings: (a) a massive absorption of nitrates that reacted with calcium carbonate and promoted the unbinding of pigment grains, (b) the formation of black crusts in the vault of the presbytery and (c) the thermodecomposition of pigments due to a fire.     

In situ analysis of mediaeval wall paintings: a challenge for mobile Raman spectroscopy

Raman spectroscopy is an analytical technique, which is gaining attention as a molecular technique for the investigation of objects of art. Especially the non-destructive properties of the method make this application suitable for the in situ analysis of artefacts. However, although using mobile, fibre optics Raman instrumentation for this type of research seems to be straightforward, some practical obstacles may hamper the investigation. In this paper, pitfalls and solutions are described when applying a dedicated spectrometer to the analysis of mediaeval wall paintings. It is shown how some practical problems may be overcome, and the results of the analysis are presented. Although the mediaeval wall paintings from the chapel of the castle of Ponthoz are well-preserved, still some interesting degradation phenomena could be observed: the identification of a black degradation product, likely to be meta-cinnabar, a degradation product of the red pigment vermilion (HgS); the formation of gypsum (CaSO₄·2H₂O) as a weathering product of calcium carbonate (CaCO₃); the observation of copper(II)hydroxychlorides.     

Non-destructive and in situ identification of rice paper, seals and pigments by FT-IR and XRD spectroscopy

This paper studied the chemical characteristics of rice paper, pigments and seals on Chinese calligraphies and traditional Chinese paintings. The techniques used here were Fourier transform infrared (FT-IR) spectroscopy and X-ray diffraction (XRD). FT-IR allows good identification of the substances present in pigments and inkpads and differentiates each era of rice paper. This can be the base of estimating the age of rice paper. Different crystalline phases can be identified by XRD, which is further evidence to separate different kinds of pigments or inkpads. Both of these methods were non-destructive in situ analysis and can be used in the identification in calligraphies and traditional Chinese paintings. These results confirmed that the applied techniques are relatively quicker and more reliable than traditional approaches authenticated by years of experience.     

Near-crater discoloration of white lead in wall paintings during laser induced breakdown spectroscopy analysis

During Laser-Induced Breakdown Spectroscopy (LIBS) analysis of white lead pigment (basic lead carbonate, 2PbCO₃·Pb(OH)₂), used in wall paintings of historical interest, a yellow–brown discoloration has been observed around the crater. This phenomenon faded after a few days exposure under ambient atmosphere. It was established that the mechanism of this discoloration consists in lead oxides (PbO) formation. It was verified by further experiments under argon atmosphere that recombination of lead with oxygen in the plasma plume produces the oxides, which settle around the crater and induce this discoloration. The impact of discoloration on the artwork's aesthetic aspect and the role of atmosphere on discoloration attenuation are discussed. The mechanism is studied on three other pigments (malachite, Prussian blue and ultramarine blue) and threshold for discoloration occurrence is estimated.     

Raman spectroscopic study of a post-medieval wall painting in need of conservation

Raman spectroscopic studies of four specimens from an important angel wall painting in need of conservation work in a medieval church have provided some information about the pigments and pigment compositions which will influence possible future preservation and restoration strategies. Excitation of the Raman spectra at 1,064 nm in macroscopic mode and at 785 nm in microscopic mode revealed that the white pigment on the angel's wings was a mixture of barytes with calcite and lead white in minor composition. Although the specimens provided were not directly associated with coloured regions of the painting, yellow and blue microcrystals were found and they were identified as chrome yellow and lazurite, respectively. Red and brown particles were identified as cinnabar/vermilion and haematite. Several green particles were also found but could not be identified. The green and blue crystals could be related to neighbouring coloured regions of the artwork and the yellow colour could be identified as a background to the angel figure. Particles of carbon were found to be dispersed throughout the specimens and can be ascribed to soot from candles, heating stoves or oil lamps providing lighting in the church. No evidence for biological deterioration was found from the spectra. The unusual pigment palette is strongly suggestive of a later date of painting than was originally believed but there is a possibility that an earlier rendition exists underneath. Following a review of the spectroscopic data, a more extensive sampling protocol is recommended, from which some stratigraphic evidence could identify the underlying plaster and possible artwork.     

In situ Raman spectroscopy at the Voroneţ Monastery (16th century,Romania): New results for green and blue pigments

The Voroneţ Monastery is one of the greatest cultural treasures of Romania, dating from the 15th century. In the present study, the green and blue pigments of its exterior frescoes (16th century) were analyzed through fibre-coupled Raman spectroscopy. A wide range of typical pigments, including malachite, basic Cu sulphates, azurite, lazurite, smalt, gypsum, anhydrite and calcite were found, together with other “rare pigments,” such as conichalcite and dolerophanite. The green pigment is either a mixture of malachite and conichalcite or Cu sulphates while the blue pigment contains either lazurite, or a mixture of azurite and a minor quantity of smalt, gypsum and anhydrite. The identification of these pigments is very important for the restoration work, the monastery being a UNESCO World Heritage Site.     

拉曼光谱与红外光谱无损检测技术新进展

综述了拉曼光谱和红外光谱无损分析技术在医学、药物、文物、宝石鉴定和法庭科学等领域的最新进展。     

Nature of light-absorbing pigments from Brazilian lichens identified by Raman spectroscopy

Light-absorbing pigments from different chemical classes have been identified from the lichens Usnea sp. and Crocodia aurata using Raman spectroscopy supported by quantum mechanical DFT calculations. Raman spectra were obtained directly from the lichen tissues as well as from isolated extracts. Usnic acid, a chemomarker of Usnea spp has been reported together with a minor constituent, namely stictic acid, which has been unambiguously identified by ¹H and ¹³C NMR spectral analysis. The structures of calycin and pulvinic dilactone isolated from Crocodia aurata have been confirmed by single crystal X-ray diffraction. The ubiquitous carotenoids have been characterized by FT-Raman and dispersive Raman microimaging in tissues of Usnea sp. and C. aurata, respectively. The Raman map has revealed the presence of a mixture of carotenoids heterogeneously distributed in the upper layer of C. aurata. In this work we have demonstrated that Raman spectroscopy can be used to monitor aromatic and conjugated polyenic pigments in different layers of lichen tissues.     

A Comparative Study of Pigments from the Wall Paintings of Two Greek Byzantine Churches

The goal of this study was to characterize pigments used in the murals of two Byzantine churches, from Kastoria, northern Greece. The identification of the iconographer was also investigated by comparing the pigments applied in the wall paintings of the churches. Pigment microsamples of various colors were collected and analyzed by environmental scanning electron microscopy coupled with an energy dispersive system to characterize the elemental composition. Raman spectroscopy was employed to collect molecular spectra for characterization of mineralogical phases. Hematite, cinnabar, and minium were identified in red surfaces. Brown and yellow colors were assigned to mixtures of iron oxides, iron hydroxides, and calcite. Mixtures of iron, lead, and mercury compounds were used to produce different hues in the murals. Black tones were prepared primarily using charcoal and bone black. Grey colors were produced by a mixture of black carbon with calcite; blue hues, by a mixture of iron oxides, calcite, and black carbon. The minerals used were similar for both churches. However, the green color was prepared either by green earth or mixtures of iron oxides and calcite. A modern pigment, lithopone, was also determined, demonstrating restoration or overpainting and thus complicating possible correlations. Based on these preliminary results, the wall paintings could not be ascribed to a specific iconographer.     

The identification by Raman microscopy and X-ray diffraction of iron-oxide pigments and of the red pigments found on Italian pottery fragments

The technique of Raman microscopy has been used to identify and characterise the pigments used in red shards of medieval and earlier items of pottery which have been found in various archaeological sites in the South of Italy. The research has led to the identification, on the basis of their characteristic Raman/resonance Raman spectra, of the red pigments as iron(III) oxide (e.g. Indian Red, Red Ochre or Venetian Red) and the yellow pigments as hydrated iron(III) oxyhydroxide (e.g. Yellow Ochre and Mars Yellow). X-ray powder diffraction experiments confirm the conclusions drawn above.     

Study of a XVIII century hand-painted Chinese wallpaper by multianalytical non-destructive techniques

In this work, hand-painted wallpaper belonging to a private Portuguese collection was analyzed in order to identify the pigments used. The analyzed artwork was an extraordinary XVIII century Chinese wallpaper that depicts exotic birds and flowers, which was painted with considerable accuracy and expertise. Thorough, in situ, X-ray fluorescence analyses were performed on nearly all the wallpaper. Since the elemental content of several colors was consistent for the four papered walls, strategic micro-samples were taken and analyzed by confocal Raman spectroscopy to further identify the pigments used. Pigments such as yellow ochre, lead white and barium white, vermilion, carmine, azurite and malachite were identified. Optical microscopy was used to analyze the fibers in the paper support, and fibers such as kozo, ramie and hemp or linen were identified.     

Analysis of artist’s palette on a 16th century wood panel painting by portable and laboratory Raman instruments

Non-destructive analysis of the artist’s palette of ancient wooden panel paintings is a difficult task and studies are rare. Here we compare different methods of analysis of a wooden panel painting, dated to the early sixteenth century, mainly by Raman and infrared spectroscopies. Raman spectra were recorded on collected/sampled micrometric fragments using portable Raman instruments with laser excitation lines at 532 and 785 nm and transportable Raman instruments at 532, 633 and 785 nm; a fixed 1064 nm Raman spectrometer was also used. Infrared analyses were performed in Attenuated Total Reflection (ATR-FTIR) mode. Using the portable instrument, the Raman spectra evidenced white lead, calcite and vermilion only. Raman spectra recorded by transportable and fixed instruments enabled the identification of most of the artist’s palette: (i) white lead, calcite, gypsum and cerussite for white colour; (ii) vermilion, red lead, litharge, haematite for red; (iii) azurite, indigo and lapis lazuli for blue. IR spectra gave information on the organic binding media. XRF analysis on a brown pigment suggested an heterogeneous mixture of a red pigment (such as haematite and/or minium) and a green one as malachite. GC-MS analysis allowed identifying terpenic resin in the composition of the outer protective layer.     

Pigment identification on “Pietà” of Barletta, example of Renaissance Apulian sculpture: A Raman microscopy study

A study of the original painting layer of the “Pietà” of Barletta, a polychrome statue, important example of Renaissance Apulian sculpture, was performed by μ-Raman spectroscopy. Vermilion was identified in the original layer of the blood drops on Jesus knee. Lazurite was identified as the original blue pigment on Our Lady's veil and lace, currently a yellow ochre-like color. The use of lazurite demonstrates the historical-artistic importance of this polychrome statue, and supports the hypothesis that this artwork was probably commissioned by Our Lady's devotees to itinerant artists inspired by the more precious Vesperbilder model.     

Studying lithium intercalation into graphite particles via in situ Raman spectroscopy and confocal microscopy

The electrochemical intercalation of lithium into single graphite particles was studied in situ using Raman microscopy combined with confocal microscopy. The degree of intercalation during cycling was obtained from changes in the Raman bands of carbon. Confocal microscopy was used to image the graphite electrode in order to monitor the intercalation into single graphite particles. An industrial button cell was modified such that Raman spectra and microscopic images of the back side of the negative electrode could be taken through a window in the cup of the cell. The liquid electrolyte consisted of a 1:1 mixture of ethylenecarbonate/dimethylcarbonate (EC/DMC) with 1 M LiPF₆. The spectroscopy and microscopy showed that lithium does not intercalate into the graphite in a homogeneous manner. Inhomogeneous lithium intercalation was even observed in single graphite particles.     

A new non-invasive, quantitative Raman technique for the determination of an active ingredient in pharmaceutical liquids by direct measurement through a plastic bottle

The concentration of an active pharmaceutical ingredient (povidone) in a commercial eyewash solution has been measured directly through a plastic (low-density polyethylene: LDPE) container using a wide area illumination (WAI) Raman scheme. The WAI scheme allows excitation using a 6 mm laser spot (focal length: 248 mm) that is designed to cover a wide sample area. As a result, it has the potential to improve the reliability Raman measurements by significantly enhancing representative sample interrogation, thus improving the reproducibility of sampling. It also decreases the sensitivity of sample placement with regard to the excitation focal plane. Simultaneously, isobutyric anhydride was placed in front of the bottles to use for a synchronous external standard configuration. This helps to correct the problematic variation of Raman intensity from the inherent fluctuation in laser power. Using the WAI Raman scheme combined with the synchronous standard method, the povidone concentration was successfully measured with spectral collection that was performed through a plastic barrier. The conventional Raman scheme was difficult to employ for the same purpose because of the degraded spectral reproducibility resulting from the smaller laser illumination area and the sensitivity of such an approach to the position of the sample bottle. The result from this study suggests that the WAI scheme exhibits a strong potential for the non-destructive quantitative analysis of pharmaceuticals measured directly in plastic containers. Preliminary work also shows that similar measurements can also be made in glass bottles. If implemented, this technique could be utilized as a simple and rugged method for quality assurance of final products in a manner consistent with Process analytical technology (PAT) requirements.     

A new approach to non-destructive analysis of biofilms by confocal Raman microscopy

Confocal Raman microscopy (CRM) of biofilms enables one to determine the distribution of different microorganisms and other substances inside physiological intact microbial communities. These biofilms are of outstanding interest for biological wastewater treatment. In contrast to invasive techniques, such as fluorescent in situ hybridization (FISH), we were able to identify anaerobically ammonium-oxidising (anammox) bacteria without pretreatment processes of the samples just by its Raman vibrational signature. The presented results provide new insights into the complex interactions of different organisms in microbial communities without interfering with them.     

Fast identification of rubrene polymorphs by lattice phonon Raman microscopy

Confocal Raman microscopy in the lattice phonon region has been used to study the polymorphism of the organic semiconductor 5,6,11,12-tetraphenyl-tetracene (rubrene). Following literature guidelines, crystals of rubrene have been prepared using a number of solution growth and vapour deposition methods, obtaining samples of different morphologies which could be related to the various polymorphs of this compound. The technique has enabled us an easy and non invasive identification of the three known polymorphs and of their phase homogeneity with a lateral spatial resolution below 1 μm.     

Towards a nondestructive chemical characterization of biofilm matrix by Raman microscopy

In this study, the applicability of Raman microscopy (RM) for nondestructive chemical analysis of biofilm matrix, including microbial constituents and extracellular polymeric substances (EPS), has been assessed. The examination of a wide range of reference samples such as biofilm-specific polysaccharides, proteins, microorganisms, and encapsulated bacteria revealed characteristic frequency regions and specific marker bands for different biofilm constituents. Based on received data, the assignment of Raman bands in spectra of multispecies biofilms was performed. The study of different multispecies biofilms showed that RM can correlate various structural appearances within the biofilm to variations in their chemical composition and provide chemical information about a complex biofilm matrix. The results of RM analysis of biofilms are in good agreement with data obtained by confocal laser scanning microscopy (CLSM). Thus, RM is a promising tool for a label-free chemical characterization of different biofilm constituents. Moreover, the combination of RM with CLSM analysis for the study of biofilms grown under different environmental conditions can provide new insights into the complex structure/function correlations in biofilms.