Journal of Raman Spectroscopy

Cover image for Vol. 41 Issue 11

Special Issue: Raman spectroscopy in art and archaeology

November 2010

Volume 41, Issue 11

Pages i–i, 1389–1561

Issue edited by: Juan Manuel Madariaga

  1. Errata

    1. Top of page
    2. Errata
    3. Editorials
    4. Research Articles
    1. You have free access to this content
      Erratum (page i)

      Article first published online: 23 JAN 2011 | DOI: 10.1002/jrs.2911

  2. Editorials

    1. Top of page
    2. Errata
    3. Editorials
    4. Research Articles
  3. Research Articles

    1. Top of page
    2. Errata
    3. Editorials
    4. Research Articles
    1. Raman microscopy of prehistoric rock paintings from the Hoz de Vicente, Minglanilla, Cuenca, Spain (pages 1394–1399)

      Antonio Hernanz, Juan F. Ruiz-López, José M. Gavira-Vallejo, Santiago Martin and Egor Gavrilenko

      Article first published online: 19 FEB 2010 | DOI: 10.1002/jrs.2582

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      Raman microscopy in combination with SEM/EDX has enabled the determination of the composition and microstratigraphy of prehistoric rock paintings from the Hoz de Vicente (Minglanilla, Cuenca Spain). The results obtained suggest possible causes of deterioration. The presence of whewellite in the pigment and adjacent layers would be very useful for radiocarbon dating of this rock art.

    2. Raman spectroscopy as a tool to diagnose the impact and conservation state of Pompeian second and fourth style wall paintings exposed to diverse environments (House of Marcus Lucretius) (pages 1400–1409)

      M. Maguregui, U. Knuutinen, K. Castro and J. M. Madariaga

      Article first published online: 26 APR 2010 | DOI: 10.1002/jrs.2671

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      Raman spectroscopy was used as a principal analytical technique to characterize the original composition and decay products in mortars and pigments from walls and mural paintings from the House of Marcus Lucretius (Pompeii). These spectroscopic results were complemented with quantitative analysis (ionic chromatography) and chemometric and chemical equilibrium calculations.

    3. A detailed micro-Raman spectroscopic study of wall paintings of the period AD 100–200: effect of atmospheric conditions on the alteration of samples (pages 1410–1417)

      Odile Cristini, Christophe Kinowski and Sylvia Turrell

      Article first published online: 21 APR 2010 | DOI: 10.1002/jrs.2656

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      Results for fragments from Gallo–Roman, Roman and Greek sites from first and second century AD made it possible to identify the presence of red ocher and green earth pigments. We report for the first time that the pigments in the pictorial layer can serve as a protection for the calcite preparatory layers.

    4. Spectroscopy study of mural paintings from the Pyrenean Church of Saint Eulàlia of Unha (pages 1418–1424)

      Robin J. H. Clark, Richard R. Hark, Nati Salvadó, Salvador Butí and Trinitat Pradell

      Article first published online: 11 MAY 2010 | DOI: 10.1002/jrs.2687

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      Complementary techniques have been used to identify pigments and other materials on Romanesque to 16th century mural paintings in the Pyrenean Church of St. Eulalia of Unha in the Val d'Aran. The artists' palette was found to vary with the period. The only blue pigment in the Romanesque frescoes was shown to be aerinite, a rare Fe(II)/Fe(III)-containing aluminosilicate found locally in the Pyrenees region.

    5. Microbiologically influenced corrosion of archaeological artefacts: characterisation of iron(II) sulfides by Raman spectroscopy (pages 1425–1433)

      Céline Rémazeilles, Mandana Saheb, Delphine Neff, Elodie Guilminot, Khoi Tran, Jacques-André Bourdoiseau, René Sabot, Marc Jeannin, Henning Matthiesen, Philippe Dillmann and Philippe Refait

      Article first published online: 22 JUN 2010 | DOI: 10.1002/jrs.2717

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      Mackinawite (FeS) and greigite (Fe3S4) were characterised by micro-Raman spectroscopy in rust layers of archaelogical ferrous objects and archaeological wet wooden fragments contaminated by iron. The formation and oxidation processes of metastable iron(II) sulfides in such objects could be described.

    6. Identification of copper carboxylates as degradation residues on an ancient manuscript (pages 1434–1440)

      Maurizio Aceto, Angelo Agostino, Enrico Boccaleri, Fabrizio Crivello and Anna Cerutti Garlanda

      Article first published online: 28 MAR 2010 | DOI: 10.1002/jrs.2650

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      Copper carboxylates were identified as degradation residues on the surface of a metallic pigment used in the illumination and in the writing of a 9th century Italian manuscript. These compounds could be due to the interaction of copper with vapours of carboxylic acids generated by wood. Raman analysis, coupled to scanning electron microscopy-energy dispersive X-ray (SEM-EDX) analysis, allowed the investigation on the nature of these compounds.

    7. Assessment of limestone deterioration due to salt formation by micro-Raman spectroscopy: application to architectural heritage (pages 1441–1448)

      Sabina Kramar, Maja Urosevic, Helmut Pristacz and Breda Mirtič

      Article first published online: 30 MAY 2010 | DOI: 10.1002/jrs.2700

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      Micro-Raman spectroscopy together with X-ray powder diffraction was used to study the occurrence of mineral phases in limestone samples and their weathering products from historical monuments.

    8. Optimisation of Raman analysis of walnut oil used as protective coating of Galician granite monuments (pages 1449–1454)

      A. Pan, E. Rebollar, S. Chiussi, J. Serra, P. González and B. León

      Article first published online: 29 APR 2010 | DOI: 10.1002/jrs.2686

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      In this work, different types of walnut oil are analysed. A comparative Raman study is performed using five different laser excitation wavelengths, and 532 and 488 nm turned out to be the most appropriate wavelengths for oil detection on aluminium substrates. Additionally, Raman spectroscopy allows studying the evolution of the treatment once applied and the determination of curing times and chemical transformation.

    9. Extractionless non-hydrolysis surface-enhanced Raman spectroscopic detection of historical mordant dyes on textile fibers (pages 1455–1461)

      Z. Jurasekova, E. del Puerto, G. Bruno, J. V. García-Ramos, S. Sanchez-Cortes and C. Domingo

      Article first published online: 28 MAR 2010 | DOI: 10.1002/jrs.2651

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      Validation of SERS for mordant dyes belonging to the anthraquinone and flavonoid families is here presented. Laser-photoreduced silver nanoparticles produced on the fiber allowed the SERS detection of alizarin and carminic acid in wool and linen reference fibers dyed with madder and cochineal, respectively. Alizarin was also detected in a historical Coptic cloth. The same method provided identification of flavonols in wool fibers dyed with natural Central and South American plants following pre-Columbian recipes.

    10. Advances in Raman mapping of works of art (pages 1462–1467)

      Polonca Ropret, Costanza Miliani, Silvia A. Centeno, Črtomir Tavzes and Francesca Rosi

      Article first published online: 27 JUN 2010 | DOI: 10.1002/jrs.2733

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      Raman mapping in works of art has been traditionally performed using a motorized x–y microscope stage. A novel method based on a set of scanning mirrors that direct the laser beam in two spatial directions, vertically through the microscope head or through a horizontal exit on the Raman micro-spectrometer, is described. The advantages and limitations of both mapping approaches are discussed and compared on the basis of an example of a contemporary oil painting on canvas.

    11. Verdigris pigment: a mixture of compounds. Input from Raman spectroscopy (pages 1468–1476)

      M. San Andrés, J. M. de la Roja, V. G. Baonza and N. Sancho

      Article first published online: 26 SEP 2010 | DOI: 10.1002/jrs.2786

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      The different varieties of verdigris pigments obtained from the reproduction of an old recipe have been characterized by Raman and ATR-FTIR in order to create reference patterns.

    12. Raman microscopy study of synthetic cobalt blue spinels used in the field of art (pages 1477–1485)

      Michel Bouchard and Alessa Gambardella

      Article first published online: 28 MAR 2010 | DOI: 10.1002/jrs.2645

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      This study aims to provide a better understanding of the Raman spectra of cobalt-based pigments in works of art. Systematic analyses of 21 industrial blue cobalt-based pigments were carried out by using elemental energy dispersive spectroscopy and phase analyses by XRD and Raman microspectroscopy, which led to the identification of 17 spinel Co-based pigments. All the minerals composing each pigment were characterised by all three techniques and subsequently attributed to diluents, extenders, mineralisers, or unreacted reagents or to the main mineral phase, whether it was pure or contained doping or lattice modifier elements. In the particular case where doping elements were in low concentration in the host mineral lattice, their distinction by XRD from non-doped spinel was impossible. At the contrary, Raman microspectroscopy turned out to be a perfect tool for detecting the presence of the doping agents in the spinel lattice. The determination of the elemental and mineralogical composition of the industrial blue cobalt-based pigments commercially available for artist and studied in this survey represents a significant increase in the amount of analytical data available for this type of pigment as well as a valuable addition in characterisation by Raman microspectroscopy of these compounds in situ, in works of art.

    13. Raman spectroscopic discrimination of pigments and tempera paint model samples by principal component analysis on first-derivative spectra (pages 1486–1493)

      Natalia Navas, Julia Romero-Pastor, Eloisa Manzano and Carolina Cardell

      Article first published online: 25 MAR 2010 | DOI: 10.1002/jrs.2646

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      Principal components analysis (PCA) performed on first-derivative Raman spectra were applied to investigate historical tempera paint model samples. Various paint model samples were prepared with that aim, containing pure pigments (whites, blues and reds), pure egg yolk as binder and tempera obtained by mixing each of the pigments with the binder. These samples were further characterized by Raman spectroscopy. Multivariate analyses were performed on Raman spectra of the model samples by testing different pretreatments of the data. Results showed the excellent ability of PCA, when applied to first-derived Raman spectra, to discriminate model samples according to their differing composition. Nevertheless, the multivariate analysis of the original Raman spectra was able to track alterations of sensitive pigments due to laser interaction.

    14. A joint use of Raman and infrared spectroscopies for the identification of natural organic media used in ancient varnishes (pages 1494–1499)

      Céline Daher, Céline Paris, Anne-Solenn Le Hô, Ludovic Bellot-Gurlet and Jean-Philippe Échard

      Article first published online: 12 MAY 2010 | DOI: 10.1002/jrs.2693

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      The identification of natural organic reference materials representative of resins, glues, gums and oils is proposed by the joint use of vibrational spectroscopies. The combination of FT-Raman spectroscopic features with IR ones succeeded in building an algorithm that identifies and discriminates between the different media. It is shown that the different families (gums, glues, oils and resins) and subfamilies (di/triterpenoids) are easily differentiated.

    15. Direct analysis of the central panel of the so-called Wyts triptych after Jan van Eyck (pages 1500–1509)

      A. Deneckere, F.-Ph. Hocquet, A. Born, P. Klein, S. Rakkaa, S. Lycke, K. De Langhe, M. P. J. Martens, D. Strivay, P. Vandenabeele and L. Moens

      Article first published online: 4 MAY 2010 | DOI: 10.1002/jrs.2679

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      The central panel of the Wyts triptych was investigated using two complementary analytical techniques: energy dispersive X-ray fluorescence spectroscopy (EDXRF) and Raman spectroscopy. Different pigments could be identified, which provide information about the restorations the central panel underwent during history.

    16. Characterization of two pairs of 16th century Nanbam folding screens by Raman, EDXRF and FTIR spectroscopies (pages 1510–1516)

      Sofia Pessanha, Maria Luisa Carvalho, Maria Isabel Cabaço, Sara Valadas, Jean-Luc Bruneel, Marcel Besnard and Maria Isabel Ribeiro

      Article first published online: 29 MAR 2010 | DOI: 10.1002/jrs.2652

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      We report the study of two pairs of hand-painted Japanese Nanbam folding screens in order to characterize the materials used in their production. Japanese folding screens are one of the oldest and most highly refined forms of Japanese art. Nowadays, only about 60 examples of this Nanbam genre remain, so this study is of utmost importance to the knowledge of this precious craft.

    17. Characterization of calcium sulfate grounds and fillings of applied tin-relief brocades by Raman spectroscopy, Fourier transform infrared spectroscopy, and scanning electron microscopy (pages 1517–1524)

      Ainhoa Rodríguez, Katherine Eremin, Narayan Khandekar, Jens Stenger, Richard Newman, Fernando Bazeta and María Teresa Escohotado

      Article first published online: 4 NOV 2010 | DOI: 10.1002/jrs.2824

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      The painting technique of applied tin-relief brocade is studied in six early 16th century altarpieces of Guipúzcoa, Spain. Raman spectroscopy, Fourier transform infrared spectroscopy, and scanning electron microscopy with energy dispersive X-ray spectroscopy used on cross sections identified the inorganic and organic components of the ground and filling layers. The results for the grounds agreed with the documentary sources. The fillings showed a rich variety of mixtures of organic and inorganic materials.

    18. Russian avant-garde… or not? A micro-Raman spectroscopy study of six paintings attributed to Liubov Popova (pages 1525–1532)

      Steven Saverwyns

      Article first published online: 13 APR 2010 | DOI: 10.1002/jrs.2654

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      The applicability of micro-Raman spectroscopy to identify copies of Russian avant-garde paintings was evaluated. Six paintings attributed to one of the most prominent figures of the Russian avant-garde—Liubov Popova (1889–1924)—formed the basis for this study. The successful identification by Raman spectroscopy of several anachronistic pigments, mainly synthetic organic pigments, could unmask the paintings as modern copies.

    19. Gristhorpe Man: a Raman spectroscopic study of ‘mistletoe berries’ in a Bronze Age log coffin burial (pages 1533–1536)

      Howell G. M. Edwards, Janet Montgomery, Nigel D. Melton, Michael D. Hargreaves, Andrew S. Wilson and Elizabeth A. Carter

      Article first published online: 10 FEB 2010 | DOI: 10.1002/jrs.2593

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      Raman spectroscopy has been used to analyse three small spherical nodules initially identified as ‘mistletoe berries’ found in the coffin of a Bronze Age skeleton. It was concluded that the purported mistletoes berries were in fact human calculi, small stones found in organs such as the kidney and gall bladder.

    20. Pigments used in Roman wall paintings in the Vesuvian area (pages 1537–1542)

      Irene Aliatis, Danilo Bersani, Elisa Campani, Antonella Casoli, Pier Paolo Lottici, Silvia Mantovan and Iari-Gabriel Marino

      Article first published online: 24 MAY 2010 | DOI: 10.1002/jrs.2701

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      Powdered pigments found in bowls from the Pompeii archaeological site and some wall-painting fragments from the Vesuvian area are investigated by micro-Raman and FTIR spectroscopies, XRD and SEM-EDX. Pompeian artists used a wide range of colours, both natural and artificial. The uncommon white pigment huntite (CaMg3(CO3)4) is found in a bowl.

    21. Characterisation of fine wall and eggshell Roman pottery by Raman spectroscopy (pages 1543–1549)

      M. Olivares, M. C. Zuluaga, L. A. Ortega, X. Murelaga, A. Alonso-Olazabal, M. Urteaga, L. Amundaray, I. Alonso-Martin and N. Etxebarria

      Article first published online: 21 JUL 2010 | DOI: 10.1002/jrs.2748

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      A non-destructive methodology based on the combination of micro-Raman spectroscopy and X-ray diffraction has been proposed in order to characterise Roman pottery. The comparison of the minerals found in the different Roman potteries with the characteristic mineralogy of the archaeological site has suggested the use of raw materials coming from different source areas, thereby opening up an interesting discussion about the commercial networks.

    22. Micro-Raman investigation of terra sigillata slips: a comparative study of central Italian and southern Gaul productions (pages 1550–1555)

      Y. Leon, C. Lofrumento, A. Zoppi, R. Carles, E. M. Castellucci and Ph. Sciau

      Article first published online: 6 MAY 2010 | DOI: 10.1002/jrs.2678

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      The Raman spectrum of hematite is shown to be very sensitive to small variations in clays composition and firing temperature. Thus it has been used as an in situ and sensitive probe for discriminating between Italian and south Gallic productions.

    23. Multi-technique investigation of archaeological pottery from Parma (Italy) (pages 1556–1561)

      D. Bersani, P. P. Lottici, S. Virgenti, A. Sodo, G. Malvestuto, A. Botti, E. Salvioli-Mariani, M. Tribaudino, F. Ospitali and M. Catarsi

      Article first published online: 6 MAY 2010 | DOI: 10.1002/jrs.2669

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      Pottery samples from a factory discovered in Parma (Italy), active from the 14th to the 17th century, are investigated. Micro-Raman spectroscopy and scanning electron microscopy–energy dispersive spectroscopy (SEM-EDS) are used to study the glazes and the painting materials, while time-of-flight neutron diffraction and X-ray diffraction are applied to characterize the ceramic bodies. The firing temperatures of the glazes and ceramic bodies are estimated.