Journal of Raman Spectroscopy

Cover image for Vol. 43 Issue 11

Special Issue: Raman spectroscopy in art and archaeology

November 2012

Volume 43, Issue 11

Pages 1523–1844

Issue edited by: Juan Manuel Madariaga, Danilo Bersani

  1. Editorial

    1. Top of page
    2. Editorial
    3. Review
    4. Research articles
    1. You have free access to this content
      Applications of Raman spectroscopy in art and archaeology (pages 1523–1528)

      Danilo Bersani and Juan Manuel Madariaga

      Version of Record online: 8 NOV 2012 | DOI: 10.1002/jrs.4219

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      The Sixth edition of the International Congress on the Application of Raman Spectroscopy in Art and Archeology (RAA 2011) was held in Parma (Italy) from 5 to 8 September 2011, with five Plenary Lectures, 45 Oral Presentations and 83 Poster Presentations. The number of active participants was 130 delegates from 26 countries among the 502 authors that presented at least one work to the Congress.

  2. Review

    1. Top of page
    2. Editorial
    3. Review
    4. Research articles
    1. The on-site/remote Raman analysis with mobile instruments: a review of drawbacks and success in cultural heritage studies and other associated fields (pages 1529–1535)

      Philippe Colomban

      Version of Record online: 7 SEP 2012 | DOI: 10.1002/jrs.4042

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      The miniaturisation of laser sources, charge-coupled device electronic control boxes and increasing lap-top computer capacity led to a revolution in Raman spectrometry: Measurements can be performed outside the laboratory with transportable, mobile and ultra-mobile instruments, even in severe conditions (e.g. rock shelters in mountains or forthcoming Mars mission). The present state of the art and future development are discussed.

  3. Research articles

    1. Top of page
    2. Editorial
    3. Review
    4. Research articles
    1. Identification of synthetic organic pigments: the role of a comprehensive digital Raman spectral library (pages 1536–1544)

      Wim Fremout and Steven Saverwyns

      Version of Record online: 25 JUL 2012 | DOI: 10.1002/jrs.4054

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      Raman spectra of nearly 300 synthetic organic pigments have been recorded. A selection of these and different identification approaches are critically compared using four case studies of contemporary paintings. A website containing all spectra in digital format is announced.

    2. Some ideas on the definition of Raman spectroscopic detection limits for the analysis of art and archaeological objects (pages 1545–1550)

      Peter Vandenabeele and Luc Moens

      Version of Record online: 18 SEP 2012 | DOI: 10.1002/jrs.4055

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      An evaluation of the definition of Raman spectroscopic limits of detection and limits of identification was made. They are discussed in the context of cultural heritage analysis, along with some particular situations that are typically encountered.

    3. Surface-enhanced Raman spectroscopy spectra of Mexican dyestuffs (pages 1551–1559)

      Edgar Casanova-González, Angélica García-Bucio, José Luis Ruvalcaba-Sil, Víctor Santos-Vasquez, Baldomero Esquivel, Tatiana Falcón, Elsa Arroyo, Sandra Zetina, María Lorena Roldán and Concepción Domingo

      Version of Record online: 11 AUG 2012 | DOI: 10.1002/jrs.4086

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      From the wide variety of Mexican dyes, only a handful had been studied at length. In this work, carminic acid, cochineal (Dactylopius coccus), achiote (Bixa orellana), muitle (Justicia spicigera), zacatlaxcalli (Cuscuta sp.), brazilwood (Caesalpinia echinata), and cempazuchitl (Tagetes erecta) SERS spectra were recorded in aqueous solution and directly on dyed wool fibers, using silver colloids as SERS substrate. In the case of cempazuchitl, muitle, and zacatlaxcalli, these are probably the first reported Raman spectra of such plants.

    4. FT-Raman spectroscopy for quantitative analysis of salt efflorescences (pages 1560–1566)

      Alessandra Broggi, Elisabetta Petrucci, Maria Paola Bracciale and Maria Laura Santarelli

      Version of Record online: 1 AUG 2012 | DOI: 10.1002/jrs.4153

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      Salt crystallization is a frequently encountered problem in the field of cultural heritage and is considered to be one of the most powerful weathering factors of the stones and plasters. The capability of FT-Raman spectroscopy for the fast and nondestructive quantitative analysis of salt mixtures in efflorescences was tested, and the results were compared to those obtained by ionic chromatography.

    5. Simulation of vibrational spectra of crystals by ab initio calculations: an invaluable aid in the assignment and interpretation of the Raman signals. The case of jadeite (NaAlSi2O6) (pages 1567–1569)

      Mauro Prencipe

      Version of Record online: 20 JUL 2012 | DOI: 10.1002/jrs.4040

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      First principles calculation of the Raman-active normal modes and wavenumbers of jadeite. The average discrepancy between the position of the calculated and experimental Raman signals is less than 4 cm–1. The attribution of each signal to a specific pattern of atomic motion has been performed.

    6. Degradation potential of airborne particulate matter at the Alhambra monument: a Raman spectroscopic and electron probe X-ray microanalysis study (pages 1570–1577)

      Sanja Potgieter-Vermaak, Benjamin Horemans, Willemien Anaf, Carolina Cardell and René Van Grieken

      Version of Record online: 4 JUL 2012 | DOI: 10.1002/jrs.4052

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      Single particle analysis has been performed on airborne particulate matter (APM) collected at the Alhambra monument, using micro-Raman spectroscopy (MRS) and electron probe X-ray microanalysis. MRS and molar abundance ternary diagrams elicited the chemical structure of individual APM. The APM proved to be largely acidic, hygroscopic and/ or carbonaceous in composition, resulting in potential chemical attack and soiling of the artefacts.

    7. Raman investigation of artificial patinas on recent bronze – Part I: climatic chamber exposure (pages 1578–1586)

      Polonca Ropret and Tadeja Kosec

      Version of Record online: 18 SEP 2012 | DOI: 10.1002/jrs.4068

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      Green chloride and green nitrate patinas, applied over the brown artist's patina, were tested, and also brown patina and the patina that develops on bare bronze. Chemical patinas were characterized before and after exposure in a climatic chamber. After 12 weeks of exposure, the corrosion products changed. In general, clinoatacamite and paratacamite are the end corrosion products, after an intermediate brochantite stage on the green chloride and green nitrate type patinas. The end products of each patina type are given.

    8. Raman investigation of artificial patinas on recent bronze‒part II: urban rain exposure (pages 1587–1595)

      Tadeja Kosec, Polonca Ropret and Andraž Legat

      Version of Record online: 16 JUL 2012 | DOI: 10.1002/jrs.4124

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      Green chloride and green nitrate patinas, applied over the brown artist's patina, were tested, as well as the brown patina and the patina that develops on bare bronze. Chemical patinas were characterized after exposure to simulated urban rain for 35 days. After the exposure, the corrosion products changed. The end products of each patina type are given.

      In the figure, the corrosion products on green chloride patina on bronze after exposure to simulated urban rain are presented. The presence of brochantite/langite and atacamite are confirmed.

    9. The characterization of Sn-based corrosion products in ancient bronzes: a Raman approach (pages 1596–1603)

      Francesca Ospitali, Cristina Chiavari, Carla Martini, Elena Bernardi, Fabrizio Passarini and Luc Robbiola

      Version of Record online: 10 JUN 2012 | DOI: 10.1002/jrs.4037

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      Tin and its insoluble salts play an important role in the mechanism of formation of bronze patinas, and their characterization becomes fundamental, although quite problematic. This work reports several case studies where Sn-containing compounds were identified in bronzes exposed to different environments (to the atmosphere, in both natural and accelerated ageing conditions, and to the soil), thanks to the hyphenated system scanning electron microscopy–energy dispersive spectrometry–Raman structural and chemical analyser. The main issues regarding the interpretation of Raman spectra of these compounds, mainly crystalline and nano-sized tin dioxides, are presented and discussed.

    10. μ-Raman mapping to study calcium oxalate historical films (pages 1604–1611)

      C. Conti, I. Aliatis, C. Colombo, M. Greco, E. Possenti, M. Realini, C. Castiglioni and G. Zerbi

      Version of Record online: 31 AUG 2012 | DOI: 10.1002/jrs.4072

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      Characterization of the oxalate films observed on several ancient monuments is essential in order to study their formation process. μ-Raman mapping on cross-sections allowed, for the first time, to unequivocally identify the mineralogical phases occurring in the films and to obtain direct information on their spatial distribution. Collected data show random distribution of oxalate phases and a higher content of weddellite in the external portions of the films.

    11. Spectroscopic characterization of an innovative biological treatment for corroded metal artefacts (pages 1612–1616)

      Edith Joseph, Anaële Simon, Rocco Mazzeo, Daniel Job and Marie Wörle

      Version of Record online: 17 OCT 2012 | DOI: 10.1002/jrs.4164

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      Biological treatments are being evaluated for the preservation of metal artefacts. The capacity of a fungal strain, Beauveria bassiana, to precipitate copper oxalates is exploited for the stabilization of soluble patinas (copper hydroxysulfates) or the transformation of active corrosion products (copper hydroxychlorides). Raman mapping is used for evaluating the effective formation of the protective layer of copper oxalates on bronze coupons.

    12. Micro-Raman spectroscopy for the characterization of artistic patinas produced on copper-based alloys (pages 1617–1622)

      Valeria Bongiorno, Serena Campodonico, Roberta Caffara, Paolo Piccardo and Maria Maddalena Carnasciali

      Version of Record online: 13 SEP 2012 | DOI: 10.1002/jrs.4167

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      Various ‘artistic patinas’ (i.d. coatings artificially made on metal artworks for aesthetic and protective purposes) were produced both on metallic substrate reproducing the typical copper-based alloys used for statuary and on a copper sheet. They were analysed with different analytical techniques, before and after ageing in salt spray chamber, to understand the reactions involved in all patinas. The results of the analyses will contribute to the improvement of restoration and conservation sciences of metallic artefacts belonging to Cultural Heritage.

    13. Structural characterization of a third-generation commercial cement superplasticizer by Raman spectroscopy and density functional theory calculations (pages 1623–1629)

      Maria Vega Cañamares, Santiago Sanchez-Cortes and Sagrario Martinez-Ramirez

      Version of Record online: 23 OCT 2012 | DOI: 10.1002/jrs.4082

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      The structure of an unknown polycarboxylate based cement superplasticizer was determined by the comparison of the experimental FT-Raman and the density functional theory calculated spectra. Different models based on polycarboxylates were proposed. The final structure was the one of a polycarboxylic acid.

    14. Characterisation and diagnosis of the conservation state of cementitious materials exposed to the open air in XIX century lighthouses located on the coast of the Basque Country: ‘The case of Igueldo lighthouse, San Sebastian, North of Spain’ (pages 1630–1636)

      Héctor Morillas, Maite Maguregui, Olivia Gómez-Laserna, Josu Trebolazabala and Juan Manuel Madariaga

      Version of Record online: 16 JUL 2012 | DOI: 10.1002/jrs.4130

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      Raman spectroscopic analysis combined with other analytical techniques allowed to characterise different pathologies affecting the integrity of the cementitious materials. A wide variety of nitrate salts (nitratine, niter and/or nitrocalcite) were identified by means of Raman spectroscopy formed as a consequence of the reaction between ammonium nitrate, coming from seagulls droppings decomposition, and the carbonaceous part of the cementitious materials. Moreover, the dissolved sulphates from the original materials (e.g. gypsum) react with sodium carbonate (coming from the carbonation of original sodium oxide additive) giving rise to sodium sulphate crystallisations.

    15. The first in situ micro-Raman spectroscopic analysis of prehistoric cave art of Rouffignac St-Cernin, France (pages 1637–1643)

      Sophia Lahlil, Matthieu Lebon, Lucile Beck, Hélène Rousselière, Colette Vignaud, Ina Reiche, Michel Menu, Patrick Paillet and Frédéric Plassard

      Version of Record online: 15 JUL 2012 | DOI: 10.1002/jrs.4115

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      The first in situ micro-Raman spectroscopic study of prehistoric drawings found in the cave of Rouffignac-Saint-Cernin (Dordogne, France) was carried out. The adaptability of portable equipment, as well as the feasibility of in situ micro-Raman analyses in a cave environment was tested. The results obtained are compared with in situ X-ray fluorescence and X-ray diffraction microanalysis performed at the same time in the cave.

    16. Spectroscopy of Palaeolithic rock paintings from the Tito Bustillo and El Buxu Caves, Asturias, Spain (pages 1644–1650)

      Antonio Hernanz, José M. Gavira-Vallejo, Juan F. Ruiz-López, Santiago Martin, Ángel Maroto-Valiente, Rodrigo de Balbín-Behrmann, Mario Menéndez and Jose J. Alcolea-González

      Version of Record online: 30 DEC 2011 | DOI: 10.1002/jrs.3145

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      The composition of Palaeolithic rock paintings from the Tito Bustillo and El Buxu caves (30 000–10 000 bp, Asturias, Spain) have been characterised by Raman microscopy with auxiliary techniques (scanning electronic microscopy/energy dispersive X-ray, infrared, X-ray diffraction and X-ray photoelectron spectroscopy). A supposed source of pigment is discarded. Possible relationships among pictographs from both caves are established.

    17. Raman spectroscopy analysis of Palaeolithic industry from Guadalteba terrace river, Campillos (Guadalteba county, Southern of Iberian Peninsula) (pages 1651–1657)

      V. Hernández, S. Jorge-Villar, C. Capel Ferrón, F. J. Medianero, J. Ramos, G.-C. Weniger, S. Domínguez-Bella, J. Linstaedter, P. Cantalejo, M. Espejo and J. J. Durán Valsero

      Version of Record online: 26 JUL 2012 | DOI: 10.1002/jrs.4104

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      A representative set of Palaeolithic stone tools collected in different archaeological sites of the Guadalteba county (Málaga, Spain) has been investigated by means of Raman spectroscopy, using both portable and benchtop Raman spectrometers, with the aim of characterizing the mineral composition of chert and sandstone artefacts.

    18. The Heslington brain: a challenge for analytical Raman spectroscopy (pages 1658–1662)

      Howell G. M. Edwards, Esam M. A. Ali and Sonia O'Connor

      Version of Record online: 11 JUL 2012 | DOI: 10.1002/jrs.4049

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      The survival of brain tissue in archaeological depositional environments is a very unusual occurrence that has generated much discussion and conjecture forensically. Here, we report the Raman spectroscopic analysis of biomaterial found in the cranial cavity of a decapitated skull dating from the Iron Age, some 2500 years ago, from which the presence of degraded protein consistent with it being naturally preserved brain is concluded.

    19. A novel piece of Minoan art in Italy: the first spectroscopic study of the wall paintings from Phaistos (pages 1663–1670)

      Angela Zoppi, Cristiana Lofrumento, Marilena Ricci, Emma Cantisani, Tiziana Fratini and Emilio Mario Castellucci

      Version of Record online: 26 JUL 2012 | DOI: 10.1002/jrs.4029

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      Some fragments of wall paintings of Phaistos (Crete), belonging to the Bronze Age, were analysed to investigate the material composition of their pictorial layers, and the pictorial technology. In accordance with similar Aegean Bronze painted plasters, the obtained results show a rather homogenous palette mostly made of mineral pigments, which recur in the different tones in all the fragments. The absence of organic binders and the possibility to differentiate calcite grains were indicative of fresco–secco technique.

    20. Micro-Raman spectroscopy of carbon-based black pigments (pages 1671–1675)

      Eugenia P. Tomasini, Emilia B. Halac, María Reinoso, Emiliano J. Di Liscia and Marta S. Maier

      Version of Record online: 20 SEP 2012 | DOI: 10.1002/jrs.4159

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      Carbon-based black pigments are a wide group of dark-colored materials. In this work, reference carbon-based pigments were studied by micro-Raman spectroscopy. All pigments showed the characteristic bands at approximately 1580 and 1350 cm−1; however, a clear difference in position, width, and relative intensity could be observed for most of the samples. Micro-Raman spectroscopy allowed the discrimination of most of the reference pigments and the identification of carbon-based black pigments in two South American colonial paintings dated from the early 18th century.

    21. In situ Raman spectroscopy analysis combined with Raman and SEM-EDS imaging to assess the conservation state of 16th century wall paintings (pages 1676–1684)

      Mireia Irazola, Maitane Olivares, Kepa Castro, Maite Maguregui, Irantzu Martínez-Arkarazo and Juan Manuel Madariaga

      Version of Record online: 10 JUN 2012 | DOI: 10.1002/jrs.4036

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      A multianalytical methodology was proposed to carry out the analysis of two wall paintings from the Basque Country. Raman, assisted with EDXRF and DRIFT spectrometers, was employed in the in situ analysis. Furthermore, a deeper analysis was performed by means of SEM-EDS and Raman imaging techniques in some cross-sections.

    22. Micro-Raman and GC/MS analysis to characterize the wall painting technique of Dicho Zograph in churches from Republic of Macedonia (pages 1685–1693)

      Lidija Robeva Čukovska, Biljana Minčeva – Šukarova, Anna Lluveras-Tenorio, Alessia Andreotti, Maria Perla Colombini and Irena Nastova

      Version of Record online: 23 OCT 2012 | DOI: 10.1002/jrs.4183

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      Micro-Raman spectroscopy, Py/GC/MS and GC/MS were applied for the characterization of pigments and binders used in the 19th century wall paintings ascribed to the work of Macedonian iconographer, Dicho Zograph. A rich palette of pigments, both natural/mineral and synthetic were identified, while the binders were mainly a mixtures of proteinaceous materials, linseed oil and pine resin.

      A comparison between the pigments and binders identified in this study and those suggested in Dicho's Painter's Manual (from 1851) showed that some materials, both inorganic and organic ones, had not been mentioned in his written source.

    23. Micro-spectroscopic Raman investigation on the canvas oil painting ‘Rebecca at the well’ of Neapolitan anonymous (pages 1694–1698)

      E. Cazzanelli, E. Platania, G. De Santo, A. Fasanella and M. Castriota

      Version of Record online: 24 SEP 2012 | DOI: 10.1002/jrs.4174

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      Modern pigments have been used for restoration work in old paintings, sometime without any written documentation about. In this case, the characteristic spectra of copper phthalocianine have been found in a micro-Raman study on the oil painting ‘Rebecca at the well’, preserved in MAON museum of Rende, (Cosenza), Italy. Art historians believe that the painting was created in the XVIII century by an artist of the Neapolitan school. The main pigments were identified, and important information were found about the restoration works and the painting's history.

    24. Evaluation of the intervention of a folding screen belonging to the Momoyama period by Raman spectroscopy using different wavelengths (pages 1699–1706)

      Sofia Pessanha, Agnès Le Gac, Teresa Isabel Madeira, Jean-Luc Bruneel, Stéphane Longelin and Maria Luisa Carvalho

      Version of Record online: 9 NOV 2012 | DOI: 10.1002/jrs.4094

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      The materials used in an unknown restoration intervention performed in a 17th-century Namban folding screen were studied by means of in situ energy dispersive X-ray fluorescence and Raman spectroscopy using different wavelengths. The investigation performed allowed a date for the western restoration to be inferred.

    25. Automatic identification system of Raman spectra in binary mixtures of pigments (pages 1707–1712)

      J. J. González-Vidal, R. Perez-Pueyo, M. J. Soneira and S. Ruiz-Moreno

      Version of Record online: 17 OCT 2012 | DOI: 10.1002/jrs.4177

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      A system to automatically identify Raman spectra of binary mixtures of pigments is presented to decrease complexity and to speed up the identification process. The methodology is based on building mathematical spectra and quantifying the similarity between them and the unknown spectrum after being projected onto the reduced space generated by the principal components analysis, which saves resources and time, becoming a useful support tool to help the analyst in the decision-making process.

    26. Comparison of English portrait miniatures using Raman microscopy and other techniques (pages 1713–1721)

      Lucia Burgio, Anna Cesaratto and Alan Derbyshire

      Version of Record online: 19 SEP 2012 | DOI: 10.1002/jrs.4133

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      Eighteen V&A miniatures were analysed in order to characterise the palette used by the artists, paying attention not only to the identity of the materials but also to the shape, size and distribution of the pigment particles. This approach permitted to help distinguishing between different miniaturists and, associated with curatorial and art historical expertise, was used to suggest an attribution for three miniatures the maker of which was uncertain or disputed.

    27. Identification of colorants on XVIII century scientific hand-coloured print volumes (pages 1722–1728)

      Paolo Zannini, Pietro Baraldi, Maurizio Aceto, Angelo Agostino, Gaia Fenoglio, Danilo Bersani, Eleonora Canobbio, Elisabetta Schiavon, Giusi Zanichelli and Andrea De Pasquale

      Version of Record online: 26 OCT 2012 | DOI: 10.1002/jrs.4119

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      Two series of volumes printed in Parma and in Vienna in late XVIII century were analysed with non-invasive techniques to characterise the palettes used in the hand-coloured miniatures and to determine whether decoration had been carried out simultaneously or after the time of printing. A thorough knowledge of the colorants present was yielded; artists used a mixing of traditional materials (e.g. cinnabar, minium, indigo) and materials of recent introduction in late XVIII century (e.g. gamboge, Prussian blue, blue verditer).

    28. Micro-Raman spectroscopic analysis of inks and pigments in illuminated medieval old-Slavonic manuscripts (pages 1729–1736)

      Irena Nastova, Orhideja Grupče, Biljana Minčeva-Šukarova, Servet Turan, Merve Yaygingol, Melih Ozcatal, Violeta Martinovska and Zorica Jakovlevska-Spirovska

      Version of Record online: 20 SEP 2012 | DOI: 10.1002/jrs.4084

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      Micro-Raman spectroscopy was applied in characterisation of inks and pigments used in the text, illuminations and miniatures of two old-Slavonic manuscripts: Vrutok four gospels (13th–14th centuries) and Benche four gospels (16th century). Only four colours/pigments were used in the simple miniature and ornaments in Vrutok book: orpiment, vermilion, organo-copper complex and mixed ink. Much richer palette of pigments was revealed in the Benche book: calcite, gypsum, lead white, yellow ochre, pararealgar/realgar, vermilion, red lead, red ochre, organo-copper complex, malachite, indigo, iron gall ink, carbon black and pure metallic gold.

    29. Micro-Raman study of Medieval Cistercian 12–13th century manuscripts: Santa Maria de Alcobaça, Portugal (pages 1737–1746)

      Vânia S. F. Muralha, Catarina Miguel and Maria João Melo

      Version of Record online: 18 SEP 2012 | DOI: 10.1002/jrs.4065

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      The colour palette of a set of fifteen 12–13th centuries manuscripts from Santa Maria de Alcobaça Monastery (Portugal) was determined by Raman microscopy. The Alcobaça collection shows consistently the use of pink and grey paints, mostly achieved by mixing vermilion and/or an organic red or a carbon-based black pigment with lead white, respectively. Other pigments include the ubiquitous lazurite, and vermilion, red lead, lead white and orpiment. Two colours are suffering degradation processes: bottle green and white. The degradation mechanisms are discussed.

    30. Field Raman analysis to diagnose the conservation state of excavated walls and wall paintings in the archaeological site of Pompeii (Italy) (pages 1747–1753)

      Maite Maguregui, Ulla Knuutinen, Irantzu Martínez-Arkarazo, Anastasia Giakoumaki, Kepa Castro and Juan M. Madariaga

      Version of Record online: 20 JUL 2012 | DOI: 10.1002/jrs.4109

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      Field Raman analysis evidences that the chemical attacks of SO2 pollutants (e.g. gypsum formation) and biological colonisations (e.g. carotenoids identification) can be considered the most important processes impacting walls and wall paintings, excavated more or less 150 years ago, in two houses from Insula IX 3 inside the archaeological site of Pompeii. A possible impact of airborne particulate matter (e.g. anhydrous calcium nitrate identification) and a possible negative influence on ancient mortars (e.g. sodium sulfate crystallisations) of sulfates included in new cement mortars used in recent restorations should be studied in further expeditions

    31. The mural paintings of Ala di Stura (Piedmont, Italy): a hidden treasure investigated (pages 1754–1760)

      Maurizio Aceto, Giorgio Gatti, Angelo Agostino, Gaia Fenoglio, Valentina Giordano, Michelangelo Varetto and Giorgio Castagneri

      Version of Record online: 8 AUG 2012 | DOI: 10.1002/jrs.4066

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      A large unexplored artistic heritage from Ala di Stura (Piedmont, Italy), made of mural paintings datable among XVI and XXI century, has been studied with Raman analysis. This allowed to elucidate phenomena of chromatic alteration (changing of lead pigments), to individuate pigments acting as time markers (synthetic ultramarine blue, arsenical green pigments) and to have information on the origin and exploitation of pictorial materials used by the artists who worked in this mountain zone.

    32. Pablo Picasso to Jasper Johns: a Raman study of cobalt-based synthetic inorganic pigments (pages 1761–1771)

      F. Casadio, A. Bezúr, I. Fiedler, K. Muir, T. Trad and S. Maccagnola

      Version of Record online: 4 JUL 2012 | DOI: 10.1002/jrs.4081

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      The Raman spectra of 20 historical and modern reference samples of cobalt titanate green and cobalt violet artists' pigments were acquired to assist in the identification of unknown cobalt-based pigments in works by Pablo Picasso (1881–1973) and Jasper Johns (b. 1930). Some of the spectra are presented here for the first time. This research advances the knowledge of 20th century synthetic inorganic pigments used by artists and documents their usage in actual works of art.

    33. Contribution to the identification of α-, β- and ε-copper phthalocyanine blue pigments in modern artists' paints by X-ray powder diffraction, attenuated total reflectance micro-fourier transform infrared spectroscopy and micro-Raman spectroscopy (pages 1772–1780)

      C. Defeyt, P. Vandenabeele, B. Gilbert, J. Van Pevenage, R. Cloots and D. Strivay

      Version of Record online: 15 JUL 2012 | DOI: 10.1002/jrs.4125

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      Dry pigments of α-, β- and ε-CuPc have been investigated by X-ray powder diffraction, attenuated total reflectance micro-Fourier transform infrared spectroscopy and micro-Raman spectroscopy. On the basis of the results obtained for dry pigments, several polymorphic markers have been highlighted for the CuPc polymorphs distinction in artists' paints. The reliability of the polymorphic markers is demonstrated with acrylic, vinylic, alkyd, arabic gum and oil-based paint samples.

    34. Raman investigations on marker pen inks (pages 1781–1787)

      A. Sodo, M. Bicchieri, M. Guiso, M. A. Ricci and G. Ricci

      Version of Record online: 13 JUL 2012 | DOI: 10.1002/jrs.4070

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      We report Raman spectra of marker pen original and ‘laboratory’ drawings. Raman spectra of yellow, orange and red standard samples of commercial (Carioca and Giotto) and technical brands (Stabilo and Staedtler) have been recorded and identified. A comparison among old and new marker pen inks composition is discussed. Food additives have been used as colour agents in marker pen inks and their standard Raman spectra are reported.

    35. Micro Raman spectroscopy (MRS) and energy dispersive x-ray microfluorescence (μEDXRF) analysis of pigments in the Iberian cemetery of Tutugi (from the fourth to the third century bc, Galera, Granada, Spain) (pages 1788–1795)

      Alberto Sánchez, José Tuñón, Manuel Montejo and David Parras

      Version of Record online: 19 JUL 2012 | DOI: 10.1002/jrs.4080

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      The spectroscopic analyses of several archaeological samples (ceramics, a fragment of a glass paste vessel and fragments of a stone funerary urn) recovered from the Iberian cemetery of Tutugi, allowed identifying the type of pigments used in their decoration, i.e. hematite, cinnabar, gypsum, amorphous carbon, Egyptian blue and Naples yellow.

    36. Petrographical and micro-Raman analysis of Terra Sigillata shatters from a Vandalic settlement in North-Eastern Hungary (pages 1796–1804)

      Krisztian Fintor and Zsófia Gyalai

      Version of Record online: 13 SEP 2012 | DOI: 10.1002/jrs.4176

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      Temper grains of samples originated from Pfaffenhofen and Westerndorf contain more calcic minerals, including plagioclases, augite, diopside, actinolite, apatite and titanite. Conversely, the temper grains of samples from Rheinzabern contain only potassium feldspars, while anatase and rutile represent their heavy mineral content. The largest difference between the slip and body can be observed in samples from Westerndorf, while the largest heterogeneity of the slip and body material is observable in samples from Pfaffenhofen.

    37. New results in the characterization by Raman spectroscopy of yellow pigments used in ceramic artworks of the 16th and 17th centuries (pages 1805–1810)

      P. Ferrer, S. Ruiz-Moreno, A. López-Gil, M. C. Chillón and C. Sandalinas

      Version of Record online: 5 SEP 2012 | DOI: 10.1002/jrs.4160

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      A comparative investigation, temporal and geographical, is carried out with a new and portable optical fiber Raman system about the use of yellow pigments based on a triple Pb, Sn, and Sb oxide in Italian and Spanish ceramics, both, produced in the 16th and 17th centuries. The artworks belong to the Museo de Cerámica de Barcelona.

    38. Classification of glazed potteries from Christian and Muslim territories (Late Medieval Ages, IX–XIII centuries) by micro-Raman spectroscopy (pages 1811–1816)

      Maria Cruz Zuluaga, Ainhoa Alonso-Olazabal, Maitane Olivares, Luis Ortega, Xabier Murelaga, Juan Jose Bienes, Alfredo Sarmiento and Nestor Etxebarria

      Version of Record online: 16 JUL 2012 | DOI: 10.1002/jrs.4056

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      Micro-Raman spectroscopy was used for the classification of pre-Islamic, Muslim, and Mudejar-glazed ceramics. Mineralogical assemblage indicates a similar pottery-making style in Muslim and Mudejar ceramics, whereas a local procedure is detected in Christian ones. Raman data allows establishing glazed composition and the processing temperature, and not only in differentiating between Muslim and Mudejar potteries but also in detecting the Mudejar style in Christian territory.

    39. Raman study of model glass with medieval compositions: artificial weathering and comparison with ancient samples (pages 1817–1823)

      L. de Ferri, D. Bersani, Ph. Colomban, P. P. Lottici, G. Simon and G. Vezzalini

      Version of Record online: 11 JUN 2012 | DOI: 10.1002/jrs.4103

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      Medieval-like glass, synthesized with different amounts of K2O as fluxing agent, has been studied by Raman spectroscopy and artificially aged in H2SO4 and in hot high pressure water. Structural changes as a function of the glass K content are compared with those observed in Middle Ages samples.

    40. The intriguing case of silicon crystals unveiled in ancient mosaic tesserae (pages 1824–1827)

      Daniela Di Martino, Anna Galli and Marco Martini

      Version of Record online: 18 SEP 2012 | DOI: 10.1002/jrs.4135

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      Some silicon nanocrystals were disclosed within the silica amorphous matrix of glass mosaic tesserae belonging to Daphni Monastery (Greece, XI century).

      The singleness of this finding can be interpreted as a marker of a local production site.

    41. Raman spectroscopy in gemmology as seen from a ‘jeweller's’ point of view (pages 1828–1832)

      Marco Giarola, Gino Mariotto, Marianna Barberio and David Ajò

      Version of Record online: 16 JUL 2012 | DOI: 10.1002/jrs.4129

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      Some gemmological objects (diamonds, coloured stones or assembled gems) found in the jewellery's commerce when observed by an optical microscopy or even at naked eye, exhibit unusual characteristics, such as inclusions incorporated at different depths beneath the sample surface. Their investigation by confocal Raman micro-spectroscopy allowed for the identification of a blue sapphire and of nanocrystalline anatase in the same surface region of a cut and polished diamond gem. Moreover, several inclusions of unusual shape, embedded into the bulk of a coloured gemstone, were identified as α-Fe2O3. Finally, a detailed micro-Raman characterization investigation of the different component parts of an assembled gem, evidenced spectral features that can be put in relation with its fabrication process.

    42. Micro-Raman spectroscopy on two chalices from the Benedictine Abbey of Einsiedeln: Identification of gemstones (pages 1833–1838)

      Stefanos Karampelas, Marie Wörle, Katja Hunger and Hanspeter Lanz

      Version of Record online: 11 AUG 2012 | DOI: 10.1002/jrs.4069

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      The gems that adorn two golden chalices from Einsiedeln Abbey (Switzerland) crafted on 1609 and 1629 were investigated using Raman spectroscopy and other non-destructive means. The chalice made in 1609 was adorned with 16 corundum (15 rubies and 1 sapphire), four garnets (two almandine and two grossular), seven quartzes (six amethysts and one citrine) and one peridot (forsterite olivine) and saltwater pearls. The chalice crafted in 1629 was adorned with 23 diamonds.

    43. Provenance investigations of amber jewelry excavated in Lower Silesia (Poland) and dated back to Early Iron Age (pages 1839–1844)

      Barbara I. Łydżba-Kopczyńska, Bogusław Gediga, Jan Chojcan and Michał Sachanbiński

      Version of Record online: 17 OCT 2012 | DOI: 10.1002/jrs.4187

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      The unique amber jewelry dated back to early Iron Age was discovered in burial chambers of archeological excavations in Domasław, Lower Silesia (Poland). Based on the Raman analysis supported by positron annihilation spectroscopy provenance of over 100 studied objects was established.