Book of Abstracts RAA2011

Book of Abstracts
Book of Abstracts: RAA2011

6th International Congress on the Application of Raman Spectroscopy in Art and Archaeology
Parma, 5-8 September 2011
Committees
Scientific Committee
Danilo Bersani (Italy)
Juan Manuel Madariaga (Spain)
Peter Vandenabeele (Belgium)
Howell G. M. Edwards (U.K.)
Pietro Baraldi (Italy)
Sandrine Pags-Camagna (France)
Francesca Casadio (USA)
Organizing Committee
Danilo Bersani
Pier Paolo Lottici
Guglielmina Gnappi
Laura Bergamonti
Irene Aliatis
Angelo Montenero
Antonella Casoli
Emma Salvioli-Mariani
Mario Tribaudino
Iari-Gabriel Marino
Manuela Catarsi
Gloria Bianchino

PLENARY
LECTURES

An evaluation of the effectiveness of SERS in the
identificaton of textile dyes in real archaeological and
historical samples
Silvia Bruni
Universit degli Studi di Milano, Dipartimento di Chimica Inorganica, Metallorganica

e Analitica Lamberto Malatesta, Via G. Venezian 21, 20133 Milano (Italy), Tel. +39
0250314393, silvia.bruni@unimi.it
In the last few years the application of surface-enhanced Raman spectroscopy to the
identification of historical dyes has significantly developed from the point of view of
analytical protocols, aiming to reduce the need for sample pre-treatment, the
required amount of sample [Brosseau et al. 2011] or even to completely avoid
sampling [Leona et al. 2011]. These aspects of the evolution of the technique were
extensively reported and reviewed in the literature.
Whenever an analytical chemist is involved in the solution of a problem concerning
the cultural heritage, he has to deal with two different issues: the development of
suitable methods and the need to give precise answers to the questions of
archaeologists and art historians. At the present stage of improvement of the SERS
technique for the identification of dyes, it is therefore useful to evaluate its capability
in recognising such substances, especially those used for textile dyeing, in a field
where other analytical methods, i.e. those based on high-performance liquid
chromatography (HPLC), are still most commonly and routinely used by specialised
laboratories.
Examples concerning the possibility of recognising by SERS dyes used in
archaeological and historical samples from particular geographical areas or in the
decoration of unusual textile artefacts will be discussed, with special attention to
those cases where identification is made more difficult by the need of a widened
database or by the use of dyes in mixtures or even by degradation effects.
References
Brosseau C. L., Casadio F., Van Duyne R. P., Journal of Raman Spectroscopy 2011; 42:
1305.
Leona M., Decuzzi P., Kubic T. A., Gates G., Lombardi J. R., Analytical Chemistry, 2011; 83:
3990.

1
The on-site Raman analysis: difficulty and success !
Philippe Colomban1
1
Universit Pierre-et-Marie-Curie (UPMC) -CNRS, LADIR, C49 4 Place Jussieu,
75252 Paris Cedex 05 (France), philippe.colomban@upmc.fr
The miniaturization of laser sources, CCD electronic control boxes and the
increasing PC capacity led to a revolution in the Raman spectrometry:
measurements can be made outside of the laboratory with mobile instruments, even
in severe conditions (e.g. rock shelter in mountains!). However many specific
difficulties have to be solved: the variety of mobile laser sources is limited, the
positioning/focusing and the protection against solar/bulb lighting are difficult and,
more important, the spectral resolution and spectral window are limited due to the
necessarily small size of the spectrometer chamber. Nevertheless the definition of
good procedures and the use of advanced optics allow the on-site analysis of
various cultural heritage materials: pigments of pastels, miniatures, drawings,
glasses, enamels and glazes, rock art, crystalline and amorphous phases of pottery,
enamelled glass artefacts or stained glasses, bronze and brass patinas, etc.
Our experience gained since the first success in 2003 will be discussed at the light of
the most representative case studies.
References
Colomban Ph, Milande V, Lucas H. Journal of Raman Spectroscopy 2004; 35: 68.
Colomban Ph, Milande V, Le Bihan L. Journal of Raman Spectroscopy 2004; 35: 527.
Colomban Ph, de Laveaucoupet R, Milande V. Journal of Raman Spectroscopy 2005; 36:
857.
Colomban Ph, Milande V. Journal of Raman Spectroscopy 2006; 37: 606.
Ricciardi P, Colomban Ph, Tourni A, Milande V. Journal of Raman Spectroscopy 2009; 40:
604.
Colomban Ph, Tourni A. Journal of Cultural Heritage, 2007; 8: 242.
Kirmizi B, Colomban Ph, Blanc M. Journal of Raman Spectroscopy 2010; 41: 1240.
Caggiani MC, Colomban Ph. Journal of Raman Spectroscopy 2011; 42: 790.
Tourni A, Prinsloo LC, Paris C, Colomban Ph, Smith B. Journal of Raman Spectroscopy
2011; 42: 399.
Mancini D, Tourni A, Caggiani MC, Colomban Ph. Journal of Raman Spectroscopy
2011;DOI 10.1002/jrs.3010.

2
A new Raman tool to study art and archaeology?
Quantitative coherent anti-Stokes Raman scattering (CARS)
microscopy
James Day1, Mischa Bonn1

1
FOM Institute AMOLF, Science Park 102, Amsterdam 1098 XG, The Netherlands,
Tel: +31 20 754 7130, day@amolf.nl
Whilst micro-Raman spectroscopy has been very helpful in addressing many

challenges in material science, its applicability is often limited by low signal levels
and the loss of axial resolution during 3D sectioning experiments. These limitations
are largely surpassed with coherent anti-Stokes Raman scattering (CARS)
microscopy a nonlinear, coherent analogue of spontaneous Raman spectroscopy.
The coherent nature of CARS offers a significant signal enhancement compared to
spontaneous Raman scattering, opening the way to rapid sample imaging.
Furthermore, because CARS is a nonlinear microscopy, it exhibits submicron spatial
resolution that does not degrade in sectioning experiments. We have also recently
demonstrated that CARS microscopy can be made quantitative, further extending
the flexibility of this technique [Day et al., 2011]. In this contribution, we will discuss
the background of CARS microscopy and its various modalities, as well as its
application to a variety of challenges in the material sciences.
References
Day, J. P. R., Domke, K. D. Rago, G., Kano, H., Hamaguchi, H., Vartiainen, E., Bonn, M.
Journal of Physical Chemistry B 2011; 115: 7713, Feature Article.

3
Simulation of vibrational spectra by ab initio calculations:
an invaluable aid in the assignment and interpretation
of the Raman signals
Mauro Prencipe
University of Torino, Mineralogical and Petrological Sciences Department,

Via Valperga Caluso 35, 10125 Torino, (Italy), Tel. +390116705131,
mauro.prencipe@unito.it.
The development of sophisticated codes for quantum mechanical calculations on

crystalline materials, the continuous research and refinement of suitable
Hamiltonians, based on the Density Functional Theory (DFT) approach, which are
able to accurately reproduce structural, elastic and vibrational properties of crystals,
together with the ever increasing availability of computational resources at a
relatively low cost, allows the simulation of Raman spectra of crystalline materials,
with accuracies which parallels those experimentally obtainable. To date, the best
Hamiltonians for a successful reproduction of the properties of crystals are the hybrid
HF/DFT ones, which include a contribution from the exact, non local Hartree-Fock
(HF) electronic exchange to correct for the approximate nature of the DFT exchange;
the widely used B3LYP Hamiltonian [Becke, 1993] and the recent WC1LYP one [Wu
and Cohen, 2006] are particularly suitable for the calculation of vibrational spectra
[Prencipe et al., 2011a; Prencipe et al. 2011b; Ungureanu et al., 2010; Prencipe et
al., 2009; Prencipe et al., 2006; Prencipe et al., 2004]. In particular, the average
absolute discrepancies of the calculated Raman (and IR) frequencies with respect to
the experimental ones (<||>) are less than 5 cm -1, at the WC1LYP and B3LYP
levels. Such discrepancies can be significantly higher if purely DFT Hamiltonians,
like the popular PBE one [Perdew et al., 1996] are employed; as reported in
Prencipe et al. (2011a), for example, in diopside (CaMgSi 2O6), the <||> values are
3.2 (WC1LYP), 4.7 (B3LYP) and 18.0 cm-1 (PBE). See also Prencipe et al. (2009) for
a comparison of the relative performances of the B3LYP and PBE Hamiltonians in
the case of lizardite [Mg3Si2O5(OH)4].
If the structures contain hydrogen, special care must be paid, and ad-hoc
corrections for anharmonic effects must be performed in the cases of O-H stretching
and M-O-H bending modes (M being a cation), as the anharmonic frequencies can
be up to 150 cm-1 lower than the uncorrected harmonic ones [Prencipe et al. 2009].
As an example of application of the computational methodology, results will be
here presented concerning the case of jadeite (NaAlSi 2O6), a mineral whose
structure (monoclinic, C2/c space group) is made of chains of Si-centred tetrahedra,
sharing a vertex (an oxygen ion, Obr), and 6-coordinated Na+ and Al3+ cations, in
between. The Raman spectrum of jadeite has been calculated at the WC1LYP level,
and compared to the experimental ones [Gendron et al., 2002]. The animations of
the calculated normal modes, corresponding to each frequency, can be seen at the
web page http://www.personalweb.unito.it/mauro.prencipe/vibs/jadeite. All the
Raman signals observed experimentally do correspond to calculated frequencies,
with very small discrepancies. The strongest signals from the experimental spectra
are at (i) 203-206 cm-1 [here and below, the range given for the experimental
frequency is the result of different measurements on different samples, as reported
in Gendron et al. (2002)], to be compared to the calculated A g mode at 202 cm-1 (due
to the tilting of the SiO 4 tetrahedra); (ii) 221-225 cm-1, corresponding to the
calculated Bg mode at 224 cm-1, mainly due to vibrations of the Na ions; (iii) 252-257

4
cm-1, calculated Bg mode at 256 cm-1 (due to vibrations of Na and Al, and libration of
the chains of tetrahedra); (iv) 288-295 cm-1, calculated Ag mode at 291 cm-1 (due to
vibrations of the Na and Al cations, accompanied by rigid translations of the chains);
(v) 309-312 cm-1, calculated Bg mode at 308 cm-1 (Na and Al vibration, plus tilting of
tetrahedra); (vi) 326-328 cm-1, calculated Ag mode at 330 cm-1 (vibration of cations
and tilting of tetrahedra); (vii) 373-377 and 429-436 cm-1, respectively corresponding
to calculated Ag modes at 369 and 435 cm-1 (both modes are torsions of the
tetrahedral chains around their axis); 522-525 cm-1, corresponding to the calculated
modes at 524 (Bg) and 527 cm-1 (Ag; the first mode being due to vibration of the Al
cation, accompanied by tilting of the tetrahedra; whereas, in the second mode, the
Na and Al cations are immobile); (viii) 573-578 cm-1, calculated Ag mode at 582 cm-1
(mainly tilting of the tetrahedra and translations of the Al cations); (ix) 698-702 cm-1,
calculated Ag mode at 705 cm-1 (Si-Obr-Si bending); (x) 775-778 cm-1, calculated Bg
mode at 789 cm-1 (O-Si-O bending); 986-992 cm-1, calculated Ag modes at 986 and
992 cm-1 (Si-O stretching); (xi) 1036-1042 cm-1, calculated Bg and Ag modes
respectively at 1032 and 1041 cm-1 (Si-O stretching).
References
Becke A.D. Journal of Chemical Physics 1993; 98: 5648.
Gendron F., Smith C.D., Gendron-Badou A. Journal of Archeological Science 2002; 8: 837.
Perdew J.P., Burke K., Ernzerhof M. Physical Review Letters 1996; 77, 3865.
Prencipe M., Pascale F., Zicovich-Wilson C.M., Saunders V.R., Orlando R., Dovesi R.
Physics and Chemistry of Minerals 2004; 31: 559.
Prencipe M., Noel Y., Civalleri B., Roetti C., Dovesi R. Physics and Chemistry of Minerals
2006; 33: 519.
Prencipe M., Noel Y., Bruno M., Dovesi R. American Mineralogist 2009; 94: 986.
Prencipe M., Mantovani L., Tribaudino M., Bersani D., Lottici P. European Journal of
Mineralogy 2011a; submitted.
Prencipe M., Scanavino I., Nestola F., Merlini M., Civalleri B., Bruno M., Dovesi R. Physics
and Chemistry of Minerals 2011b 38; 223.
Ungureanu C.G., Prencipe M., Cossio R. European Journal of Mineralogy 2010; 22: 693.
Wu Z., Cohen R.E. Physical Reviews B 2006; 73: 235116.

5
Raman spectroscopy in archaeometry: trends and prospects
Peter Vandenabeele1 and Luc Moens2
1
Ghent University, Archaeometry Research Group, Department of Archaeology, Sint-
Pietersnieuwstraat 35, B-9000 Ghent (Belgium) Peter.Vandenabeele@UGent.be
2
Ghent University, Raman Spectroscopy Research Group, Department of Analytical
Chemistry, Krijgslaan 281(S-12), B-9000 Ghent (Belgium).
Since almost 2 decades, Raman spectroscopy is becoming increasingly popular as

analytical technique for the analysis of objects of art and archaeological findings.
This is mainly due to instrumental improvements that make that Raman
instrumentation is becoming increasingly available for the analysis of cultural
heritage objects. Microscope optics allows us to investigate micro-samples with a
spatial resolution of ca. 1 m, so that easily different pigment layers or pigment
grains can be distinguished. Using motorized XYZ-stages, even mappings can be
obtained, giving a molecular image of an area. Mobile instrumentation, small
instruments, and fibre-optics probe heads make it possible to perform direct analysis,
bypassing the need to sample the object.
Moreover, apart from instrumental improvements, increasingly more research papers
are published on the use of chemometrical methods of spectral data processing, as
well as on spectral searching algorithms for fingerprinting and identification of the
materials. Advanced data processing techniques can be used to identify spectra of
unknowns, but also to study phenomena that occur, for instance during pigment
degradation. Finally, special care has to go to the definition of detection limits and
limits of identification in Raman spectroscopy, especially in the art and archaeology
context.
A last trend which is increasingly more observed in recent research topics is that
Raman spectroscopy is often combined with other, complementary analytical
techniques, such as X-ray fluorescence (XRF) spectrometry. Indeed, this technique
is an atomic spectroscopic technique, which yields complementary information to the
molecular information obtained by Raman spectroscopy. Although combining these
techniques may seem straightforward, special attention has to go to positioning the
instrumentation, so that exactly the same points are measured. Moreover,
processing of merged spectral data is another interesting topic.
In this presentation, we aim to illustrate these actual trends with a broad range of
examples.

6
ORAL
PRESENTATIONS

The mural paintings of Ala di Stura (Piedmont, Italy): a hidden
treasure investigated
Maurizio Aceto1, Angelo Agostino2, Gaia Fenoglio2, Valentina Giordano2,

Michelangelo Varetto3 and Giorgio Castagneri4
1
Universit degli Studi del Piemonte Orientale, Dipartimento di Scienze
dell'Ambiente e della Vita, viale Teresa Michel, 11 - 15121 Alessandria (Italy); Centro
Interdisciplinare per lo Studio e la Conservazione dei Beni Culturali (CenISCo); Tel.
+39 0131 360265, Email maurizio.aceto@mfn.unipmn.it.
2
Universit degli Studi di Torino, Dipartimento di Chimica Generale e Organica
Applicata, corso M. dAzeglio, 48 - 10125 Torino (Italy); Centro di Eccellenza NIS
(Nanostructured Interfaces and Surfaces).
3
Consorzio San Luca per la cultura, larte ed il restauro, via dei Mille, 14 - 10123
Torino (Italy).
4
Graphic Computer, Via Parini, 16/1 - 10078 Venaria - Torino (Italy).
The small mountain hamlet of Ala di Stura (Piedmont, Italy) lying at 1080 metres
a.s.l., owns a remarkable art treasure: dispersed among its different fractions, not
less than 110 mural paintings are present on walls of private houses, churches and
chapels. The paintings are divided into paintings with religious themes and
meridians. They are datable in the range XVI century present day, with paintings
dating generally older than meridians. While the presence of meridians is all but
unusual in mountain architecture, their quantity is nevertheless surprising, making
Ala di Stura the site with the highest number of meridians per inhabitants all over
Europe. Moreover, the wide presence of paintings witnesses the deep religious
feelings of mountain people.
To make this hidden treasure known to visitors outside the valley, in 2007 the
Commune of Ala di Stura started a project in order to organise and spread
information on its heritage. Systematic classification of the artworks was performed
and updated on the basis of a previous architectural research dating to 1992; this
information was used to prepare paths equipped with notice boards inside the
different fractions. It was quickly apparent, though, that many of these artworks
needed restoration interventions, caused by the severe atmospheric conditions
typical of a mountain location. It was therefore decided to investigate the
conservation emergencies from the scientific point of view, performing chemical
analysis on the most relevant artworks. This research project aimed also to improve
the artistic-historical knowledge on the artworks collection. Diagnostic investigation
was directed to three major themes:
identification of alteration phenomena occurring on paintings, in order to suggest
proper restoration interventions;
a more accurate dating of artworks, by identification of pigments acting as time
markers;
improvement of knowledge of the pictorial materials used by artists and their
relationship with local raw materials: Ala di Stura is located inside a mountain
area rich in minerals, so that painters could have different pigments at their
disposal.
Since in situ analysis was hard to perform due to the difficulty in reaching most of the
artworks with portable instrumentation, it was decided to proceed to micro
samplings. In the first part of the project, whose results are presented in this
contribution, nearly a third of the artworks were sampled and analysed in laboratory
with Raman spectroscopy. A high-resolution dispersive Jobin Yvon-Horiba
(Villeneuve dAscq, France) LabRAM HR model spectrophotometer was used,

7
equipped with a confocal microscope, a 632.8 nm excitation laser, a 600 lines/mm
dispersive grating, a 800 mm path monochromator and a Peltier cooled CCD
detector. This allowed to fully characterising paints, identifying not only pigments but
also accessory mineral phases accompanying the main colorant phase or the
preparation layers. Complementary diagnostic information was obtained with micro
X-ray spectrometry and X-ray diffraction spectroscopy.
From the conservation point of view, apart from evidences of mechanical stress on
some paintings, some chromatic alteration phenomena have been identified. The
darkening of pigments containing lead was noted in different occasions, possibly due
to interaction of lead white - PbCO3Pb(OH)2 - or of red lead - Pb3O4 with H2S, in
both cases generating PbS, a phenomenon already noted by Clark on miniature
paintings [Clark et al., 2006]. Causes are at present unknown but cannot be related
to environmental pollution, due to the high pureness of Ala di Stura air. Another
chromatic alteration was noted on copper pigments, with azurite changing to
atacamite, possibly due to chlorine contribution from water percolating on the
paintings. For what concerns dating of artworks, in several instances the presence of
ultramarine blue was noted which, upon visual inspection with optical microscopy,
resulted to be composed by small, regularly shaped blue particles. This suggested
that synthetic ultramarine blue had been used, so that all artworks containing it can
be dated, at latest, after 1828. In other cases, arsenical pigments such as Scheele's
green and Emerald green were identified, again giving a precise date for the
paintings containing them.
For what concerns the origin of raw materials, in most cases Raman analysis put into
evidence a link among the pigments used by artists and sources of minerals
available in the surrounding geographic area, allowing to give value to the
hypothesis that artists supplied themselves with local raw materials only, in particular
for what concerns the older artworks. For the more recent artworks, pigments were
obtained preferably, even if not exclusively, from local sources. In some cases,
surprising solutions were chosen such as for the mineral olivenite, a copper
arseniate used to paint green areas, which has been rarely identified outside the
geographic area discussed in this work. Another typical feature evidenced in all
paintings is the occurrence of asbestos minerals, due to the overall presence of
serpentine rocks in the valley. Interesting is also the relationship among diagnostic
information and historical information regarding the exploitation of mineral sources
inside the area. Identification of some pigments on paintings bearing a certain date
can spread light on the history of the use of minerals as sources for pigments, in
parallel with their use for civil or military reasons. This is typically the case of cobalt
minerals, whose presence has been identified on some XVI-XVII century paintings,
but whose exploitation from local sources is reported, on bibliographic basis, from
the first half of XVIII century only: in this case, most probably the historical
information must be updated according to analysis results.
Finally, in the course of analysis the role of Giovanni Oldrado Perini di Novalesa, an
almost unknown Renaissance painter, has been put into evidence. His paintings,
dating from the second half of XVI century, are among the oldest and so most
valuable - in the whole of Ala di Stura artwork collection. Raman analysis allowed to
elucidate details of his pictorial technique: of particular relevance is the use of pyrite,
a mineral available in the area, mixed with smalt to give a more shining appearance
to the Virgins robe. Unfortunately, smalt has been almost completely detached from
the painting, possibly due to a poor paint preparation.
References
Clark RJH, Gibbs PJ. Analytical Chemistry 1998; 70: 99A

8
A Multitechnique Investigation on some early Printed
decorated books
Maurizio Aceto1, Pietro Baraldi2, Danilo Bersani3, Giusi Zanichelli4,

Paolo Zannini2, Andrea de Pasquale5, Elisabetta Schiavon3
and Eleonora Canobbio3
1
Dipartimento di Scienze dell'Ambiente e della Vita & Centro Interdisciplinare per lo
Studio e la Conservazione dei Beni Culturali (CenISCo), Universit degli Studi del
Piemonte Orientale, viale Teresa Michel, 11 - 15121 Alessandria, Italy,
maurizio.aceto@mfn.unipmn.it
2
Department of Chemistry, University of Modena and Reggio Emilia, Via G. Campi,
183, 41100 Modena,
3
Department of Physics, University of Parma, V.le Usberti 7/A, 43124 Parma,
4
Department of Latinity and Middle Age, University of Salerno, Via Ponte D. Melillo,
24, Salerno,
5
Biblioteca Palatina, Strada alla Pilotta,3 - 43100 Parma.
With the Renaissance and the birth of printing with mobile characters, many
traditional works were reproduced. In the first decades of the XVI century many
books of hours ad other uncommon works were printed on beautiful white
parchments in more copies than previously. Their elegance was improved by adding
some engraved pages that were subsequently decorated by some specialized
artisans in their ateliers.
Parma has, in its Palatina Library, some important items of this kind that were
produced abroad, possibly in France in the same years and bought in previous
centuries by librarians in the service of the Duke. However, this city was also the
place where Giambattista Bodoni worked till his death producing extraordinary
masterpieces in the art of printing. A Museum in Parma has been dedicated to him
with some important remains of his activity, such as the Greek Ilias.
As a group of Italian researchers in the field of scientific investigation of illuminated
codices and books, we elaborated a program for studying a number of them with
many non destructive techniques. This program was formulated in order to identify
what kind of materials were used in the artifacts, wheat were the inks used and the
techniques for applying the materials to the parchment or paper.
Two groups of important books were chosen, a first dated to the early XVI century,
and a second one dated to the XVIII century. The techniques employed were mainly
Raman microscopy with a red laser at 632.8 nm in a LabRAM instrument from Horiba.
Moreover, in order to identify the materials on surfaces were fluorescence was high,
infrared and ultraviolet photography and FORS techniques were applied. In doubtful
cases XRF technique was of help by indicating the main elements present in a spot.
Taking into account the different spectral and spatial resolutions, a comparison
among the data obtained was made.
In the printed books of the XVI century a series of compounds already known in
illumination were encountered. The palette was typical of a painter of this time. Lead
tin yellow type I was abundantly employed, together with litharge; indigo and azurite
were used as blues; vermilion and minium were the red pigments used; carbon and
white lead were used as darkener and whitener. Concerning the green hues a light
shade was obtained in some items with a basic copper sulfate, possibly properly
prepared for this use.

9
Raman spectroscopy as a tool for rapid screening of ancient
window glass: An 18th century fanlight (Antwerp) as a case
study
Kitty Baert1, Wendy Meulebroeck2, Hilde Wouters3, Andrea Ceglia1,

Karin Nys3, Hugo Thienpont2 and Herman Terryn1
1
Research Group Electrochemical and Surface Engineering, Department Materials
and Chemistry, Vrije Universiteit Brussel, Pleinlaan 2, 1050 Brussels (Belgium),
Tel.+32 2 629 3265, kibaert@vub.ac.be
2
Brussels Photonics Team B-PHOT, TONA-FirW, Vrije Universiteit Brussel,
Pleinlaan 2, 1050 Brussels (Belgium)
3
Department of Art Sciences and Archaeology, Vrije Universiteit Brussel,
Pleinlaan 2, 1050 Brussels (Belgium)
The potential of Raman spectroscopy as a fast method for screening glass has been
applied to a collection of glass fragments from a fanlight in a secular building in
Antwerp. Because only a limited number of these typical 18 th century window
glasses have left, this investigation is of historical interest.
A quantitative study of ancient window glass showed that Raman spectroscopy
allows a fast classification of different glass types [Baert et al., 2010]. Beside the
dedicated research during the past ten years of specific glass collections [Colomban
et al., 2006], a broad corpus of archaeological window glass still needs to be
investigated [Meulebroeck et al., 2010]. For many sites the amount of excavated
glass artefacts is enormous and a selection of the most appropriate samples for
chemical analysis is necessary.
Glass is a three-dimensional network of SiO4 tetrahedral units. The typical Raman
fingerprint of silicate glass consists of two broad bands originating from bending
(~500cm-1) and stretching (~1000cm-1) Si-O vibration. The Raman spectra yield
information about the covalently bonded network former (Si 4+) and also reflect the
influence of the network-modifying cations (fluxing agents: Na, K - stabilisers: Ca, Mg
colouring agents: Fe, Mn, Cu), leading to less connected tetrahedral units.
Based on the typical Raman signatures for the different kind of glasses (Alkali-glass,
High Lime-Low Alkali glass (HLLA), Pb-rich) [Schalm et al., 2007], a classification
can be made. Even in case of strong fluorescence (glasses containing manganese),
an uncomplicated treatment (normalization instead of baseline subtraction) of the
measured signals makes it possible to distinguish between the different types of
glass.
The preliminary screening of glass artefacts with Raman spectroscopy is a useful
tool in the study of historical glass and can already answer some questions about
provenance, period of production and authenticity of the glass samples. On the basis
of the Raman results, archaeologists can select a limited number of samples for
further chemical analysis
The case study concerns the material of an 18th century wrought iron fanlight above
the main entrance door in a private building situated in Belgium/Antwerp
(Gratiekapelstraat 24), rediscovered by the current owner in 2000 [Grieten].
Based on the typical classical style attributes of the stone frame and the wrought
iron, the fanlight can be placed between 1760 and 1795. This so called Louis XVI
style was very popular in Antwerp at that time.
The fanlight is glazed with plain glass in different grey, green and pink shades.
Exceptional is the amount of 18th and 19th century preserved material and
especially several glass pieces signed and dated by different glaziers. The research
10
of this glass gives some unique information about the Belgian window glass industry
and especially the hinge point between the production of HLLA glass and glass
produced with industrial soda.
The non-destructive Raman analyses help in placing the different glass pieces in
their historical context and will form a guideline for conservation and further
restoration of the fanlight (see Figure 1).
1.8
1.6 HLLA
Raman Intensity (normalized)
1.4 Na1
Na2
1.2
1088
1.0
0.8
0.6
0.4
0.2
Na - no Mn
0.0
200 400 600 800 1000 1200

-1
Wavenumber / cm
Figure 1: Raman signatures and picture from a fanlight situated in a private

building/Antwerp - Raman analysis can cluster the sampled fragments into four
groups
Acknowledgements. The authors would like to express their gratitude to Stefaan

Grieten to put the material at our disposal.
References
K. Baert, W. Meulebroeck, H. Wouters, A. Ceglia, K. Nys, H. Thienpont, H. Terryn, Journal of

Raman Spectroscopy. 2010 ; published online.
Ph. Colomban, A. Tournie, L. Bellot-Gurlet, Journal of Raman Spectroscopy 2006 ; 37, 84.
S. Grieten, Herontdekking van een poortje, in Infoblad Antwerpse Vereniging voor Bodem- en
Grotonderzoek, 2006/ ; 2, 9.
W. Meulebroeck, H. Wouters, K. Baert, A. Ceglia, H. Terryn, K. Nys, H. Thienpont; Photonics
Europe - Optical Sensing and Detection 2010
O. Schalm, K. Janssens, H. Wouters, D. Caluw, Spectrochimica Acta Part B 2007 ; 62, 663.

11
The Officina Pigmentaria in Pompei: pigments and cosmetics
Pietro Baraldi1, Samantha Petrullo1, Cecilia Baraldi2, Giorgio Trojsi3 and

Antonio Varone4
1
University of Modena and Reggio Emilia, Department of Chemistry, Via G. Campi,
183, 41100 Modena (Italy), pietro.baraldi@unimore.it
2
University of Modena and Reggio Emilia, Department of Pharmaceutical Sciences,
via G. Campi, 181, Modena, Italy
3
University Suor Orsola Benincasa, Laboratory of applied Sciences and Techniques,
Via di Santa Caterina 37,Napoli, Italy,
4
Special Superintendances for Archaeological Heritage of Naples and Pompeii,
Via Villa dei Misteri, 2, Pompeii , Italy.
According to the Giornale di Scavo of the Archaeological Superintendance of

Pompeii, the first excavation in the Regio I, Insula 9 (I,9,9) took place in 1952. In a
building of seven rooms there was a stair in opus incertum with the floors in
cocciopesto. Near the skeletons of four individuals, about 150 globular bowls, fritilla
and ollae were found. They were assigned the numbers between 9389 and 9700.
Due to the high number of containers and to the presence of material inside, they
have a high importance for the history of materials in Pompeii and in the Roman
world. In particular, they should be important for the reconstruction of the painting
history and techniques of this period.
An investigation with different techniques for the identification of the contents

composition and subsequently for the understanding of the materials present was
then undertaken. For the study two molecular techniques were used, that is FT-IR
spectroscopy and Raman microscopy. The first is able to supply information about
the general composition of the compound present in the samples at least in the
concentration of about 1 %. The second techniques can inform on the composition of
single grains as small as 1-2 micrometers. Therefore, the results of the two
techniques must help each other to understand what the analyzed powder is. The
analyses of all the bowl contents are summarized in a long table, of which we report
only a section.
By comparing the results obtained some considerations come to light. Many

containers have quartz and calcite, which are the main component of plasters, to
which feldspars and pyrite can be added. At the same time diopside can come from
eruptive rocks or from silicate materials heated to high temperature. Aragonite is
present, sometimes at high concentration, in many pigments, and its presence can
be due to natural provenance from white minerals, but more probably can be due to
the grinding of shells. This is an important testimony of what is identified in white
lines on colored background in Roman wall paintings.
The blue pigment is always based on Egyptian blue, at the time of Pompeii
destruction coming from Puteoli or Liternum. Green can be obtained by mixing a
yellow and a blue, and this is generally found on wall paintings; more frequently
green is ascertained to be a mixture of green earth and some Egyptian blue.
Malachite and azurite are encountered as degradation products of copper and brass
containers.
Other rare occurrence are cuprite, also coming from alterations of a metal, and
litharge, from alteration of cerussite or lead objects. The case of cerussite or
12
hydrocerussite is different. It can be identified in many recipients, but it is not a
pigment for wall paintings. Since it is known from Pliny and other authors that it was
used as a fard, this can be a proof of the production and filling also of cosmetics
containers in I, 9, 9.
References
Varone A., Barat H. 1996, Pittori al lavoro, Proc. of the Int. Workshop on Roman Wall
painting, Fribourg 199-206.
Mazzocchin G. A,. Orsega E. F, Baraldi P., Zannini P. 2006, Aragonite in Roman wall
paintings, Ann. Chim 96. 377-87.

13
Archaeometry of Man-Made Ancient Chinese Blue and Purple
Barium Copper Silicate Pigments with Emphasis on Studies
of the Newly Discovered BaCu2Si2O7 Compound
(Chinese Dark Blue)
Heinz Berke1, Qinglin Ma2, Armin Portmann1,Tristan Corbiere1,

Eva Freisinger1, Jrg Hutter3, Zhiguo Zhang2, Ferdinand Wild1, Xia Yin4,
Lu Pan5
1
University of Zurich, Institute of Inorganic Chemistry, Winterthurer Str. 190, CH-
8057 Zurich (Switzerland), Tel. +41 446354681, hberke@aci.uzh.ch
2
Chinese Academy of Cultural Heritage, No.2 Gao Yuan Street, Chao Yang District,
Beijing 100029 (PR China)
3
University of Zurich, Institute of Physical Chemistry, Winterthurer Str. 190, CH-8057
Zurich (Switzerland)
4
Museum of the Terracotta Warriors and Horses of Qin Shihuang, Shaanxi Province
Xian 710600 (PR China)
5
National Museum of China, 16, East Chang'an Street, Dongcheng District
Beijing 100006 (PR China)
This study comprises micro-Raman and SEM/EDX analyses of 4 ancient Chinese

objects with blue and purple barium-copper-silicate pigments. 3 samples were
faience beads from Majiayuan village, Zhangjiachuan County, Gansu Province,
dated to the Late Warring States period (474 - 221 BC).
Figure 2. Views of the purple or blue bead samples from the archaeological site of Majiayuan
village, Zhangjiachuan county, Gansu Province consisting of a terracotta body and a blue or
purple strongly weathered pigment layer.
In 1983 E. Fitzhugh put forward that a blue pigment (BaCuSi 4O10) and later in 1992
[1] that also a purple pigment (BaCuSi 2O6) found on painted ancient objects and in
colour sticks of octagonal shapes contained barium copper silicates as defined
chemical compounds and it was suggested that these materials were artificially
prepared by ancient Chinese craftsmen [2].
In addition a single crystal was studied isolated from a wall painting of the Weishan
Terracotta Tomb, Zhangqiu, Shandong Province, dated to the Western Han Dynasty
(206 BC - 8 AD). One bead and the single crystal showed the presence of Chinese
Dark Blue, BaCu2Si2O7, a barium-copper-silicate phase newly discovered as a
pigment. In analogy to the already known pigment phases BaCuSi4O10 (Chinese or
Han Blue) and BaCuSi2O6 (Chinese or Han Purple), this BaCu 2Si2O7 compound was

14
named as Chinese or Han Dark Blue [3]. The faience beads contained in the
pigment layer also Chinese Blue (BaCuSi4O10) and Purple (BaCuSi2O6) contents.
The single crystal was additionally analyzed by single crystal X-ray diffraction
revealing the known structure of the BaCu 2Si2O7 compound. From modern times
synthetic studies it was extrapolated that the forth phase of the barium-copper-
quartz phase diagram, the whitish or light blue Ba 2CuSi2O7 compound, has only low
probability to be found as a pigment in conjunction with historical Chinese artifacts.
Acknowledgements. We are grateful to Dr. Wang Hui and Mr. Mao Ruilin, Gansu
Provincial Institute of Cultural Relics and Archaeology, Lanzhou, China, and Dr. Ma
Xiaolin and Mr. Wei Xingtao, Henan Provincial Institute of Cultural Relics and
Archaeology, Zhengzhuo, China, for supplying archaeology samples.
References
[1] FitzHugh, E. W. & Zycherman, LA Studies in Conservation, 1983; 28:15; FitzHugh, E. W.

& Zycherman, LA, Studies in Conservation, 1992; 37:145.
[2] Berke H, Chem. Soc. Rev. 2007; 36:15.
[3] Berke H, Corbiere T, Portmann A, Freisinger E, Wild F, Hutter J, Zhang Z, Yin X, Pan L,
Wenbo, Shanxi, China, 2009, 251.

15
Non-contact Raman mapping of works of Art
Alex Brambilla1, Iacopo Osticioli2, Daniela Comelli1, Austin Nevin1 and

Gianluca Valentini1
1
Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32 20133
Milano, Italy; tel: 02 23996088, mail: alex.brambilla@mail.polimi.it
2
Institute of Applied Physics Nello Carrara (IFAC-CNR), Via Madonna del Piano, 10,
Sesto Fiorentino (FI), 50019, Italy
Raman spectroscopy is widely employed thanks to its capability of identifying

different materials in a non-destructive and, in some cases, non-invasive manner [1].
Nevertheless, in Cultural Heritage such a punctual analysis cannot be considered
representative of the entire surface of a work of art, whereas macro imaging
techniques are preferred. For Raman imaging spectroscopy, two main options are
available: a wide-field approach (direct Raman imaging) or a reconstruction of the
Raman image by sequential single-point acquisitions (point Raman mapping).
In this study a novel prototype of a Raman system capable of performing point-to-
point spectral mapping of a surface of interest at a long working distance (20 cm) is
presented (fig. 1). A model painting is used to evaluate the performances of the
device in reconstructing a Raman map of the surface under analysis and identifying
the spectral features of the main pigments.
The head of set-up is based on a diode laser (785 nm); two galvanometric mirrors
and a custom-designed optical system made of four lenses provide the deflection of
the beam and the collection of the Raman signal. The detection system (a
spectrograph and a Peltier-cooled CCD camera) is connected by an optical fibre to
the head. The dimensions of the overall set-up (75x45 cm2) have been limited as far
as possible in order to permit the transportation of the device.
The model painted panel chosen to test this device was made by A. using
traditional pigments; Raman analysis has been performed on a custom selection of
areas without moving the painting, which was positioned at 20 cm from the head.
Raster scan mode has been used to acquire Raman maps of the surface of interest.
Laser power density has been kept low (<100 W/cm2) to avoid any damage to
sensitive materials. The instrumentation can be used to obtain a significant Raman
signal from an area of 5x5 cm2.
The main spectral fingerprints of selected inorganic pigments were recorded on the
test painting [2]: the collected spectra are approximately independent of the position
of the analyzed point over the scanned surface. In addition, the device is insensitive
to variations of the working distance of 3 cm. Spectral maps of the analyzed areas
have been reconstructed after the acquisition process by means of a home-made
software.
A relatively wide area of a painted surface has been examined with the proposed
device without the need to reposition the object. The strength of this instrumentation
lies in its long working distance and the wide depth of field, which makes it suitable
for the analysis of non-flat and immobile objects, including those found in Cultural
Heritage. Further steps to transform the current laboratory device in a fully
transportable one are currently under way. Other examples of application of this
instrument, like detection of binding media and identification of phosphorescent
pigments will be discussed in the presentation.

16
Figure 1: Set-up of the Raman scanning device. The instrument works in backscattering
configuration: the laser beam is focalized onto the object surface and scattered light is
collected by the same optical system. Scan is performed by means of a 2D galvanometric
mirror (GM) stage; detection of the Raman signal is obtained by a spectrograph (SG) and a
CCD sensor. Interferential (IF) and Notch filter (NF) are inserted along the beam path in order
to respectively transmit and stop the 785nm-wavelength of the diode laser. Faraday isolator
(FI) prevents the light reflected by the dichroic mirror (DM) from entering the laser cavity.
References
1. P. Vandenabeele, H.G.M. Edwards, L. Moens. A decade of Raman spectroscopy in art
and archaeology. Chemical reviews 2007; 107, no. 3: 675-686.
2. L. Burgio, R. J.H. Clark; Library of FT-Raman spectra. Spectrochimica Acta Part A 2001;
57: 14911521.

17
SERS spectra of Mexican dyes
Edgar Casanova-Gonzlez1, Vctor Santos-Vasquez2,

Baldomero Esquivel3, Lorena M. Roldn4, Concepcin Domingo4,
Jos Luis Ruvalcaba-Sil1
1
Departamento de Fsica Experimental, Instituto de Fsica, Universidad Nacional
Autnoma de Mxico, Circuito de la Investigacin Cientfica, Ciudad Universitaria,
Delegacin Coyoacn, Ciudad de Mxico, Mxico, C.P. 04510. Tel. 0052 1 55 54 10
28 10. E-mail: casanova@fisica.unam.mx
2
Instituto de Investigaciones Estticas, Universidad Nacional Autnoma de Mxico
3
Instituto de Qumica, Universidad Nacional Autnoma de Mxico
4
Instituto de Estructura de la Materia, CSIC, Serrano 121, 28006-Madrid, Spain
Mexico is one of the countries that count with a wide variety of pre-Hispanic cultures
and a great biological diversity as a source of pigments and dyes, but there is not
enough data available that compiles the characteristics of the pigments and dyes
that were used on pre-hispanic and novo-hispanic times. At the same time, there is
an extensive knowledge of the ancient ways of extraction and usage of the dyes,
which could be useful for its study and identification on artistic, historical or
archaeological investigations.
Raman has been applied in Mexico, in the analysis of the Mayan wall paintings in
Ek'Balam [Vandenabeele et. al., 2005] and other artistic and historical artifacts.
Although SERS have been used for the identification of organic dyes since 1987
[Guineau et. al., 1987] the main impulse have come on the last decade, when
several papers have been published dealing with pure dyes and artwork samples
[Chen et. al., 2006], [Leona et. al., 2006], [Chen et. al., 2007], [Peica et. al., 2008],
[Centeno et. al., 2008], [Bernie, 2009], [Leona, 2009], [Brousseau et. al., 2009],
[Caamares et. al., 2009], [Brousseau et. al., 2009 (2)], [Wustholz et. al., 2009],
[Bruni et. al., 2010], [Jurasekova et. al., 2010] and even for the study of synthetic
dyes from common pens. [Geiman et. al., 2009] The wide range of mexican dyes
hasnot been studied using SERS, except maybe for carminic acid and brazilin, the
main colorants of cochineal and brazilwood (also known as Campeche wood). A
paper from 1997 is probably the only work published on the Raman spectrum of
axiote, [de Oliveira et. al., 1997] while there is little information available about muitle
and zacatlaxcalli and not even the structure of its main components is well
established.
In this work, carminic acid, cochineal, axiote, muitle and zacatlaxcalli SERS spectra
were recorded at different pH values using silver colloids as SERS substrate. Ag
nanoparticles were prepared by chemical reduction with sodium citrate and
characterized by UV-Vis spectroscopy and High Resolution Transmission Electronic
Microscopy. Pure carminic acid were used for control SERS spectra and then
samples of cochineal, axiote, muitle and zacatlaxcalli were tested. Natural dyes
samples were prepared by extraction from its natural sources, following traditional
recipes. Although differs for each dye, best results were achieved by performing
SERS experiments at pH neutral to basic.
The spectrum of extracted cochineal is in good agreement with that of pure carminic
acid, used as reference, while the spectrum of axiote reproduces the bands reported
by de Oliveira.
Although its molecular structures have not yet been elucidated, muitle and
zaclataxcalli have been related to indigo and flavonoids in the case of muitle, and to
18
carotenoids and also flavonoids, for the later. Nevertheless, no published articles can
be found supporting such beliefs. From our work, it seems clear that SERS spectra
of muitle differ from that of indigo.
Moreover, the spectra of both dyes suggest a flavonoid structure.
Acknowledgements. This work has been financially supported by UNAM PAPIIT

grant In403210 and a CONACYT PhD Scholarship on behalf of Edgar Casanova.
References
B.H. Berrie; Proceedings of the National Academy of Science, 2009; 106:36: 15095
C.L. Brousseau, A. Gambardella, F. Casadio, C.M. Grzywacz, J. Wouters, R.P. Van Duyne;
Analytical Chemistry, 2009; 81(8): 3056
C.L. Brousseau, K.S. Rayner, F. Casadio, C.M. Grzywacz, R.P. Van Duyne; Analytical
Chemistry, 2009; 81(17): 7443
S. Bruni, V. Guglielmi, F. Pozzi; Journal of Raman Spectroscopy, 2010; 41: 175
M.V. Caamares, M. Leona, M. Bouchard, C.M. Grzywacz, J. Wouters, K. Trentelman;
Journal of Raman Spectroscopy, 2009, 41: 391
S.A. Centeno, J. Shamir; Journal of Molecularl Structure, 2008: 873: 149
K. Chen, M. Leona, K.C. Vo-DinhF. Yan, M.B. Wabuleye, T. Vo-Dinh; Journal of Raman
Spectroscopy, 2006;, 37: 520
K. Chen, M. Leona, T. Vo-Dinh; Sensor Review, 2007; 27/2: 109
I. Geiman, M. Leona, J.R., Lombardi; Journal of Forensic Science, 2009; 54(4): 947
B. Guineau, V. Guichard; ICOM Committee for Conservation: 8th Triennial Meeting, vol 2. The
Getty Conservation Institute, Sidney, Marina del Rey, CA, 1987; 659: 6
Z. Jurasekova, E. del Puerto, G. Bruno, J.V. Garca-Ramos, S. Sanchez-Cortes & C.
Domingo. Journal of Raman Spectroscopy, 2010; 41: 1165
M. Leona, J. Stenger, E. Ferloni; Journal of Raman Spectroscopy, 2006; 37: 981
M. Leona; Proceedings of the National Academy of Science, 2009; 106:35: 14757
N. Peica, W. Kiefer; Journal of Raman Spectroscopy, 2008; 39: 47
L.F.C. de Oliveira, S.O. Dantas, E.S. Velozo, P.S. Santos & M.C.C. Ribeiro, Journal of
Molecular Structructure, 1997: 435/2: 101
P. Vandenabeele, S. Bod, A. Alonso, L. Moens; Spectrochimica Acta Part A, 2005; 61: 2349
K.L. Wustholz, C.L. Brousseau, F. Casadio, R.P. Van Duyne; Physical Chemistry Chemical
Physics, 2009; 11(34): 7350

19
Raman and UV/VIS/NIR spectroscopy as tools for the
classification of ancient glasses
Andrea Ceglia1,2, Wendy Meulebroeck1, Kitty Baert2, Hilde Wouters3,

Karin Nys3, Herman Terryn2 and Hugo Thienpont1
1
Brussels Photonics Team B-PHOT, TONA-FirW, Vrije Universiteit Brussel,
Pleinlaan 2, 1050 Brussels (Belgium), Tel. +32 2 629 34 51, and.ceglia@gmail.com.
2
Research Group Electrochemical and Surface Engineering, Department Materials
and Chemistry, Vrije Universiteit Brussel, Pleinlaan 2, 1050 Brussels (Belgium).
3
Department of Art Sciences and Archaeology, Vrije Universiteit Brussel, Pleinlaan
2, 1050 Brussels (Belgium).
The town and the castle of Middelburg were built in 1448 by Pieter Bladelin,
treasurer of the Dukes of Burgundy. The building was a monumental element of the
skyline because of its predominant presence and its symbolic and social function.
Thanks to careful excavation methods it is now possible to visualise the fenestration
of the castle between 1448 and the end of the 17th century [De Clercq et al, 2010].
In this work, two types of window patterns were considered: the lozenge-type and
the Flemish Renaissance type (Figure 1). The lozenge-type was used for the glazing
in the 15th century, while from about 1550 and during the 17th century the Flemish
Renaissance-type was commonly used for the fenestration [Meulebroeck et al,
2010].
Raman and optical absorption spectroscopy were carried out on a set of samples in
order to reveal sensing parameters for the chemical characterization of glass. Prior
to spectroscopic analyses, the chemical composition of the glass fragments was
determined by means of SEM-EDX analysis.
All the selected
glasses belong to the
High Lime Low Alkali
(HLLA) glasses. The
only exception is a
mirror glass, which
has a sodium rich
composition. For the
HLLA glasses, a
measurable
difference in iron
concentration exists
between the samples
belonging to the
Figure 1 - Two different types of patterns, Lozenge and Flemish
Flemish Renaissance Renaissance, were considered (a schematic drawn of the window is
(Fe2O3 > 1 wt%) presented on the right). A linear correlation exists between the UV
group and the earlier absorption edge (see text) and the iron oxide concentration. In the plot
dated fragments of also the only sodium rich finding in the archaeological context of
the lozenge group Middelburg is represented.
(Fe2O3 < 1 wt%).
Applying optical spectroscopy we were able to distinguish among the HLLA material
using the UV absorption edge (A.E.). This is an optical parameter defined as the
wavelength for which 50% of the incident light is transmitted [Meulebroeck et al,
2010]. In simple silicate glasses, the UV A.E. is determined by the bonding state of
the oxygen ions. The introduction of network modifiers (such as Fe) causes the
formation of non-bridging oxygens and the absorption edge is shifted towards longer

20
wavelengths [Scholtze, 1991]. In Figure 1 it is illustrated the linear correlation
between the UV absorption edge position and the iron oxide concentration.
In literature Raman spectra of ancient glass are normally baseline subtracted using a
three segments line [Colomban et al, 2006]. However, using a green excitation
wavelength of 514 nm, all the spectra of the glasses of Middelburg show a strong
overlapping fluorescence, making the baseline subtraction a meaningless approach.
Although it is possible to reduce the fluorescence by changing the excitation
wavelength or by recording spectra at high temperature, the first method is not
always practicable, while the second is to be avoided for deontological reasons.
On the other hand, it has been
noticed that there is a specific
change in the slope of the
fluorescence signals according to
the different glass types. In order
to compare signals of different
intensity, the spectra were
normalized dividing the data by
the value measured at 750 cm1.
This is the middle position of the
recorded spectrum (2001300
cm1) and is situated between the
bending and stretching vibration
modes. This manipulation showed
a clear separation between the
two main classes of glass, i.e.
alkali glass and calcium rich glass Figure 2 Normalized Raman signals of three different
(Figure 2). It is even possible to glass fragments of the Middelburg castle. A
discrimination between HLLA glass and sodium rich
distinguish subclasses of the glass is possible because of the difference in slope of
HLLA material in accordance with the fluorescence signals.
optical spectroscopy. Variations in
composition bring to a deviation of the normalized signal: a higher amount of calcium
leads to a higher intensity at 1300 cm1, while higher sodium and/or potassium
concentrations decrease the intensity of the normalized spectra. For the HLLA
samples with higher iron content, a bend in the curve at 950 cm1 is noticed [Baert
et al, 2010]. This work shows how a combined use of Raman and optical
spectroscopy is valuable for the characterization of ancient glasses. Raman is able
to identify the flux agents, while UV/VIS/NIR can recognize sand impurities such as
Fe which reveals information about the provenance. We proved that a simple
treatment of the Raman data allows the study of glasses even when the Raman
signal is hidden by fluorescence. There is no need to use complex mathematical
methods or algorithms; only a normalization of the spectra recorded with the same
equipment is required.
References
Baert K, Meulebroeck K, Wouters H, Ceglia A, Nys K, Thienpont H, Terryn H. Journal of

Raman Spectroscopy 2010; published online.
Colomban Ph, Tournie A, Bellot-Gurlet L. J.Raman Spectrosc. Journal of Raman
Spectroscopy 2006; 37: 841.
De Clercq W, Caluwe D, Cooremans B, De Buyser F, De Groote K, Deforce K, Ervynck A,
Lentacker A, Mortier S, Pype P, Vandenberghe S, Van Neer W, Wouters H. Post-Medieval
Archaeology 2007 ; 41(1):1.
Meulebroeck W, Wouters H, Baert K, Ceglia A, Terryn H, Nys K, Thienpont H. Proc. of SPIE
Vol. 7726 77261E-9, 2010.
Scholze H, Glass nature, structure and properties, Springer-Verlag, New York, USA, 1991.
21
Comparison of English portrait miniatures by Raman
microscopy and other techniques
Anna Cesaratto3, Lucia Burgio1,2 and Alan Derbyshire 4

1
Science Section, Conservation Department, Victoria and Albert Museum, South
Kensington, London SW7 2RL, UK,
2
C. Ingold Laboratories, University College London, 20 Gordon Street, London
WC1H 0AJ, UK
3
Physics Department, University of Parma, Viale G. P. Usberti, 7/a, 43124 Parma,
Italy, anna.cesaratto@studenti.unipr.it. (+39) 0331 969319
4
Paper Conservation Section, Conservation Department, Victoria and Albert
Museum, South Kensington, London SW7 2RL, UK,
Eighteen English portrait miniatures from the Victoria and Albert Museums
collections were analysed using Raman microscopy and optical microscopy in order
to obtain information on the materials used and map the exact pigment mixtures
used by various artists. The miniatures were all painted between the second half of
the 16th century and the beginning of the 17 th century, by well known miniaturists
such as Lavina Teerlinc, Nicholas Hilliard and Isaac Oliver. A handful of miniatures
were of uncertain attribution.
A non-destructive and non-intrusive approach was chosen for this investigation
[Derbyshire et al., 1999; Bell et al., 1997], as the miniatures are very small and
delicate and sampling was not considered an ethical option. To gather comparable
data, each miniature was studied following the same analysis pattern: images of
each miniature were taken with a stereo microscope first and a more powerful optical
microscope afterwards; then the Raman analysis proper took place, starting with the
miniatures background, the physiognomic details and ending with the decorative
elements such as clothing and jewellery. Occasionally, further analysis by XRF was
carried out.
The ultimate purpose of this study was to monitor the occurrence and distribution of
the artists materials used in each part of the miniatures, such as the grade of the
pigment, its particle size, and shape and the distribution of the particles in mixtures
etc., This information would be used to build up a database of the various artists
palettes with a view to helping with attribution.
The characterisation of the artists palettes revealed some important features as
differences between the pigments used by each artist were noted: the comparison
between the pigment mixtures used for some of the facial features revealed that the
earliest artist, Teerlinc, used only vermilion as a red or orange pigment in her
carnation mixtures; Hilliard, on the other hand, preferred to mix red lead and
vermilion but on some occasions used vermilion alone. Isaac Oliver, Peter Oliver and
John Hoskin did not use vermilion at all, but only red lead. Another trend in the use
of preferred mixtures was discovered when looking at details such as hair, beard,
nostrils and ears: Hilliards mixtures are characterised by a significant presence of a
brown organic compound, while the Olivers prefer to mix hematite and goethite with
the other pigments.
The trends discovered were applied to three miniatures, the attribution of which is
uncertain. The miniatures of Mr and Mrs Croker (P.139-1910) have a troubled history
of attributions [Coombs et al., 2007] and they are now thought to be original Tudor
miniatures, although they present a number of retouched areas. The orange
particles in their carnation mixtures gave the Raman spectrum of both vermilion and
red lead.

22
Artist Carnation mixtures - orange Other physiognomic details -
particles mixtures
L. Teerlinc vermilion Orpiment, red lead and

vermilion.
N. Hilliard Red lead and vermilion or Brown lake, carbon, and red
vermilion lead
I. Oliver Red lead Hematite, goethite, red lead,

carbon, etc.
P. Oliver Red lead Hematite, goethite, red lead,

carbon, etc.
J. Hoskin Red lead Hematite, goethite, red lead,

carbon, etc.
Table 1 Most common pigments mixtures
The pigment mixtures used for some of the other facial features are characterised by
a brown organic compound. These results supported the hypothesis that the
miniatures were painted in the Tudor period, probably by Hilliard or one of his
followers. The miniature with accession number 630-1882 is signed by Isaac Oliver,
but it was recently suggested that the signature may not be authentic.
The Raman analysis
Figure 1 Raman
orange crs
28 February 2011, XploRA 638 nm
carried out on the
filename: P139-1910Mrs carnation
spectra of orange
545
particle miniature revealed
in P.139-1910 Mrs
120 Croker carnation.
that vermilion is
present in the
red lead
carnation and a
147
brown organic
Raman intensity
20 (orange cr) material is the

250
predominant element
in the hair, nostrils
and ears. No trace of
341 hematite or goethite
vermilion 17 was found in the
(bright orange cr)
same areas. The
200 400 600 800 1000 1200 1400 1600 1800 results support the
-1
Wavenumber/cm hypothesis expressed
by V&A experts that
Oliver is not the author of this miniature, and demonstrates that the approach used
for the analysis of this set of V&A miniatures can provide valuable assistance when
the attribution to a particular artist is in doubt.
References
Derbyshire A. and Withnall R. Journal of Raman Spectroscopy 1999; 37: 185.

Bell I.M, Clark R.J.H., Gibbs, P.J. Spectrochimica Acta 1997; 53: 2159.
Coombs K., Derbyshire A., Frayling N. and Tallian T., in Hermens E.(Editor), 'A multifaceted
approach to the study of Tudor portrait miniatures: a case study of the Croker miniatures' in
Art, Conservation and Authenticities: Material, Concept, Context. Glasgow, UK, 2007
Hilliard N., Nicholas Hilliards Art of Limning, Northeastern University Press, Boston, 1983.

23
Raman mapping to study calcium oxalate historical films
Claudia Conti1, Chiara Colombo1, Marinella Greco1, Elena Possenti1,

Marco Realini1, Chiara Castiglioni2, Giuseppe Zerbi2
1
National Research Council (CNR), Istituto per la Conservazione e la Valorizzazione
dei Beni Culturali (ICVBC), Via Cozzi 53, 20125 Milano (Italy), Tel. +39 0266173337,
3
Politecnico of Milano, Dip. Chimica, Materiali e Ingegneria Chimica Giulio Natta,
Piazza Leonardo da Vinci 32, 20133 Milano, Italy.
One of the most controversial issues still under discussion among conservation
scientists is about the oxalate films observed on the surfaces of several ancient
monuments. They are constituted by calcium oxalate in the most common forms,
namely whewellite (CaC2O4 . H2O) and weddellite (CaC2O4 . (2+x) H2O), which
chemically differ only by the amount of water molecules; the mineralogical structure
is completely different, being monoclinic for whewellite and tetragonal for weddellite.
They have been detected both on natural stone materials as marble, calcarenite,
sandstone, granite and on artificial stone materials as plasters or terracotta [VV. AA.,
1996, Rampazzi et al., 2004].
At present the main hypotheses on their origin (biological or chemical) are matter
of scientific debate; in both cases the reaction between oxalic acid and calcium
compounds of the stone yields calcium oxalate in two different forms. Whewellite is
stable at environmental conditions, while weddellite, under the same conditions,
quickly changes into whewellite. Some questions arise: why have whewellite and
weddellite been often detected within the same film? Is there a recurrent stratigraphy
of the two calcium oxalates from the surface to the inner portions of the substrate?
Answering these questions means to contribute to the understanding of the origin
and evolution of these films.
In the literature very little attention has been paid to the stratigraphy of calcium
oxalate films, due to the lack of analytical techniques able to discriminate between
whewellite and weddellite in cross sections with a suitable resolution. The results
obtained with polarized light microscopy and X-Ray micro-diffractometry showed that
whewellite, in many cases, is in contact with the stone substrate, while weddellite is
in the external portion of the films [Appolonia L et al., 1996, Gratziu C, 1986]. On the
contrary, other authors reported a larger amount of weddellite in contact with the
substrate surface [Matteini M et al.,1986].
In the present study Raman mapping on polished cross sections has been
proposed as an effective analytical direct technique able to define the stratigraphy, if
it exists, of whewellite and weddellite in calcium oxalate historical films.
Several samples of oxalate films have been studied, belonging to different
monument faades as the Church of Santa Maria delle Grazie and S.Ambrogio both
in Milan, Charterhouse of Pavia, the Cathedrals of Milan and Trento and the Temple
of Castore in Rome. Films have been detected on different stones such as marbles
(Carrara, Candoglia) and limestones (Red Verona).
Two kinds of problems have been highlighted by the spectroscopic analyses: a)
many samples showed strong fluorescence which obscured the Raman scattering; in
many cases even no results have been obtained; b) for some of the samples
showing a clear Raman spectrum, only a kind of calcium oxalate (whewellite or
weddellite) has been detected in the film; this observation is in contrast with our
attempts that aims to define the stratigraphy of the two phases within the oxalate
films. However, Raman mapping allowed, for the first time, to unequivocally identify
24
the presence of calcium oxalates and, most of all, to obtain direct information, at high
spatial resolution, of their distribution with respect to the material surface (Figure 1).
The results so far obtained on the samples examined seem to indicate that, for a yet
unknown reason, the phase distribution is random.
Figure 1: scheme of the oxalates (WD = weddellite and WH = whewellite) distribution

detected by linear mapping acquired in 6 points (white circles) on a polished cross section of
an oxalate film. On the right, Raman spectra of whewellite (a) and weddellite (b) in the range
100 1800 cm-1.
References
VV.AA. Proceedings of II International Symposium "The oxalate films in the conservation of
works of art" 1996.
Rampazzi L, Andreotti A, Bonaduce I, Colombini MP, Colombo C, Toniolo L. Talanta 2004;
63: 967.
Appolonia L, Giamello M, Sabatini G. Proceedings of II International Symposium "The oxalate
films in the conservation of works of art" 1996; 361.
Gratziu C, Proceedings of "Scienza e Beni Culturali" 1986, 752.
Matteini M, Moles A, OPD Restauro 1986; 65.

25
Identification of natural resins by vibrational spectroscopies:
impact of their ageing
Cline Daher1, Cline Paris 1, Ludovic Bellot-Gurlet1, Anne-Solenn Le H2

and Martine Regert3
1
Laboratoire de Dynamique, Interactions et Ractivit (LADIR), UMR 7075 CNRS -
UPMC (Universit Pierre et Marie Curie Paris 6), 2 rue Henry Dunant, 94320 Thiais
(France), Tel. +33 (0)149781108, celine.daher@glvt-cnrs.fr
2
Centre de Recherche et de Restauration des Muses de France (C2RMF), UMR
171 CNRS - Ministre de la Culture et de la Communication, Palais du Louvre-Porte
des Lions, 14 quai Franois Mitterrand, 75001 Paris (France)
3
Centre dEtudes Prhistoire, Antiquit, Moyen-ge (CEPAM), UMR 6130 CNRS -
Universit de Nice-Sophia Antipolis, Campus St-Jean-d'Angly 3, 24 avenue des
Diables Bleus, 06 357 Nice 04 (France)
Numerous analytical strategies using separative methods and mass spectrometry

are developed for the identification and differentiation between natural organic media
used in art (resins, oils, glues, gums, lacquers) [Colombini et al., 2009]. However,
alternative methods such as Raman and Infrared spectroscopies are easier to
implement because neither sampling nor sample preparation are necessary, and
seem to allow the characterization and differentiation of such organic substances
[Daher et al., 2010]. But when working on ancient samples, in other words taking into
account their possible alteration, the vibrational signatures may be modified and,
hence, hamper the identification. Indeed, some chemical transformations may
happen during the ageing leading to spectral modifications such as intensity
variations, enlargements, and shifts of specific bands.
In order to document the effect of the materials ageing on their identification,

a study by FT-Raman and IR-ATR was done on diterpenoid resins (copals) from an
archaeological site (12th century) located in Sharma (Yemen) [Rougeulle, 2004].
These copals were chosen as reference materials [Regert et al., 2008] because of
the variability of their aspects and colors. Indeed, some are pale yellow and seem
unaged, and some are more or less red, with a degraded and brittle surface.
Samples from the internal and external parts of each grain of resin were analyzed
and compared using both vibrational spectroscopies. Some spectral regions (CH and
CC stretching vibrations) showing notable differences were highlighted.
One part of this study was to understand these differences between the fresh
and the degraded parts. The mentioned spectral regions were studied by spectral
decomposition in order to determine the parameters that describe the bands
morphology and to find the chemical bonds and structures that are sensitive to
ageing. An interpretation of these changes and hypotheses on the chemical
processes that occur may be given. Another part of this study was to determine if the
ageing has an influence of the material recognition. Thus, multivariate analyses
(Principal Components Analyses) were done, first on the raw data (parts of the
spectra), and then on the spectral decomposition data.
This study shows the variability of the vibrational signatures depending on the
alteration states of the resins, and provides tools to qualify these degradation states
thanks to Raman and IR spectroscopies.

26
References
Colombini MP, Modugno F, Organic Mass Spectrometry in Art and Archaeology, Ed. John
Wiley & Sons, 2009.
Daher C, Paris C, Le H A-S, Bellot-Gurlet L, Echard J-P. Journal of Raman Spectroscopy
2010; 41: 1204.
Rougeulle A. Annales Islamologiques, 2004; 38: 201.
Regert M, Devise T, Le H A-S, Rougeulle A. Archaeometry, 2008; 50: 668.

27
Raman study on medieval-like glass samples: glass
characterization, artificial weathering and comparison with
ancient K-based glasses
Lavinia de Ferri1, Danilo Bersani2, Philippe Colomban3,

Pier Paolo Lottici2, Guilhem Simon3, Giovanna Vezzalini1
1
Dipartimento di Scienze della Terra, Universit di Modena e Reggio Emilia, Largo
S. Eufemia 19, 41100 Modena, Italy. Tel: +39 059 2055808.
lavinia.deferri@unimore.it
2
Dipartimento di Fisica-Istituto Nazionale di Fisica della Materia, Universit di
Parma, Viale G.P. Usberti 7/A (Parco Area delle Scienze) 43124 Parma, Italy
3
Laboratoire de Dynamique, Interaction et Ractivit (LADIR), UPMC, CNRS, 2 rue
Henry Dunant 94320 Thiais, France
Ash-based glass, enriched in K2O (PLS, potash-lime-silica) used as flux agent, are
typical of medieval glass windows used in the Northern Europe since 1000 A.D.
They are very sensitive to the alteration phenomena due to the attack of atmospheric
pollutants conveyed by water in liquid or vapor form (rain, humidity, fog). The
dissolution of the silica network may occur through hydrolysis reactions and
crystalline weathering products can be identified on the glass surface.
This study focus on two main points: i) the description of the glass structure changes
induced by increasing quantity of modifier ions in the glass; ii) the study of the glass
alteration degree in terms of structural modifications [Melcher et. Al 2008]. For these
purpose three kinds of PLS medieval-like glass samples were produced for 12-16-23
%wt K2O content (V1, V2 and V3, respectively). They were chemically analyzed by
XRF spectroscopy and their vibrational properties were investigated by Raman
spectroscopy (at 488 nm). The aging experiments were carried out on small glass
fragments both in hot concentrated sulfuric acid and in water. On each Raman
spectrum a Gaussian de-convolution of the stretching band (750-1250 cm-1) into the
different vibrational contributions of SiO4 structural units Qn was performed. Q1 and
Q2 configurations increase at the expense of Q 3 and Q4 with increasing K+ content.
The position of the main Si-O stretching component is consistent with the ones
observed in medieval K-Ca rich glasses. A small blue-shift of the stronger Si-O
bending band (max shifts from 593 to 602 cm-1) is observed and can be related to a
Si-O bonds lengthening with increasing the K 2O amount.
For all the samples the polymerization index Ip was calculated from the ratio of the
bending to the stretching Raman bands areas. The nearly constant low values 0.3-
0.4 obtained for all glass compositions are consistent with the ones of medieval
glass, [Colomban et al. 2006] and seems to indicate that Ip is more sensible to the
processing/annealing temperature than to flux quantity.
The results are compared with the ones obtained on three medieval glass coming
from Rouen (13.6% K2O), Strasburg (14.1 % K2O), Le Mans (14.5 % K2O), and
Amiens (18.5 % K2O, XIXsec). The de-convolution analysis is reported in Fig.1. The
Qns components exhibit similar quantitative variations increasing the fluxing
amounts, if compared with the reproduced samples.
The max values found for the medieval samples varies from 599 in the Strasbourg
sample, to 610 cm-1 in the Rouen one, confirming the behavior already observed for
the produced glasses.

28
Fig. 1: Raman spectra and de-convolution analysis of the Qn components of the stretching
band of the medieval-like glass samples and of the ancient samples from Rouen (R), Le
Mans (LM) and Amiens (AM).
Raman measurements after aging tests were performed on the samples cross
sections: gypsum and bassanite hydrated sulphates were identified on acid aged
glasses, while in the water attacked ones the Raman spectra depth profiling revealed
crystallization in the superficial layer of Ca-phyllosilicate gyrolite and K-phyllosilicate
reyerite. The alteration layer of V3 sample is completely crystallized into a mixture of
phyllosilicate phases with hydroxyapatite and charoite (hydrated Ca-K inosilicate).
The main structural change after the ion exchange is evidenced by the red shift of
the Q3 stretching peak, due to the lengthening of the SiO bond. This is induced by
the interaction of the NBO atoms with the protonic species substituting K ions during
ageing [Tourni et al. 2008]. In glasses submitted to acid attack, max is generally
lower [Colomban et al. 2006]. Moreover, Q4 components disappear in the altered
layers of the water aged samples and Ip increases (from 0.4 to 0.9) from the
unaltered samples to the K-depleted glasses.
References
1. Melcher M., Schreiner M., Kreislova K. Physics and Chemistry of Glasses: European
Journal of Glass Sciences and Technology B 2008; 49: 346
2. Colomban Ph., Tourni A., Bellot-Gurlet L. Journal of Raman Spectroscopy 2006; 37:
841
3. Tourni A., Ricciardi P., Colomban Ph. Solid State Ionics 2008; 179: 2142
4. Colomban Ph., Etcheverry M. P., Asquier M., Bounichou M., Tourni A. Journal of
Raman Spectroscopy 2006; 37: 614

29
Synthetic organic dyes in the embroidery
Plants and flowers on a grey fond by Emile Bernard
S. de Groot1, M.R. van Bommel1, M. de Keijzer1, L.O.E.S. Vermeij1,
R. Boitelle2
1
The Netherlands Cultural Heritage Agency (RCE formerly ICN), Movable Heritage
Knowledge Sector , P.O. Box 1600, 3800 BP Amersfoort, The Netherlands,
+31203054740, s.de.groot@cultureelerfgoed.nl
2
Van Gogh Museum, PO Box 75366, 1070 AJ Amsterdam, The Netherlands
In the period of 1856-1900 nearly a thousand early synthetic organic dyes were
developed and patented and hence hundreds became available. Dyestuff analyses
on art objects of historic or cultural value often result in interesting historical
information, such as a better understanding of the original color, origin and date, and
can sometimes establish a relation between different objects. In some cases,
knowing to which dye class a dyestuff in an object belongs is sufficient. Due to the
large number of the synthetic organics, it was decided to focus this research on 65
dyes, based on the selection made by Dr. H. Schweppe, which includes most dye
classes from that period.
The analyses of these synthetics in textiles and paint layers are currently performed
using High Performance Liquid Chromatography (HPLC) coupled to Photo Diode
Array detection (PDA). Although the dyes can be distinguished, two HPLC systems,
one for basic and one for acid dyes, are required for full identification [1] and
therefore twice the sample size is needed. Can Raman spectroscopy (785 nm laser),
be used as an alternative for HPLC analyses (thus utilizing less sample material), or
act as a pre-selection method for HPLC?
To be able to distinguish between the different dyes classes a flow chart [2] based
on Raman shifts was developed and therefore spectra of the dyes of the Schweppe
collection were measured. Some dyes show extreme fluorescence or are poor
Raman scatterers and to improve these spectra the possibility of using Surface
Enhanced Raman Scattering (SERS) has been explored. Four different methods for
preparing silver colloid solutions, spheres and rods, were compared in order to
obtain silver particles that are the most effective in combination with the 785 nm
laser. The resulting flowchart offers the possibility to distinguish between different
dye classes.
To establish the suitability of the Raman technique described above, the embroidery
Plants and flowers on a grey fond (dated 1892-1904) (fig.1) designed by Emile
Bernard (1868-1941) from the Van Gogh Museum was examined. This embroidery is
part of a series of five embroideries in the collection of the museum of which two
have been analyzed using different techniques [3]. Owing to its date and fading,
early synthetic dyes were expected to be present. Long yarn ends present at the
back of the embroidery allowed for the easy removal of twenty different colored
samples without disturbing the integrity of the object. Raman and SERS were
performed on one single fiber of the sample and to verify these results the samples
were also analyzed using HPLC.
From a total of twenty samples, in eight samples not only the dye class, but also the
main dye components could be identified using Raman (see table 1). The Raman
spectra of the remaining samples showed only the spectrum of wool. SERS using
silver rods was applied in an attempt to enhance the signal of the dye, but
unfortunately this did not have the desired effect. All dyes present in the twenty
samples were identified by HPLC-PDA.

30
Figure 1: Plants and flowers on a grey fond (1892-1904) by Emile Bernard (1868-1941)
Color Raman result Dye class HPLC-PDA result
1 red-scarlet Cochineal Red A monoazo Cochineal Red A

Ponceau RR monoazo Ponceau RR
Ponceau G
Silk scarlet , component 1
5 vermillion Ponceau G monoazo Ponceau G
Naphthol Yellow S nitro Naphthol Yellow S
6 orange Naphthol Yellow S nitro Naphthol Yellow S
Martius Yellow nitro trace of Martius Yellow
Ponceau G
7 yellow, dark Naphthol Yellow S nitro Naphthol Yellow S
Ponceau G
10 yellow-lemon Naphthol Yellow S nitro Naphthol Yellow S
Martius Yellow nitro
Ponceau G
12 blue-green, Patent blue V triarylmethane Patent blue V and 5 equivalents
dark
15 blue, dark Patent blue V triarylmethane Patent blue V and 5 equivalents
18 khaki Naphthol Yellow S nitro Naphthol Yellow S

Picric acid
Ponceau G
Table 1: Raman and HPLC results of eight samples
The limitations of Raman spectroscopy have been demonstrated in this study.

Research with references produced good results, but the reality of analyzing an art
object shows that this technique will not always produce the desired outcomes.
Therefore Raman spectroscopy can not replace HPLC-PDA for the analyses of
synthetic dyes in the future, but it can be used as a first quick scan, using one single
fiber.
References
[1] van Bommel, M.R., et al., J. Chromatogr., 2007. 1157(1-2): p. 260-272.

[2] Vandenabeele, P., et al., J. Raman Spectrosc., 2000. 31(6): p. 509-517.
[3] van Bommel, M.R, et al., Analysis of synthetic dyes in an embroidery of Emile Bernard
th
(circa 1892) Preprints Vol II, 14 Triennial Meeting ICOM-CC, 2005: p. 969-977

31
A combination of Raman and X-ray fluorescence
spectroscopy to investigate porcelain cards.
Annelien Deneckere1, Bart Vekemans2, Lieke De Vries1, Laszlo Vincze2,

Peter Vandenabeele3 and Luc Moens1
1
Ghent University, Department of Analytical Chemistry, Research group Raman
spectroscopy, Krijgslaan 281, S12, B-9000 Ghent (Belgium), Tel. +32 92644845,
annelien.deneckere@ugent.be
2
Ghent University, Department of Analytical Chemistry, Research group X-ray
microspectroscopy and imaging, Krijgslaan 281, S12, B-9000 Ghent (Belgium),
3
Ghent University, Department of Archaeology, Sint-Pietersnieuwstraat 35, B-9000
Ghent (Belgium),
In the Flemish region (Belgium) porcelain cards were very often used in the 19 th
century as business cards, New Year greetings, calendars, funeral notices,... A lot of
these cards were not only printed with text, but also brightened with illustrations of
professions, workshops, etc. and give therefore a view of the daily life in Flanders in
the 19th century. The production of these cards was done by a lithographical
procedure, but because the manufacturing process has not been described in
literature, it is considered as being lost. Nevertheless, there seems to be some
common belief amongst collectors and curators that the front of the cardboard is
covered with a thin layer of lead white (2PbCO 3Pb(OH)2) mixed with kaolin
(Al2Si2O5(OH)4). This mixture was pressed on the cardboard to give a high-gloss
finish, having the look of porcelain. This characteristic probably explains the name of
the cards [Vandenabeele et al., 2008].
The porcelain cards were analysed with Raman spectroscopy and X-ray
fluorescence (XRF) spectroscopy. Both techniques allow the investigation of
samples on the microscopic level in a non-destructive way, which is essential in
cultural heritage projects. Moreover, combining Raman spectroscopic and XRF data
promises a more easy interpretation of the spectroscopic data by complementing
molecular with elemental information.
In this work, a combination of micro-Raman spectroscopy and micro-XRF

spectroscopy is explored in order to describe the selected porcelain cards. Special
attention has been paid to data evaluation strategies using the resulting combined
data, consisting of the data of the two techniques. Also the effect of the combined
data on the interpretation compared to the interpretations based on only one
spectroscopic technique (i.e. only Raman data or only XRF data) is evaluated.
Acknowledgments: This work is supported by the BELSPO Interuniversity Attraction

Pole Program P6/16 (Belgium).
References
Vandenabeele P, De Paepe P, Moens L. Journal of Raman Spectroscopy 2008; 39: 1099.

32
Identification of synthetic organic pigments:
the role of a comprehensive Raman spectral library
Wim Fremout and Steven Saverwyns
Royal Institute for Cultural Heritage (KIK/IRPA), Laboratories department, Painting

laboratory, Jubelpark 1, 1000 Brussels (Belgium), Tel. +32 2 739 68 46,
wim.fremout@kikirpa.be
The first synthesis of mauveine - the first synthetic organic dye - in 1856 by Sir
William Perkin heralded a revolution in the colour industry. Inspired by its
commercial success, many other synthetic organic colorants and pigments would
soon follow. This still ongoing process resulted in thousands of commercially
available synthetic organic colorants and pigments. It was mainly during the 20 th
century and especially after World War II that many of these pigments found their
way into artists paints, partially replacing the existing organic and inorganic
pigments. The extensive choice in pigments, however, thwarts the analytical study of
contemporary paintings, which is essential prior to any conservation treatment, to
develop long-term preventive conservation strategies and to answer questions
regarding authenticity issues.
Micro-Raman spectroscopy (-RS) has become common practice in many art
research labs for both inorganic and synthetic organic pigment identification. Many
synthetic organic pigments are known to exhibit strong Raman signals, characterised
by a large number of distinct peaks. Over the recent years, a moderate number of
these Raman spectra have been published in scientific literature. Pigments of the
same chemical class may produce highly similar spectra that are difficult to discern,
especially when comparing with published, non-digital reference spectra. In
incomplete libraries this could easily lead to false identifications. Having an extensive
reference library and specialised search software capable of distinguishing different
spectra based on subtle differences is thus crucial.
During this presentation an extensive Raman spectral library will be presented. A
collection of about 400 reference synthetic organic pigments (figure 1) was used to
create the library. Most of these pigments give a distinct Raman spectrum and
unknowns are readily identified using the spectral search program Spectral ID
(Thermo-Fisher). In some cases however, due to the high similarity between the
Raman spectra of the pigments of the same chemical class, only the pigment class
could be identified.
The few pigments that turned out to be indiscernible with -RS were analysed using
other techniques, such as Fourier transform infrared spectroscopy (FTIR) and
pyrolysis gas chromatography - mass spectrometry (py-GC-MS).
The synthetic organic pigments library was thoroughly tested using paint samples of
both modern commercial and self-made paints and used to identify the pigments in a
series of contemporary paintings. The library has also been employed successfully in
discovering fakes using the pigments documented discovery and first usage dates
[Saverwyns, 2010]. The digital Raman spectral library will be made available in the
near future.

33
Figure 1. A part of KIK/IRPAs collection of synthetic organic pigments
Acknowledgements. This work has been financially supported by the Belgian

Science Policy in the framework of the project "Modern and Contemporary Art in the
laboratory: Analytical study of 20th century paint" (project number MO-39-010). The
authors would like to express their gratitude to Dr. Tom Learner (Getty Conservation
Institute, GCI) and Dr. Maarten van Bommel (The Netherlands Cultural Heritage
Agency (RCE) Movable Heritage Knowledge Sector) for kindly sharing their
reference collections of synthetic organic pigments, to Frederika Huys and Marieke
Verboven (Stedelijk Museum voor Actuele Kunst, SMAK) for giving access to their
contemporary painting collection, and to Marie-Christine Maquoi and Alexia Coudray
for a large number of -RS measurements.
References
Saverwyns S. Journal of Raman Spectroscopy 2010; 41: 1525.

34
Exploring the roots of garnet jewellery: Raman spectroscopic
and microscopic analysis of Hellenistic engraved gems
Norbert Gast1, H. Albert Gilg1, Carina Wei2, Rupert Gebhard3,

Wolfgang Schmahl4 and Robert Stark5
1
Technische Universitt Mnchen, Lehrstuhl fr Ingenieurgeologie, Arcisstr. 21,
80333 Mnchen (Germany), Tel. +49 (163) 888 25 81, norbert.gast@gmx.de
2
Archologisches Institut der Universitt, Residenzplatz 2 Tor A, 97070 Wrzburg
(Germany)
3
Archologische Staatssammlung Mnchen, Lerchenfeldstr.2, 80538 Mnchen
(Germany)
4
Ludwig-Maximilians-Universitt Mnchen, Department fr Geo- und Umweltwissen-
schaften, Theresienstr. 41, 80333 Mnchen (Germany)
5
Technische Universitt Darmstadt, Center of Smart Interfaces, Physics of Surfaces,
Petersenstr. 32, 64287 Darmstadt (Germany)
Red garnet became a popular gemstone in the Hellenistic period. Its use declined
somewhat during Roman Imperial times, before it became the favoured red gem for
polychrome jewellery in the Late Antiquity and Early Medieval Period [Gilg, 2008].
The chemical compositions of cloisonn garnets are very well characterized with
more than 2000 PIXE and EMPA analyses [e.g., Calligaro et al. 2007, Gilg et al.,
2010]. These data reveal 3 almandine and 2 pyrope clusters plus a heterogeneous
group of intermediate almandines and pyropes with a distinct temporal distribution
pattern [Gilg et al., 2010]. Very little, however, is known about garnet types used in
classical antiquity [Brandt, 1968; Gartzke, 2004; Pappalardo et al., 2006]. Therefore,
we investigated 28 Hellenistic engraved red garnet gems from the Staatliche
Mnzsammlung Mnchen (SMM) and the Staatliche Antikensammlung und
Glyptothek Mnchen (Loeb and Hansmann collections) using a combination of
micro-Raman spectroscopy and optical microscopy.
Smith [2005] and Bersani et al. [2006] developed techniques to derive chemical
compositions of garnets from Raman spectra. Both methods are based on analyses
of a set of chemically well-characterized natural standard samples and linear
relationships between shifts of Raman band positions and garnet end-member
variations. We apply a similar, but modified approach that significantly improves the
quality of predictions by a) increasing the number of Raman bands used for
calculations, b) concentrating on only two narrow compositional variation fields
(almandines and pyropes with up to 10 wt.% of CaO and MnO, and up to 4 wt.%
Cr2O3) that cover the expected garnet compositions, and c) predicting cation oxide
compositions instead of garnet end-members that depend on assumed or calculated
Fe2+-Fe3+ ratios for iron-rich garnets.
Our results show that earlier attributions of Hellenistic gems in the SMM to specific
garnet types, such as almandine, pyrope, hessonite, and spessartine, mainly based
on colour [Brandt, 1968] are in most cases wrong and thus untenable.
More than half of the investigated Hellenistic garnet gems pertain to a compositional
group that was not in use during the Migration and Early Medieval period. The
almandine garnets are MgO-poor (<4 wt%) and show variable, but high CaO
contents (3 to 10 wt.%). Manganese contents appear also variable but are generally
less than 4 wt.%. The inclusion inventory of the garnets (many healed fractures, few
mineral inclusions) is also clearly distinct from that of garnets used in Early Medieval
35
times. The characteristic composition matches that of almandines from the
Menderes Massif, Western Turkey (Alabanda?) and gem-quality garnets from the
Alpine deposits in the Zillertal, Austria. Further detailed studies on garnet chemistry
and mineral inclusions are necessary to unambiguously locate the source of this new
garnet type.
The remaining engraved gems can be ascribed to previously known garnet types.
Six stones are attributed on the basis of mineral chemistry and inclusion
characteristics to cluster A almandines and four to the heterogeneous group X. The
two garnet types often occur together in cloisonn jewellery of the 4th and 5th century
and most probably derive from the granulite belts in Southern Asia (India, Sri Lanka)
or Eastern Africa [Gilg et al., 2010]. Three inclusion-free garnets with an orange tint
show the characteristic Raman spectra of chromium-poor, Ca-rich magmatic cluster
D pyropes. This rare garnet type was hitherto exclusively known from cloisonn
jewellery dating from the end of 6 th and 7th century, and the stones were always less
than 5 mm in diameter. The three, more than 1 cm large Hellenistic engraved gems
are, therefore, remarkable both with respect to age and size. The Cr-poor magmatic
pyropes may have been derived from the alkali basalt-hosted deposits of Monte
Suimo near Lisbon, Portugal, or the volcanoes in the Jos Plateau, Nigeria
(Carchedonian or Garamantian garnets?).
Four chemically distinct groups of Hellenistic gem garnets can be distinguished on

the basis of Raman spectroscopy and mineral inclusion analysis. Three of them were
still used for garnet cloisonn jewellery during the Migration and Early Medieval
period. We have not found any Hellenistic garnet that pertain to cluster B
almandines, the predominant garnet type used in the 6 th century cloisonn jewellery
and most probably derived from Rajasthan, the Scandinavian cluster C almandines,
and the Bohemian Cr-rich peridotitic pyropes of cluster E. These garnet deposits are
probably late discoveries.
Acknowledgements. This work was supported by Staatliche Mnzsammlung

Mnchen (K. Ehling) and Staatliche Antikensammlung und Glyptothek Mnchen (M.
Steinhart). We are grateful to R. Hochleitner, Mineralogische Staatssammlung
Mnchen, and T. Calligaro, Centre de Recherche et de Restauration des Muses de
France, CNRS UMR-171, Paris, for their help during the study.
References
Bersani D, Lottici PP, Vignali F, Zanichelli G. Journal of Raman Spectroscopy 2006; 37:
1012.
Brandt E. Antike Gemmen in Deutschen Sammlungen I. Staatliche Mnzsammlung Mnchen
1, 1968.
Calligaro T, Perin P, Vallet F, Poirot JP. Antiquits Nationales 2007; 38: 111.
Gartzke E. Unpubl. magister thesis, Univ. Wrzburg, Germany, 2004
Gilg HA in Gilg HA et al. (Editors) Garnet Great Balls of Fire, Lithographie, LLC, East
Hampton, CT, USA, 2008, p. 12.
Gilg HA, Gast N, Calligaro T, in Wamser L. (Editor), Karfunkelstein und Seide, Neue Schtze
aus Bayerns Frhzeit, Ausstellungskataloge der Archologischen Staatssammlung, Band 37,
Verlag Friedrich Pustet, Regensburg, Germany, 2010, p. 87.
Pappalardo L, Karydas AG, Kotzamani N, Pappalardo G, Romano FP, Zarkadas Ch. Nuclear
Instuments and Methods in Physical Research. B 2005; 239: 114.
Smith DC. Spectrochimica Acta Part A 2005; 61: 2299.

36
Automatic Identification System of Raman Spectra of Pigment
Mixtures
Juan Jos Gonzlez Vidal, Rosanna Prez-Pueyo, M Jos Soneira and

Sergio Ruiz-Moreno
Universitat Politcnica de Catalunya, Signal and Communication Department, c/ Sor

Eullia de Anzizu s/n, Mod. D5, Campus Nord, 08034 Barcelona (Spain),
+34934016442, juanjoglezvidal@gmail.com
The characterization of constituent materials in artworks is important for the

cataloging, conservation and restoration of paintings. Raman spectroscopy is a
suitable technique for the non-destructive identification of artists materials. This
identification is generally carried out by visual comparison between the unknown
Raman spectrum with an appropriate set of reference Raman spectra. Frequently,
pigments in artworks are mixed up and the identification is actually done on Raman
spectra of pigment mixtures. Nevertheless, identifying Raman spectra of synthetic
organic pigment mixtures may turn out to be a complex task due to its large amount
of bands located close together. To decrease complexity whilst also speeding up this
process, an automatic identification system of Raman spectra of pigment mixtures is
presented in this work. This system is based on the chemometric technique of
Principal Components Analysis and a decision algorithm developed to automatically
select the corresponding reference Raman spectra of the unknown mixture (Figure).
In order to demonstrate the performance of the proposed methodology, the effect of
different practical problems on spectral identification is studied, verifying the correct
behaviour of the implemented system with experimental cases of Raman spectra
measured directly on the paintings.
Figure - Example of identification of a Raman spectrum of a pigment mixture. On the left

side, the Raman spectrum of the unknown mixture is presented. On the right side, the
reference Raman spectra selected automatically by the implemented system are represented
(from top to bottom PY109 and PY151).

37
In situ non-invasive multi-methodological characterization of
the pigments of a 17th century Japanese paper screen from
the Stibbert Museum in Florence
Francesco Grazzi1, Maurizio Aceto2, Angelo Agostino3, Elisa Barzagli1,

Francesco Civita1,4, Roberta Iannaccone5, Marcello Picollo5, Filomena
Salvemini1 and Marco Zoppi1
1
Consiglio Nazionale delle Ricerche, Istituto dei Sistemi Complessi, Via Madonna
del Piano 10, 50019, Sesto Fiorentino (FI), Italy, Tel. +39 0555225301,
francesco.grazzi@isc.cnr.it
2
Interdisciplinare per lo Studio e la Conservazione dei Beni Culturali (CenISCo),
3
Universit di Torino, Dipartimento di Chimica Generale e Organica, C.so M.
D'Azeglio 48, 10125, Torino, Italy,
4
Stibbert Museum, Japanese, Indian and Middle East Section, Via F. Stibbert 26,
50100, Firenze, Italy,
5
Consiglio Nazionale delle Ricerche, Istituto di Fisica Applicata Nello Carrara, Via
Madonna del Piano 10, 50019, Sesto Fiorentino (FI), Italy.
Stibbert Museum, in Florence, owns one among the most important collections in
Europe concerning Asian artworks, especially Japanese ones. We have already
started a characterization work, applying a non-invasive approach using thermal
neutrons, on steel and copper alloy artworks, which constitute a large part of the
collection in the Japanese Section [Grazzi et al. 2009, Grazzi et al. 2011]. In this
work, we are dealing with some very high quality silk and paper paintings, present in
the same collection, which are rather ancient and in good conservation conditions.
In particular, we concentrate on a 17 th century paper screen representing some
battles during the struggle between the Taira and Minamoto families in 12 th century.
With the aim of identifying the pigments, and the relative working technique of
painting on a large surface of rice paper, we have started a non invasive
characterization work using portable Raman Spectroscopy, X-Ray Fluorescence,
and Fibre Optic Reflectance Spectroscopy. The use of several complementary
methods permitted the identification of the pigments, of the substrate, and of the
preparation layer.
Raman measurements have been performed with a portable system assembled by
Horiba Jobin-Yvon (Villeneuve dAscq, France). The system is composed by a
microHR spectrometer with a spectral resolution of 5 cm -1, a CCD Synapse detector,
a ModularHead analytical probe containing a video camera for visualisation of
samples, a notch filter for elimination of Rayleigh radiation, and a microscope
objective (10x, 20x, 50x or 80x). The system is complemented by a tripod,
supporting the analytical probe, equipped with an XYZ stage with micrometric
movements to allow accurate focusing and two different laser sources: a Nd-YAG
532 nm and a helium-neon 632 nm lasers. A system of optical fibres is used to
convoy the laser radiation onto the sample and to transfer the Raman radiation to
the spectrometer. A laptop computer, equipped with dedicated software LabSpec 5
running under Windows completes the whole system.
XRF measurements have been performed with a portable Thermo NITON XL3T
GOLDD. The GOLDD (Geometrically Optimized Large Drift Detector) technology
exploits an SDD (Silicon Drift Detector) with a larger surface, as compared to
traditional models, and a geometry where the detector can be placed in close

38
contact to the sample, thus reducing the acquisition time and the detection limit. In
particular, the actual detector is a LDD (Large Drift Detector) with a 25 mm2 active
surface, 500 m thickness, and 135 eV energy resolution.. The instrument, equipped
with an Ag target, can operate with a voltage ranging between 6 and 50 kV, a
maximum current of 100 A, and a working distance 2 mm. Every acquisition is
made after several sequential individual measurements, using four different voltages
and three different filters, in order to optimize the signal of the sample in all the range
of the energy spectrum. The configuration used for the present measurements are:
main Al/Fe (40 kV); low Cu, 20 kV; High Mo (50 kV); light no filter (6 kV). The spectra
have been analysed by using the WinAxil software.
UV-Vis-NIR FORS spectra in the 350-2200 nm range were performed by using the
single beam Zeiss MCS601 (200-1000 nm range) and MCS611 NIR 2.2WR (900-
2200 nm range) spectroanalysers. These two devices are hosted in a single and
transportable chassis ideal for in-situ analysis. The data acquisition range is 0.8
nm/pixel for 1024-elements silicon photodiode array detector (MCS601) and
approximately of 6.0 nm/pixel for the 256-elements InGaAs diode array detector
(MCS611 NIR 2.2WR). The radiation between 320-2700 nm, provided by a tungsten-
halogen lamp (module Model CLH500), is carried to the sample by bundle of optical
quartz fibres which also transport the reflected radiation into the detectors (8/8
geometry). The reflectance spectra were recorded on an area less than 1 mm in
diameter. As a reference, a 99% Spectralon diffuse reflectance standard is used.
For some spectra, a discontinuity, such as a sharp increase/decrease in reflectance,
can be observed at about 980 nm. This happens when the measurement transitions
between the two detectors. The acquisition time for each measurement is fractions of
second.About 20 different points have been selected on the sample in order to
analyse them with the three techniques. It is interesting to observe, incidentally, that
the different characters appearing in the scenes have been painted using different
pigments, in order to evidence the most important ones in a way that is immediately
visible to the observers eye. The present multi-methodological approach has been
of great help in identifying the artists materials. The identification of the pigments in
white, yellow, and brown areas was possible by looking at the FORS and XRF data.
The composition of the preparation layer has been identified thanks to XRF. All other
pigments have been identified thanks to Raman measurements and, when
applicable, confirmed by the other techniques. The pigments have been identified as
pertaining to the ones traditionally used for 17 th century Japanese paintings [Winter
2008].
Acknowledgements. The authors wish to acknowledge the cooperative attitude and

invaluable help of the Stibbert Museum staff.
References
Grazzi F, Bartoli L, Civita F, Zoppi M. Analytical and Bioanalytical Chemistry 2009; 395:
1961.
Grazzi F, Barzagli E, Civita F, Scherillo A, Zoppi M, Proceedings of 10th International
Conference on non-destructive investigations and microanalysis for the diagnostics and
conservation of cultural and environmental heritage 2011 ; in press.
Winter A, East Asian Paintings: Materials, Structures and Deterioration Mechanisms,
Archetype Publications, London, UK, 2008.

39
Raman analysis of 16th Century Wall paintings in the Basque
Country (Spain) assisted with DRIFTS and XRF
Mireia Irazola, Maitane Olivares, Kepa Castro, Maite Maguregui,

Irantzu Martinez-Arkarazo, Juan Manuel Madariaga
1
University of the Basque Country, Department of Analytical Chemistry P.O. Box 644
E-48080, Bilbao, Basque Country, mireia.irazola@gmail.com
The colour palette study as well as the preservation state of wall paintings is one of
the first steps in their restoration processes. The analysed works belong to two
churches located in Biscay (Basque Country, North of Spain), concretely, the San
Andres Church in Biaez and the San Juan Bautista Church in Axpe. The first one is
decorated with wall paintings circa 1535-1540, while the paintings of the second one
belong to the end of the 16 th century.
The wall paintings were characterised by non-invasive in situ techniques such as
Raman spectroscopy, Diffuse Reflection Infrared Spectroscopy (DRIFTS) and X-ray
Fluoresce (XRF). The Raman spectra were acquired by using a mobile BWTEK
InnoRam system equipped with a diode 785 nm laser and with the aid of a tripod
coupled to a 20x objective. In order to complete the information obtained, the
elemental composition was determined by handheld XRF (Oxford X-MET5100). The
DRIFT spectra were acquired with the handheld A2 Technologies Exoscan [1].
Afterwards, some microsamples were removed from the wall paintings and mounted
as cross sections in order to analyse he different layers. The cross sections were
prepared with an acrylic resin (cold embedding) followed by a careful polishing.
These samples were analysed with the Renishaw In Via spectrometer coupled to a
confocal microscope using a 514nm excitation laser. The use of this laser sometimes
is crucial, especially for the characterisation of green pigments.
In situ analysis performed with the mobile Raman spectrometer provided information
about most of the pigments found in both locations. On one hand, in the San Andres
Church, calcite (white colour), lead tin yellow type I, yellow iron oxide, vermilion
(red), carbon based pigments (black) and a mixture of red iron oxide and massicot
(orange colour) pigments were found. On the other hand, in San Juan Bautista
Church, pigments such as calcite (white colour), white lead, vermilion (red), carbon
based pigments (black), a mixture of vermilion, red lead and sometimes massicot
(orange) and a mixture of red and yellow iron oxides (brown) were found.
In order to evaluate the preservation state of the analysed wall paintings, it is
essential to characterise the nature of the degradation products. In the San Andres
Church, the most important salts determined by Raman spectroscopy were
potassium and calcium nitrate and ammonium sulphate. However, in the San Juan
Bautista Church evidences of the dehydration that is suffering the mortar (mixture of
calcite and gypsum) were seen after having corroborated the presence of the three
hydration states of calcium sulphate.
In order to determine the composition of the green pigments, elemental analyses by
means of XRF was required, due to the fact that the 785nm excitation laser did not
offer the best Raman scattering of such pigments. These analyses showed that
copper green pigments were presented in green areas. Besides, this technique also
provides information about the proportion of mixed pigments needed to obtain the
desired colour. In fact, the in situ XRF analysis shows semi-quantitative information
about the elemental composition of the wall painting. In San Juan Bautista Church,
for example, it was possible to determine the gradient of the composition in the

40
orange area being the vermilion in lower concentration than the red lead, probably
due to the high cost of the former.
The results obtained by the DRIFT spectra in San Andres Church showed the
presence of Paraloid B67 as a protection layer of the wall painting. In the San Juan
Bautista Church the presence of copper oxalate in the green pigments and the
evidences of the use of Paraloid B82 were the most important facts. The copper
oxalate found could also mean, as some author state [2], evidences of the original
pigment degradation.
In situ analysis of the non-altered green areas of the wall painting of San Andres
Church showed the presence of calcium oxalate dihydrate. Nevertheless, for the
study of the areas with possible modern repaintings or restorations, the performance
of cross sections was needed. During the study of such sections the presence of
phthalocyanine green was firstly determined. In the micro Raman measurements
performed on the cross sections from the San Juan Bautista Church, malachite was
identified as the original green pigment.
Portable spectroscopic techniques offered a whole vision of the wall paintings both,
the original and the decay components. However, in order to make an in depth study
and to characterise directly the green pigments with micro Raman spectroscopy, the
preparation of cross sections can be useful as a complementary technique in the
methodology.
Figure 1. Portable Raman analysis in the wall painting of San Andres Church
Acknowledgements. This work has been financially supported by the Basque

Country Governments Research Project CTP09-P04. Mireia Irazola is grateful to
Karrantza Council, Garbie Aja and Diocesan Museum of Bilbao (J.M. Cembellin).
References
[1] Maguregui M, Knuutinen U, Castro K, Madariaga J.M. Journal of Raman Spectroscopy

2010; 41, 1110.
[2] Castro K, Sarmiento A, Martinez-Arkarazo I, Madariaga J.M, Fernndez L.A, Analytical
Chemistry 2008; 80: 4103-4110

41
Raman spectroscopy analyses of Palaeolithic industry from
Guadalteba terrace river, Campillos (Guadalteba county,
Southern of Iberian Peninsula)
Susana Jorge-Villar1, Cristina Capel2, Vctor Hernndez2,

Javier Medianero3, Jos Ramos4, Gerd Weniger5, Salvador Domnguez-
Bella6, J. Linstaedter5, Pedro Cantalejo7, Mar Espejo7.
1
University of Burgos, rea de Geodinmica, C/ Villadiego s/n (Spain), Tel. +34
947258772, seju@ubu.es;susanajorgevillar@hotmail.com
2
University of Mlaga, Departamento de Qumica Fsica, Facultad de Ciencias,
Campus de Teatinos, s/n, 29071, Mlaga, (Spain).
3
Escuela Taller, Consorcio Guadalteba. Paseo de Pearrubia, s/n, 29320,
Campillos, Mlaga, (Spain).
4
University of Cdiz, rea de Prehistoria, Facultad de Filosofa y Letras, Avda.
Gmez Ulla, s/n, 11003, Cdiz, (Spain).
5
Stiftung Neanderthal Museum. Talstrasse, 300, D-40822 Mettman, (Germany).
6
University of Cdiz, Departamento de Ciencias de la Tierra, Campus Rio San
Pedro, 11510, Puerto Real, Cdiz (Spain).
7
Red Patrimonio Guadalteba, Consorcio Guadalteba, Paseo de Pearrubia, s/n,
29320, Campillos, Mlaga (Spain).
A variety of artefacts from Palaeolithic industry found in Mlaga (Guadalteba county),

Southern of Iberian Peninsula (figure 1), have been suitably selected for
spectroscopy analysis using both portable and benchtop Raman spectrometers. The
lithic manufactures were collected from a variety of ecosystems of the Gaudalteba
basin. A representative selection of lithic specimens for Raman monitoring was
made on the basis of their wide range of processing activities by different social
groups in the Middle-Upper Pleistocene .
Specimens were found in the terraces of the Guadalteba river, at around 368 altitude
meters; carbonated pebbles are the most common material, together, but in lower
proportion, quartzite, flint and even igneous fragments can also be found and form
the petrology of the quaternary formations [Medianero et al. 2011].
The lithic tools analysed comprise unifaceted and multifaceted instruments which
show colours that range between brown, yellowish, grey, black, white and pinkish;
they were made mainly by flint but quartzite and other rocks were also used. Almost
all specimens are partially covered by a patina or crusts (figure 2).
Both, lithic instruments and patinas were analysed using a portable Delta-nu
Inspector Raman spectrometer of 2.3 Kg weight, working at 758 nm laser
wavelength; spectra were collected using a Nuscope microscope attachment, which
have a 100x magnification objective. For laboratory analyses, a Bruker Senterra
Raman spectrometer, operating with 785, 633 and 532 nm laser excitations with
microscope attached was used; magnifications range between x20 and x40 and
x100. Laser power was chosen as lower as possible to avoid mineralogical changes,
particularly when iron oxides were analysed. Accumulations extend between 5 for
the portable spectrometer to 80 for dispersive Raman instrument to improve signal-
to-noise ratios.

42
Figure 1: situation of Guadalteba basin.
Figure 2: Palaeolithic tools showing patinas and crusts.
References
Medianero EJ, Ramos J, Palmqvist P, Weniger G, Riquelme JA, Espejo M, Cantalejo P,

Aranda A, Prez-Claros JA, Figueirido B, Espigares P, Ros-Montoya S, Torregrosa V.
Quaternary International 2011 in press
.

43
Investigation of a Group of Byzantine Ceramics from
Kuadas Kadkalesi/ Anaia by Using Raman Spectrometry
Burcu Krmz1, E.Hale Gktrk2, Philippe Colomban3, Lale Doer4,

Zeynep Mercangz4
1
Middle East Technical University Archaeometry Program 06531, Ankara (Turkey),
Tel. +90 3122103273, arkeoburcu@yahoo.com
2
Middle East Technical University Archaeometry Program and Department of
Chemistry 06531, Ankara (Turkey)
3
Laboratoire de Dynamique Interactions et Ractivit (LADIR), UMR 7075 CNRS,
Universit Pierre et Marie Curie, 94320 Thiais (France)
4
Ege University, Faculty of Letters Department of Art History, 35100 zmir (Turkey).
The glaze parts of a group of Zeuxippus type ware from Kuadas-Kadkalesi/ Anaia
have been analyzed by Raman spectrometry for their characterization. Kadkalesi
was a Byzantine fortress in Western Anatolia region of Turkey. It was associated
with the ancient city of Anaia, a significant harbour-town within the context of
medieval Mediterranean trade routes and an episcopacy center during the Late
Byzantine period. Kadkalesi seems to have been one of the important ceramic
production centers which had started to build up in Western Anatolia after the fall of
Constantinople in 1204 by the Fourth Crusaders. Excavations have been directed by
Prof. Zeynep Mercangz since 2001 and have yielded high quality glazed ceramics
of rich variety which were either locally produced or imported from other sites.
Zeuxippus ware is a specific type of Late Byzantine glazed pottery, getting its
definition from the baths of Zeuxippus located in the vicinity of the Hippodrome of
Constantinople. They were first recovered during the excavations in 1927. The main
characteristics of Zeuxippus ware are its fine dense red fabric, thin rimmed forms
and a superior type of glaze quality comparing to the other types of the Byzantine
glazed ware of the same period [Megaw, 1968]. The finds of Zeuxippus ware in
stanbul are called as genuine Zeuxippus ware. As the wares with similar
characteristics in forms and decorations, produced outside of stanbul are
considered within the concept of Zeuxippus ware family, the finds from Kuadas
Kadkalesi/ Anaia, dating to Late 12th-13th centuries, are defined as Zeuxippus type
ware. Anaia Zeuxippus type ware displays glaze colors with tones of yellow, orange,
brown and green and the decorations include usually sgraffito, incision and
champlev techniques. Zeuxippus type ware constitutes the most common type of
glazed pottery finds in the excavations of Kadkalesi/ Anaia. These ceramics were
also found in the state of unfinished pieces and defective productions suggesting
that their local production was carried out in Kadkalesi/ Anaia.
Raman spectrometry investigations show that Anaia Zeuxippus type ware glazes are
high-lead glazes. High intensity of the Boson peak and the Si-O stretching maxima of
the Raman spectra recorded at around 950 cm -1 indicate that the glazes all have
lead based compositions. Polymerization indexes of these glazes range from 0.02 to
0.05, also confirming the presence of high lead content. Raman spectra of most of
the samples display only the characteristic glass signature, which suggests that the
colors were achieved by the addition of coloring ions. In all the glazes labeled as
green, yellow and brown, the presence of Fe 2+ or Fe3+ species may be the source for
the observed colors.

44
The yellow glaze on one of the samples, displays peaks at 149, 330, 463 and 517
cm-1, which may be attributed to a solid solution of Naples yellow type of pigment.
This result seems interesting, since the use of Naples yellow type pigments, as a
colorant for vitreous materials, is known to be very rare between ancient times and
the 16th century. In addition to our findings, a new evidence found in the Byzantine
ceramics from the Republic of Macedonia, may also confirm that this pigment could
have been used during 12 th 14th centuries [Tanevska et al., 2009]. However, further
analyses are required to confirm the use of this synthetic pigment in the glazes of
Late Byzantine Kuadas Kadkalesi/ Anaia ceramics.
References
Megaw A.H.S. The Annual of the British School at Athens 1968; 63: 67.
Tanevska V, Colomban Ph, Minceva-Sukarova B, Grupce O. Journal of Raman
Spectroscopy 2009; 40:1240.

45
The first in situ micro-Raman spectroscopic analysis of
prehistoric cave art of Rouffignac St-Cernin, France
Sophia Lahlil1, Matthieu Lebon2, Colette Vignaud1, Ina Reiche1, Hlne

Rousselire 1, Lucile Beck1, Michel Menu1 and Frdric Plassard3
1
C2RMF-UMR171 Centre de Recherche et de Restauration des Muses de France,
14 quai Franois Mitterrand, Palais du Louvre Porte des Lions, 75001 Paris
(France), Tel. +33 140202491, sophia.lahlil@culture.gouv.fr
2
Musum National d'Histoire Naturelle, Dpartement de Prhistoire, 1 rue Ren
Panhard, 75013 Paris (France), lebon@mnhn.fr - UMR 7194
3
Grotte de Rouffignac, 24 580 Rouffignac-St-Cernin (France)
The first in situ micro-Raman spectroscopic study of prehistoric drawings found in

the cave of Rouffignac-Saint-Cernin (Dordogne, France) was carried out. Rouffignac
cave art, assigned to the Upper Palaeolithic period (Magdalenian), is constituted by
more than 250 drawings all made of black pigments including 158 mammoths. Until
now, destructive chemical analyses performed on one sample [1], as well as recent
micro X-ray fluorescence (-XRF) in situ analyses [2], have shown that the drawings
contain manganese oxides. Since no carbon as yet been found, no direct dating of
the drawings could be performed. This new study of Rouffignac cave using non-
destructive in situ micro-analyses aims at confirming or not the absence of carbon-
based drawings and at understanding the apparent homogeneity of the parietal
representations by the identification of the crystalline phases constituting the black
pigments. For the first time, the adaptability of portable equipment as well as the
feasibility of -Raman analyses in situ in a cave environment was tested. Results
obtained are compared to in situ -XRF and X-ray diffraction (XRD) microanalysis
performed in parallel in the same site [3]. Furthermore, in order to get clues on the
pigments provenance, reference samples of manganese oxides coming from
Rouffignac geographical area are analysed in the laboratory using -Raman and
Proton Induced X-ray emission (PIXE). We demonstrate that portable Raman
instrument is very useful to analyse non-destructively drawings in difficult conditions:
high humidity, various walls geometry, small amounts of material studied. During
three days of analyses, four different locations were analysed and more than sixty
data points were recorded. These preliminary results show that black manganese
oxides romanechite and pyrolusite are the most frequently used pigments. Carbon
and carotenoids have been found locally. Differences between the various figures
are highlighted and hypotheses about the drawings production are proposed.
Acknowledgements. This work has been financially supported by French Research

Agency (ANR) in the framework of the project Micro-Analyses and Dating of
Prehistoric Art in Archaeological Context (MADAPCA) coordinated by P. Paillet.
References
[1] Graziosi P., La Nature, Ed. Dunod, n3260, Paris, France, 1956.
[2] De Sanoit J, Chambellan D et Plassard F. Archosciences 2005, 29, 61.
[3] Beck L, Rousselire H, Castaing J, Lebon M, Duran A, Plassard F. Poster in
Archometrie 2011, Lige.

46
Recent advances for in-situ Raman sampling and combining
methods for artwork analysis
Elose Lancelot
HORIBA Scientific, 231 rue de Lille, 59650 Villeneuve dAscq (France),

Tel : +33(0)3 20 59 18 00, eloise.lancelot@horiba.com
Raman Spectroscopy is now a well established method for the characterization of

historical artefacts in the field of cultural heritage field. However analysis of these
artefacts can still present some difficulties including location, sample size and
fluorescence. New trends are evolving to overcome such problems: among them, the
use of multiple laser excitations to avoid fluorescence competition, the use of
portable systems for in-situ investigation and multi-technique approaches.
An example of a combined method approach will be illustrated with the recent study
carried out on King Henri IVs head. Indeed, his head was rediscovered very recently
and a group of scientists attempted to confirm its identification using multiple
scientific techniques including radiocarbon testing, embalming procedures and
spectroscopic analysis [Charlier et al]. HORIBA Scientific was involved in this
fascinating study and results obtained by X-Ray Micro Fluorescence and Raman
Spectroscopy will be presented .
Fig 1: Left lateral (A) and right lateral (B) view of the mummified head
The second part will focus on portable Raman systems that are dedicated for in-situ
analysis. Indeed, much effort has been applied to improve their compactness and
performance. A new compact, rugged and true confocal micro-Raman system, the
XploRA, allows micro Raman studies at different excitation wavelengths to be carried
out with an easily transportable unit. Moreover remote analyses are possible thanks
to efficient probes connected through fibres to the laser and the spectrometer. A new
compact in-situ probe providing sample visualization and Raman measurements
simultaneously, together with integrated piezo-electric movement has been recently
developed and will be presented. It allows detection of possible laser degradation
while running Raman analysis, thereby preventing irreversible damage to the
artefact.
References
Charlier P. et Al, Multidisciplinary medical identification of a French kings head (Henri IV),
BMJ 2010; 341:bmj.c6805

47
Provenance investigations of amber jewellery excavated in
Lower Silesia (Poland) and dated back to Early Iron Age
Barbara I. ydba-Kopczyska1, Bogusaw Gediga2,

Micha Sachanbiski3
1
University of Wroclaw, Faculty of Chemistry, F. Jilot-Curie 14, 50-383 Wroclaw
(Poland), Tel. +48 71 3757379, barl@wchuwr.pl
2
Polish Academy of Sciences, Institute of Archaeology and Ethnology, Wiezienna 6,
50-118 Wroclaw (Poland)
3
College of Handicraft and Management, Drobnera 5, 50-257 Wroclaw (Poland)
During recent archaeological excavations in Domaslaw, Lower Silesia south-

western region of Poland, there were discovered remains of various settlements.
Interestingly, the discovered remnants date from Neolithic to the beginnings of XXth
century, and when investigated properly, they can fill many gaps in archaeological
knowledge of the area.
The analysis of objects found in nearly 1000 burial chambers dated back to Early
Iron Age allowed archaeologists to verify the theories about influences of Hallstatt
culture on local community and its relationships with the Mediterranean culture
(especially with the Northern Italy).
The biggest group of excavated objects consists of pottery, some displaying a black
surface and other with a cream surface featuring patterns in black, red, and white.
These findings were subjected to the investigation focusing on identification of
pigment(s) and conditions of firing, performed by the Cultural Heritage Research
Laboratory at the University of Wroclaw.
Among the other findings there were discovered several unique and valuable pieces
of amber jewellery, including whole sets of amber beads of various shape and size
[Fig. 1]. The quality of amber and ceramic objects strongly suggests that the
community was affluent, with well-established contacts with Mediterranean region,
including Etruria.
Fig. 1 Amber jewellery from Domaslaw (Poland) dated back to Early Iron Age
Because of the excavation location and the relationships of the local community with
the Mediterranean culture, the provenance of found amber beads was questioned.
In the most probable scenario, the raw material used in the production of discovered
jewellery had originated from tertiary deposits of Baltic amber (succinite). However,
because of the localisation of archaeological site, two other possible amber deposits
have to be considered, one of them being amber from Lower Silesia (cenoman from
Boleslawiec, Poland) and the other originating from Moravia (valchovite and/or
neudorfite). Due to the unique character of the archaeological amber objects, the
48
Cultural Heritage Research Laboratory, the developer of the newest and, to our
knowledge, most comprehensive scientific database on amber and copal, has been
asked to determine the excavated jewellery origins [Fig. 2].
Fig.1 Raman spectra of Baltic amber A-succinite; B- white succinite
As a method of choice, the FT-Raman spectroscopy was implemented in the

investigations and all measurements were performed in situ [Edwards et al., 1996;
Edwards, 2010]. In the analysis, the Raman spectra of investigated amber beads
were compared with the reference spectra of original samples from the considered
deposits, as well as with the reference samples from the biggest deposit of amber in
the world (Kaliningrad, Russia).
The results indicate the Baltic origin of the investigated amber objects, thus
confirming the trade relations with the North, whereas the character of burial vessels
suggests contacts with the Mediterranean region. As for the moment, the origin of
investigated jewelry has been confirmed while the investigation of the pottery is still
in progress.
References
Edwards H. G.M., Farrell D. W., Spectrochimica Acta Part A 1996; 527, 1119
Edwards H. G.M., Analytical and Bioanalitycal Chemistry, 2010; 397, 2677

49
Analytica Pompeiana Universitatis Vasconicae: field
multianalytical analyses in Pompeii
Irantzu Martinez-Arkarazo1, Ulla Knuutinen2, Maite Maguregui3, Kepa

Castro1, Juan Manuel Madariaga1
1
University of the Basque Country, Dept. of Analytical Chemistry, P.O. Box 664, 48080
Bilbao, Spain. Tel. +34 946012707, juanmanuel.madariaga@ehu.es
2
Helsinki Metropolia University of Applied Sciences, Lummetie 2b, 01300 Vantaa, Finland.
3
University of the Basque Country, Dept. of Applied Chemistry, Faculty of Chemistry, P.O.
Box 1072, 20080 Donostia, Spain.
Pompeii, a Roman town-city located in south-western Italy, near the Bay of Naples,
is one of the most important archaeological sites of that period, proclaimed UNESCO
World Heritage Site in 1997. The eruption of the volcano Mount Vesuvius in 79 AD
buried Pompeii under several meters of ash and pumice, and it was lost for over
1,500 years before its accidental rediscovery in 1599, although most important
excavations were conducted only 150 years ago. Many majestic buildings richly
decorated with beautiful wall paintings survived to that catastrophe, but the exposure
of the excavated elements to the past and current polluted atmosphere has
irreversibly affected their state of conservation.
The aim of the Analytica Pompeiana Universitatis Vasconicae expedition (APUV
project, May 2010) was to describe the degradation pathways and new products
formed as a consequence of the exposure of wall and wall paintings to the
environment. Moreover, the conservation state of the wall paintings currently
exposed was compared with that of the wall paintings preserved in the Museo
Archeologico Nazionale di Napoli (MANN) since late 19th century. The work was
done in cooperation with the EPUH (Expeditio Pompeiana Universitatis
Helsingiensis) research team and site study was authorized by the Soprintendenza
Speciale per i Beni Archeologici di Napoli e Pompeii. The analyses were focussed in
the study of mortars and wall paintings from two houses of the Insula IX, Regio 3:
Marcus Lucretius House (IX 3,5/24) and House IX 3, 1-2 (see Figure 1).
Figure 1: (a) In situ analysis on a wall painting in Marcus Lucretius House by means of portable Raman
spectroscopy and (b) a detail of Raman and handheld ED-XRF spectrometers during
measurements in the National Archaeology Museum of Naples (MANN).
Three handheld spectrometers were taken to the field. Raman analysis was done
using a innoRam (B&WTEKINC) spectrometer mounted on a tripod with a X-Y-Z axis
motorized stage (spatial resolution of 1 micron per electrical pulse, Raytest); the
Raman microprobe and a micro-video camera are set on top of the tripod to focus on
the specific pigment or plaster grain; the spectrometer is provided with a 785 nm
excitation laser and a 20X long-distance lens was used to collect spectra. Infrared
50
analyses were performed using an Exoscan handheld FTIR with a diffuse reflectance
sampling head. Elemental analyses were carried out by an energy-dispersive X-ray
fluorescence spectrometer (EDXRF), Innov-X Alpha Series. The combination of the
three analytical techniques showed a satisfactory performance. To properly interpret
the Raman spectra of the in situ measurements, the interferences related to the
sunlight must be taken into account. A group of Raman bands with variable
intensities were systematically obtained in outdoor measurements: sharp and well
defined bands at 578, 964, 1025, 1187 and 1609 cm-1 almost always occurring, and
some band groups in the ranges 425-800, 1500-2000 and 2000-2500 cm-1. Such
problem was not observed during indoor analyses.
Figure 2: Raman spectra of (a) sunlight signals together with calcite Raman bands (b)
mirabilite (Na2SO410H2O) appearing as efflorescence on a wall from Marcus Lucretius
House.
Diverse decay products such as sulphates (mirabillite, thernardite, gypsum) and

calcium nitrate (nitrocalcite) were found in the most deteriorated walls and wall
paintings. The occurrence of the cited salts indicates that acid aerosols (SO 2, NOX,
etc.) resulted from surrounding urban, industry and harbour activities reach the
archaeological site and attack the porous supports. Those decay products (partially
soluble salts) coming mainly from the transformation of calcite (CaCO 3), which is the
main component of plasters and/or binder of the polychromy, can dissolve by the
effect of rainwater. The main consequences are pigment and even support loss,
which is in fact visible nowadays in the walls of both studied houses. On the
contrary, wall painting pieces preserved in the museum (MANN) present a better
state of conservation. The cycle (acid attack to form soluble salts)-(rainwater
dissolution), repeated several times in a year, can be considered the responsible for
the observed lost of carbonate in wall paintings (binder) and walls (plaster). Apart
from the formation of sulphates and nitrates, degradation pathways of original
pigments were established as well. Furthermore, some biodeterioration evidences
such as calcium oxalate presence, orange-brown biofilms with high carotenoid
content, etc. were also found [Maguregui et al. 2010].
Acknowledgements. This work was financially supported by the Basque Government
through the Environmental Analytical Chemistry project (ref. IT-245-07), the Spanish
Government (MICINN) through IMDICOGU project (ref. BIA2008-06592) and the
Accompanying Action APUV 2010 (ref. CTQ2010-10820-E).
References
Maguregui M, Knuutinen U, Castro K, Martinez-Arkarazo I, Madariaga JM, in Vlek J, Groot
C and Hughes JJ (Editors), Historic Mortars and RILEM TC 203-RHM Final Workshop
HMC2010, RILEM Publications S.A.R.L., Bagneux, France, 2010, p. 527-536.

51
The Use of Raman Spectroscopy for Forensic Paint Analysis
Genevive Massonnet1, Cyril Muehlethaler1, Patrick Buzzini2

1
University of Lausanne, School of Forensic Science, UNIL Sorge, Batochime, 1015
Lausanne (Switzerland), Tel. +41 21 6924600, genevieve.massonnet@unil.ch
2
University of West Virginia, Forensic & Investigative Program, 304 Oglebay Hall,
1600 University Ave, P.O. Box 6121, Morgantown, WV 26506-6121.
This presentation will illustrate the work of the authors concerning the use of Raman
spectroscopy for paint analysis in a forensic context. Raman spectroscopy is now
established as one of the analytical methods used for the forensic examination of
paints which includes cases like traffic accidents, vandalism and graffiti.
The authors have carried out several population and market studies on automotive
paints [Massonnet and Stoecklein, 1999], spray paints [Buzzini and Massonnet,
2004] and domestic paints [Muehlethaler et al., 2011] encountered in forensic cases.
The aims of these surveys are to establish the pigment variety used for a given paint
set of a similar colour. The Raman results were compared to the one obtained with
more conventional techniques like infrared spectroscopy (FTIR) in terms of paint
characterization and discrimination. Raman databases were created in order to
provide intelligence to the justice system and to help assessing the evidential value
of the evidence based on frequency of occurrence of a given analytical result. This
presentation will illustrate the use of these surveys in two different cases (graffiti and
vandalism) to provide either intelligence or discuss the evidential value of the
findings.
Over the last years, we encountered several cases were Raman spectroscopy was
found to be the best technique for the in-situ analyses of contact traces [Buzzini et
al., 2006] and examples will be shown in this presentation. The ease of sample
preparation means that the Raman technique can be used to rapidly discriminate
between different paints or traces. Analysis of such samples by other techniques
such as infrared would require that each trace will be meticulously scraped and
analysed. This is a time consuming exercise and the precious (possibly unique)
sample can be damaged or contaminated during this procedure.
Finally, there is a need of a more robust and systematic approach to classify and
compare a large set of Raman spectra. Multivariate statistical analysis is a powerful
tool to help the forensic scientists for identification and interpretative purposes as it
allows objective comparisons of the spectra. This methodology is also applicable, by
analogy, to comparisons involving smaller data sets, like comparing replicates from
an unknown trace with one or a few comparison materials. This situation is by far
more encountered by criminalists in case works and chemometrics can provide
objective basis to help dealing with such situations [Muehlethaler et al., 2011].
References
Buzzini P., Massonnet G. Science & Justice 2004; 44(3): 123-131.

Buzzini P., Massonnet G., Monard Sermier F. Journal of Raman Spectroscopy 2006; 37(9):
922-931.
Massonnet G., Stoecklein W. Science & Justice 1999; 39 : 181-187.
Muehlethaler C., Massonnet G., Esseiva P. Forensic Science International 2011 in press.

52
The colour palette of the Roman Villa at Piazza Armerina in
Sicily
Bartolomeo Megna1, Giovanni Rizzo1 and Laura Ercoli1

1
Universit of Palermo, Dipartimento di Ingegneria Civile, Ambientale e
Aerospaziale, La.Ma.R.C. Laboratory of Materials for Restoration and Conservation,
Viale delle Scienze ed. 9, 90128 Palermo (Italy), Tel. +39 09123863750,
bartolomeo.megna@unipa.it
The Roman villa at Piazza Armerina in Sicily was included in the UNESCO list of
world heritage due to its magnificent mosaic floors [Carandini, 1982]. Only a few
years ago due attention has been paid to the paintings, which decorate the walls
with a varied palette matching the mosaic floors. Every wall, both indoor and
outdoor, is decorated with subjects related to the use of the rooms or with patterns
imitating the precious stones of the opus sectile in the Basilica [Finotti, Zandonai
2005; Rizzo et al. 2007].
In a previous work [Megna et al. 2010] the mineralogical petrographic study of
sinters, mortars and plasters was performed by XR diffractometry and by optical
microscopy using polarized light through thin sections. The colours, rich in tone and
gradation, were catalogued and the paint technique was investigated.
In this work the pigments were analysed by micro-Raman spectroscopy, using a
Renishaw INVIA Raman microscope equipped with two laser sources, 633 nm and
532 nm wavelength respectively, both transmitting to the sample a power of 1 mW.
The detector was a CCD with 1100 pixels cooled by Peltier effect. The spectral
range varied, but in all cases was extended down to 200 cm -1.
The following colours were analyzed: pale and dark blue, white, dark blue (pale blue
plus a black veil), brown, yellow, black, pink, pale and dark red, pale and dark green,
pomace, reddish brown. For each sample both the micrograph of the analyzed area
and the Raman spectra are reported, as shown in the figure for sample 05PA. The
results indicate that many colours were obtained by mixing in different proportions
five basic colours.
The results will afford an unpublished view of both materials and techniques used in
the wall paintings of the Villa at Piazza Armerina, giving the opportunity for
interesting comparison with others archaeological sites under study, such as the
hypogeum of Crispia Salvia at Marsala, Sicily.
Sample 05PA Bordeaux. Micrograph of the analyzed area

53
30000
25000
20000
Co u n ts
15000
10000
5000
500 1000 1500 2000
Raman shift / cm-1
Sample 05PA Bordeaux. The pigment is identified as Hematite
Aknowledgements. Thanks are due to Alto Commissariato per La Villa Romana del
Casale di Piazza Armerina for the financial support to this study and to the Centro
Regionale per la Progettazione e il Restauro of Sicily.
References
Carandini A., Ricci A., De Vos M., Filosofiana. La villa di Piazza Armerina, S. F. Flaccovio
editore, Palermo, 1982
Rizzo G., D'Agostino F., Megna B., Parlapiano M., Ercoli L., 2007, Indagini chimico fisiche
sulle malte di allettamento e di finitura, in Progetto di recupero e conservazione della villa
romana del Casale di Piazza Armerina, I Grandi Restauri n. 12/1, a cura di E. Lentini, Centro
Regionale per la Progettazione ed il Restauro, ISBN 88-88559-79-7, 112-115
Baraldi P., Baraldi C., Curina R., Tassi L., Zannini P., Vibrational Spectroscopy, 43 (2007),
420426
Finotti F., Zandonai F. I colori degli affreschi della Villa Romana di Isera, Ann. Mus. Civ.
Rovereto, Sez.: Arch., St., Sc. Nat., Vol. 21 (2005), 137-152
Megna B., Rizzo G., Ercoli L. (2010) Mortars and Plasters under the Mosaics and the Wall
Paintings of the Roman Villa at Piazza Armerina, Sicily Historic Mortars and RILEM TC 203-
RHM Final Workshop HMC2010 Proceedings of the 2nd Conference and of the Final
Workshop of RILEM TC 203-RHM, e-ISBN: 978-2-35158-112-4, pp.275-283

54
Investigation of polychrome medieval sculptures with a
mobile Raman microprobe
Jacqueline Menzel, Christoph Herm
Dresden Academy of Fine Arts, Laboratory of Archeometry, Gntzstr. 34, 01307

Dresden (Germany), Tel. +49 (0) 351 44022106, menzel@serv1.hfbk-dresden.de
In situ analyses with mobile Raman microprobes have been showing a remarkable
increase in the last years. The identification of pigments from mural paintings,
illuminated manuscripts or the determination of minerals have already been
described in the literature [Vandenabeele et al., 2005; Bersani et al., 2006; Ziemann,
2006]. In Naumburg Cathedral (Germany) a mobile Raman microprobe was applied
to identify the pigments and supplements of the polychrome medieval stone
sculptures (13th century) located in the west choir and the reliefs at the west rood
screen. Since there are several coloured layers from different centuries, the
interdisciplinary collaboration with the conservators proved to be essential, especially
for preselection and documentation of measuring points.
The Raman measurements on the surface of the sculptures in Naumburg Cathedral

needed installation of a scaffold because of the height of about 3.5 metres above the
floor. The analyses were carried out with the portable Raman microscope XploRA
(HORIBA Jobin Yvon) equipped with a 785 nm diode laser. The appropriate fibre-
optic microprobe head (Vis-HEAD) is fitted with a video camera to select the desired
point of measurement (Figure 1). The microprobe was mounted on a custom-made
xyz microscopic stage which was attached to a heavy-duty stand designed for a
surgical stereo microscope. The exposure time and number of scans was adapted to
the layer and its condition. Collecting spectra with satisfying S/N ratio from black
layers demanded exposure times up to 20 seconds, thus one whole measurement
with 30 scans lasted about 9 minutes. By comparing the measured Raman spectra
to spectra from both published and own databases, inorganic pigments were
identified definitely.
Figure 1: Fibre-optic head at the west rood screen
On-site several pigments of the medieval colour palette were identified using the
mobile Raman microprobe: vermilion, red lead, lead white, lead-tin yellow and
carbon black. Besides paints of a single pigment also mixtures of two components
55
like lead white and vermilion for flesh colour were established (Figure 2).
Furthermore, gypsum was found to be applied as filler and supplement of the original
stone substrate of the sculptures.
Figure 2: Raman spectrum of vermilion and lead white used for flesh colour. V=vermilion,
L=lead white
Due to absorption of the red laser radiation, green and blue pigments did not result
in distinct Raman spectra using the mobile Raman microprobe. Therefore samples
had to be taken by the conservators to allow analyses in the laboratory. Mainly on
cross sections more pigments can be identified, e.g. using the green laser (532 nm)
attached to the XploRA Raman microscope.
The mobile Raman spectroscopy provides - like other portable methods - the
advantage to assay cultural heritage and artworks in situ without contact or
destruction. The investigation of pigments of polychrome stone sculptures in situ in
Naumburg Cathedral described here, represents a new application for Raman
microprobes.
Complementary analytical techniques like portable X-ray fluorescence and SEM-
EDX will be used to identify artistic materials on the sculptures which are not
susceptible to Raman spectroscopy like metal foils and lake pigments.
Acknowledgements. This work is part of the interdisciplinary postgraduate research

program Naumburg Kolleg funded by the Volkswagen Foundation.
References
Bersani D, Lottici PP, Vignali F, Zanichelli G. Journal of Raman Spectroscopy 2006; 37:
1012.
Vandenbeele P, Lambert K, Matthys S, Schudel W, Bergmans A, Moens L. Anal Bioanal
Chem 2005; 383:707.
Ziemann MA. Journal of Raman Spectroscopy 2006; 37: 1019.

56
Micro-Raman study of Medieval Cistercian 12th century
manuscripts: Santa Maria de Alcobaa, Portugal
Vnia S. F. Muralha1, Catarina Miguel2, Maria Joo Melo2,3

1
VICARTE (Glass and Ceramics for Art) Research unit, Faculdade de Cincias e
Tecnologia,Universidade Nova de Lisboa, 2829-516, Caparica, Portugal.
solange@fct.unl.pt
2
REQUIMTE-CQFB - Faculdade de Cincias e Tecnologia, Universidade Nova de
Lisboa, Monte da Caparica, 2829-516 Caparica, Portugal.
3
Conservation and Restoration Department, Faculdade de Cincias e
Tecnologia,Universidade Nova de Lisboa, 2829-te516, Caparica, Portugal
Santa Maria de Alcobaa Monastery, a Cistercian monastery was established in

1153, in the year of St. Bernard of Clairvaux death. Nevertheless, the manuscript
production in Santa Maria de Alcobaa Monastery only began in 1179. From the ca.
160 manuscripts produced during the late 12th -early 13th century, a set of fourteen
manuscripts were selected for characterize the medieval colour palette of this
scriptorium. Colour paints were fully characterized by Raman microscopy (-RM),
infrared spectroscopy (-FTIR) and micro X-ray fluorescence (-EDXRF).
The Alcobaa collection shows consistently the use of pink and grey colour paints,
mostly achieved by mixing vermilion with white lead, and carbon black with white
lead. Occasionally, this grey colour is also due to a mixture of indigo with white lead.
Lazurite was the chosen pigment for the blue colour, being ubiquitous in the studied
collection. Azurite was only found in one manuscript (Alcobaa 433). The green
colour is defined as a bottle-green (a copper based pigment), commonly seen in
Portuguese Medieval manuscripts [Miguel et al, 2010].
-FTIR determined that the pigments were applied in a proteinaceous binding media.
The manuscripts confirm a very good state of conservation, with exception of the
bottle-green colour, evidencing loss of cohesion and adhesion to the support.
Another sign of pigment degradation is the darkening of white lead based paints in
Alcobaa 249 and Alcobaa 446. Further analyses have to be performed but
evidence so far suggests a degradation of white lead to galena, a lead sulphide
(PbS).[ Miguel et al, 2009]. The causes that may lead to the darkening of white lead
in these tow codices will be discussed, bearing in mind that white lead was
extensively applied for brightness effect and that no sign of degradation was
observed on those cases.
This work follows a project on Portuguese Medieval illuminations and the study of
colour in the Portuguese context.

57
Acknowledgements: This work has been financially supported by FCT-MCTES under
the projects PTDC/EAT/65445/2006 and PTDC/EAT-EAT/104930/2008. Catarina
Miguel would like to thank FCT-MCTES for a PhD grant (SFRH/BD/44374/2008).
The authors would also like to thank the staff and director of Biblioteca Nacional de
Portugal for their generous support and collaboration.
References
Miguel C, Claro A., Lopes J.A. and Melo M.J., in Hermen E. and Townsend JH (editors),
Sources and Serendipity - Testimonies of Artists' Practice, Archetype, UK, 2010, p. 33.
Miguel C, Claro A., Gonalves A.P., Muralha V.S.F., Melo M.J., Journal of Raman

58
Degradation potential of particulate matter: A Micro-Raman
spectroscopy study at the Alhambra.
Sanja Potgieter-Vermaak1,2, Benjamin Horemans3, Willemien Anaf3,

Velichka Kontozova3, Carolina Cardell4, and Rene Van Grieken3
1
Manchester Metropolitan University, Division of Chemistry & Environmental
Science, Chester Street, M1 5GD, Manchester, United Kingdom, Tel. +44
1612471220, s.potgieter@mmu.ac.uk.
2
Molecular Science Institute, School of Chemistry, University of the Witwatersrand,
Private Bag X3, PO Wits, 2050 South Africa.,
3
Department of Chemistry, University of Antwerp, Universiteitsplein 1, 2610 Antwerp,
Belgium
4
Department of Mineralogy and Petrology, University of Granada, Campus
Fuentenueva s/n, 18071 Granada, Spain
It is well-known that the fate of airborne particulate matter (APM) is not only
determined by its mass and size distribution, but also by its chemical composition.
Moreover, effective preventative conservation can only be practised when the
chemical composition and structure of these particles are known, so as to estimate
its degradation potential. A limited number of articles have been published on the
sequential application of elemental and molecular techniques applied to APM in
environments of cultural heritage importance [Worobiec et al. 2006; Godoi et al.
2008; Potgieter-Vermaak et al. 2010] and most of it concerned indoor environments.
As part of an air quality investigation (Assessment of atmospheric environmental
risks related to artworks in the UNESCO World Cultural Heritage complex of
Alhambra (Granada, Spain) with the emphasis on the analysis of a unique collection
of authentic pigment samples) the APM in the Alhambra was collected and
characterised, to determine its potential degradation profile.
The Alhambra represents one of
the grandest and finest
examples of Islamic art and
architecture from the Middle
Ages still standing in the
Western world. The Alhambra
was a fortified palatial citadel
whose construction took from
the 11th to the 15th century,
with the most outstanding
palaces built during the Nasrid
dynasty (12381492). The 'Hall
of the Ambassadors' is the main
hall of the Comares palace Fig. 1. Patio in the Comares palace viewing at the
(Figure 1), and although the 2.5 entrance of the Hall of the Ambassadors
m thick walls prevent the room
from heating and keep it relatively cool during a hot summer day, the open entrance
and windows (covered with wooden drawn works) do not protect the interior from
ambient air. Polychromatic stucco, mosaic tiling and a wooden ceiling describes the
splendour of this hall. Two sets of APM were collected from this room, representing
different meteorological conditions. The use of a 7-stage May-type cascade impactor
enabled collection of size segregated particles where a 50% cut-off efficiency

59
ensured the delivery of particles with an equivalent aerodynamic diameter (EAD) of
0.25, 0.5, 1, 2, 4, 8, and 16 m, respectively on a Ag substrate. Sampling time was
optimised to ensure the collection of single particles. These were analysed by means
of micro-Raman spectroscopy (MRS) and electron probe micro analysis with X-ray
detection through an ultra-thin window under liquid nitrogen temperatures (EPXMA).
The Raman data indicated the presence of (NH4)2SO4 Stage 5 - Lapis Lazuli (NH4)2SO4+NaNO3
various mixed salts of acidic nature, especially 976
1050
1043
in the finer fraction, some of which are
illustrated in Figure 2. This was confirmed by
Raman Intensity
the results obtained from the single particle
analysis done by automated EPXMA, and the
fraction containing acidic salts could be as high
as 50%. It is well-known that ammonium
sulphate specifically is of concern, as it attacks 200 300 400 500 600 700
Wavenumber (cm-1)
800 900 1000 1100 1200
the varnish layers of works of art

[Brimblecomb, 1990]. Apart from the potential acid attack, the soiling due to
carbonaceous matter deposition would be a real concern. Soot was identified by
MRS and EPXMA in all size fractions (reaching values of up to 55% in the finest
fraction during the summer campaign) and was often intertwined with soluble
inorganic salts. The identification of brightly coloured particles is evidence of possible
on-going degradation of the pigments present in the building. These proved to be
mostly Lapis Lazuli as illustrated in Figure 2.
Acknowledgements. The authors thank the research group RNM-179 (CICE, JA,
Spain) and the Patronato de la Alhambra y Generalife for making this research
possible.
References
Brimblecomb P. Atmospheric Environment 1990 ; 24B : 1 8.

Godoi, RHM, Potgieter-Vermaak, S Godoi, AFL, Stranger, M, Van Grieken, R. X-Ray
Spectrometry 2008; 37:298-303.
Potgieter-Vermaak S, Worobiec A, Darchuk L, Van Grieken R, Micro Raman Spectroscopy
for the analysis of environmental particles, in Fundamentals and Applications in Aerosol
Spectroscopy, Taylor and Francis Ed Ruth Signorell, Jonathan P Reid, 2010 ISBN:
9781420085617.
Worobiec A, Stefaniak EA, Kontozova V, Samek L, Karaszkiewicz, van Meel K, Van Grieken
R. e-Preservation Science 2006; 3:63-68.

60
Comparative study of surface-enhanced Raman scattering
(SERS) methodologies for the detection of organic colorants
in cultural heritage investigations
Federica Pozzi1,2, Marco Leona1
1
Department of Scientific Research, The Metropolitan Museum of Art, 1000 Fifth
Avenue, New York, NY 10028 (USA). Tel. +1-2126502724,
Federica.Pozzi@metmuseum.org
2
Dipartimento di Chimica Inorganica, Metallorganica e Analitica Lamberto
Malatesta, Universit degli Studi di Milano, via G. Venezian 21, 20133 Milano (Italy).
Tel. +39-0250314413, federica.pozzi@unimi.it
In recent years, the introduction of surface-enhanced Raman spectroscopy (SERS)

in the field of cultural heritage investigations has significantly improved the
possibilities of successfully identifying organic colorants, a class of artists materials
that has been widely used in textile dyeing, paintings and other polychrome works of
art since antiquity. Over the years, a number of SERS methodologies have been
developed by different research groups to be applied to the analysis of dyes,
including many types of metal substrates as well as several procedures of sample
pre-treatment. In the present work, a comparative study has been carried out to shed
light on the main advantages and disadvantages of the most relevant SERS
approaches recently introduced in art analysis, namely SERS on Ag nanoparticles
produced by laser photoreduction of AgNO3 solutions [Caamares et al., 2007] and
SERS on Ag colloids synthesized by microwave-supported glucose reduction of
silver sulfate in the presence of sodium citrate as a capping agent [Leona, 2009].
Experiments on citrate/glucose microwave nanoparticles were conducted both in
association with an extractionless HF gas-solid hydrolysis procedure [Leona et al.,
2006] and without any pre-treatment [Brosseau et al., 2009]. The performances of
such methodologies for the ultrasensitive detection of a number of colorants from
different supports were evaluated. Results obtained from pure dyes were compared
with those achieved on
actual samples, i.e. fragments from dyed paper and textiles, as well as lakes
and glazes from several works of art. Extraction in HF vapours followed by the
deposition of Ag citrate/glucose microwave nanoparticles on top of the sample was
found in most cases to be the easiest and most rapid way to obtain high quality
spectra.
Indeed, such approach allowed us to record well resolved and extremely
reproducible SERS spectra with high enhancement factors in less than 10 minutes
for the great majority of samples here examined, leading to achieve, for colorants on
different supports, a reliable fingerprint within very short times of analysis.
References
Caamares MV, Garcia-Ramos JV, Gmez-Varga JD, Domingo C, Sanchez-Cortes S.

Langmuir 2007; 23: 5210.
Leona M. Proceedings of the National Academy of Sciences 2009; 106: 14757.
Leona M, Stenger J, Ferloni E. Journal of Raman Spectroscopy 2006; 37: 981.
Brosseau CL, Gambardella A, Casadio F, Grzywacz CM, Wouters J, Van Duyne RP.
Analytical Chemistry 2009; 81: 3056.

61
Tandem technique of a standard Raman spectroscopy and
man-portable LIBSpectrometer as a routine tool at present for
pigment identification
Sergei Raikov1, Elena Dovnar-Zapolskaya2 and Vasiliy Kiris1

1
Institute of Physics, National Academy of Sciences of Belarus, 68 Nezavisimosti
Ave, 220072 Minsk, Belarus, sergeiraikov@tut.by
2
Institute of Art, Ethnography and Folklore, National Academy of Sciences of
Belarus, 1/2 Surganov Str., 220072 Minsk, Belarus
The optical Raman and laser-induced breakdown spectroscopes, the rapid

componential analysis techniques, which are applicable in situ and are almost non-
destructive, offer a potential alternative to other optical spectroscopic, mass
spectrometric, or X-ray techniques.
The standard Raman spectra have been recorded with the modified spectrometer
SpectraPro-500i (Acton, USA). The excitation laser was Nd:YAG with wavelength of
the second harmonic of 532 nm and the angle of detection was of 180. The
scattering radiation after the transmission trough the holographic filter has been
directed on the grating (600 lines/mm) and the Raman spectra has been recorded by
the cooled CCD detector.
The fundamental (1.06 m) or the second (0.53 m) harmonic of a nanosecond Q-
switched Nd:YAG laser with a pulse duration of 6-8 ns and 10-Hz pulse repetition
rate is employed in our LIBS experiments. The laser used (Lotis, Belarus) is an
improved version with variable reflectivity mirrors. Such variant provides a high
stability of the emitted radiation. Besides, it gives excellent harmonic conversion
efficiency due to an increased spatial uniformity of the output beam, a low
divergence and a short pulse. The light emitted from the vertically expanding plasma
plume is imaged (1:1) onto the horizontal entrance slit of a compact spectrograph.
The spectrum is recorded with the help of the optical multichannel analyzer with a
linear CCD detector.
Both techniques have been successfully applied for the pigment material analysis
from the medieval painting of unknown artist.
This recently founded painting represents the very important historical event in the
history of Belarus and Poland. Only the combination of both techniques has provided
the exact determination of all pigments from the painting.

62
Micro-Raman and GC/MS analysis of pigments and binders in
the 19th c. wall paintings in three churches from
Republic of Macedonia
Lidija Robeva ukovska1, Biljana Mineva-ukarova2, Anna Lluveras3,

Maria Perla Colombini3 and Irena Nastova2
1
National Conservation Centre, Central Chemical Laboratory, Evlija elebija b.b.,
1000 Skopje, Republic of Macedonia; + 389-70-227-052; e-mail:
lidija2603@gmail.com;
2
Institute of Chemistry, Faculty of Natural Sciences & Mathematics, Ss Cyril &
Methodius University, Arhimedova 5, POB 162, 1001 Skopje, Republic of
Macedonia;
+389-70-226-787; biljanam@pmf.ukim.mk
3
Laboratory of Chemical Science for Safeguarding the Cultural Heritage,
Department of Chemistry and Industrial Chemistry, University of Pisa, Via
Risorgimento 35, 56126 Pisa, Italy
Micro-Raman spectroscopy, Pyrolysis Gas Chromatography-Mass Spectrometry

(Py/GC/MS) and Chromatography-Mass Spectrometry (GC/MS) were applied for the
characterization of pigments and binders used in the wall paintings ascribed to the
works of the prominent 19th century Macedonian iconographer, Dicho Zograf. During
the mid of the 19th century he and his co-workers painted nearly 2000 religious
paintings (wall paintings, icons, reliquaries and pennants) not only in many orthodox
churches and monasteries in todays Republic of Macedonia, but also in the
neighbouring countries, like Serbia and Bulgaria [Grozdanov, 2004].
Dicho Zograph is known for his rich pallet of pigments and vivid colours in his sacral
paintings. He is also known for his Painters Manual documented as Dichos
Hermeneia (written in 1851), where guidelines on manufacturing pigments, binders
and other painting materials concerning traditional iconography are given. However,
it should be noted that despite numerous works left by Dicho Zograph and his co-
workers, there is a lack of experimental data about the materials used by this
creative 19th c. painter.
The purpose of this micro-Raman and GC/MS analysis is to characterize the pallet of
pigments and the origin of binders used in the work of this iconographer and/or his
co-workers. Bearing in mind that there is written evidence about the use of pigments
and binders by Dicho Zograph, one of the goals was to know if they correspond to
the actual applied once.
Micro-Raman spectra were recorded on LabRAM300 (Horiba Jobin Yvon) with 633
nm laser line and a resolution 3 cm-1. A 6890N GC System Gas Chromatograph
(Agilent Technologies, Palo Alto, CA, USA), coupled with a 5975 Mass Selective
Detector (Agilent Technologies, Palo Alto, CA, USA) single quadrupole mass
spectrometer, equipped with a PTV injector was used for GC/MS analysis. Finally,
Py/GC/MS analysis were performed by means of a pyroprobe CDS Analytical Inc.
5000 Series (Oxford, USA) coupled on-line with the injection port of a 6890N GC
System Gas Chromatograph (Agilent Technologies, Palo Alto, CA, USA), coupled
with a 5973 Mass Selective Detector (Agilent Technologies, Palo Alto, CA, USA)
single quadrupole mass spectrometer, equipped with split/splitless injector
[Bonaduce, Andreotti, 2009].
Among numerous works attributed to Dicho Zograph, wall paintings from three
churches in the Western part of todays Republic of Macedonia: (1) St. George the
Victorious church, in the village of Rajica; (2) St. Peter and Paul church, in the

63
village of Tresone and (3) St. Ilija church, in the village of Stene have been
selected for pigment and binder analysis. These churches were known to be
decorated by Dicho Zograph and his co-workers, between 1844 and 1866
[Grozdanov, 2004].
A rich palette of pigments, both natural/mineral and synthetic were identified by

micro-Raman spectroscopy. A summary of the results on pigments are presented on
Table 1.
Table 1. Pigments identified by micro-Raman analysis in the 19 c. wall paintings.
St. Peter and Paul St.George Victorious St. Ilija

Red ochre
Red ochre Red ochre
RED Vermilion
Vermilion Lead red
Lead red
Massicot Massicot
YELLOW/ Chrome
Orpiment Mars yellow*
ORANGE yellow deep
Chrome yellow deep Mars orange*
Azurite Azurite Azurite
BLUE
Lapis lazuli Lapis lazuli Lapis lazuli
Emerald green,
(1) Chrome green (Chrome Green earth Emerald
GREEN
Yellow+ Prussian blue) Hostasol green** green
(2) Orpiment+ Prussian blue
Carbon
BLACK Carbon black Carbon black
black
Lime white
WHITE Lime white Lime white
Anatase**
* The Raman spectra of some yellow/orange pigments could be related to the synthetic iron
pigments, Mars yellow and Mars orange, but this could not be confirmed, since many other
natural iron pigments give similar Raman spectra.
** Most probably due to previous conservation treatments during 1986/87.
Organic material analysis evidenced the use of mixtures of proteinaceous materials

(mainly animal glue and egg) with linseed oil and pine resin while sacharide
materials were excluded. Moreover, results open for a debate on the presence of a
synthetic material mixed with the natural ones.
A comparison between the pigments and binders identified in our spectroscopic and
chromatographic study and those suggested in Dichos Herminia (Painters Manual)
showed that some of the materials identified, both inorganic and organic ones, had
not been mentioned in the written source.
Data on pigments, binding materials and varnishes used by Dicho Zograph obtained
from Raman, Py/GC/MS and GC/MS will be presented in detail. Discussion on the
painting technique of the three churches studied and comparison with the written
source, Dichos Hermeneia will be also provided.
References
Bonaduce, I., Andreotti, A., Py-GC/MS of organic paint binders, in M.P. Colombini, F.
Modugno (Editors), Organic Mass Spectrometry in Art and Archaeology, John Wiley & Sons
Ltd, Chichester, UK, 2009, p. 303-326.
Grozdanov, C., in Umetnosta i kulturata na XIX vek vo Zapadna Makedonija, studii i prilozi -
MANU, Skopje, Republic of Macedonia, 2004, p. 5-15.

64
Spectroscopic investigation of artificial patinas on recent-
type bronze
Polonca Ropret1, 3, Tadeja Kosec2
1
Conservation Centre, Institute for the Protection of the Cultural heritage of Slovenia,
Poljanska 40, 1000 Ljubljana, Slovenia, Tel:+38612343118, polona.ropret@rescen.si
2
National Building and Civil Engineering Institute, Dimieva 12, 1000 Ljubljana,
Slovenia
3
Museum Conservation Institute, Smithsonian Institution, 4210 Silver Hill Rd.,
Suitland, MD 20746
Copper and its high copper alloys-bronze tend to form an oxide layer (patina) in
humid air. In unaggressive environments the natural patina protects copper and its
alloys from further corrosion processes. But aggressors in air may induce secondary
corrosion processes on patina. However, the bronze surface is rarely exposed to
environment without pre-treatment. Artists usually deliberately patinate bronze for
final visual effects. It is of great importance to study the patina changing mechanism
in order to follow its chemical changes and to predict the corrosion process in
advance. The aim of the present study is to follow transformation process of bronze
itself and patina as applied by artists, in different environments.
Green colour patina was chosen to be tested, namely green chloride and green
nitrate patina, applied over brown artists patina. Brown patina and patina that
developed on bronze are investigated as well. The Raman spectra are studied after
chemical patination, before and after exposing patina samples to climatic chamber
for 12 weeks and to acid rain for 35 days. The corrosion products of Preern statue-
Slovene national pride are studied and presented as well.
The structures of the patina and corrosion products are characterized by scanning
electron microscopy (SEM), Raman spectroscopy, and X-ray diffraction (XRD). The
composition of artificial brown patina, green chloride patina and green nitrate type
patina are given. After exposure to industrial chamber and urban acid rain the
corrosion products are changed. The end products of each patina are presented.

65
Micro Raman spectroscopy (MRS) and Energy dispersive X-
ray flourescence (EDXRF) analysis of pigments in the
Iberian
cemetery of Ttugi (Galera, Granada, Spain)
Alberto Snchez1, Jos Tun1 and Manuel Montejo2
1
University of Jan. Centro Andaluz de Arqueologa Ibrica. Campus Las
Lagunillas
s/n, Ed. C-6, 23071 Jan (Spain). Tel. +34 953213501, vizcaino@ujaen.es
2
University of Jan. Departamento de Qumica Fsica y Analtica. Campus Las
Lagunillas s/n, Ed. B-3, 23071 Jan (Spain).
Recent archaeological research on the Iberian cemetery of Tutugi (4th-3rd ct. bC), in
the administrative term of Galera (Granada, Spain), has granted access to a range of
materials revealing major features of Iberian culture. Despite past plundering, the
amount and quality of materials retrieved allow physico-chemical pigment analysis of
the decoration of a range of highly important archaeological items, both for their
location in a cemetery and their aesthetic value [Figure 1].
The only information available on pigments in the Iberian culture refers to domestic
ceramic [Parras et al., 2010] and the inside covering of burials [Parras et al., 2006].
This paper enlarges on the above by incorporating pigment studies of the decoration
of highly symbolic ceramic vessels, a burial urn and a glass paste vessel of three
burials of the cemetery of Tutugi.
Regarding the method, pigment study relied on the mineralogical and elemental
analysis using non-destructive spectroscopic techniques like micro Raman
spectroscopy (MRS) and Energy Dispersive X-Ray Microfluorescence (EDXRF).
These studies are used more and more frequently for research on archaeological
items for their advantages over other techniques: they operate on small samples, the
samples do not need previous processing, and its high spatial resolution allows
microscopic analysis of the sample, like heterogeneities in the matrix analysis. Joint
use of both techniques yields more information on the chemical composition of the
sample under study [Burgio et al., 2003; Smith et al., 2004; Vandenabeele et al.,
2007].
The results obtained separate the two ceramic vessels studied in a number of
respects. Thus, the pigment of the first was made with high clay content hematite
(1a), whereas the second applied a mixture of cinnabar and hematite on a gypsum
base (1b).
The pigments used for the urn (1c) were made with hematite (red), gypsum (white)
and amorphous vegetal carbon (black). The EDXRF revealed a much higher
concentration of Fe in the red pigment than in the ceramic vessel.
In the glass paste vessel (1d), bindhemite forms the yellow pigment (Naples Yellow)
[Bouchard et al., 2007] and Egyptian blue most likely forms the blue pigment, as
suggested by the concentration of Ca, Si and Cu revealed by the EDXRF.
Overall, joint use of MRS and EDXRF provides highly valuable data on the
processes used for pigment-making, on the use of certain minerals that are highly
symbolic among Iberians, like cinnabar, and provides new evidence for preservation
of the archaeological items retrieved from the cemetery.

66
References
Bouchard M, Smith DC, Carabatos-Nedelec C. Spectrochimica Acta Part A 2007; 68: 1101.
Burgio L, Clark RJH, Theodoraki K. Spectrochimica Acta Part A 2003; 59: 2371.
Parras D, Montejo M, Ramos N, Snchez A. Spectrochimica Acta Part A 2006; 64: 1133.
Parras D, Vandenabeele P, Snchez A, Montejo M, Moens L, Ramos N. Journal of Raman
Smith GD, Clark RJH. Journal of Archaeological Science 2004; 31: 1137.
Vandenabeele P, Edwards HGM, Moens L. Chemical Review 2007; 107: 675.

67
Micro-Raman and Surface-Enhanced Raman Scattering
Analysis of Pigments in Ancient Islamic Manuscripts of
Meknes (Morocco)
S. Sanchez-Cortes1, S. Ait Lyazidi2, M. Haddad2,

A. El Bakkali2, E. del Puerto1
1
Instituto de Estructura de la Materia, CSIC. Serrano, 121. 28006 Madrid. Spain
2
Laboratoire de Spectromtrie des Materiaux et Archomateriaux, URAC 11, Facult
des Sciences, Universit Moulay Ismail, 11201 Zitoune, Mekns, Morocco.
In this work we have carried out a Micro-Raman analysis of pigments corresponding

to blue, green, black, red and yellow pigments contained in a series of manuscripts
found in a Madrasa of Meknes (Morocco) from the XIXth century.
Two different methods were applied on these manuscripts to get information
about the nature of the existing pigments. Non-fluorescent pigments were directly
analyzed by applying conventional micro-Raman spectroscopy. This is the case of
bright red, blue, green and yellow (Figure 1). For the fluorescent pigments the
application of Ag nanoparticles was necessary in order to quench the fluorescence
emission and observe the intensification of the Raman spectrum by Surface-
Enhanced Raman Scattering (SERS). This was the case of pink red and a red
component of the yellow pigment (Figure 2).
Bright red and blue areas were clearly identified as vermilion and lazurite,
respectively (Figure 1a and b). However, the green areas were more complex to be
studied as they were composed by a mixture of different pigments: green, blue and
red. The blue pigment detected in the latter area corresponds to lazurite, the green
was identified as malachite (Figure 1c), but the red in this case corresponds to
hematite (Figure 1d). The yellow pigment is integrated by two different areas with
yellow and red colours but leading to only one spectrum (Figure 1e) identified as
pararealgar, although some of the bands can be attributed to orpiment 1. In addition,
in the latter zones, medium vermilion bands at 343 and 253 cm-1 were also identified.
(a)
(b)
(c)
(d)
Figure 1. Micro-Raman spectra registered on

the red ink (a), blue ink (b), green ink (c), red
(e) points inside the green ink (d), and yellow ink
(e). Excitation at 785 nm.
Top image: Piece of the manuscript analyzed

in this work

68
Finally, the pink red did not yield a Raman spectrum (Figure 2a), thus it may
corresponds to some organic pigment as also reported by other authors. 1
Red and Yellow pigments were also analyzed by SERS (Figure 2b and c) on
applying a drop of an Ag colloid prepared by using hydroxylamine as reductor. The
suspension drop (<1L) was directly deposited on the ink without a pre-
concentration process, thus leading to a very small and imperceptible spot (Figure 2,
inset image). The SERS spectra displayed strong bands at 1630, 1582, 1444, 1330,
1223 and 482 cm-1, which are present in both the red and yellow areas, and which
can be attributed to anthraquinone dyes. This is demonstrated by the great similarity
of these spectra with the SERS spectrum of carminic acid recorded as reference
(Figure 2d). Most probably this pigment corresponds to kermesic acid due to the
great affinity with the SERS of this compound 2, although it is not discarded its
attribution to carmine. In the SERS obtained on the yellow ink, also pararealgar
features can be seen at 343 and 230 cm -1. The Raman spectra of paper areas
without pigments are also shown in Figure 2e and f. The latter spectrum corresponds
to areas of the paper were a drop of Ag colloid was applied.
Figure 2. Micro-Raman
spectrum of the pink red area (a)
100 m
and Micro-SERS spectra
(a) registered by applying a Ag
1330
colloid drop on the pink red ink

1223
(b) and the yellow ink (c).

1444
1582
(d) SERS spectrum of carminic

1630
acid (10-5 M) obtained in Ag

482
colloid in a cuvette. (e) and (f)

343
Raman Intensity
are the direct Raman spectrum

of paper and the SERS of the
(b) same area, respectively.
Inset image: Micrograph of the

(c) deposited Ag colloid drop onto
the pink red ink zone. Excitation
at 785 nm. Baseline corrected
(d) spectra.
x10 (e)
(f)
1600 1400 1200 1000 800 600 400

-1
Wavenumber / cm
Acknowledgements. This work has been financially supported by the Spanish

Ministerio de Ciencia e Innovacin (grant FIS2010-15405) Comunidad de Madrid
through the MICROSERES II network (grant S2009/TIC-1476) and CSIC/CNRST
Spain/Morocco agreement grant no. MA2009MA0005.
References
1
Burgio L, Clark RJH, Vnia SF, Stanley T. Journal of Raman Spectroscopy 2008; 39: 1482.
2
Leona M. Proceedings of the National Academy of Sciences USA 2009; 106:14757.

69
A Systematic SERS Study of Eosin Combining Theory and
Experiments
N. Shah1, F. Casadio2, R.P. Van Duyne 1, G. Schatz1 A. Davis1, N. Valley1

N. Greeneltech1, N. Daly1
1
Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston,
IL, USA, 60208
2
The Art Institute of Chicago, 111 S. Michigan Ave., 60603 Chicago, IL, USA. Tel:
+1.312.857.7647; email: fcasadio@artic.edu
Eosin is a fluorone dye (C20H6O5Br4Na2; C.I. number: 45380; CI name: Acid red 87),
synthesized by Caro in 1871 that is well known in the art field as it was extensively
used by 19th C artists, most notably by Vincent Van Gogh (18531890) [Rioux,
1999]. The bright fuchsia pigment, sold by color makers as a lake pigment (most
often precipitated with alumina) with the name Geranium lake, is also notoriously
prone to rapid fading [Burnstock et al. 2005]. Several paintings by the Dutch
postimpressionist master are known where only minute remnants of color are still
visible today on an otherwise completely discolored whitish-yellowish paint.
Thus, the motivation for this work was to develop ultra-sensitive methods for
identification of Eosin when only a few pigment particles remain. Although it is
possible to acquire FT-Raman spectra of Eosin, the spectrum is very weak.
Acceptable signal/noise levels of the bulk powdered pigment can only be achieved
using long acquisition times and low laser powers. These conditions make it
impossible to obtain spectra when only a grain or two of pigment is available.
In this work we use deep near-infrared surface-enhanced Raman scattering (NIR-
SERS) spectroscopy to overcome the limitations of FT-Raman. A systematic study of
the adsorption and spectral pH-dependence of Eosin on different SERS
nanostructured substrates is presented. The SERS spectra were obtained at several
pHs and excitation wavelengths using a colloidal Ag nanoparticle paste) and silver
film over nanospheres (AgFONs) in order to achieve highly sensitive detection of
Eosin. SERS yields are discussed as well as the utility of theoretical calculations with
time-dependent density functional theory (TDDFT) to aid the interpretation of the
complex and highly variable SERS spectra.
Acknowledgements. Conservation science research at the Art Institute of Chicago

and Northwestern University is made possible by generous grants from the Andrew
W. Mellon Foundation and the National Science Foundation (Grants: CHE-0414554,
CHE-0911145, and DMR-0520513).
References
Rioux J P, in Preprints of the 12th triennial meeting of the ICOM Committeefor Conservation,
London, James & James, 1999, p. 403
Burnstock A., Lanfear I., Van den Berg K.J., Carlyle L., Clarke M., Hendriks E. and J. Kirby,
in Preprints, of the 14th triennial meeting of the ICOM Committee for Conservation, The
Hague, James & James, 2005, p. 459

70
Spectroscopic investigations on marker pen inks
Armida Sodo1, Marina Bicchieri2, Maria Antonietta Ricci1,

Giuseppe Ricci3
1
Physics Department, Universit degli Studi di Roma Tre, Via della Vasca Navale 84,
00146 Roma (Italy), Tel. +39 06 57337238, sodo@fis.uniroma3.it
2
Istituto centrale restauro e conservazione patrimonio archivistico e librario,
Laboratory of Chemistry, Via Milano 76, 00184 Roma (Italy),
3
Fondazione Federico Fellini, Via Nigra 26, 47900 Rimini (Italy).
Characterization and conservation of materials involved in contemporary art are

a big challenge for scientists and restorers due to the huge variability and the large
heterogeneity of their uses and compositions [Coddington et al. 2002]. Aim of this
work is to provide a contribution to the knowledge of the degradation mechanisms
occurring in new materials extensively applied in contemporary works of art, namely,
the marker pen inks. They have been used by a large amount of artists not only in
their own works, but also in sketches and in documents such as diary or letters that
often contain important information on their realization. Marker pen inks represent a
great problem for restorers as they fade in few years, changing colour and shade
moreover they are often soluble in the most common used solvents.
In collaboration with the Federico Fellini Foundation, owner of more than 500
original drawings of the famous movie director - most of them realised by marker
pens - we started an important project aimed at the investigation of composition and
degradation processes of marker pen inks. These are indeed a complex mixture of
different components, principally colorants (dye), solvents, dispersant, wetting
agents and humectants to retard premature drying; the exact composition is usually
under patent.
In this work we report chemical and spectroscopic investigations (Raman and
IR absorption spectroscopy and XRF investigation) on original and standard samples
in order to identify the colouring agents and their degradation products. For this
purpose, two commercial (Carioca and Giotto) and two technical brands (Stabilo and
Staedter) have been used. As an example, in fig.1 we report the Raman spectra of
the four different red marker pen inks. These spectra, combined with other
techniques, allowed the identification of the different dyes as azo-pigments, and in
particular a mono-azo pigment for Giotto and di-azo pigment for Carioca, Stabilo e
Staedler [Schulte 2008; Nadim 2009]. A more detailed identification will be diffusely
discussed.
Investigation of degradation products for each single dye after artificial ageing will be
also reported and compared to original Fellini drawings.

71
Fig.1: Raman spectra (785.5 nm) of standard paper and four different commercial red marker
pen inks on paper. The comparison of the reported spectra allowed to recognise in the
inks the contribution of paper and the bands that belong to the red inks.
References
J. Coddington, C. Mancusi-Ungaro, and K.Varnedoe, Time and Change: A Discussion About

the Conservation of Modern and Contemporary Art, Levin, J. ed., Conservation, The Getty
Conservation Institute Newsletter, vol. 17, no. 3, 2002, pp.11-17
C. S. Nadim, S. Zumbuehl, F. Delavy, A. Fritsch, R. Kuehnen Synthetic organic pigments of

the 20th and 21st century relevant to artists paints: Raman spectra reference collection
Spectrochimica Acta Part A, 2009; 73: 505524
F. Schulte, K.W. Brzezinka,K. Lutzenberger, H. Stege and U. Panne Raman spectroscopy of

synthetic organic pigments used in 20th century works of art J. Raman Spectrosc. 2008; 39:
14551463

72
Raman spectroscopy latest techniques in Art restoration
studies
Riccardo Tagliapietra
Renishaw S.p.A.
Riccardo.Tagliapietra@Renishaw.com
Physical and chemical characterisation of the materials employed in the works of art,
from the original constituents to the degradation products, is becoming and essential
tool in the hands of the restoration operator. For almost a decade Raman
Microscopy has been playing a major role in this field, due to its characteristics: it is
a non-destructive and fast technique, does not need sample preparation and with the
aid of optic fibres has met the increasing demand of portability.
To meet the operators wishes, Renishaw has responded to growing demand of
accessories and combined techniques in a multi-analytical approach necessary for
the full understanding of the nature of the material. Beside the more traditional
Raman microscopy-based techniques, we want to present here the combination on a
single instrument of Raman spectroscopy, X-ray analysis, chemical maps and SEM
back-scattered low vacuum images; various examples will be given to illustrate the
advantages of the technique.

73
Raman spectroscopy of pigments based on carbon
Eugenia Tomasini1, Beatriz Halac2, Mara Reinoso2, Emiliano Di Liscia2

and Marta Maier1
1
University of Buenos Aires, Faculty of Exact and Natural Sciences, Department of
Organic Chemistry, Pabelln 2, Ciudad Universitaria, 1428 Buenos Aires
(Argentina), Tel. +54 1145763385, eugeniatomasini@gmail.com,
maier@qo.fcen.uba.ar
2
Comisin Nacional de Energa Atmica, Dto. Materia Condensada, Avda. Gral Paz
1499, B1650 Buenos Aires (Argentina), halac@cnea.gov.ar.
Carbon-based pigments are a group of dark-colored materials that are classified

according to the starting material used and their method of manufacture. This group
of pigments is composed of substances formed by the burning or pyrolysis of organic
materials as well as natural forms of carbon such as coal and graphite [Winter,
1983]. Some of them contain inorganic materials as hydroxyapatite in ivory black or
alkali metal carbonates in cokes and chars made from vegetable precursors that
may be helpful in the identification of the pigment [Winter et al., 2007]. Raman
spectroscopy is an ideal technique for the characterization of carbonaceous
materials: crystalline carbon materials present well defined peaks which can be
easily assigned; amorphous carbon materials, on the other hand, present broad
bands between 1300 and 1600 cm-1. The variations in intensity, width and peak
position of these bands are related to the samples microstructure: degree of
amorphization, grain size, structural defects, etc. [Escribano et al., 2001].
The aim of this work is the discrimination between reference carbon-based pigments
by Raman spectroscopy. Six pigments provided by Zecchi (lampblack, vine black,
ivory black, bistre, bitumen and graphite) and two humic-earth materials (Van Dyck
(Kremer) and earth of Cassel (Zecchi)) were studied.
Raman spectra were recorded using a LabRAM HR Raman system coupled to an
imaging microscope. Two different laser excitation sources were used: 514.5 nm (Ar)
and 632.8 nm (He-Ne).
Raman spectra of all the samples present the characteristic G band (~1580 cm-1)
associated to sp2 carbon bonds in graphite and D band (~1350 cm-1) associated to
grain size, denoting the lack of long range order. In some cases, the carbon bands
dominate the spectra, however a clear difference in width and relative intensity can
be observed in most of the samples as it is shown in Figure 1 presenting the spectra
of bistre and lampblack. In some other cases, extra bands have been observed in
addition to D and G bands, denoting the presence of precursors that allows a clear
identification of the pigment. This is the case of ivory black which shows a small
peak at 965 cm-1 together with a band around 580 cm-1 corresponding to a
carbonated calcium phosphate. It is also the case of vine black, where strong peaks
at 1100 and 290 cm-1 are observed indicating the presence of CaMg(CO3)2 together
with the bands at 220, 280 and 400 cm-1 corresponding to a heated iron/manganese
oxide. These spectra are shown in Figure 2.
A deep analysis of each reference carbon-based pigment is presented. It is shown
that Raman spectroscopy allows to discriminate most of them and could be a useful
tool to identify different black pigments in pictorical and archaeological samples.

74
Intensity (arb. unit)
bistre
lampblack
200 400 600 800 1000 1200 1400 1600 1800 2000
-1
Raman shift (cm )
Figure 1. Raman spectra of bistre and lampblack samples.
Intensity (arb. unit)
vine black
ivory black
200 400 600 800 1000 1200 1400 1600 1800 2000
-1
Raman shift (cm )
Figure 2. Raman spectra of vine and ivory black samples.
Acknowledgements. This work has been financially supported by the University of

Buenos Aires (Grant X124).
References
Escribano R, Sloan JJ, Siddique N, Sze N, Dudev T. Vibrational Spectroscopy 2001, 26: 179.
Jehlicka J, Urban O, Pokorn J. Spectrochimica Acta Part A 2003, 59: 2341.
Winter J. Studies in Conservation 1983, 28: 49.
Winter J, West Fitzhugh E, in Berrie BH (Editor), Artists Pigments: a Handbook of their
History and Characteristics, vol. 4, Oxford University Press, Archetype Publications, UK,
2007, p. 1.

75
In situ Raman and XRF analysis of a 16th century maiolica tile
floor.
Jolien Van Pevenage1, Melissa Vandevijvere1,2, Lien Van de Voorde1,

Bart Vekemans1, Laszlo Vincze1, Peter Vandenabeele3
and Luc Moens1
1
Ghent University, Department of Analytical Chemistry, Krijgslaan 281 S12, B-9000
Ghent (Belgium), Tel. +32 (0)9 264 47 19, Raman@UGent.be
2
Artesis University College, Blindestraat 9, 2000 B-Antwerp (Belgium)
3
Ghent (Belgium).
In this study in situ Raman and XRF analysis of a maiolica tiled floor was performed.
This floor is situated in the chapel of the Rameyenhof Castle in Gestel (Belgium)
and it is unique in its kind as it is the only known in situ maiolica tiled floor in Belgium
dating from the 16th century.
In this investigation, the technology and production processes of maiolica tiles are
examined, the characterization of pigments and elements are investigated, and
connections are made with regard to degradation. Both, a mobile Raman
spectrometer (MArtA) and a handheld XRF spectrometer (InnovX) were used to
characterize this unique colorful glazed ceramic floor.
The in situ measurements were performed during 6 days, staggered over a period of
6 weeks. As the maiolica tiled floor is so unique, the measurement conditions had to
be in this way that the floor was certainly not damaged.
For the Raman analyses, the experimental set-up of the probe head and articulating
arm were fixed by means of magnets onto a board. Then, this board together with
the probe head set-up was placed on a thick cloth on the floor. In this way, certainly
no damage was done. The spectrometer was set onto a wooden bench in the
chapel. The distance between the probe head and the spectrometer could be
bridged using optical fibers. The computer was placed outside the chapel, at the
entrance.
For the XRF analyses, it was possible to put the instrument as such on the floor,
indeed carefully, keeping in mind not to damage the floor. The instrument was
connected to the computer, which was placed outside the chapel, at the entrance.
The points of interest were selected in this way that the research questions could be
answered. During this research, for the Raman analysis, ca. 80 points have been
examined. For the XRF analysis, 181 points of interest were examined.
For the Raman analysis, another problem had to be taken into account. As the castle
is occupied, the measurements had to be performed during the day. The stray light
that is entering through the stained glass windows causes strong interference.
Therefore, measurements were executed by covering the point of interest and the
probe head with black cloth. For positioning and focusing artificial light was used.
In this presentation, the results of the Raman analyses, combined with XRF
analyses, are presented.
Acknowledgements. Special attention goes to Mr. and Mrs. De Gruyter, the owners
of the Rameyenhof Castle, and to Mr. Caignie, expert in maiolica tiles. This work is
supported by the BELSPO Interuniversity Attraction Pole Program P6/16 (Belgium)
and BOF.

76
Raman microspectrometry as an efficient tool for the
determination of potential sources of Paleolithic artifacts in
Belgium
Yves Vanbrabant1, Christian Burlet1, Ccile Jungels2,

Dominique Bonjean3, Stphane Pirson4, ric Goemaere1,
Grgory Abrams3 and Kvin Di Modica3
1
Royal Belgian Institute for Natural Sciences, Geological Survey of Belgium, Jenner
street, 13, BE-1000 Brussels (Belgium), Tel. +32-2 788 76 35,
yves.vanbrabant@naturalsciences.be
2
Prhistosite de Ramioul / Muse de la Prhistoire en Wallonie, Rue de la grotte
128, BE-4400 Flmalle (Belgium)
3
Centre de recherche de la grotte Scladina, rue Fond des Vaux 339d, BE-5300
Sclayn (Belgium)
4
Service public de Wallonie, Direction de larchologie, rue des Brigades dIrlande 1,
BE-5100 Jambes
An important issue in prehistoric archaeology concerns the geographical origin of the

lithic raw materials worked by men for the creation of tools or art. In Belgium, a large
variety of lithic raw materials were used and most of them exhibit features allowing
their differentiation. One of these rocks, a highly-siliceous black stone, is commonly
called phtanite by archaeologists. Since several Paleolithic sites have been
formerly discovered close to the outcrop of the so-called phtanites (banded silicites)
beds of Ottignies (Duprel, 1937), there is a tendency among the prehistorians to
consider each macroscopically similar rock samples found in archaeological context
as coming from the area of Ottignies. This interpretation is even applied for sites
located several tens of kilometers away (Caspar, 1982). The collaboration between
archaeologists and geologists and more specifically the application of analytical tools
of mineralogy to the artifacts provides a more rigorous approach.
The potential source(s) of these archaeological objects made in highly-siliceous
black rocks is (are) however not yet well-constrained, since different geological
formations in the region contains macroscopically comparable rocks: 1) the so-called
phtanites (banded silicites) beds of Ottignies (Formation of Mousty, Upper
Cambrian); 2) the chert nodules (nodular silicites) within Dinantian limestones (Lower
Carboniferous); 3) the 'phtanites' beds of Namurian age (Upper Carboniferous) and
4) the flint nodules and beds within the Cretaceous chalk horizons. Some of these
formations underwent different thermal and tectonic evolutions.
Our study aims to show the utility of Raman microspectrometry for the interpretation
of the potential sources of these materials. The technique focuses on the Raman
response of the Carbonaceous Material (CM) which is widespread within these black
stones. Previous Raman spectrometric studies on this compound [Beyssac et al.,
2002; Rahl et al., 2005] showed that the degree of organisation of CM is reflected by
the definition of specific bands. The method represents an accurate geothermometer
of the peak temperature recorded by the rock formations during their geological
evolution.
In our study, several artifacts from major Middle Paleolithic sites in Belgium were
investigated with the Raman microspectrometer from the Geological Survey of
Belgium (Royal Belgian Institute for Natural Sciences). The recorded spectra show

77
different degree of ordering of CM. Figure 1 illustrates a comparison of first-order CM
Raman peaks of two artifacts apparently made from a similar black rock.
The thermal interpretation following the methodology presented in the above-
mentioned references indicates that the rock source of one sample (lower spectrum)
underwent a thermal geological event higher than 400C, while the upper spectrum
corresponds to a geological formation with a very low temperature (T) history (<
200C). According to regional geological setting data, the high-T sample is more
likely an origin close to the outcrop zone of the Upper Cambrian 'phtanites of
Ottignies, whereas the rock source of the low-T sample should be related to younger
formations. The origin of these black rocks used for the production of paleolithic
artifacts in Belgium is thus not unique.
The application of the Raman microspectrometry on highly-siliceous black stones
collected in archaeological sites in Belgium opens a new perspective for the
determination of samples from the existing collections with all the consequences on
the archaeological interpretation about prehistoric behavior. The technique follows a
quantitative approach, less subjective than the current macroscopic examination. Its
also non-destructive and so easily applicable to archaeological material. Another
advantage of this technique is that it is fast since a Raman spectrum is commonly
recorded in few tens of seconds.
Figure 1 - Examples of recorded Raman spectra of Palaeolithic artifacts from the Spy cave
(Belgium). See text for explanation.
References
Beyssac, O., Goff, B., Chopin, C., Rouzaud, J.-N. J. metamorphic Geol. 2002; 20: 859.
Caspar, J.-P. Notae Praehistoricae 1982, 2: 63.
Duprel, E., 1937. Bul. Soc. Roy. Belge d'Anthropologie et de Prhistoire 1937; 52 : 124.
Rahl, J., Anderson, K.M., Brandon, M.T., Fassoulas, C. Earth and Planetary Science Letters
2005; 240: 339.

78
Micro-Raman spectroscopy on two chalices from Benedictine
Abbey of Einsiedeln (Switzerland): identification of
gemstones.
Marie Wrle1, Stefanos Karampelas2, Katja Hunger1, Hanspeter Lanz1

1
Laboratory for conservation research, Centre of collections, Swiss National
Museum, Lindenmoostrasse 1, CH-8910 Affoltern am Albis, Switzerland
2
Gbelin Gem Lab, Maihofstrasse 102, CH-6006 Lucerne, Switzerland;
s.karampelas@gubelingemlab.ch
A group of sacral objects, made around the beginning of the 17th century, recently
come to light. These objects are belonging to the Einsiedeln Abbey (which is situated
in the central Switzerland) and were loaned for one month to the Collection Centre of
the Swiss National Museum for identification of the colored stones and metals used
in their creation. The goal of the study was to characterize the alloys and the gems
which adorned those items. The results on two chalices (figures 1 and 2), made of
gold and enamel and are adorned with uncolored and colored gems as well as
pearls, are presented here. Detailed information regarding the history, the stylistic
and iconographic description of the objects could be found to Distelberger and Lanz,
2009.
Figure 1: Chalice (1609) Figure2: Chalice Laubenberg

Height: 21.2cm Height: 22.9 cm
Diameter Foot: 14.5 cm Diameter Foot: 13.9 cm
Diameter Bowl : 9.5 cm Diameter Bowl: 10.2 cm
Weight: 822.6 g Weight: 968.8 g
28 colored stones 23 diamonds
24 pearls
For security reasons, all the analyses took place in the laboratory for conservation
research at the Collection Centre in Affoltern am Albis in collaboration with
79
conservator and curator from the museum. Only non-destructive analytical methods
could be used to examine those items. The chalices were difficult to handle and due
to the conservation state of the object, dismantling of the different piece was
excluded.
The cuts and the shapes of the stones were studied macroscopically (or using a
loupe -x10- ). When possible, the stones were observed under optical microscope.
The reaction of the gems is also observed under long-wave and short-wave UV
lamps. Raman spectra on the accessible gems were obtained with a Horiba Jobin
Yvon, LabRAM Aramis spectrometer coupled to an Olympus microscope.
Measurements were carried out using excitation wavelengths of 532 nm (Nd:YAG
laser), 633 nm (He:Ne Laser) and 785 nm (diode laser). Semi-quantitative chemical
analyses (on the stones and the metals) were performed by using a micro X-ray
fluorescence spectrometer. The results of this study were compared with the
observations of Father Eustach Tonassini (Tonassini, 1798), who was in charge of
the treasury between 1794 and 1798.
The cuts of all the stones were old; no modern cut was observed. Moreover, no
imitations were found to the stones observed under the microscope. Comparison of
the chemical analysis using EDXRF on some of the pearls of the chalice, with a
database built with the same instrument on samples of known origin, shows that
these pearls are probably of freshwater origin. For the other gems, comparing our
chemical and spectroscopic results (in the vast majority of cases the conclusive
identification was done by Raman spectroscopy) with those observed by Father
Tonassini, it appears that what he had correctly identified all the rubies, except of
some which dark coloured garnets are, belonging to pyralspite group (mainly
almandine). He had correctly identified all diamonds, amethysts and sapphires.
Moreover, the stone that he called chrysolith is olivine (the gems quality is a.k.a.
peridot), and those called Topaz are either quartzes (citrine) or garnets of ugrandite
group (mainly grossular). Finally, Father Tonassini in his manuscript mentioned that
the gems are orientalisch, i.e. from oriental countries. Studies of gems inclusions
did not exclude this possibility.
References
Distelberger R, Lanz HP. Journal of Swiss Archeology and Art History 2009; 66: 193.
Father Eustache Tonassini, Beschreibung des Kirchenschatzes Teil I, Archive of Einsiedeln,
Switzerland, 1794-1798.

80
Raman Spectroscopy for the detection and characterization
of elemental carbon; its relevance in the field of cultural
heritage.
Giuseppe Zerbi1, Matteo Tommasini1, Claudia Conti2, Anna Ferrugiari1

1
Politecnico of Milano, Dip. Chimica, Materiali e Ingegneria Chimica G. Natta,
Piazza Leonardo da Vinci 32, 20133 Milano, (Italy), Tel. +39 0223994708,
giuseppe.zerbi@polimi.it.
2
dei Beni Culturali (ICVBC), Via Cozzi 53, 20125 Milano (Italy).
The blackening of the surfaces of works of art exposed to the atmosphere (and the
consequent aging or degradation) originates from the ubiquitous particulate which is
at present a subject of many studies in the fields both of Environmental Science and
of Cultural Heritage. Elemental Carbon (EC) forms the insoluble fraction of the
heterogeneous particles found as aerosols and/or deposited on surfaces. EC
consists of a fraction of very large and insoluble molecules (Polycyclic Aromatic
Hydrocarbons, PAHs) and a fraction of carbonaceous material. Because of its
insolubility, the analysis of EC through physical chemical methods is challenging.
The carbonaceous fraction observed with optical and/or electron microscopy allows
determining the morphology of the particles. This may be correlated with some
chemical or physical processes which have originated the carbonaceous material.
EC consists mostly of aggregates of graphite (GT, the most stable allotropic form of
Carbon) and can be found in inhomogeneous materials of many kinds: from graphite
to coal, soot, industrial smokes and exhausts of cars, atmospheric particulate matter
deposited on surfaces, from tires to carbon powders used as absorbers in chemistry,
medicine, etc. While optical or electronic microscopies can describe the morphology
of the particles, they do not provide any information on their molecular properties.
In recent years GT has gained much attention in basic and applied science, since
isolated single sheets of graphene (GPH) have been produced [Novosilov et al.
2005]. The relevance of the discovery of GPH has been recognized with the award
of the 2010 Nobel Prize in Physics.
The Raman spectrum of GT (and GPH) has been the subject of extensive studies
[Castiglioni et al. 2004, Tommasini et al. 2007, Ferrari et al. 2007, Tommasini et al.
and Barbon et al. submitted] and has been already suggested [Ferrugiari, 2009] as
an easy way to recognize EC even in the most complex real samples. Necessarily
the Raman spectrum is recorded in resonance conditions, thus allowing to observe
relatively strong Raman lines near 1600 cm-1 (G line) and 1300 cm-1 (D line, see
Figure 1) even when GT occurs in small relative concentration in the sample under
study. The interpretation of the Raman spectrum of GT and GPH has been the
center of great attention in Physics and Chemistry, even if based on the different
scientific approaches by these two communities (see, for instance Castiglioni et al.
2004, Tommasini et al. 2007).
Our interpretation of the Raman spectrum of GT and GPH is based on the theoretical
and experimental studies carried out in terms of molecular properties (the so called
Molecular Approach). The Raman spectra of model molecules (suitably synthesized
PAHs) and of GT (GPH) have been investigated with quantum chemistry [Castiglioni
et al. 2004, Tommasini et al. 2007] and experiments carried out with many laser
excitations [Tommasini et al. and Barbon et al. submitted]. In the characterization of
GT we should account for: (i) the finite size of any PAH, even if very large on a
molecular scale, (ii) the relation of defects with model molecular structures (PAHs),

81
(iii) the roughness of the edges of realistic graphitic flakes, (iv) the chemical nature of
the edges. This offers a model for the GT/GPH flakes as consisting of a large
graphitic core with diameter d, surrounded by a poly-aromatic edge with thickness
with possible chemical groups of some kind attached on its outside very edge
[Tommasini et al. and Barbon et al. submitted]. For large enough flakes (d >> ) the
ID/IG ratio of the Raman intensities can be related to the average size d of the platelet
[Tuinstra et al. 1970].
The possibility of the characterization of the carbonaceous particles at the molecular
level offers the possibility to study their origin and their history. With this molecular
approach in mind, we have studied, and are studying, the Raman spectra of a variety
of samples of practical interest in the research for Cultural Heritage (Figure 2). Case
studies will be reported.
Our message is that EC is easy to be detected by Raman spectroscopy, also in the
most difficult samples. When possible, different excitation lines should be used.
Raman scattering is a tool for the characterization of the material at the molecular
level and it can offer useful new parameters to be related to the origin of the sample,
which has been subjected to a certain environment.
Figure 1: micro-Raman mapping ( Figure 2: Raman spectrum ( 780 nm) of a sample

780 nm) of a graphite platelet from a fresco of a church in Milan; the gray pigment,
showing (B) the G line (ordered indicated in the picture with S, shows the G and D
inner structure) and (A) the D line lines.
(disordered edge).
References
Novosilov KS, Jiang D, Shedin F, Booth TJ, Khotkevich VV, Morozov SV Proc. Nat. Acad.
Sci. U.S.A. 2005; 102: 10451.
Castiglioni C, Tommasini M, Zerbi G Phil. Trans. Roy. Soc. Lond. A 2004; 362: 2425.
Tommasini M, Castiglioni C, Zerbi G Phys. Chem. Chem. Phys. 2009; 11:10185.
Ferrari AC, Solid State Comm. 2007; 143: 47.
Tommasini M, Fustella G, Castiglioni C, Zerbi G, Barbon A, Brustolon M Phys. Chem. Chem.
Phys. (submitted). Barbon A, Brustolon M, Zerbi G, Tommasini M Phys. Chem. Chem. Phys.
(submitted).
Ferrugiari A PhD thesis, 2009, Politecnico di Milano.
Tuinstra F, Koenig JL J. Chem. Phys. 1970; 53: 1126.

82
Pigment alteration of mediaeval wall paintings in Herzberg
and Ziesar, Germany
Martin A. Ziemann1, Frank Schluetter2 and Steffen Laue3

1
Institute of Earth and Environmental Sciences, Universitaet Potsdam,
Karl-Liebknecht-Str. 24 / H27, D-14476 Potsdam (Germany), Tel. +49 331 977 5876,
ziemann@geo.uni-potsdam.de
2
Amtliche Materialpruefungsanstalt Bremen (MPA), Analytische Baustoffmikroskopie,
Paul-Feller-Str. 1, D-28199 Bremen (Germany)
3
Studiengang Restaurierung, Fachhochschule Potsdam, Pappelallee 8-9, D-14469
Potsdam (Germany)
Mediaeval wall paintings are well preserved in the chapel and the palace of the
former episcopal see Castle Ziesar and in the church St. Marien in Herzberg/Elster,
Germany. The paintings of the ceiling in St. Marien are exceptional in Germany due
to their complete and unrestored state since the early 15 th century, whereas the
paintings on the walls and ceiling of Castle Ziesar were whitewashed, and thereby
protected for a period of about 260 years until a first restoration in 1952/53.
In the last centuries alterations of the copper and lead pigments occurred on these
wall paintings. As part of on-going restoration campaigns we have taken micro
samples from parts of the paintings that show apparent colour changes, in order to
determine substances and processes. Raman spectroscopy combined with EDX
analysis and electron microprobe investigations (including element distribution
mapping) were performed on thin cross sections. A confocal LabRAM HR800 with a
532 nm laser and a 100x microobjective was used for the Raman measurements in
high resolution mode. Laser power was reduced to < 1 mW to prevent sample
heating. The high lateral resolution of the applied analytical methods allowed to
detect mineral transformations within selected single grains of respective pigments,
responsible for colour changes of parts of the paint layers. These observed
transformations can be correlated with associated morphological changes of the
pigment grains and the structure of the paint layer. Moreover, this provides
indications on the mineral composition of the geological raw material of the used
pigments.
Acknowledgements. This work has been financially supported by the Deutsche

Bundesstiftung Umwelt DBU Project 23367.

83
A novel piece of Minoan art in Italy: the first spectroscopic
study of the wall paintings from Phaistos
Angela Zoppi1, Cristiana Lofrumento1, Marilena Ricci2, Emma Cantisani3,

Tiziana Fratini4 and Emilio Mario Castellucci1,5
1
University of Florence, Chemistry Department, Polo Scientifico e Tecnologico, Via
della Lastruccia 3, 50019 Sesto Fiorentino (Italy), Tel. +39 0554573078,
angela.zoppi@unifi.it
2
University of Florence, Department of Construction and Restoration, Via Micheli 8,
50121 Florence (Italy),
3
dei Beni Culturali (ICVBC), Via Madonna del Piano 10, 50019 Sesto Fiorentino
(Italy),
4
University of Florence, Department of Science of Antiquity G. Pasquali, Piazza
Brunelleschi 4, 50121 Florence (Italy),
5
University of Florence, European Laboratory for Non-Linear Spectroscopy (LENS),
Polo Scientifico e Tecnologico, Via Nello Carrara 1, 50019 Sesto Fiorentino (Italy).
Some fragments of wall paintings of Phaistos (Crete), belonging to the Cretan

Bronze Age, from Archaelogical Museum of Florence [Fratini et all., 2008], were
analyzed to investigate the material composition of the pictorial layer and the
technology. These samples belong to the oldest surviving examples of decorative
painting on plaster from Crete and are assignable, according on the dating of
Knossos, to the phases between the First and Second Palace. [Militello 2001]
The fragments of wall painting were studied to define the composition of plaster used
as substrate of pictorial layers and to identify the techniques utilized for the pictorial
layers.
The colored strata were investigated through micro-Raman analyses by acquiring
the vibrational spectra on different points selected for every hue, whereas the plaster
samples were analyzed by different techniques, as optical microscopy, XRD and
FTIR for the identification of organic and inorganic compounds present in the
pigments and in the mortar.
The importance of this study relies on the fact that they could be considered as
valuable archaeological indicators for the contribution that they could offer to the
comprehension of different painting techniques and materials used in Crete in the
Medium Minoan period. The obtained results show a rather homogenous color
palette mostly made of mineral pigments, which recurs in the different tones in all the
fragments and are similar to the studied Aegean Bronze painted plasters [Brysbaert
et al., 2004].
References
Fratini T, Gonzato F. Atti del II Convegno F.Halbherr, 27-29 Febbraio 2008, Roma.
Militello P. Studi di archeologia cretese, II parte, Padova, Italy, 2001, p.1.
Brysbaert A, Vandenabeele P. Journal of Raman Spectroscopy 2004; 35: 686.

84
POSTER
PRESENTATIONS

Study of Chromatic Changes Phenomena in Ancient Egyptian
Mural Paintings
Shaaban Abd El Aal1
Restoration and Conservation Department, Faculty of Archaeology, Fayoum

University, Egypt.Bo.pox:63511.Tele\ Fax:0020486333178.
E-Mail:smm00@fayoum.edu.eg.
The internal walls of Pharaonic tombs are extensively decorated with various scenes
which are reflecting the daily life activities and religion beliefs of ancient Egyptian.
The ancient Egyptian Painters used different natural and artificial pigments which
were from different natural raw sources and have different physio-chemical
properties.
For this reason the ancient Egyptian Palette is considered unique and rich. Due to
the severe actions of physio-chemical and biological deterioration factors most of
pigments have been deteriorated and became pale and fragile. The present scientific
work focus on studying the mechanism and the serious effects of chromatic changes
phenomena took place to these pigments.
Various samples have been collected from the mural paintings which are presenting
on the walls of some other pharaonic tombs and investigated by XRD, PLM and
PIXEetc. The obtained results showed that the pigments seriously deteriorated
and changed specially the blue pigments, green and black pigments due to the
severe effects of deterioration factors previously mentioned.
(Fig.1) O.M of Blue sample from Minya tombs, (Fig.2) Cross Section of Blue sample from
showing of chromatic changes phenomena in Tomb of Thutmose the third, showing of
ancient Egyptian pigments chromatic changes phenomena in pigments.
References
[1]Shaaban A, Korman A, Stonert A, Muunik F, Turos A. journal of VACUUM 2009;83:S4-S8.
[2]Lucas A. Ancient Egyptian Materials and Industries. Kessinger Publishing, 2003

85
Alteration of copper metal pigments on 18th - 19th century
Iranian manuscripts
Maurizio Aceto1, Angelo Agostino2, Gaia Fenoglio2, Javad Mousavi3,

Abbas Abed-Esfahani3, Muhamad Mortazavi3 and Hossein Ahmadi3
1
Interdisciplinare per lo Studio e la Conservazione dei Beni Culturali (CenISCo); Tel.
+39 0131 360265, Email maurizio.aceto@mfn.unipmn.it.
2
Universit degli Studi di Torino, Dipartimento di Chimica Generale e Organica
Applicata, corso M. dAzeglio, 48 - 10125 Torino (Italy); Centro di Eccellenza NIS
(Nanostructured Interfaces and Surfaces).
3
Art University of Isfahan, Department of Conservation and Restoration of Cultural
Heritage, Hakim Nezami St. - P.O. Box 1744 Isfahan (Iran).
An alteration of copper metal pigments has been identified on some 18th - 19th
century manuscripts from Iran. The phenomenon is similar to the one described in
previous works [Aceto et al., 2006; Aceto et al., 2010] on early medieval Western
European manuscripts, i.e. a chromatic change from golden aspect to a greenish,
inhomogeneous aspect.
Three illuminated manuscripts made in Qajar period and belonging to Soltanabad
Museum of Arak (Iran) were taken into consideration in this study. The manuscripts
are richly decorated with metal pigments.
The first manuscript is named Bay. Golden and silvery particles were identified on
its papers. Bay usually designates a small paper notepad opening lengthwise, with
covers made of leather. The interest of Bay lies in the fact that several such
books, kept in various libraries, contain notes by people of distinction. These notes
sometimes contain lines of poetry, aphorisms, ethical and philosophical maxims and
amusing phrases.
The second manuscript is named Golan-e rz. It is a concise didactic manawi, i.e.
a prose composition made of nearly a thousand couplets on the key terms and
concepts of Sufism, which has for long served as the principal text of theoretical
mysticism in the Persian-speaking and Persian-influenced world. It was written by
ay Mamud abestari. This manuscript contains illumination with golden borders
on every page; moreover, also the sheets of the manuscript are made precious by
application of fine particles of gold on the support. Paper flecked with gold or silver
dust was known as Kaghadh-e afshan in Iranian traditional artistic practices [Floor,
2003].
The third manuscript is named Juz (part) 22 of Quran. This manuscript contains
borders and initials inside text made with golden illumination.
Microscopic samples of the golden particles were collected from the three
manuscripts. The samples were firstly analysed with SEM-EDX to identify the main
elements present: all three resulted to be composed of a copper/zinc alloys with
minor impurities of tin and lead, instead of the expected gold. Then Raman analysis
was performed on the samples to identify the nature of the compounds present in
the altered areas. Measurements were performed with a bench-top high-resolution
dispersive Jobin Yvon-Horiba (Villeneuve dAscq, France) LabRAM HR model
spectrophotometer, equipped with a confocal microscope, 632.8 nm excitation laser,
1800 lines/mm and 600 lines/mm dispersive gratings, an 800 mm path
monochromator and a Peltier cooled CCD detector. Spectra were collected with
exposure times of 120 seconds, due to the low intensity of Raman bands. In order to

86
avoid thermal degradation of compounds, attenuated laser energy was mandatory:
to collect reliable spectra, energy on the sample was lower than 2 mW. Raman
analysis on the altered greenish particles verified the similarity of the compounds
present with the compounds identified in the works by Aceto, that is organic salts of
copper due to the possible conversion of metallic copper to copper carboxylates. As
bands in the Raman spectrum are wide, not sharp as usual, we can think about a
bunch of molecules rather than a single copper compound: acetate, formate and
also acetate/formate are possible candidates. Moreover we can think that only
copper compounds are responsible for the green hue because zinc is not known to
form green compounds. To elucidate the real structure/structures, application of XRD
spectroscopy should be executed in the next future.
It is difficult to verify how intensive had been the use of copper metal pigments in
Persian manuscripts because only few analytical works [Ciomartan and Clark, 1996;
Hayez et al., 2004; Clark and Mirabaud, 2006] or conservation studies [Barkeshli and
Ataie, 2002; Stanley, 2006] exist at the concern and in no case the use of copper
metal pigments has been recorded. It is possible also that green painted areas had
been considered as made by intentional green pigments rather than being the effect
of an alteration process.
References
Aceto M, Agostino A, Boccaleri E, Crivello F, Cerutti Garlanda A. Journal of Raman

Spectroscopy, 2006; 37: 1160.
Aceto M, Agostino A, Boccaleri E, Crivello F, Cerutti Garlanda A. Journal of Raman
Spectroscopy, 2010; 41: 1434.
Barkeshli M, Ataie GH. Restaurator, 2002, 23: 154.
Ciomartan DA, Clark RJH. Journal of Brazilian Chemical Society, 1996; 7: 395.
Clark RJH, Mirabaud S. Journal of Raman Spectroscopy, 2006; 37: 235.
Hayez V, Denol S, Genadry Z, Gilbert B. Journal of Raman Spectroscopy, 2004; 35: 781.
Floor W, Traditional Crafts in Qajar Iran (1800-1925), Mazda, USA, 2003.
Stanley T. Restaurator, 2006, 27: 162.

87
THE MATERIALS OF EARLY ILLUMINATED BYZANTINE MANUSCRIPTS
Maurizio Aceto1, Angelo Agostino2, Gaia Fenoglio2, Pietro Baraldi3,

Paolo Zannini3, Christa Hofmann4, Ernst Gamillscheg4
1
Dipartimento di Scienze dell'Ambiente e della Vita & Centro Interdisciplinare per lo
Studio e la Conservazione dei Beni Culturali (CenISCo), Universit degli Studi del
Piemonte Orientale, viale Teresa Michel, 11 - 15121 Alessandria, Italy,
maurizio.aceto@mfn.unipmn.it
2
Dipartimento di Chimica Generale e Chimica Organica & Centro di eccellenza NIS
(Nanostructured Interfaces and Surfaces), Universit degli Studi di Torino, corso M.
dAzeglio, 48 - 10125 Torino, Italy,
3
Dipartimento di Chimica & Centro Universitario Interdipartimentale di Ricerca
Applicata ai Beni Culturali (Cu.Be.), Universit di Modena e Reggio Emilia, Via G.
Campi, 183 - 41100 Modena, Italy,
4
sterreichische Nationalbibliothek, Josefsplatz 1, A-1015 Wien, Austria.
Our present knowledge on the history of painting materials and techniques is still
lacking because a rather negligible part of artworks have been analyzed recently.
This history on pigments and dyes used by ancient painters is based more on written
sources (such as the medieval treatises, e.g. The Lucca manuscript and the Cennino
Book of Art) than on analytical measurements. Illumination is a typical example: most
of the oldest illuminated manuscripts existing, though profoundly studied from the
historical and artistic point of view, are sometimes completely unknown from the
material and technical ones. The oldest manuscripts analyzed, such as the Irish
Book of Kells and The Lindisfarne Gospel are dated at least to the VIII century.
Indeed, analysis on early medieval manuscripts could shed light on a field largely
unexplored, allowing to obtain information on the introduction of new colorants into
the illuminators palettes.
New analytical data could change the chronology of use of a certain colorant and
thereby change the date of an illumination. Ultramarine blue, obtained from the lapis
lazuli stone, is one of the most known pigments, but information concerning its
introduction in art history is not clear. Though identified in some mural paintings of
the VI century A.D. in Central Asia, its use in Western art is still questioned, the
earliest analytical evidences dating not before IX century. A parallel example is the
chronology of Egyptian blue in illumination. Indeed, does this historical information
mean that the precious pigments were really not available to early medieval
European painters (or no more available in the case of Egyptian blue), or is it just a
matter of scantiness analytical information?
A research project has been started on early manuscripts (byzantine, peninsular and
continental illumination) in order to gain information on pigments and dyes used by
ancient illuminators. As a first step, two byzantine manuscripts of the VI century,
preserved in the sterreichische Nationalbibliothek in Wien, were analyzed. The
manuscripts are known as Dioskurides (ms. Med. gr. 1) and Vienna Genesis (ms.
theol. graec. 31). These manuscripts are considered as the top quality artworks in
their time, and were created in a place, such as Byzantium, that had wider
possibilities of trade than any other cities.
Only in situ, non-invasive analysis with portable instrumentations were allowed. -
Raman spectroscopy, UV-Visible diffuse reflectance spectrophotometry with optical
fibres (FORS) and -XRF spectrometry were used to characterise the palette of both
manuscripts.
The main feature of Dioskurides and Vienna Genesis palettes is their richness,
88
exemplified by the simultaneous presence of gold and ultramarine blue; in the
Dioskurides, cinnabar also is present. The identification of ultramarine blue is
surprising, the analytical evidence of its use being reported as situated three
centuries before its use in Western manuscripts. From the historical point of view it is
not surprising to find such wealth on byzantine artworks, since the Byzantine Empire
was the dominant culture in those centuries in the Eastern Mediterranean World.
Another interesting feature is the lack of green pigments: to obtain green hues,
important for a herbal, byzantine illuminators used a mixture of indigo and orpiment,
the well-known vergaut that was ascertained also in Irish manuscripts. Other
materials include azurite, minium, orpiment, red and yellow ochres. dyes were used
also, such as madder, and some lakes prepared from plant extracts.
The presence of gold leaf and ultramarine in only some pages of the codex supports
an hypothesis of its assembling from a more ancient herbal. The non invasive
examination of these two VI century manuscripts allowed to obtain information on the
pigments and dyes used, introducing new chronological data and on the economic
level of the committents. Further analysis on other early medieval manuscripts is
then needed in order to reinforce this information.

89
Theoretical investigation on the molecular structure, FT-
Raman, FT-IR, NMR and UV-VIS studies of a hetarylazoindole
dye
Ebru Aktan1, Berna atkka2, Zeynel Seferolu1
1
Department of Chemistry, Gazi University, 06500, Ankara (Trkiye), Tel. +90
5332552765, ebruaktan@gazi.edu.tr
2
Department of Physics, Mustafa Kemal University, 31034, Hatay (Trkiye)
Dyes have an important role in human life not only in painting and decoration but
also in technology. Natural dyes are still used in the arts application areas. But it is
not possible to provide the demand for natural dyes used in coloring now. Natural
dyes made from plants, animals and shells. They are difficult to prepare and give too
weak colors and quantities. Therefore dyes have accelerated the process of
production of synthetic dyes. Azo dyes, according to the number and amount of
production of the most important group among all synthetic dyes. Azo dyes have
wide application areas such as dyeing of textile fibers, plastics, leather, paper and
various materials. The dyes obtained by selecting heterocyclic compounds as diazo
component and / or the coupling component, give more brilliant and bathocromic
colors and they show much better fastness properties [Towns, 1999].
We report here on the computational study of hetarylazo dye derived from 1-methyl-
2-phenyl-1H-indole as azo component. The molecular geometry and vibrational
frequencies of 3-[(5-Ethyl-1,3,4-thiadiazol-2-yl)diazenyl]-1,2-dimethyl-1H-indole in
the ground state have been calculated by using DFT/ PBE0 methods with 6-
31+G(d,p) basis set [Perdew et al, 1996]. The FT-IR and FT-Raman spectra of the
compound have been recorded and compared to the calculated frequency values.
The total energy distributions (TED) of the fundamental modes have been obtained
by using Scaled Quantum Mechanical (SQM) program. The 1H and 13C chemical
shifts were calculated using the gauge-independent atomic orbital (GIAO) approach.
The theoretical electronic absorption spectra were calculated using time-dependent
density functional theory (TD-DFT). The calculations have been performed using the
Gaussian 03 package program.
References
Towns AD, Dyes and Pigments 1999; 42: 3.
Perdew JP, Burke K, Ernzerhof M, Physical Review Letters 1996; 77: 3865.

90
Multianalytical study of Christian and Muslin glazed pottery
and technological evolution along Late Medieval Ages (IX-XIII
centuries) in Northern Spain
Ainhoa Alonso-Olazabal1, Maria Cruz Zuluaga1, Maitane Olivares2,

Luis Ortega1, Xabier Murelaga3, Juan Jose Bienes4, Alfredo Sarmiento2,
Nestor Etxebarria2
1
University of the Basque Country, Department of Mineralogy and Petrology, P.O.
Box 644, E-48080 Bilbao (Spain), Tel. +34946015450, ainhoa.alonso@ehu.es
2
University of the Basque Country, Department of Analytical Chemistry, P.O. Box
644, E-48080 Bilbao (Spain),
3
University of the Basque Country, Department of Stratigraphy and Palaeontology,
P.O. Box 644, E.48080 Bilbao (Spain),
4
Ein Arqueologia SLU, Avda Zaragoza, 76-78 bajo, 31500, Tudela (Spain).
Technological evolution in pottery making is one of the knowledge transference

evidence of Islamic culture in the Iberian Peninsula. Hispano-Moresque ware was a
style of Islamic pottery created in Islamic Spain (al-Andalus). Moreover, replacing
alkaline type pre-Islamic glazed, several ceramic techniques were introduced such
as lead glazing, glazing with an opaque white tin-glaze, and metallic luster painting.
Several samples of glazed potsherds corresponding to a wide historical period were

analyzed to assess the culture transference. In order to study the evolution of pottery
making techniques, three cultural stages pre-Islamic, Muslim and Mudejar (Muslim
who remained in Spain after Christians recapture) ceramics were considered.
Analysed potsherds are from Cerro Santa Barbara site (Tudela, Navarre) that was a
Muslim citadel located on the ChristianMuslim border. Besides, coetaneous glazed
ceramic from Christian territory are analysed in order to compare the manufacturing
techniques. The aim of this work is mainly focused on the characterization of pottery
making and glazing techniques over four centuries by means of micro-Raman
spectroscopy, X-ray diffraction (XRD), Scanning-Electron-Microscope coupled to
Energy Dispersive X-ray Microanalysis (SEM-EDX).
Differences in the raw material mineralogical and elemental composition were

observed. High content of calcium in Muslim and Mudejar potsherds are detected
suggesting lime addition during raw material processing. Different Ca/Mg ratio
between Islamic and Mudejar pottery can be attributed to different provenance area
of the carbonate used for lime production. The lack of carbonates in the analysed
samples discards deliberate tempering which supports the lime addition hypothesis.
Potters in Christian territory apply different manufacturing techniques using local raw
material without lime addition. Additionally, firing conditions were established.
Diopside and anorthite occurrence suggests firing temperatures for potsherds bodies
above 900 C.
Concerning to glazed technology evolution, performed analyses provide data to

discriminate alkaline glazed potteries (Early Medieval Ages) from lead-glazed ones
(Late Medieval Ages). The chemometric treatment of EDX data by means of
Principal Components Analysis (PCA) allows distinguishing between Muslim lead-
glazes and Mudejar glazes according to the observed compositional heterogeneities.
91
The Raman spectra of alkali based hard-paste glazed potsherds consist of a strong
band at 500 cm-1 and a weak band at 1000 cm-1, whereas the 1000 cm-1 massif
dominates the spectrum of Pb-O rich glazes [Colomban et al. 2006]. According to the
literature, the study of different parameters in lead glazes such as the polymerisation
index (Ip), the Si-O stretching Q2/Q1 component area ratio or the displacement of Si-
O stretching band, allowed determining the glaze composition and the processing
temperature [Cesaratto et al. 2010]. Differences found in these parameters are
basically associated to the different lead content used in glazes along the different
historical periods. Furthermore, the low Ip values (<0.30) obtained for the analysed
glazes suggest firing temperatures close to 500 C for the glazing process.
Acknowledgements. This work has been financially supported by IT315-10 research

project of the Basque Country Government. Thanks also to the SGIker service from
the University of the Basque Country.
References
Colomban P, Tournie A, Bellot-Gurmet L. Journal of Raman Spectroscopy 2006; 37: 841.

Cesaratto A, Sichel P, Bersani D, Lottici P.P, Montenero A, Salvioli-Mariani E, Catarsi M.
Journal of Raman Spectroscopy 2010; 41: 1682.

92
The Use of Pigments on Ivory Plaques from Begram,
Afghanistan
Janet Ambers1, Emma Passmore1, Giovanni Verri1 and St John

Simpson2
1
Department of Conservation and Scientific Research, The British Museum, London
WC1B 3DG, UK. JAmbers@thebritishmuseum.ac.uk
2
Department of Middle East, The British Museum, London WC1B 3DG, UK
In the 1930s the excavation of two ancient storerooms within the ancient city-site of
Kapisa near modern Begram in northern Afghanistan [Hackin, 1939, 1954] yielded
large numbers of spectacular finds including bronze, alabaster, glass and ivory
objects. The exact dating of this material is still disputed but the most probable date
range is in late 1st or early 2nd century AD. Among the finds were over 1000 carved
ivory and bone pieces, decorative plaques which had originally been attached to
wooden furniture. The wood had rotted away, but the inlays were found still in their
original positions, making it possible to assign individual pieces to specific articles of
furniture, mostly foot stools and chairs.
Following the excavations the finds were divided between the National Museum of
Afghanistan in Kabul and the Muse Guimet in Paris. In late 1980s political events
forced the Kabul Museum to close and in 1993 the upper part of the building was
destroyed by shelling. During this period of turmoil the museums displayed
highlights had been packed and moved several times, with museum staff taking
great personal risks to ensure their safety. In 2004 many of the finest pieces were
retrieved from storage, restored and used to construct an exhibition which has been
travelling the world since 2006 [Hiebert and Cambon, 2011]. However, many objects
had already been stolen from storage during the civil war between 1992 and 1994. In
2010 a number of carved ivories from the Begram hoard surfaced in Britain. A
private individual stepped in and has very generously acquired them on behalf of the
museum in Kabul. They were deposited in the British Museum and were exhibited
temporarily in the exhibition Afghanistan: Crossroads of the Ancient World prior to
return to Kabul. This opportunity not only allowed conservation of the pieces to make
them safe for exhibition and travel but also offered the chance for the first scientific
examination of any of these ivories. This work was carried out with the permission of
the National Museum of Afghanistan and was supported by Bank of America Merrill
Lynch.
The twenty pieces brought to the BM varied in shape, style and state of preservation
but a number clearly bore signs of an original polychromy [for a full account see
Simpson, 2011]. With the aid of non-destructive in-situ Raman spectroscopy and X-
ray fluorescence (XRF) analysis an original palette including vermilion, indigo and
carbon black was established, while technical imaging, including ultraviolet-induced
visible luminescence imaging, suggested the possible use of a now degraded
organic pigment. The choice of indigo to provide a blue pigment rather than
ultramarine derived from the mineral lapis lazuli may well be significant. Afghanistan
contains one of the very few deposits of lapis lazuli in the world. This was arguably
the earliest such source to be exploited [Tosi, 1974]. Lapis was certainly being
extensively used for jewellery, inlays, seals and as a pigment at this period and was
exported far beyond the immediate region [Searight, 2010]. The designs on the
plaques themselves are closely paralleled in architecture and a small number of
objects found in India. The discovery of indigo adds further weight to the belief that
these pieces were either imported ready constructed from India or were produced in
Afghanistan by local or imported craftsmen to Indian patterns and styles. The other
objects found in the Begram storerooms including Chinese lacquer bowls and
93
Roman glass, polished stone tablewares and bronzes imported by sea from Egypt
certainly reflect the cosmopolitan tastes of a powerful kingdom at the crossroads of
the ancient world.
The information gathered from these investigations has also been used to produce a
suggested recolouring of one of the pieces, showing how what now appear to be
pale and subdued objects would once have glowed with vivid colours.
Figure 1. Ivories from Begram examined in this study; left, Female musicians, KM inv. no. 58-
1-164; right, Seated figure, KM inv. no. 58-1-213
References
Hackin, J, Recherches archologique Begram: Chanier no.2, 1937. Dlgation

Archologique Franaise en Afghanistan, Mmoire XI, Paris, France, 1939
Hackin, J, Nouvelles recherche archologique Begram, ancient Kpici. Dlgation
Archologique Franaise en Afghanistan, Mmoire IX, Paris, France, 1954.
Hiebert, F. and Cambon, P. (eds) Afghanistan: Crossroads of the Ancient World. British
Museum Press, London, 2011.
Searight, S., Lapis Lazuli. In pursuit of a celestial stone. East & West Publishing Ltd, London,
2010.
Simpson, St J, The Begram Hoard. British Museum Press, London, 2011.
Tosi, M., The Lapis Lazuli Trade Across the Iranian Plateau in the Third Millennium BC, in:
Gururajamanjarika: Studi in onore di Giuseppe Tucci, Ist. Universitario Orientale, Naples,
1974: 3-22.

94
Raman Spectroscopy in Sedimentology
Sergio And1 and Eduardo Garzanti1

1
Laboratory for Provenance Studies, Earth Science and Geotechnology Department,
University Milano-Bicocca, Piazza della Scienza 4, 20126 Milano (Italy),
Tel. +39 0264482094, sergio.ando@unimib.it
Raman spectroscopy is an innovative, efficient, and user-friendly technique

representing the ideal complementary tool to classical provenance analysis of
sediments and sedimentary rocks. The method is non-destructive, does not require
specific preparation, and can be used directly on thin sections, heavy-mineral slides,
and polished rock. Raman analysis also allows us to obtain information on
polymorphs, hydrated minerals, amorphous materials, and inclusions that cannot be
easily obtained with classical optical methods.
Detrital minerals are determined by comparison of obtained Raman peaks with
reference spectra reported in the literature (e.g., [Freeman et al., 2008] for feldspars;
[Geiger, 2008] for garnets; [Wang et al., 2004] for Fe-Ti-Cr oxides), calibrated
spectra obtained from minerals of specific chemistry [And et al., 2009; Bersani et
al., 2009], and mineralogical databases available online (e.g., www.rruff.info;
www.fis.unipr.it/phevix/ramandb.php). It is often convenient to photograph and label
each single grain on the thin section or heavy-mineral slide, in order to observe
optical properties under the microscope after identification with Raman
spectroscopy, and viceversa.
Raman spectroscopy is a powerful tool to confidently identify dubious grains
independently of their size and orientation, and thus to efficiently solve thorny long-
standing problems in provenance studies [And and Garzanti, 2011]. Last but not
least, Raman spectroscopy allows routine identification of minerals as fine grained
as fine silt [And et al., 2011], and it is consequently an unrivalled tool for
quantitative analysis of silt and siltstone, which represent a huge fraction of fluvial,
turbiditic and eolian transport [Garzanti et al., 2011].
Acknowledgements. This work benefited from contributions and advice by Laura

Borromeo, Mara Limonta, Manuel Valagussa, Alberto Paleari, Danilo Bersani and
Pietro Vignola.
References
And S., Bersani D., Vignola P., Garzanti E., Spectrochimica Acta A 2009; 73: 450.
And, S., Vignola, P., Garzanti, E., Rendiconti Lincei 2011; in press.
And S. and Garzanti E., in Mange M. and Wright D. (Editors), Heavy Minerals in Colour,
Cambridge University Press, in prep.
Bersani, D., And, S., Vignola, P., Moltifiori, G., Marino, I.G., Lottici, P.P., Diella, V.,
Spectrochim. Acta A 2009; 73 : 484.
Freeman, J.J., Wang, A., Kbler, K.E., Jolliff, B.L., Haskin, L.A., Canadian Mineralogist 2008;
46: 1477.
Garzanti, E., And, S., France-Lanord, C., Galy, V., Censi, P., Vignola, P., Earth Planetary
Science Letters 2011; 302: 107.
Geiger, C.A., American Mineralogist 2008; 93: 360.
Wang, A., Kbler, K.E., Jolliff, B.L., Haskin, L.A., American Mineralogist 2004; 89: 665.

95
Characterization of lapis lazuli from different provenances by
means of micro-Raman spectroscopy
Debora Angelici1,2,3, Alessia Fabiola Biondi1, Alessandro Lo Giudice1,2,

Giovanni Pratesi4, Alessandro Re2
1
Dipartimento di Fisica Sperimentale, Universit di Torino, Via P. Giuria 1, 10125,
Torino (Italy), Tel. +39 0116707366, debora.angelici@unito.it
2
Istituto Nazionale di Fisica Nucleare (INFN), Sezione di Torino, Via P. Giuria 1,
10125, Torino (Italy)
3
Dipartimento di Scienze Mineralogiche e Petrologiche, Universit di Torino, Via
Valperga Caluso 35, 10125, Torino (Italy)
4
Dipartimento di Scienze della Terra and Museo di Storia Naturale, Universit di
Firenze, Via G. La Pira 4, 50121 Firenze (Italy)
Lapis lazuli is a blue semi-precious stone widely used since the antiquity for the
manufacture of precious objects and jewellery. Its characterized by the presence of
the mineral lazurite, giving the typical blue colour to the rock, traversed by gray-white
or yellowish veins, due to the presence of various accessory minerals such as
calcite, wollastonite, phlogopite, plagioclase, diopside and others. There are few
quarries of lapis lazuli in the world, and only some of them could be used since 7000
years ago. In particular the Afghan mines in the Badakhshan region have been
considered for long time as the only source of lapis lazuli already exploited to provide
the raw material to ancient civilization of Mesopotamia, Egypt, Indus Valley and
China. In more recent times also other sources have been taken in consideration:
Pamir mountains (Lyadzhuar Dara, Tajikistan) [Herrmann, 1968; Casanova, 1989;
Delmas, and Casanova, 1990], Pakistan (Chagai Hills) [Casanova, 1989; Delmas,
and Casanova, 1990; Ballirano and Maras, 2006], Siberia (Irkutsk, near Lake Baikal)
[Herrmann, 1968] and others not yet geologically confirmed. Despite the knowledge
of the provenances of the raw material can help reconstructing trade routes of the
past, a systematic and exhaustive provenance study of the raw material utilized in
artworks is still lacking.
For this reason we started a multi-technique characterization of twelve samples of
certain provenance (Afghanistan, Pamir, Siberia and Chile), coming from the
collection of the Mineralogy and Lithology section of the Museum of Natural History,
University of Firenze. The final aim of the work is to find some markers to distinguish
among the analysed provenances and to use them to identify the origin of the raw
material used for artworks and archaeological findings. The samples were prepared
as semi-thin sections and have already been analysed both with electron-beam
(SEM-EDX, SEM-CL, cold-cathodoluminescence) and ion-beam techniques (PIXE,
IL), to study both the elemental composition of the phases and their luminescence
response [Lo Giudice et al., 2009; Re et al., 2011].
To complete the characterization of the material and to recognize the various phases
present inside the samples of different provenances we performed a systematic
study by means of micro-Raman spectroscopy. We already demonstrated that
luminescence spectra can give useful information for the provenance discrimination
of the analysed provenance [Lo Giudice et al., 2009] and in this work well explore
the possibility to find some new markers studying the minor peaks of the Raman
spectra of the different phases inside lapis lazuli.
The instrument used in this work is property of the Interdepartmental Centre G.
Scansetti and its placed at the Petrology and Mineralogy Department of the

96
Figure 2. Selection of Raman spectra of lazurite and diopside compared to a reference
spectrum from the database RRUFF (University of Arizona)
University of Torino. Its composed by the spectrometer Jobin Yvon (Mod. LabRAM
HRVIS) and an optical microscope Olympus BX41. For our measurements we
selected the biggest crystals of each phase (recognised using maps of
cathodoluminescence) on each sample and we analysed it using a green laser (532
nm). To recognize the phases we compared the acquired spectra with a reference
database (RRUFF, University of Arizona).
Raman spectra confirmed and clarified results obtained with other techniques
(Figure 2) demonstrating to be useful in the recognition of the different phases inside
lapis lazuli. In the analysed samples from all the provenances we found lazurite, the
main blue phase of lapis lazuli. Moreover we identify diopside as one of the main
accessory mineral in all the Asian samples, while in the Chilean ones wollastonite
was detected. Other identified phases were calcite and K-feldspar. Moreover we
evaluate the differences among the minor peaks of the Raman spectra of samples
from different provenances to find some new markers to recognize the origin of the
raw material.
Acknowledgements. This work is supported by the FARE experiment of Istituto
Nazionale di Fisica Nucleare (INFN). The authors warmly thank Dr. Simona
Ferrando for the help during the measurements with the confocal micro-Raman.
References
Ballirano P., Maras A. American Mineralogist 2006 ; 91: 997

Casanova M. South Asian Archaeology 1989; 14: 49
Delmas A.B., Casanova M. South Asian Archaeology 1990; 66(1): 493
Herrmann G. Iraq 1968; 30(1): 21
Lo Giudice A., Re A., Calusi S., Giuntini L., Massi M., Olivero P., Pratesi G., Albonico M.,
Conz E. Analytical and Bioanalytical Chemistry 2009; 395(7): 2211
Re A., Lo Giudice A., Angelici D., Calusi S., Giuntini L., Massi M., Pratesi G. Nuclear
Instruments and Methods in Physics Research B 2011, DOI:10.1016/j.nimb.2011.02.070

97
The first in situ portable Raman and XRF study of rock art in
South America: paintings from Morro Azul caves in Paran
State, Brazil
Carlos R. Appoloni1, Claudia I. Parellada2, Fbio L. Melquiades3,

Eduardo I. Jussiani1, Fernanda C. Pereira 2 and Fbio Lopes1
1
Departamento de Fsica, CCE, Universidade Estadual de Londrina, CEP 86055-
990, Caixa Postal 6001, Londrina, Paran, Brasil. appoloni@uel.br
2
Museu Paranaense, Departamento de Arqueologia, Rua Kellers, 289 , CEP 80410-
100, Curitiba, Paran, Brasil.
3
Departamento de Fsica, Universidade Estadual do Centro Oeste, CEP 85015-430,
Caixa Postal 3010, Guarapuava, Paran, Brasil.
Morro Azul archaeological site is the biggest set of rock art paintings actually known in
South Brazil, located in Ventania municipality, Paran State, Brazil (the paintings occur
along the length of 200m, between 0.3 to 4m height, central point E 577.073 e N
7.327.349 UTM SAD 69 coordinates). This area, with two caves and a big rock shelter
[Parellada, 1993; Gottardi Neto, 1995], had three different occupations, the oldest one is
related to Umbu hunters and gatherers (from to 10,000 to 3,000 years BP). The two
more recent are related to the Itarar-Taquara farmers and ceramists of J linguistic
family (from 4,000 to 500 years BP). Rock art of this site are over sandstones and
diamictites of Itarar Group, and belong to Planalto tradition, which are common in this
region. The paintings of Morro Azul present figures in red and black, almost always with
animals, fantastic human representations, barred lines, dots, semicircles, emblematic
figures and lattice motifs. Also different styles of paintings can be observed. Rock art
paintings regions were analyzed by two portable systems: a Raman spectrometer
operating at 785 nm, 120 mW and 8 cm -1 resolution, which spectra were recorded from
200 to 2000 cm-1; an EDXRF equipment employing a 4mW X-ray tube with Ag filter and
target, a Si PIN diode detector (149eV FWHM for the 5.9keV line) and a special designed
mechanical system for the detector and X-ray tube positioning, which enables angular
and XYZ movements of the excitation-detection system respect to the measurement area.
Elements from Ca to Pb were measured. X-Ray Fluorescence spectra were analyzed
using the AXIL-WinQXAS software. PCA analysis was performed with both Raman and
PXRF spectra for grouping analysis. Red and black pigments were studied. By PXRF it
was determined Fe as key element for the red pigment. Raman spectra of the red
pigment showed hematite lines 293, 411, 502, 614, 660 and 1320 cm -1. Black pigment
presented Mn as key element and more organic matter than the red one.
Acknowledgements. This work has been financially supported by Fundao

Araucria PR and CNPq. The research in Morro Azul Site started in 1992 with
support of Secretaria de Estado da Cultura do Paran and Fundao Boticrio.
References
Gottardi Neto, A. Anlise ceramica do Projeto Cavernas de Morro Azul. Revista do Museu de
Arqueologia e Etnologia da USP 1995; 5: 63-75.
Parellada, C.I. Relatrio tcnicofinanceiro final do Projeto Cavernas de Morro Azul. Curitiba,
Museu Paranaense/ Fundao O Boticrio de Proteo a Natureza, 1993.120p.

98
Raman spectroscopic study of the degradation of CorTen
steel sculptures induced by environmental stressors
Julene Aramendiaa, Leticia Gomez-Nublaa, Nagore Prieto-Taboadaa,

Daniel Vegab, Ainhoa Sanz Lpez de Herediab, Arantza Garca Ibez de
Opakuab, Kepa Castroa and Juan Manuel Madariagaa
a
Department of Analytical Chemistry, University of the Basque Country( EHU/UPV) ,
P.O.Box 644, E-48080 Bilbao, Spain, +34 946018297, *jaramendia002@ehu.es
b
Guggenheim Bilbao Museoa, Conservation-restoration Dept., Avda. Abandoibarra
2, 48001 Bilbao, Spain
The CorTen steel is a very used material for metal works exposed outdoor because
of its resistance against the corrosion. But this protection could be affected because
of the presence of some acid gases such as SO 2 and NOx typical in an urban
atmosphere. For example, SO2 is dissolved in the moisture film present in the steel
surface forming sulphuric acid; this acid accelerates the corrosion of the material.
Apart from this, H2SO4 could generate species like SO42- [zcan et al., 2002] that
react with the different iron species, the main element in the steel [Wang et al.,
1997]; from this reactivity, compounds such as rozenite (FeSO 44H2O) or
szomolnokite (FeSO4H2O). [Oesch, 1996] can appear.
In this study several CorTen steel sculptures have been analyzed. These are
exposed in Bilbao (North of Spain) in an urban atmosphere but located in different
places. All of the pieces of the studied artworks are part of Eduardo Chillida
sculptors collection. The analyses were carried out with a handheld InnoRaman
B&WTEKinc Raman spectrometer.
According to Raman data, in the surface of these artworks, particles of calcite

(CaCO3) have been detected. This compound could be reacting with the SO 2 present
in the Bilbao atmosphere to form gypsum [Sarmiento et al., 2008], a compound
detected also in the steel surfaces. With Raman spectroscopy different hydration
forms of the gypsum can be distinguished, and in the surface of this sculpture
gypsum (CaSO42H2O) and bassanite (CaSO4~0.5H2O) have been identified. The
wet/dry cycles suffered by the identified salts could be generating a physical stress
due to the volume change associated to the hydration/dehydration process, as it can
be seen in reaction 1. This fact could cause the detachment of steel chips from the
surface of the sculptures body, a weekly phenomenon. The detachment of these
chips produced a decrease of the protective function of the rust layer of the
weathering steel and therefore the protection against environmental stressors.

99
Besides, the partial dissolution of this gypsum generated by the rain, produce
enough dissolved sulfate (SO 42-) to react with SO2 giving the required sulfite SO 32-
that reacts with the one of the main iron species present in the steel surface,
magnetite (Fe3O4), giving rise to an iron sulfate such as rozenite (reaction 2).
Apart from this, in one of the sculptures exposed in the center of Bilbao, Raman
spectra of nitrates have been identified. These nitrates could be formed because of
the reaction of the NOx with the compounds present in the surface of the artwork.
These results clearly shown the effect of the combustion and greenhouse acid gases
over the weathering steel exposed in an urban atmosphere. As it is known, one of
the consequences of these reactions is the acceleration of the corrosion of the steel,
but this study show another outcome, like the physical stress that damages the
protective rust layer of the weathering steel; the most important property that makes
this material so suitable for expositions outdoor.
Figure 1. a) Raman spectra showing the mixture of gypsum and bassanite, G (Gypsum), H
(Bassanite). b) CorTen steel sculpture with damages in the rust layer.
Acknowledgements. This work has been financially supported by Basque

Government and Guggenheim Bilbao Foundation through CAUTAPA project (ref.
UE09+/109). J. Aramendia, L. Gomez-Nubla and N. Prieto-Taboada are grateful to
the Basque Government, to the University of the Basque Country (UPV-EHU) and to
the FPI Programme of the Spanish MEC, respectively, for their pre-doctoral
fellowship. We would like to thank BBVA bank and Excmo. Ayuntamiento de Bilbao
for all the support during the analysis of the sculptures.
References
Oesch S, Corrosion Science 1996; 38: 1357.
zcan M, Dehri I, Erbil M. Progress in Organic Coatings 2002; 44: 279.
Sarmiento A, Maguregui M, Martinez-Arkarazo I, Angulo M, Castro K, Olazabal MA,
Fernandez LA, Rodriguez-Laso MD, Mujika AM, Gomez J, Madariaga JM. Journal of Raman
Wang JH, Wei FI, Chang YS, Shih HC. Materials Chemistry and Physics 1997; 47: 1.
de Proteo a Natureza, 1993.120p.

100
Micro-Raman characterization of pigments used in modern
paintings from north of Italy
Giulia Azzi, Camilla Celona, Denise Minoli, Danilo Bersani

and Pier Paolo Lottici
University of Parma, Physics Department, Viale G.P. Usberti 7a, 43124 Parma
(Italy), Tel. +39 0521905278, giulia.azzi@studenti.unipr.it
This study includes three different cases in which micro-Raman Spectroscopy was
applied for investigation of paintings of the period ranging between the second half
of XIX century and the first half of XX century. All paintings come from a small region
of North of Italy including the provinces of Parma and Mantova. Micro-Raman
technique was very effective in finding solutions to problems of restoration,
conservation, dating and authentication. A careful sampling was performed on the
tree paintings; submillimetric fragments of paint materials were taken from damaged
areas of the operas. The characterization of the materials and pigments from
artworks required samples including all the layers, from the varnish to the support
(canvas or plaster). The cross sections were observed through stereo and optical
microscopes before the Raman measurement obtained using a Horiba Jobin-Yvon
LabRAM apparatus equipped with a He-Ne laser (632.8 nm) as excitation.
The first case regards the oil painting Il martirio di S. Agata by Riccardo Cessi
(1840-1913) situated in the church of Villastrada (Mantova), and dated 1863. The
figure of S. Agata is in the central part of the painting, surrounded by few other
characters. The spectral analysis revealed that the palette comprise gypsum, lead
white, cinnabar, ultramarine blue, litharge, massicot, carbon black and several
chromate compounds. Special attention was given to the Raman characterisation of
chrome orange and chrome green. Chrome orange was the first pure, intense and
opaque orange to become available to painters and its use was in practice limited to
the 19th century. Chrome green is an intimate mixture of Prussian blue and chrome
yellow. The classification of these chromate pigments its not definitive yet and
different denominations are frequently attributed to the same compound. In this
study we observe the shift of the characteristic chrome oranges bands due to the
thermal effect.
The second studied artwork is the mural painting of Galileo Chini located above the
portal of Moorish hall in the Grand Hotel des Thermes in Salsomaggiore (Parma).
The mural painting is of certain award, as signed and dated 1926, and it was never
retouched over the years. Galileo Chini (Florence 1873-1956) has been recognized
by critics as one of the major protagonists of art nouveau in Italy. From 1911 to 1913
he worked in Siam and in 1925 he was called in Salsomaggiore to decorate the
luxurious Grand Hotel des Thermes with oriental reminiscences. The analysis of the
green areas was interesting. The green color was obtained by the painter in many
different ways: mixing ultramarine blue with lead chromate, using only emerald green
and, finally, mixing prussian blue with yellow zinc. In combination with other
pigments, carbon black has been recognized in order to create darker shades. In a
several spectra with reference to blue areas appears ultramarine blue, while looking
yet a blue zone appears barite (white barium) and ultramarine blue together. It is
assumed that barite was used as pigment for mixing with blue to get light blue. It is
also interesting to note that a blue area reveals only one of the characteristic peaks
of ultramarine blue, showing Raman spectra similar to the one of ultramarine green.
The presence of this synthetic green product, which becomes blue through
oxidation, was evaluated. Lacquer Alizarin was also identified in red parts, while
vermilion was found in an orange area. Also iron oxide (hematite) was found in red
101
grains. This study revealed a palette extremely rich in synthetic pigments including:
emerald green, prussian blue, chrome yellow, zinc yellow and barium white. Also the
other pigments found in the painting (ultramarine blue, vermilion, hematite, alizarin
lacquer) have to be considered of artificial nature especially given the historical
period. The only exception is carbon black, which is of natural origin. The colors
above are all commercially available since early 1800, with the only exceptions
prussian blue and chrome yellow, colors used as early as 1700 and carbon black,
used even in remote time. Spectra related to gypsum refer to the ground layer.
The last case regards Davide e Golia, an oil painting on canvas by an anonymous
artist. It is dated to the first half of XX century and it is conserved in the Gambarotta
Museum situated in the castle of Compiano (Parma). On a dark background there is
the imposing figure of Davide with the Golias head on the ground. The painting
shows four main colors areas: pink (flesh-color), red and white (clothes) and dark
brown (background). Micro-Raman study was focused on the pigments of the first
tree areas.
The main pigments identified in the red areas are vermilion and minium, while basic
lead carbonate (lead white) is found in the white and in the pink areas. The main
obstacle met during the analyses was the determination the red dye used in the pink
areas that is alizarin, an organic lake also called Madder Lake o Rose Madder. This
dye is very hard to detect using dispersive Raman systems (with visible excitation)
due to its strong fluorescence, which often completely hides the Raman signal.
Notwithstanding this, with very long measurements, increasing the number of
accumulations, the alizarin peaks, though weak, emerged from the background.

102
Combined technique analysis on Punic cosmetic powders
Cecilia Baraldi1, Giada Freguglia1, Maria Cristina Gamberini1

and Pietro Baraldi2
1
University of Modena and Reggio Emilia, Department of Pharmaceutical Sciences,
via G. Campi 183, 41125 Modena (Italy), cecilia.baraldi@unimore.it
2
University of Modena and Reggio Emilia, Department of Chemistry, via G. Campi
183, 41125 Modena (Italy).
The Whitaker Museum in Mozia (Sicily) conserves some funerary vessels coming
from the isles archaic necropolis. Greek, Phoenician and Etruscan amphorae, a rich
collection of jars of Birgi necropolis and also materials coming from Mozia Tofet and
houses are exposed. Also jewels and weapons, amulets, scarabs and objects with
original inscriptions engraved are found, as well as cosmetic and surgical
instruments and fragments of inscribed stones coming from the Lilibaeum necropolis.
From the collection of the Mozia Museum 77 samples from an interesting variety of
containers including Unguentaria, Balsamaria, Alabastra, pyxes and shell valves
were taken.
The powders found in this cosmetic vessels have been analyzed by using FT-IR,
micro-Raman, SERS (Surface Enhanced Raman Spectroscopy) and XRF
techniques and the results are reported in this work. The analyses carried out have
shown the presence of a variety of compounds.
The white powders, that are the more frequent ones, present in lead pyxes, were
identified by micro-Raman as made of Cerussite PbCO3 coming from a complete
carbonatation of hydrocerussite PbCO 3*Pb(OH)2. This is compatible with the high
chronology of the samples: instead, hydrocerussite has been identified in Pompeii
samples. Its presence, confirmed by XRF measurements, can be a clear indication
of cosmetic use, since it is well known that its use in mural painting is not advisable.
At the time, cerussa (lead white) was employed as a foundation. Other white
powders are mainly composed of calcite or aragonite: the first could come from the
soil where the ancient founds were situated, the second one could derive from
ground sea shells. Among white samples, but not only, TiO2 is frequently attested. Its
presence should amount to the cosmetic use of ground rocks or could come from the
Mozia soil, for example if ophiolites are available in the region.
Litharge, an oxide present in many containers, could derive from the alteration of
cerussa, or from a proper addition, whether the yellow colour had a special meaning
for the population of the site. As to the yellow pigments a yellow ochre based on
goethite was found together with lepidocrocite.
Among the red pigments, beloved by Phoenician people, there are cinnabar and
hematite: the latter can be found as a natural compound or as a thermodegradation
product from goethite. The presence of red lead chromates crocoite and
phoenicocroite, two rare minerals, in a particularly precious unguentary is a singular
discovery.
In one sample a trace of blue material was seen, that gave the spectrum of
indigotine, a dye extracted in the past from many plants and used for dyeing tissues
and in cosmesis.
Among black materials carbon is one of the most frequently attested, alongside
MnO2 (pyrolusite) and magnetite.
Three samples analyzed exhibited red organic compounds, all fluorescent with
normal Raman technique. By applying a SERS technique it has been possible to

103
record spectra relative to these red dyes, but till now, with a comparison of reference
materials, it was only possible to exclude the common red such as madder, purple
and kermes. Other comparisons are outstanding.
In comparison with other sites, such as Pompeii, Herculaneum and Oplontis, these
cosmetic powders showed a wider range of materials.
References
P. Baraldi, C. Fagnano, C. Baraldi, M.C. Gamberini, Automata,1, 49, (2006).

M.C.Gamberini, C. Baraldi, F. Palazzoli, E. Ribechini, P. Baraldi, Vib. Spectrosc., 47 (2), 82,
(2008).
E. Van Elslande, M.C. Gamberini, C. Baraldi and P. Walter, An overview of the Raman
studies on cosmetic powders from Pompeii, Bilbao, Sept. 2009.

104
Renaissance Painted facades in Northern Italy: The court of
Carpi
Pietro Baraldi, Marcella Barbieri and Paolo Zannini
University of Modena and Reggio Emilia, Department of Chemistry, Via G. Campi,

183, 41100 Modena (Italy), pietro.baraldi@unimore.it
In the late gothic and the first Renaissance periods in Northern Italy there were many
little States having their capital cities. There the leader aimed to imitate the great cities
of Italy, like Florence and Urbino, by reorganizing the topography and by decorating
the facades with fresco painting. Their exposure to rain and circumstances of history
lead mainly to their disappearance in the course of five centuries, but in cities like
Verona (Case Mazzanti, Casa Golfino), Vicenza, Mantova (piazza Broletto), Ferrara
(Casa Romei) and in small ones like Correggio, Mirandola, Guastalla, Novellara,
Vignola, Carpi some paintings have survived.
In Carpi a great fresco painted surface is in the portico that was reorganized parallel to
the front face of the Castle in such a way to form a rectangular square having in its
northern side the cathedral. There lived all the noble families having contact with the
court. This square is still one of the most beautiful of Italy. Its elegance is recalled by
writers. The first arcade of the portico is present in the cadastre of the 1472, with the
name of the proprietor, Taliano Delci Pio, a warrior in the service of the Venetian
Republic. The former facade was repristinated between 1943 and 1949, with a
rediscovery of the late gothic elements.
In the palace the painter Prospero Donati from Correggio made important paintings,
similar to the ones in Casa Romei in the nearby Ferrara. Also Fedele Petrazzoni
decorated the inside rooms and the vaults with Prospero Donati: pine branches and
flowers and fruits describe strings, with shields reporting the Pio armies. Some details
of the medallion reveal features of the XVII century, with palm leaves and red ribbons.
Some microsamples were taken from the vault of the portico, from the external surface
( a late gothic painting in a window) of the house just in front of the castle entrance and
from the architectural terracotta that decorate all the portico. By means of Raman
microscopy, FT-IR spectroscopy and XRF a series of data were obtained for the
characterization of the materials and techniques employed. Tab.I reports the data
collected.
sample description color FT-IR Raman

Sa. 5 Rose window cartouche azure Ca, Gy Ca, La, Ox, He.
Sa. 6 Rose window cartouche Pink CaOx Gy, Ox, He
Sa. 7 Pio eagle arms Black Ca C, Ca
Sa. 8 Frame and rose window cartouche Light yellow Ca Ca, Gy, Go, Si.
Sa. 9 Rose window frame Light green TV, Ca TV, Ca, Gy, Si, Go.
Sa. 10 Rose window Pio army Light red Ca, He, Gy Ca, Gy, Ox, Si, He.
Sa. 11 Pio army cartouche Violet red Ca, He Ca, Gy, Ox, Si, He.
Sa. 12 Rose window cartouche Violet Ca Ca, Gy, Si, Go.
Tab. 1. Synopsis of composition of 8 samples taken in 2010 from the Carpi portico.

105
A microRaman and FT-Raman investigation on some
Wallpaper catalogues
Pietro Baraldi1, Anna Tinti2 and Paolo Zannini1

1
Department of Chemistry, University of Modena and Reggio Emilia, via G. Campi,
183, Modena (Italy), pietro.baraldi@unimore.it
2
Department of Biochemistry, University of Bologna, via Belmeloro, Bologna.
It was an old tradition to decorate the inside walls of the house with precious tissues
and the ceilings with paintings. In important houses of the Renaissance period the
ceiling beams were covered with decorated papers. In more recent centuries the
walls were decorated with papers with many kinds of subjects and by using many
materials, as they were discovered, especially in the second half of the XIX century.
With the Liberty age more complex and appreciated patterns were introduced and
some were at the level of artworks, like the creations by William Morris, that were
extended also to tiles, tissues and other house objects. The wide production of
pigments and dyes coming from tar and having a low cost induced the decorator to
use these ones. The production was organized so as to produce serial artifacts and to
reduce the time necessary by using cylinder carved with the proper image. The
cylinders were used many times and with different colors.
Some catalogues out of fashion are now offered to the Museums. They are difficult to
be exposed and the degradability of some compounds used makes them difficult also
to be preserved, if not in proper conditions.
A catalogue of wallpapers probably dated to the end of the XIX century was
examined. The paper leaves were many and it was decided to carry out a series of
measurements for the identification of materials only on some of them. The
techniques of FT- Raman and microRaman spectroscopy were applied and only in
doubtful cases some FT-IR measurements were added. FT-Raman spectra in
particular were rich of information and gave an idea of the paper conservation state.
From the analysis of the data recorded it appear that in the wallpapers some
traditional materials were still applied, such as yellow and red ochres, but the
products of the Science of Chemistry were also applied. For example it was recorded
in many cases the spectrum of Prussian Blue, an XVIII century product that had a
huge success due to its stability and ability to be used in inks, writing papers, as a
dye and as a pigment.
Chromates with different metals were detected, due to their easy preparation and
hues going from pale yellow to orange-red.
At the end of the XIX and at the beginning of the XX centuries, new materials were
introduced that came from the tar industry, such as methylene blue.
The ensemble of the spectral data collected, together with a stylistic comparison of
the decorations, point to a datation of the catalogue to the first XX century.

106
Raman and other techniques for a Study of Black Pompeiian
materials
Pietro Baraldi1, Carmen Canevali2, Paolo Gentile3, Francesca Modugno4,

Jeannette Jacqueline Lucejko4, Laura Brambilla5, Sara Goidanich5 and
Chiara Riedo6
1
Department of Chemistry, University of Modena and Reggio Emilia, Via Campi 183,
Modena, Italy, pietro.baraldi@unimore.it.
2
Department of Materials Science, University of Milano-Bicocca, Via Cozzi 53, 20125
Milan, Italy,
3
Department of Geological Sciences and Geotechnologies, University of Milano-
Bicocca, Piazza della Scienza 4, 20126 Milan, Italy,
4
Department of Chemistry and Industrial Chemistry, University of Pisa, Via
Risorgimento 35, Pisa, Italy,
5
Department of Chemistry, Material and Chemical Engineering "Giulio Natta",
Politecnico di Milano, Via Mancinelli 7, 20131 Milano, Italy,
6
Department of IPM Chemistry and NIS-Centre of Excellence, University of Turin,
Via Pietro Giuria 7, 10125 Torino, Italy.
The contents of various bronze vessels, coming from the archaeological site of
Pompeii, have been analysed with the purpose of; a) studying the materials and the
degradation products; b) identifying products and technology of preparation, and c)
verifying the function and uses of the materials. The samples, in the form of powder,
have been collected as inks on the base of the shape of the vessel where they were
preserved. The vessels were divided in three types according to the form, though
they contained a black powder mixed with other substances. After the analyses it
can be affirmed that for some samples the identification of the function and uses of
the materials is still a problem, but a group of vessels can be identified as
atramentaria or ink containers, whereas others were possibly used as unguentaria,
that is contained ointments used as hair dyer, eyeliners and tooth paste.
Many complementary analytical techniques, optical microscopy, micro-FTIR, micro-
Raman, XRD, SEM-EDS have been applied.
The analysed samples are complex mixtures with an inorganic matrix, made of
gypsum or silicates, and other minor compounds. Carbon black was identified often
as the main pigment, while no traces of iron gall ink were found. Some metallic
residues mainly bronze, and copper minerals as malachite and azurite, were
identified in several samples. It is not always clear whether they were intentionally
added to the mixture or not; this issue will be carefully discussed. The discussion is
intended for the understanding of the procedure used by the Roman people to
prepare a carbon based ink.
The research was carried out as Progetto PRIN 2007 of the Italian Ministry of
Research termed CiBA and coordinated by M.P. Colombini (University of Pisa).

107
Combination of Raman spectroscopy with FTIR spectrometry
and SERS for complex examination of medieval icons
Mikhail Belkov1, Elena Klyachkovskaya 1,2 and Anna Harbachova1

1
Institute of Physics, National Academy of Sciences of Belarus, 68 Nezavisimosti
Ave, 220072 Minsk, Belarus, belkov@imaph.bas-net.by
2
National Art Museum of Republic of Belarus; 20 Lenin str., 220030 Minsk, Belarus
The most difficult task during the process of painting investigation is the identification
of pigments and bindings included in structure of the paint layers. Detailed structural
characterization and identification of key chemical constituents can uncover
important information on historical and artistic significance of artworks.
The standard Raman spectra have been recorded with the modified spectrometer
SpectraPro-500i (Acton, USA). The excitation laser was Nd:YAG with wavelength of
the second harmonic of 532 nm and the angle of detection was of 180. The
scattering radiation after the transmission trough the holographic filter has been
directed on the grating (600 lines/mm) and the Raman spectra has been recorded by
the cooled CCD detector.
IR spectra of a diffusion reflectance have been detected with the help of FTIR
spectrometer in the spectral range of 4000-400 cm-1 with the resolution of 2 m-1.
SERS is at present the most sensitive variant of Raman spectroscopy. In some
cases the increase of the Raman spectrum amplitude reaches 1014. Thus, it is
possible to determine the trace components in analysed pigments or to use the
micro amounts of the analyte. In our experiments the Ge-on-Si plates with Ag
nanoparticles for SERS has been offered.
Above mentioned techniques have been successfully applied for the pigment
material analysis from the medieval icons of the Belarusian school. The most
important example is the icon God Mother with the Child Jesus shown below.
Only the combination of these techniques has provided the exact determination of all
pigments from the icon. Taking into account the results obtained thorough restoration
of all icons has been carried out.

108
Resonance Raman spectroscopy in corals and pearls
Laura Bergamonti1, Danilo Bersani1, Davide Csermely2

and Pier Paolo Lottici1
1
Dipartimento di Fisica, Universit di Parma, Viale G.P. Usberti 7/a, 43124 Parma,
Italy, tel. +390521905238, lottici@fis.unipr.it
2
Dipartimento di Biologia Evolutiva e Funzionale, Sezione Museo di Storia Naturale,
Universit di Parma, via Farini, 90, 43121 Parma, Italy
Raman spectroscopy is a powerful tool to determine the biomineralized structure, the

nature of the pigments and the presence of artificial dyes in corals and pearls [Kupka
et al., 2010; Karampelas et al., 2007]. Here we report on Raman measurements at
473.1 nm on white to pink to red corals, both calcitic and aragonitic, and on
freshwater and saltwater pearls, to clarify the structure of the skeleton and the nature
of the pigments. Methylated (carotenoids) or non-methylated polyenes have been
proposed as responsible for the color associated with marine mineralized organisms
and the debate about the nature of the pigments in corals and pearls is still open
[Maia et al., 2011, Cvejic et a. 2007]. The resonance condition of the laser excitation
enables the observation of overtones and combinations of four main vibrational
modes of the polyenic or carotenoid pigment up to > 5000 cm -1. Corallium rubrum
coral (calcitic) and Stylaster sp. coral (aragonitic) have been investigated and
compared with museum species. The different nature of the pigments is evidenced:
in Stylaster corals the pigment main frequencies characteristic of methylated
polyenes (carotenoids like -carotene, canthaxanthin or astaxanthin) are observed
(Fig.1).
Fig. 1 Raman spectra in (calcitic) Corallium rubrum and in aragonitic Stylaster sp.

109
In addition, artificially dyed bamboo corals may be easily identified by Raman
spectra (Fig. 2).
No trace of dyeing is found in white freshwater cultured pearls, while the resonance
Raman spectrum of salt-water white pearls evidences a small quantity of polyenic
pigment.
Fig. 2 Raman spectra of some dyed commercial bamboo corals and of Isidella elongata
coral.
Resonance Raman spectra with 473.1 nm excitation line are helpful to reveal small
quantities of pigments involved in the coral or pearl coloration and are important
tests for the vibrational properties of the polyenic or carotenoid molecules.
References
Kupka, T.; Lin, M. H.; Stobiski, L.; Chen, C.-H. ; Liou, W.-J.; Wrzalike, R.; Flisak, Z. Journal
of Raman Spectroscopy 2010; 41: 651-658.
Karampelas, S.; Fritsch, E.; Mevellec, J.-Y.; Gauthier, J.-P.; Sklavounos, S.; Soldatos, T..
Journal Raman Spectroscopy 2007; 38: 217-230.
Maia, L. F.; Fleury, B. G.; Lages, B. G.; Barbosa, J. P.; Pinto, A. C.; Castro, H.V.; de Oliveira,
V. E.; Edwards, H. G. M.; de Oliveira, L. F. C. Journal of Raman Spectroscopy 2011; 42,
653658.
Cvejic, J.; Tambutt, S.; Lotto, S.; Mikov, M.; Slacanin, I.; Allemand, D. Marine Biology 2007,
152, 855-862.

110
Early Taoism and Chemistry. Archaeometrical Studies on
Man-made Barium Copper Silicate Pigments from a Tomb of
Eastern Han Dynasty (25-220 A.D.)
Heinz Berke1, Qinglin Ma 2, Tristan Corbire1, Zhiguo Zhang2,

Ferdinand Wild1
1
University of Zurich, Institute of Inorganic Chemistry, Winterthurer Str. 190, CH-
8057 Zurich (Switzerland), Tel. +41 446354681, hberke@aci.uzh.ch
2
Chinese Academy of Cultural Heritage, No.2 Gao Yuan Street, Chao Yang District,
Beijing 100029, PR China
Originating from the later period of Eastern Han Dynasty (25-220 A.D.) pottery jars
containing colored bulk pigment material were excavated from a tomb in Sanmenxia,
Henan province, China. The blue jar contained well-preserved and not significantly
weathered, powdery and grained greenish-blue and purplish-blue Chinese pigment
material, which was characterized by Raman microscopy and Scanning Electron
Microscopy (SEM) including Energy Dispersive X-ray Spectrometry (EDX).
Figures below. Left: The Samenxia blue Jar. Right: The purplish- and greenish-blue
pigment grains.
The partly vitreous and partly crystalline material consisted of quartz, dolomite,
calcium magnesium silicates (diopside, CaMgSi2O6), jadeite (NaAlSi2O6), barium
carbonate, sulphate or
silicate, lead carbonate,
galena (PbS), type I
lead/tin yellow (PbSn1-
xSixO3) and barium copper
silicates as base
constituents. The man-
made barium copper
silicates [1] rendered to be
the blue and purple
colorants Chinese Purple
(BaCuSi2O6) and Chinese Blue (BaCuSi4O10) in minor amounts and in contrast to
other ancient Chinese artifacts Chinese Dark Blue (BaCu 2Si2O7) in prevailing
amounts [2]. The greenish colorants were assigned to be either iron containing
diopside related to Hedenbergite (CaFeSi 2O6), which apparently originated from
heat-treated nephrite (green jade). Alternatively, the green colour was associated
with tetrahedral Cu(II) dissolved in vitreous phases of barium or barium-lead glass.
A related material with greenish, bluish or purplish appearance was prepared by Le
Chatelier and published 1900 in a patent [3]. In addition the green tone could be
generated from the mixture of blue and yellow pigments. The content of the
Sanmenxia blue jar was found to be coarsely heterogeneous, presumably produced
with short reaction times and a reaction temperature of over 840 C. By independent
synthesis studies on the barium copper silicates we could conclude that the synthetic
conditions must have deviated somewhat from those of the Han period procedures
for refined material.
From a utility point of view the coarse heterogeneity and the diverging mixture of
colorants of the blue jar content was attributed low pigment quality. Therefore we
have to assume that the synthetic mixture was not created for pigment purposes,
111
rather on spiritual grounds with the bluish-purplish-greenish colour tones and the
substantial jade additive standing for the presence of Taoist Deities lending
protection to the dead in the tomb and repelling evil spectres.
Acknowledgements. We would like to thank Dr. Zhou Yin from the Institute of
Inorganic Chemistry at the University of Zurich for his help in Raman microscopy and
SEM-EDX measurements. Thanks are also conveyed to researchers Xingtao Wei
and Xiaolin Ma, the archaeologists of the Institute of Cultural Relics and Archaeology
of Henan Province (China) for providing the samples. We are also very grateful to
Bhler AG, Flawil, Switzerland for access to and advice in high energy milling. The
archaeometrical work was carried out in 2009 under the auspices of a visiting
professorship project from the Institute of Inorganic Chemistry, University of Zurich
and the Laboratory of Inorganic Chemistry, ETH Zurich, Switzerland, provided to
Qinglin Ma.
References
[1] Berke H, Chem. Soc. Rev. 2007; 36:15.

[2] Berke H, Corbiere T, Portmann A, Freisinger E, Wild F, Wenbo, Shanxi, China, 2009,
251.
[3] A.F. Le Chatelier, Patent # 112 761, Verfahren zur Herstellung von grnen, blauen
und violetten Mineralfarben aus Kieselsure und Baryum- und Kupferverbindungen,
Kaiserliches Patentamt, Berlin, Germany, issued 1900.

112
Identification of copper hydroxychlorides and other corrosion
products of bronze artefacts by micro-Raman spectroscopy
Giulia Bertolotti 1, Danilo Bersani1, Pier Paolo Lottici1,

Marcella Alesiani2, Thomas Malcherek3, Jochen Schlter3
1
Dipartimento di Fisica, University of Parma, Viale G.P. Usberti 7/a, 43100 Parma,
Italy
2
Dipartimento di Energetica, University of Rome La Sapienza, Via A. Scarpa 16,
00161 Rome, Italy
3
Mineralogisches Museum, Universitt Hamburg, Grindelallee 48, D-20146
Hamburg, Germany
Three bronze samples created by CNR-ISMN (National Research Council - Institute

of Nanostructured Materials) to be similar to Punic and Roman coins found in
Tharros (OR, Sardinia, Italy) were studied to implement a Raman analytical protocol
to identify corrosion products on archaeological artefacts and enlarge existing
databases of reference spectra, particularly for what concern copper
hydroxychlorides (Cu2(OH)3Cl). Micro-Raman spectroscopy is suitable to investigate
bronze corroded surfaces as it is a non-destructive technique, it has high spatial
resolution and it gives the opportunity to discriminate between polymorphs and to
correlate colour and chemical composition. The characteristic Raman peaks of the
green copper hydroxychlorides, atacamite, paratacamite, clinoatacamite and the
recently discovered anatacamite, were identified by acquiring spectra of reference
samples (natural minerals and a powder scraped from an archaeological bronze)
previously characterized by x-ray diffraction, electron microscopy and infrared
spectroscopy. A large amount of them was detected on all the coins, mainly
paratacamite and clinoatacamite. The most widespread corrosion product on the
samples, besides hydroxychlorides, was red copper oxide cuprite (Cu2O). Other
corrosion products of the alloying elements (laurionite, plumbonacrite, zinc
carbonate) and those resulting from the interaction sample-soil components
(anatase, calcite, hematite) were also found. This study shows that identification of
corrosion products, including discrimination of copper hydroxychlorides, could be
accomplished by micro-Raman on valuable objects, such as archaeological findings
or works of art, avoiding any damage due to the extraction of samples or to the use
of a destructive analytical technique.

113
Analysis of XIX-XX century pigmented filler of tombstone
inscriptions of the Monumental Cemetery Villetta of Parma
Michela Berzioli1, Antonella Casoli1, Danilo Bersani2, Pier Paolo Lottici2,

Francesca Vignali1
1
University of Parma, Department of General and Inorganic Chemistry, Analytical
Chemistry and Physical Chemistry, Viale G.P. Usberti 17a, 43124 Parma (Italy), Tel.
+39 0521 905425, antonella.casoli@unipr.it
2
(Italy), Tel. +39 0521905278
The Villetta of Parma is the urban cemetery dating back to the beginning of XIX
century at the time of Maria Luigia of Austria government. Designed as a city with
orthogonal streets and chapels, it is rich in memorial monuments of great value for
Parma history.
The inscriptions show ancient prayers, signatures, dedications that reflect a singular
approach to the commemoration of the dead person no longer in use (Fig. 1). The
materials used for making inscriptions have not been widely studied yet: their
knowledge is important to understand ancient recipes and to identify suitable
conservation treatments.
This work is focused on the study of pigmented pastes filling carved inscriptions
preserved both along the Portico and inside the Galleries of the monumental
cemetery. They show heterogeneous conservation conditions up to the loss of
legibility.
Fig.1 - Slate tomb with dedication made of pigmented pastes filling the carved inscription.

114
Fig 2 - Black pigmented decoration changed to green.
The Raman spectroscopy analyses resulted the main useful technique to

characterize these particular pastes and their alteration products; the obtained
results were confirmed by micro-FTIR spectroscopy (ATR) and elemental analysis
coupled with the scanning electron microscope.
Black pastes, based on Carbon and Calcite, grey pastes, Carbon and Barium
Sulfate, and red one of Hematite were found on white marble tombs; gildings on
gypsum-based preparation layer and more recently yellow paste made of lead
chromates were used on slate and other dark stones.
Organic material, ranging from paraffin waxes to proteins and lipidic substances,
were also identified.
Most of the originally black inscriptions have changed to green (Fig. 2) due to the
formation of copper compounds such as Atacamite/Paratacamite, antlerite, copper
oxalates (Moolite) [Frost, 2004] copper and zinc metal soaps. The gilding layers
have detached leaving out the gypsum-made preparations.
The stratigraphy of many pastes allowed to recognize the subsequently added
materials: paraffin waxes, modern painting layers made of Rutile and lead
chromates.
The conservation planning in the monumental area of Villetta in Parma has been
defined thanks to the collected data.
Acknowledgements. This work has been financially supported by Comune di Parma,

Italy. The Authors gratefully acknowledge dott. Gabriele Righi.
References
Frost R.L., Raman spectroscopy of natural oxalates Analytica Chimica Acta 2004; 517: 207.

115
Pablo Picasso to Jasper Johns: a Raman Study of Cobalt-
Based Synthetic Inorganic Pigments
A. Bezr1, F. Casadio2, I. Fiedler2, G. Gautier2, Kim Muir2

1
The Museum of Fine Arts, Houston, P.O. Box 6826, Houston, TX 77265-6826
2
The Art Institute of Chicago, 111 S. Michigan Ave., 60603 Chicago, IL, USA. Tel:
+1.312.857.7647; email: fcasadio@artic.edu
For the past several decades Raman microscopy has been an important method
for the characterization of pigments used in fine arts, archaeology and historic
architecture. However, while considerable effort has been devoted to the scientific
investigation of old masters techniques and materials and recent interest has been
focused on modern synthetic organic pigments, the Raman study of synthetic
inorganic pigments has garnered comparatively little attention.
This work was prompted by the in-depth analysis of the paintings Near the
Lagoon (2002-3) by American painter, sculptor and printmaker Jasper Johns
(b.1930) and Pablo Picassos (1881-1973) The Red Armchair (1931) both in the
collection of the Art Institute of Chicago [Gautier et al. 2008; Bezur et al. 2008]. The
detection of cobalt greens and violets in these two paintings, respectively, provided
the motivation for a systematic study of these pigments to establish a reference
database because published Raman spectra were not available for comparison.
Approximately twenty reference samples of artists cobalt-based green and violet
pigments from various manufacturers, including some historical samples from
Lefranc & Cie and contemporary samples provided directly by Jasper Johns studio
were fully characterized. Complementary techniques such as Fourier Transform
Infrared spectroscopy (FTIR), x-ray fluorescence spectrometry (XRF) and x-ray
diffraction (XRD) were used to confirm the composition and check the purity of the
reference materials; however, the only viable techniques to characterize microscopic
cross sections from the studied artworks were scanning electron microscopy with
energy dispersive x-ray spectrometry (SEM/EDS) and Raman microscopy.
Specifically, Raman spectra are presented here for various cobalt titanate
greens (Co2TiO4), as well as the cobalt violets magnesium cobalt arsenate (MgnCo 3-
n(AsO4)2), ammonium cobalt phosphate hydrate (NH 4CoPO4H2O), cobalt phosphate
octahydrate (Co3(PO4)28H2O), and anhydrous cobalt phosphate, Co 3(PO4)2. To the
best of our knowledge only the Raman spectra for erythrite (the octahydrate of
cobalt(II) arsenate), and its partially dehydrated forms have been published in the
literature [Frost et al. 2004; Martens et al. 2003], but these constitute only a minor
component of commercial cobalt violet pigments [Corbeil et al. 2002].
The multi-analytical methodology allowed the identification of the unknown
green pigment used by Jasper Johns as cobalt titanate green (C.I. PG 50) whose
complete vibrational features are fully illustrated here. Both cobalt violet light
(magnesium cobalt arsenate) and dark (a mixture of anhydrous and octahydrate
cobalt phosphate) were identified in the Picasso painting.
These case studies illustrate not only the analytical challenges related to the
identification of modern pigments but also the importance of having reliable and
extensive collections of reference spectra. This research advances our knowledge of
the Raman characterization of synthetic cobalt-based artists pigments, adding
valuable data to the recently published database of cobalt-blue pigments [Bouchard
2010], and provides important elements for the documentation of notable
occurrences of these pigments in actual artworks.

116
Acknowledgements. The authors would like to thank the A.W. Mellon Foundation,
Jerrold A. Carsello, Douglas Druick, Stephanie DAlessandro, James Rondeau,
Allison Langley, Kelly Keegan, Kristin Lister, James Meyer, Jamie Stukenberg,
Joseph Barabe, the Shepherd Color Corporation, and the Ferro Corporation. SEM-
EDS work was performed in the EPIC facility of NUANCE Center at Northwestern
University. NUANCE Center is supported by NSF-NSEC, NSF-MRSEC, Keck
Foundation, the State of Illinois, and Northwestern University.
References
Bezr A., Muir K. in Book of Abstracts of the Eight Biennial Conference of the Infrared and
Raman Users Group, Vienna, 2008, 96.
Bouchard M., Gambardella A. Journal of Raman Spectroscopy 2010; 41: 1477.
Corbeil, M.-C.; Charland, J.-P.; Moffatt, E. A. Studies in Conservation 2002; 47: 237.
Frost, R. L.; Martens, W.; Kloprogge, J. T. Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy 2004; 60: 343.
Gautier G., Fiedler I., Casadio F., Keegan K., Lister K.in Book of Abstracts of the Eight
Biennial Conference of the Infrared and Raman Users Group, Vienna, 2008, 101
Martens, W.; Frost, R. L.; Kloprogge, J. T. Journal of Raman Spectroscopy 2003; 34: 90.

117
Micro-Raman Spectroscopy for the Characterisation of
Artistic Patinas Produced on Copper Base Alloys
Valeria Bongiorno1, Serena Campodonico1, Roberta Caffara1,

Paolo Piccardo1, Maria Maddalena Carnasciali2
1
University of Genoa, Department of Chemistry and Industrial Chemistry, Via
Dodecaneso, 31, 16146 Genoa (Italy), Tel. +39 0103536116,
serenacampodonico@gmail.com ;
2
INSTM and DCCI, Via Dodecaneso 31, 16146 Genoa (Italy).
In order to contribute to the improvement of restoration and conservation sciences of

metallic artefacts belonging to the Cultural Heritage (such as bronze statues) a wide
research, supported by Region Liguria and by the University of Genoa, has been
started on the study of artificial (artistic) and natural (corrosion or alteration) patinas
of copper base alloys. Micro-Raman Spectroscopy, coupled with SEM and EDXS
microanalyses, were applied for the characterization of a number of patinas realized
on metallic substrate meant to reproduce the typical quaternary copper base alloys
(Cu, Sn, Zn, Pb) used on statuary. A non-alloyed copper sheet has been also used
to simulate the architectural cover typically used after a specific cold spray coating.
The term artistic patina describes coating layer applied by the artist or the
foundryman on a metal artworks with aesthetic and protective purposes: it is in fact
possible to have a chromatic effect by obtaining the desired colour on the surface of
the metallic support using several kind of techniques ranging from cold applications
of solutions or pastes to hot treatments with the use of a reagent and a torch. Once
the patina has been obtained it has also a protective function being the interface
between the metallic substrate and the environment and it should be resistant in
order to not modify its colour in a too fast way. Nevertheless artists are used to say
the patina is alive meaning that the interaction between patinas and environment
produces an evolution in the patina composition that might correspond in a change
of colour and of reactivity. It is not clear so far in which amount these reactions are
affecting the metallic substrate and the nature of the reaction mechanisms involved.
This work is the first step of a more extensive research activity that investigates the
field of patinas and metallic substrates contributing to the study of protective efficacy
of inorganic artistic patinas and their rate of decay. To reach these goals a number of
patinas were experimentally produced in laboratory (DCCI, University of Genoa) on
as cast copper base alloys. The coating techniques and experimental parameters
are reported in [Hiorns, 1892; Kaup et al., 1914; Huges et al. 1991] and, for a few
specific treatments, based on interviews of artists and artisans specialised in such
activities. Among the applied methods there are: cold or hot immersion in reactive
solutions, application of pastes of reactive salts, torch on the surface after the
application of the reactive solution. These patinas are characterized by surface
techniques (e.g. SEM-EDXS, Micro-Raman Spectroscopy, X-Ray Diffraction) and
cross sections in order to observe the interface between the coating and the metallic
substrate (Figures 1 and 2). EIS measurement will be applied on the freshly made
patina and after several steps of ageing in salt spray chambers in order to check the
evolution of the patina. Surface and cross section analyses will be performed on
aged samples after an intermediate step and the final period of ageing. Micro-Raman
Spectroscopy is therefore considered of fundamental importance due to its
peculiarities: samples dont need any specific preparation and can be analysed after
the first phase of ageing and then placed in the salt spray chamber for a second step
of treatment; the results are immediate and then a rapid evaluation of the situation is
possible.
118
This paper is reporting the data acquired by Micro-Raman Spectroscopy analyses
ofthe patinas as-produced in our laboratories. For several reason and mainly to be
more consistent with the artisans practice on the statuary the results will only
concern the coating by torch (i.e. the metallic surface is heated by the flame of a
burner before and after application of the coating solution). The reactive solutions
are based on water as a solvent containing respectively copper nitrate (pale green),
iron nitrate (brown) and potassium sulphide (also known as liver of sulphur for a
dark brown colour) [Huges, 1991]. The only exception is a sample reproducing the
architectural cover of a recent building (first half of the 90s) and nearly completely
covered with copper sheets coated with copper salts. The indications on the building
journal are really precise concerning the coating and allowed us to exactly reproduce
the procedure. The water solution contains copper sulphate, ammonia and
ammonium sulphate, and is simply sprayed on the copper surface.
The latter is the only example we have of a known evolution of a patina from the
original one observable on the as-coated samples (basically copper sulphate) to the
one of the building covers after nearly 25 years of outdoor exposure (hydrated
copper chloride. The salt spray chamber will allow, thanks to the step by step
monitoring by Micro-Raman Spectroscopy, to investigate the evolution of such a
patina between the two known terms and therefore the reactions involved in all
patinas produced so far.
Figure 1 SEM-BSE image of an artistic Figure 2 Micro-Raman spectrum of the

patina produced by torch technique and same sample in figure 1.
a solution of water and copper nitrate.
Acknowledgements. This work has been financially supported by REGIONE (P.O.

C.R.O. FSE 2007-2013, Asse IV Capitale umano Ob.specifico i/4, I/5), 12.05.2009 n
533, project Study and conservation of metallic artworks belonging to the Cultural
Heritage of Liguria.
References
Hiorns A.H., in Macmillian and co. (Editors), Metal colouring and bronzing, London-New York,
1892, pp. 95-256.
Huges R., Rowe M., in Thames & Hudson (Editors), The colouring, bronzing and patination
of metals, London, UK, 1991, pp. 9-1.
Kaup W.J., Lake E.F., Metal colouring and finishing Methods of producing colours on iron,
steel, copper, bronze, brass and aluminium Burnishing metals, The Industrial Press, New
York, USA, 1914, pp. 3-26.

119
Characterization of verdigris on 16th century Turkish paper
with micro-Raman spectroscopy
Pnar akar1,2, Ayegl Belet1 and Merve Er1

1
Restoration and Research Center, Suleymaniye Manuscript Library, Ayse Kadin
Hamami Sok 35, 34116 Istanbul (Turkey) Tel. +90 2125206460,
pinar-cakar@hotmail.com
2
Yildiz Technical University, Davutpasa Campus, Department of Chemical
Engineering, Davutpasa Cad, 34210 Istanbul (Turkey)
Verdigris was a common pigment used on manuscripts in order to obtain green-blue

color. Its a copper corrosion product and basically can be defined as an acetate of
copper [Kuhn, 1970]. Many recipes were reported by ancient authors and its
destructive effect on supports is well known [Baonza et al., 2007], [Clark et al.,
2006]. In this study we synthesized verdigris by following a recipe given by an
ancient Turkish master. Then we applied the pigment on a 16th century paper using a
traditional binding medium and artificially aged it. A series of Raman spectra was
collected to characterize the pigments behaviour on paper. A complementary study
was done by means of XRF spectrometer.
References
Kuhn H., Studies in Conservation, 1970, 15, 12

Roja J.M, Boanze V.G., Andrs M. Spectrochimica Acta Part A 2007; 68: 1120
Chaplin T., Clark R., Scott D., Journal of Raman Spectroscopy, 2006, 37, 223

120
Study of a 3rd generation commercial cement superplasticizer
by spectroscopic techniques: UV-Visible, Raman and SERS
Maria Vega Caamares1, Sagrario Martnez 1

and Santiago Sanchez-Cortes1
1
Consejo Superior de Investigaciones Cientficas (CSIC), Instituto de Estructura de
la Materia, Calle Serrano 121, 28006, Madrid (Spain), Tel. +34 915616800,
mvca@iem.cfmac.csic.es
Artificial building materials have been used since Ancient times. Egyptians used
calcinated impure gypsum. Greeks and Romans first used calcinated limestone and
later learnt to ground lime with clays and pozzolans producing the first hydraulic
binding materials. It is well documented the use of different natural admixtures such
as egg, urine, blood, etc. in order to improve different properties of building
materials. So far large improvements have been done regarding knowledge and
development of artificial admixtures.
An admixture is a chemical product added to the concrete mix in quantities no larger
than 5 % by mass of cement during mixing, in order to achieve a specific
modification of the normal properties of concrete. Admixtures are usually classified
by their function in concrete such as: water-reducing, retarding, accelerating,
superplasticizing, etc. Superplasticizers are admixtures which are high range water
reducing [Neville et al. 1995]. They are polymers that maintain an adequate
workability of concrete at low water to cement ratio, for a reasonable period of time,
without affecting the setting and hardening behaviour of the cementitious system
[Ramachandran et al., 1998]. Figure 1 shows the general structure of a
polycarboxylate based superplasticizer. The main action of the polymers is to wrap
themselves around the cement particles and give them a high negative charge so
they repel each other.
Carboxylate groups
Polymer backbone chain
Neutral side chains
Figure 1. General structure of a polycarboxylate based superplasticizer.
One of the main objectives in restoration and conservation projects is to use

materials and methods as similar as possible to the one to restore. In this context it
is very important to know all the components in the original material. No information
about admixtures has been done so far. This is due to the difficulty of analysis of
these polymers because their low concentration.
The use of Raman spectroscopy can be appropriate for the study of commercial
superplaticizers. This technique gives important structural information, providing an
easy identification of these products. However, in the study of organic materials,
such as superplasticizers, fluorescence may quench the Raman signal. Besides,
they are added in very low proportions to the cement paste ( 5% of cement weight),
making its identification quite difficult. However signal-enhancing methodologies, like
surface enhanced Raman scattering (SERS) have been developed in recent years
for studying organic materials by Raman spectroscopy in complex matrixes.
[Caamares et al. 2010, Leona, 2009].
121
The objective of this work is the characterization of a commercial 3 rd generation
superplasticizer by different spectroscopic techniques since the only information
provided was that the modified polycarboxylate (PC) based admixture was made up
from two different polymers. It is important to say that commercial products are also
composed by biocides, air-entraining products, etc. Thus, the work comprises
analysis of polymers in complex matrixes. Several spectroscopic techniques were
applied in order to characterize the superplasticizer. UV-visible, Raman (figure 2)
and SERS spectra in different conditions (such as pH, silver colloids, excitation
wavelength, concentration) were recorded and a tentative structure of the
polycarboxylate was proposed.
292
487
Raman intensity / Arbitrary Units
2924
851
1474
1285
1136
1042
1715
3500 3000 2500 2000 1500 1000 500

-1
Wavenumber / cm
Figure 2. FT-Raman spectrum of a polycarboxylate based (3rd generation) commercial

superplasticizers (liquid state). Excitation at 1064 nm. Natural pH conditions (~5).
Acknowledgements. This work has been financially supported by Direccin General

de Investigacin, Spain (Project FIS2010-15405). The authors also acknowledge
Sika for their collaboration. M.V.C acknowledges CSIC for a JAE-postdoctoral
position.
References
Caamares MV, Leona M, Bouchard M, Grzywacz CM, Wouters J, Trentelman K. Journal of

Raman spectroscopy 2010; 41: 391.
Leona M. Proceedings of the National Academy of Sciences USA 2009; 106: 14757.
Neville A.M, Properties of Concrete, Addison Wesley Longman Limited, Essex, England,
1995.
Ramachandran S, Malhotra VM, Jolicoeur C. y Spiratos N, Superplasticizers: properties and
applications in concrete, CANMET, Ottawa, Canada, 1998.

122
A study by Micro-Raman spectroscopy and FT-IR of ambers
and copals
Annalisa Casella, Andrea Baraldi, Danilo Bersani, Rosanna Capelletti

and Pier Paolo Lottici
(Italy), Tel. +39 0521905278, annalisa.casella@studenti.unipr.it
Here we report on a study of fossil and subfossil resins by means of micro-Raman

and FT-IR absorption spectroscopies.
Raman spectroscopy is a fast and non-destructive technique and it requires no

sample treatment; the only limit is due to the strong fluorescence which decreases
the signal-noise ratio. More information may be obtained by FT-IR.
Micro-Raman and FT-IR spectra have been collected from ambers, copals, samples
of unknown origin and fakes: characteristic bands have been identified and their
relevance for provenance identification or as maturity tests has been discussed.
The presence of the Baltic shoulder [1] in the FT-IR spectra, identifying a type of
vegetation which produced the resin, is usually assumed as an indication of the
geographical origin (Baltic), but can also be found it in the spectra of ambers of
different origin [2].
The analysis by means of vibrational spectroscopy is commonly used to discriminate

between mature and immature resins on the basis of:
- the intensity of the IR and NIR peaks attributed to exocyclic methylene groups [1,3-
5] at 887, 1645, 3080 cm-1 and of the overtones at 6115 cm-1 and 9077 cm-1. With
increasing polymerization (i.e. with the increasing maturity), the exocyclic methylene
groups should decrease, due to the isomerization towards a more stable isomer.
Oxidative alteration, which destroys the exocyclic methylene bond, as well as heat
treatments, could produce a decrease of the exocyclic methylene groups [1, 3].
- the type of Raman spectrum (broad band for ambers, sharper band for copals [6]),
in particular [4] the spectral profile in the region 765-680 cm-1 (a doublet for copals, a
broad band followed by a weak shoulder for ambers).
The very weak peak at 2335 cm-1 observed by FT-IR spectroscopy has been
attributed to CO2 absorbed in bubbles in resins [7], which might be the characteristic
product of a wide range of bacterial and fungal fermentations [5]. It might also be the
product of a partial reaction between O2 and the amber [8].
Vibrational spectroscopy can also easily identify fakes from original ambers: we
show spectra taken from samples made by polystyrene and polyester resin.
The best method to determine the maturity of amber would be the creation of a
spectra database of resins of controlled origin and age.

123
References
[1] Guiliano M., Asia L., Onoratini G. and Mille G., Spectrochim. Acta, Part A 2007; 67: 1407.
[2] Edwards H.G.M., Farwell D.W. and Jorge Villar S.E., Spectrochim. Acta, Part A 2007; 68:
1089.
[3] Jehlika J., Villar S.E. and Edwards H.G.M., J. Raman Spectrosc. 2004; 35: 761.
[4] Brody R.H., Edwards H.G.M. and Pollard A.M., Spectrochim. Acta, Part A 2001; 57: 1325.
[5] Wolfe A.P., Tappert R., Muehlenbachs K., Boudreau M., McKellar R.C., Basinger J.F. and
Garrett A, Proc. R. Soc. B 2009; 276: 3403.
[6] Winkler W., Kirchner E.Ch., Asenbaum A. and Musso M., J. Raman Spectrosc. 2001; 32:
59.
[7] Matranga C. and Bockrath B., Journal Phys. Chem. B 2004; 108: 6170.
[8] Berner R.A. and Landis G.P., Am. J. Sci. 1987; 287: 752.

124
DFT, FT-Raman, FT-IR, NMR and UV-Vis studies on a
hetarylazo dye
Berna atkka1, Ebru Aktan2, Z. Seferolu2

1
University of Mustafa Kemal, Physics Department, Serinyol, 31034 Hatay (Trkiye),
Tel. +90 5305920225, agberna@yahoo.com
2
University of Gazi, Department of Chemistry, Teknikokullar, 06500 Ankara
(Trkiye),
Azo compounds have been very important in the field of dyes, pigments and
advanced materials for a long time [Hunger, 2003]. It has been known for many
years that the azo compounds are the most widely used class of dyes, due to their
versatile applications in various fields such as the dyeing of textile fibers, the coloring
of different materials, colored plastics and polymers, biological-medical studies and
advanced applications in organic synthesis [Hunger, 2003, Zollinger, 2003]. In
addition, they are legendary for their incredible saturated colour, sharpness, archival
stability and iridescent three-dimensional realism unmatched in photographic art.
Since azo dyes uses on a polyester base, the print will not fade, discolor or
deteriorate. As the colors formed from the azo dyes are more stable, the prints made
from the process are archival and insisted on by galleries and art collectors as they
will not fade in normal light.
In this study, the experimental and theoretical results on the molecular structure of a
azo dye, 1-Methyl-2-phenyl-3-(1,3,4-thiadiazol-2-yldiazenyl)-1H-indole are
presented. The molecular geometry and vibrational wavenumbers of the compounds
have been calculated in ground states by using DFT/B3LYP functional with 6-
311+G(d,p) basis set used in calculations [Becke, 1993, Lee et al, 1998]. The proton
and carbon chemical shifts were calculated using the gauge-independent atomic
orbital (GIAO) approach [Dichfield, 1974]. The theoretical electronic absorption
spectra were calculated using time-dependent density functional theory (TD-DFT).
The calculations have been performed using the Gaussian 03 package program.
The Fourier transform Raman and Fourier transform infrared spectra of the molecule
were recorded in the solid phase. The total energy distributions (TED) of the
fundamental modes have been obtained by using Scaled Quantum Mechanical
(SQM) program. Finally, geometric parameters, vibrational wavenumbers and
chemical shifts were compared with available experimental data of the molecule.
References
Hunger K, Industrial dyes, chemistry, properties, applications. Weinheim: WILEY-VCH Verlag
GmbH& Co. KgaA; 2003; 2035.
Zollinger H, Color chemistry: synthesis, properties and applications of organic dyes and
pigments. 3rd, revised edition. Wiley-VCH; 2003.
Becke AD, Journal of Physical Chemistry 1993; 98: 5648.
Lee C, Yang W, Parr RG, Physical Review B 1998; 37: 37785.
Dichfield R, Molecular Physics 1974; 27: 789.

125
A multivariate integrated study of red slipped ceramics by
micro- Raman and SEM techniques
Marco Cavalieri1, Antonia Fumo3, Marilena Ricci3, Cristiana Lofrumento4

1
Department of Archaeology and History Art, Institute for Civilizations, Arts and
Literature Universit catholique de Louvain (UCL) Place B. Pascal, 1 Collge
Erasme 1348 Louvain-la-Neuve Belgium
3
Dipartimento di Costruzioni e Restauro Universit di Firenze, Via Micheli 8 50100
Firenze (Italy)
4
Dipartimento di Chimica- Polo Scientifico e Tecnologico Universit degli Studi di
Firenze, Via della Lastruccia 3, 50019 Sesto Fiorentino, Firenze, (Italy)
In the archaeological site of Aiano-Torraccia di Chiusi (Siena-Italy) the remains of a

Roman Villa, dated between the beginning of 4th century and the end of the 5th
century or the beginning of the 6th A.D., were discovered. The complex, abandoned
in the 6th century A.D. was occupied by a group of barbaric artisans, in the period
between the 6th and the 7th century A.D.
The area had never been studied before the summer of 2005, when the Universit
catholique de Louvain (UCL, Belgium) decided to start an international project, called
VII Regio. Elsa Valley during Roman Age and Late Antiquity, to systematically
explore the site and re-examine, on the basis of new data, the numerous questions,
on the population, the economy, the rural environment, etc. of the Valdelsa area in
the Roman period.
Numerous ceramic findings (acrome grezze, ingobbiate, acrome depurate and
semidepurate, sigillate africane) were discovered in the archaeological site; dated 5-
7th century, they characterize the phases of existence, neglect and collapse of the
structure and of the Late Roman and early Middle Ages re-use.
The abundance of the so-called ceramics ingobbiate (red slipped) and their relative
large diffusion, represents a strongly element characterizing the last re-use phase of
the villa. This prompts to the Universit catholique de Louvain and to the University
of Florence to perform a complete archaeometry study of these ceramic typologies.
The red slipped ceramics were analyzed using different analytical methodologies
(OM, SEM- EDS, ATR FTIR and micro-Raman) in order to characterize the paste
and the cover of the ingobbiate and to determine the compositional relationship
among different kinds of ceramics. [Cantisani et al.]
The micro-Raman technique allowed dealing with a terminological difficult subject
about the cover too.
References
Cantisani E., Cavalieri M., Lofrumento C., Pecchioni E., Ricci M. Archaeological and
Anthropological Science, submitted.

126
Study of ancient ceramic potteries by different applications of
Raman spectroscopy
Giulia Cavazzuti1, Greta Zancan2, Giuseppe Capobianco2, Giada Mercuri2

Emma Salvioli-Mariani1, Danilo Bersani 2, Manuela Catarsi3
1
University of Parma, Dipartimento di Scienze della Terra, Viale G. P. Usberti 157a,
43124 Parma (Italy).
2
University of Parma, Dipartimento di Fisica, Viale G. P. Usberti 7a, 43124 Parma
(Italy). greta.zancan@studenti.unipr.it.
3
Soprintendenza per i Beni Archeologici dell'Emilia-Romagna, Museo Archeologico
Nazionale di Parma, Palazzo della Pilotta, I-43121 Parma, Italy
The study of ancient pottery by means of Raman spectroscopy has a number of

significant advantages, allowing the identification of the main minerals present in the
bodies and coatings. Thanks to this information it is possible to infer the firing
temperature and atmosphere of the artifacts. Here are presented several cases of
study having the Italian production as common denominator.
Raman spectroscopy on ceramic body is an important tool to identify the temper
fragments, as we can observe in some sherds coming from the Longobard
necropolis of Collecchio (Parma, Emilia Romagna, middle of the VII century AD).
The analysis has detected the presence of quartz, calcite and talc. The latter is a
typical component of steatite, a Mg-silicate-rich rock.
Regarding the matrix, Raman spectroscopy offers the possibility to detect the
presence of metal oxides, responsible for the color of the groundmass and
diagnostic for the firing temperature and atmosphere. This investigation has been
carried out on the bodies of cooking potteries from Porto Torres (Sassari, Sardegna),
produced between V and VII century AD. Hematite and magnetite have been
identified: the first is formed during the firing up to 400C, because of the
dehydroxylation of iron hydroxides, and at higher temperatures (800C), because of
the release of iron from clay minerals. Magnetite appears under reducing conditions
and above 800C as a metastable phase in the conversion of hematite in Fe 2+ oxide
[Jones, 1986].
Like the dough, clayey coatings owe their color to the presence of metal oxides, as in
the case of black-painted ceramics found in archaeological sites of Parma and dating
back to Roman times (IV century BC - I century AD). The results of Raman
investigations of these sherds has shown magnetite (fig.1) as the main component of
the coating, made of Fe2+-rich clays.
Fig.1

127
Raman spectroscopy is useful to investigate feldspar minerals often present in
ancient potteries, both as temper grains and as components of the matrix. A
systematic analysis was carried out by comparing the shift of the peak at 507-515
cm-1 and at 470-490 cm-1, which allows discriminating feldspars into four categories:
orthoclase-microcline-sanidine, andesine-labradorite, albite and anorthite. It is also
possible to determine the degree of structural order of the mineral considering the
bandwidth. The content in feldspars has been studied both for Roman finds of
Parma and for those of Porto Torres, mentioned above. As shown in the chart (fig.2),
the first ones have a prevalence of single crystals of albite and orthoclase, which are
the main components of Emilian Apennines sandstones together with quartz and
mica minerals. In the Sardinian sherds there are andesine, albite and orthoclase that
characterize the volcanic rocks of pre-Langhian (trachyandesites and trachydacites)
outcropping to the south-east of the archaeological site and transported in situ by
Rio Mannu.
Fig.2
References
Jones R.E., Greek and Cypriot pottery. A rewiew of scientific studies, British School at
Athens (Fitch laboratory occasional paper 1), Athens, Greece, 1986, pp. 751-73.

128
Characterization and provenance studies of garnet chlorite schist
archaeological artifacts using micro-Raman spectroscopy
Talisa Cerasoli1, Alessia Coccato1, Danilo Bersani1, Pier Paolo Lottici1,
Roberta Conversi2
1
(Italy), Tel. +39 0521905278, danilo.bersani@fis.unipr.it
2
Soprintendenza per i Beni Archeologici dell'Emilia-Romagna, Museo Archeologico
Nazionale di Parma, Palazzo della Pilotta, I-43121 Parma, Italy
Since the IV century AD, alpine populations from Aosta Valley became specialists in
manufacturing and trading shaped soapstone (pietra ollare). A trace of this kind of
commerce is provided by some mills and cooking utilities found in the plain of the Po
river. Provenance was established by means of micro-Raman spectroscopy coupled
to computational software, focusing on the garnet inclusions, and then extending it to
the rock to have an indication about the geological origin of the raw material [2, 3].
Some pietra ollare objects, a mill fragment and the bottom of a vessel turned on the
lathe, were found in the archaeological excavation Cassa di Risparmio in Parma.
The existence and effectiveness of the commerce of these artifacts from the Aosta
Valley since the late Roman period were confirmed on the basis of vibrational
analysis [2]. The evaluation of the composition of the included garnets was possible
using specific software developed in MatLab, calibrated with SEM-EDS data [3, 4].
Each mineral composition is strictly related to the provenance, in fact the presence
and the percentage of each element in a specific crystallographic site, plus those
present as minor traces, allows the identification of the geological formation of origin.
Garnets are metamorphic minerals, very common on the Earth crust, because of
their wide stability range, considering both temperature and pressure. Garnets are
nesosilicates containing a bivalent cation X (Mg, Ca, Mn, Fe) and a trivalent one Y
(Fe, Al, Cr), according to a general formula X 3Y2(SiO4)3 and pertain to the cubic
system, monometric group
It has been made a crystallographic and chemical division, with regards to the
occupancy of the tetrahedral and octahedral sites, so the pyralspite group - pyrope,
almandine and spessartine - contains Al3+ as the cation in the Y site, while the
ugrandite group contains calcium in the X site, like in uvarovite, grossular and
andradite. Natural garnets are not pure end members, but mixtures in which the
overall composition is determined by the miscibility range, based on the possibility of
substitution among cations.
The studied anhydrous garnets are included in a matrix composed of chlorite, a
phyllosilicate with tetrahedral sheets containing silicon and oxygen bonded to cations
coordinated by other six oxygens or OH groups. Chlorites are quite common in low
grade metamorphic rocks and in sedimentary ones, and are the major components
of chlorite schists and talc bearing schists, forming veins of so called pietra ollare,
from the latin word olla (vessel). This name has not a strict petrological meaning
but indicates many different litotypes, all characterized by similar chemical and
physical properties (refractoriness and low porosity values) which are very useful for
kitchen tools. The geological interest is combined to the archaeological one, to
obtain new information about the trade routes in the past.
Raman analysis was carried on with a LabRAM Jobin-Yvon Horiba spectrometer,
equipped with a He-Ne laser emitting at 632.8 nm. The collected spectra were
analyzed using the software LabSpec5. The position of each peak was obtained

129
using the fitting tool of the software (Gauss-Lorentz curves). Assuming that the
position of each Raman peak of a garnet varies linearly with the composition [5],
according to the miscibility range found in literature, it was possible to set up [1] and
then to refine [3, 4] a dedicated software to evaluate the composition of the solid
solution only by its Raman signature. The first step requires the identification of the
peaks and their position to be used as the input data. The core of the software is a
matrix containing for each pure end member the position of the peaks, using
literature data [3]. Then the software initiates the routine, first observing the peak at
~900 cm-1 to have a raw partition among piralspites and grossular-andradite
mixtures, to have a tentative composition. Hereafter the software tries all the
combination, minimizing the difference between the real data from the spectrum and
the calculated position of the peaks, which are the sum of the different end members
position for each peak, weighted by their relative percentage [5]. The software
provides for each end member the percentage which minimizes the difference
between the calculated and the real data.
The lapse of time necessary to evaluate the composition of a garnet, considering
both the Raman measurements and the software fitting, is about a few minutes, and
this kind of approach is moreover user friendly and does not require any sample
preparation, so this can be very useful to analyze valuable objects.
Micro-Raman spectroscopy was also used to determine the other minerals present in
the manufacts. Chlorites were found and the spectra were compared to the Crystal
Sleuth database to identify the mineralogical series of belonging.
Garnet inclusions present in the archaeological samples allowed the provenance
study. Almandine was found to be the main end-member, up to 95%, with minor
pyrope and in some cases spessartine. Raman spectra show that the rate of
calcium, magnesium and manganese varies gradually from the center to the edges
and produces zoning effects. The concentration profiles, from the center to the
border of the garnets, of the main elements were compared with the ones obtained
by means of SEM-EDS in garnets coming from the Saint-Marcel district in Aosta
Valley resulting in a perfect agreement.
The main constituent of the rock was identified as a member of chlorite group: a
further discrimination by means of Raman spectroscopy is very difficult. However, we
observed a perfect coincidence from the spectra of the archaeological chlorite and
the one obtained from rocks coming from Saint-Marcel district (Servette quarry).
These results confirm the Aosta Valley as the provenance of the raw material used in
the archaeological manufacts, and also give the chance to refine the area to Saint-
Marcel district, precisely Servette quarry, according to the mineralogical composition
evaluated coupling the Raman spectroscopy with proper software.
References
[1] Bersani D., Ando S., Vignola P., Moltifiori G., Marino I.-G., Lottici P.P., Diella V., Microraman
spectroscopy as a routine tool for garnet analysis, in Spectrochimica Acta Part A 73, 484-491,
2009
[2] Cerasoli T., Caratterizzazione e studio di provenienza di reperti archeologici in cloritoscisto a
granati (pietra ollare) tramite spettroscopia micro-raman, Bachelor thesis in Fisica, Academic
Year 2009/2010
[3] Coccato A., Identificazione Della Composizione Dei Granati Tramite Spettroscopia Raman,
Bachelor thesis in Scienze e Tecnologie per la Conservazione e il Restauro dei Beni Culturali,
Academic Year 2009-2010
[4] Moltifiori G.G., Potenzialit e sviluppo della spettroscopia micro - Raman nel riconoscimento e
nell'analisi semiquantitativa dei minerali: analisi di provenienza dei granati nel bacino del fiume
Po, Master thesis in Scienze e Tecnologie Geologiche, Academic Year 2005-2006

[5] Smith D.C., The RAMANITA method for non-destructive and in situ semi-quantitative
chemical analysis of mineral solid-solutions by multidimensional calibration of Raman
wavenumber shifts, in Spectrochimica Acta part A 61, 2299-2314, 2005
130
Portable Raman spectrometry to monitor synthetic treatments
used for the conservation of monument surfaces
Claudia Conti1, Chiara Colombo1, Marinella Greco1, Marco Realini1,

Jana Striova3, Luigi Brambilla2, Giuseppe Zerbi2
1
dei Beni Culturali (ICVBC), Via Cozzi 53, 20125 Milano (Italy), Tel. +39 0266173337,
c.conti@icvbc.cnr.it
2
Politecnico of Milano, Dip. Chimica, Materiali e Ingegneria Chimica Giulio Natta,
Piazza Leonardo da Vinci 32, 20133 Milano, (Italy).
3
dei Beni Culturali (ICVBC), Via Madonna del Piano 10, 50019 Sesto Fiorentino (Fi),
(Italy).
During the last few years Raman spectroscopy proved to be an effective tool in the
field of conservation of artworks. Its application is widely used mainly for the
identification of pigments, gems or other inorganic compounds. However, only few
studies report on Raman spectroscopy used in the characterization of protective and
consolidant treatments and/or of their degradation processes [Miliani et al., 2002,
Macdonald et al., 2005, Ohldalov et al., 2006, Tennent et al., 2009].
A crucial point in a conservation work is the monitoring of the treatment applied on

the surfaces. Some polymeric consolidants and protectives have a relatively short
life due to their degradation; after some years a re-treatement should be carried out.
It follows that any information about the composition of the applied products, their
chemical transformations and their distribution on the surfaces become essential
[Horie, 2005, Borgioli, 2002]. For these purposes, the conservation scientists should
seek for and test new in situ methods and this becomes of utmost importance
especially in the case of buildings where an extensive mapping is necessary
considering the large dimensions.
A study has been carried out that evaluates the relevance of portable Raman
spectroscopy in monitoring the synthetic treatments applied on plaster substrates. A
set of laboratory specimens was prepared and treated with products belonging to
three polymer classes (vinyl, acrylic and organoalkoxysilanes Figure 1). The
products have been applied in variable amounts and it was observed that their
detection with portable Raman is a function of their penetration inside the material,
depending on their viscosity and molecular weight; the lower detectable amount has
been established for each analyzed product. This study highlights, for the first time,
the limits and the advantages of portable Raman instrumentation in the detection of
products widely employed for the conservation of plasters. As comparison,
specimens have been analysed with Raman instrument and the results are
discussed.

131
Figure 1: Portable Raman spectra of the products used for the experiments.
References
Miliani C, Ombellini M, Morresi A, Romani A. Surface and Coatings Technology 2002; 151-
152: 276.
Macdonald AM, Vaughan AS, Wyeth P Journal of Raman Spectroscopy 2005; 36: 185.
Ohldalov M, Kuerov I, Novotn M. Journal of Raman Spectroscopy 2006; 37: 1179.
Tennent NH, Caen J, Courtney P, Diz EL. e-Preservationscience 2009; 6: 107.
Horie C.V., Materials for conservation, Butterworth-Heinemann, 2005.
Borgioli L, in Il prato (Ed.) Polimeri di sintesi per la conservazione della pietra, 2002.

132
Characterization of the panel painting neo-Byzantine icon
from the Church of St. Archangels Voluntari Ilfov
Ioana Cortea4, Raluca Cristache4, Ioan Emandi3, Paula Bugheanu2,

Otilia Ludmila Cinteza2, Ana Emandi1
1
University of Bucharest, Inorganic Department, 90-92 Soseaua Panduri, Bucharest,
(Romania), tel 04 0788 465 287, tel/fax 04 021 2231242, anaemandi11@yahoo.com
2
University of Bucharest, Department of Physics Chemistry, 4-12 Regina Elisabeta,
Bucharest, (Romania),
3
University of Bucharest, Faculty of Physics, 3NANOSAE Research Center, PO BOX
MG-11, 077125, Magurele-Ilfov, (Romania), tel 040 766462154,
4
University of Bucharest, Faculty of Physiscs, PO BOX MG-11, 077125, Magurele-
Ilfov, (Romania).
The word icon that is used in Byzantine art for a small scale representation of a
sacred figure or figures is taken from the Greek word for image. When the early
Orthodox Christians first began to represent such figures, however, it was both as an
act of commemoration and as a contact between human existence and God. In
Christian tradition, therefore, the word icon means an image of the invisible world
that transcends material existence, which is the reason for the figures portrayed not
to be given three-dimensional form [1]. In Byzantine tradition, icons were painted on
wood panels covered with several layers of gesso (dehydrate or anhydrite) mixed
with an aqueous protein component like animal glue [2]. After that, the ground was
polished extensively in order to provide a smooth surface. The amount of binding
material ranged from 5% to 20% (by weight) of the entire ground [3] and affected the
elasticity, stability and mechanical properties of the ground over its lifetime. The
optimum glue concentration is believed to be around 1012%, which allows the
ground to become more flexible rather than hard and rigid.
The aim of this paper is to provide a scientific background about the place of origin,
period of time, school of art and authors of the unknown origin panel painting neo-
Byzantine icon belongs to the Galactotrofusa Greek style from the Church of St.
Archangels Voluntari Ilfov. Little scientific information is available for the
understanding of the construction technique and the materials used by the neo-
Byzantine artists and whatever is available comes mainly from artists manuals. First
of all we obtained as much information as possible from the panel painting of the
unknown origin panel painting, through non-destructive methods, before proceeding
the invasive methods.
Figure 1. Holly Virgin with Child

133
The non-invasive methods used in the first stage were X-rays fluorescence (XRF),
scanning electron microscopy/energy dispersive X-ray analysis (SEM/EDX), FT-
Raman, FT-IR, EPR spectroscopic techniques and DR-radiography. The pigments,
functional groups of the organic materials as well as the possible authors and the
place of origin were identified [4-6].
The icon of Holly Virgin with Child (Fig. 1), nourishing milk is painted on a single
piece of wood panel measuring 15 20 cm 2, and was found in the Church of St.
Archangels city of Voluntari district Ilfov, Romania.
The icon is made of wood without sleepers, possibly lime tree. Mother of God is
centered inside the frame, holding the Infant in her arms on a white towel, and held
his right arm resting on left hand. The iconographic theme is known Galactotrofusa
and refers to Virgin Mary breastfeeding the Child.
The painting itself was done over the metallic thin film, in tempera technique. Most
neo-Byzantine icons are,
unfortunately, not signed,
making it very difficult to date
them. One indication suggesting
the Greek provenience is the
iconographic theme
Galactotofusa. Restorers dated
this icon around 18th century
because it is likely that they were
created by some unknown artists
within the same period [3].
Figure 2. (A) Fragment of the icon, (B) the

microscopic detail, (C) XRF results
In the garment of Holly Virgin (C) were identified by X-ray fluorescence the presence
of some specific chemical elements Fe, Pb, Ba, Ag, which were referred as pigments
red iron, ceruse, barium white and thin silver film corresponding with dyes and
materials used by painters in 18 th century. The detail about the silver thin film on the
microscopic image (B), and the nature of the pigments were related to the Ft-Raman
and FT-IR spectroscopic methods.
Acknowledgements. This work has been financially supported by UEFISCDI

Romanian Ministry, project nr. 92133/2008
References
Ganitis V, Pavlidou E, Zorba F, Paraskevopoulos K.M, Bikiaris D. Journal of Cultural Heritage

2004; 5: 349
Sotiropoulou S, Daniilia D, Bikiaris Y. Revue dArchomtrie 1999; 23: 79
Sandulescu-Verna C, Materials and Painting Techniques, Marineasa Timisoara Press, 2009,
p. 45
Abdel-Ghani M, Edwards H. G. M, Janaway R, Stern B. Vibrational Spectroscopy 2008; 48:
69
Civici N, Journal of Cultural Heritage 2006; 7: 339
Abdel-Ghani M, Edwards H. G. M, Janaway R, Stern B. Spectrochimica Acta 2009; 73: 566

134
Towards a quantitative analysis of varnish components by
vibrational spectroscopies: methodological approach
Cline Daher1, Vanessa Pimenta1, Sophie Rochut1, Cline Paris1,

Anne-Solenn Le H2, Ludovic Bellot-Gurlet1
1
Laboratoire de Dynamique, Interactions et Ractivit (LADIR), UMR 7075 CNRS -
UPMC (Universit Pierre et Marie Curie Paris 6), 2 rue Henry Dunant, 94320 Thiais
(France), Tel. +33 (0)149781108, celine.daher@glvt-cnrs.fr
2
Centre de Recherche et de Restauration des Muses de France (C2RMF), UMR
171 CNRS - Ministre de la Culture et de la Communication, Palais du Louvre-Porte
des Lions, 14 quai Franois Mitterrand, 75001 Paris (France)
Ancient varnishes whether for painting or objects protection can be of three

types: oil based varnishes, oleoresinous varnishes or spirit (or solvent) based
varnishes. The most well known are the oleoresinous varnishes, which are actually a
mixture of one or more natural resin(s) and drying oil. The resins are di- and/or
triterpenoid resins such as colophony, sandarac, copal or elemi, mastic, dammar or
fossilized resin like amber. The siccative oil is most of the time linseed oil.
Studies determining the composition of ancient varnishes were done
essentially by separative methods coupled to mass spectrometry [Echard et al.,
2007; Chiavari et al., 2008]. For these methods, the different components are
identified using one or more of their bio-markers, for example abietic acid (and its
degradations products) for colophony and linolenic acid for linseed oil [Marinac et al.,
2004]. The presence, simultaneously, of different bio-markers will give the varnish
composition. Other analytical approaches can also be considered. Indeed, previous
studies [Vandenabeele et al., 2000; Daher et al.,2010] show that Raman and
Infrared spectroscopies can identify and discriminate between natural organic media,
and also attest the presence of a compound in a mixture.
In this study, a methodology for quantitative analyses of varnishes by
vibrational spectroscopies is proposed. For that, experimental varnishes of
colophony and linseed oil were prepared following traditional recipes with an
increasing mass concentration ratio of colophony/linseed oil. FT-Raman and IR
spectra of the pure materials and of the different mixtures were recorded; and
spectral decomposition studies were done on the whole spectrum or on specific
spectral regions, considering the mixture spectra as a linear combination of the pure
materials ones. The sum of their spectra should fit the mixture experimental
spectrum, and a relative amount of each component is given. Besides, in order to
ascertain this vibrational methodology, the prepared varnishes were analyzed by gas
chromatography [Papillon et al.,1998; Dizabo et al., 1990]. The accuracy of this
technique is a good way to define the real varnish quantitative content by a ratio of
the bio-markers peaks areas. The results obtained by both techniques are actually
similar.
However, this study should be continued and completed with more complex
vanishes, for example mixtures of more than two constituents, in order to determine
the capacity of vibrational spectroscopies to first detect the different substances
used, and then eventually propose an estimation of their proportions. Another work
in progress is the effect of degradation and ageing of these varnishes, and the effect
of the possible interactions between the different components of the varnish on the
vibrational signatures.

135
References
Echard J-P, Benoit C, Peris-Vicente J, Malecki V, Gimeno-Adelantado JV, Vaiedelich S.

Analytica Chimica Acta 2007; 584: 172.
Chiavari G, Montalbani S, Otero V. Rapid Communications in Mass Spectrometry 2008; 22:
3711.
Marinac C, Papillon MC, Pepe C. Journal of Cultural Heritage 2004; 5: 231.
Vandenabeele P, Wehling B, Moens L, Edwards H, De Reu M, Van Hooydonk G. Analytica
Chimica Acta 2000; 407: 261.
Daher C, Paris C, Le H A-S, Bellot-Gurlet L, Echard J-P. Journal of Raman Spectroscopy
2010; 41: 1204.
Dizabo P, Pepe C, in Pigments & colorants, Editions CNRS, Paris, 1990, p. 163.
Papillon MC, Balcar N, Gross C, Brunel G, Journal of the Canadian Association for
Conservation. CAC 1998; 23: 26.

136
The Influence of aromatic solvents on CuPc blue pigments
Catherine Defeyt1, P. Vandenabeele2, S. Lycke2, L. Wijnberg3

and D. Strivay1
1
Centre Europen d'Archomtrie and Institut de Physique Nuclaire, Atomique et de
Spectroscopie, Universit de Lige, 4000 Lige, Belgium, Tel. +32 472 291 239
catherine.defeyt@ulg.ac.be 2 Universiteit Gent, 9000 Gent, Belgium 3Stedelijk Museum,
1071 Amsterdam, Netherlands
Currently, five forms of copper phthalocyanine (CuPc), PB15, :1, :2, :3, :4, and :6, are
used as artistic pigments. PB15, the most widespread form afterwards PB15:3 is prone to
optic modifications, induced by crystallization. Crystal growth is most often seen in paints
containing aromatic solvents [Smith and al., 1966]. However, the use of aromatic
solvents as part of conservation treatments of paintings is relatively common. The aim of
this study is to highlight the differences between these five types of pigment and to
determine if the conditions of use of aromatic solvents in conservation involves the
crystallization of PB15 present in oil paintings.
In this paper we will present the first results corresponding to the study of fifteen
CuPc blue pigments in powder form (Winsor&Newton, Lefranc, Kremer, Talens, BASF,
Ciba) considering their different phases (, , ). In order to compare and to determine
the effects of aromatic solvents on the different CuPc forms, samples have been
examined and analyzed with polarized light microscopy, SEM-EDX, Raman, XRD and
FT-IR, before and after crystallization tests. Raman and FT-IR spectra made elsewhere
have shown small differences for the distinct phases of CuPc blue before crystallization
tests. Our purpose is also to compare our own Raman results with our FT-IR analysis to
check if these differences appear more clearly since FT-IR is not as affected by
fluorescence as Raman.
In accordance with previous literature [Muller and al., 2010], PB15 powder samples
have crystallized. On one hand, polarized light microscope and SEM examination show
crystal growth of the unstabilized -form which is transformed into large needle-like
crystals. On the other hand, FT-IR spectra and XRD diffractograms have shown the
conversion from the -form into -form induced by toluene and p-xylene.
In the first part of this study, we have caracterized the five types of CuPc blue in
powder form and shown the influence of aromatic solvents on each one. The next step of
this study will focus on dried oil color whose principal pigment is one of the five forms of
CuPc blue used as artistic pigment, applied on glass slides and canvas. Aromatic
solvents cleaning tests, application of selected varnishes containing toluene and xylenes
will be carried out on paint films. These samples will be studied before and after
treatment but also compared with crystallized samples in powder forms.
Acknowledgements.This work was supported by the Inter-University Attraction Pole

program of the Federal Belgian Science Policy (NACHO P6/16), the University of Lige,
and the Institut Interuniversitaire des Sciences Nuclaires.
References
Smith F.M., Easton J.D. Phthalocyanine pigments-their form and performance, Journal Oil and
Colour Chemists Association 49 (1966) 614-630
Muller M., Dinnebier R., Jansen M., Wiedmann S., Plg C., The influence of temperature,
additives and polymorphic form on the kinetics of the phase transformations of copper
phthalocyanine, Dyes and Pigments 85 (2010) 152-161

137
Characterization of component pigments in a mixture
Renato De Vincolis1, Dorotea Fontana1,2, Anna M. Gueli1,

Giuseppe Stella1, Sebastiano O. Troja1, Agnese R. Zuccarello1
1
PH3DRA laboratory, Dipartimento di Fisica e Astronomia dellUniversit & INFN
Sezione di Catania, CSFNSM, Via Santa Sofia 64, 95123 Catania (Italy), Tel. +39
0953785354, dorotea.fontana@ct.infn.it
2
Dipartimento di Fisica, Universit di Palermo, Viale delle Scienze Edificio 18, 90128,
Palermo (Italy), Tel. +39 09123899041
This work is part of Raman spectra database constitution of pigments and materials
of Cultural Heritage interest for polychrome artworks characterization.
The colours of paintings are often obtained mixing pigments of palette artists. The
attribution of a work of art to an author and the individuation of fakes are related to
the identification of used pigments and also to the detection of mixture constituents.
The main research objective is the extension of PH3DRA laboratory database with
information useful to detect not only each single pigment but also quantitative data
regarding its relative ratio in the examined mixture.
The availability of spectra as revealed represents the primary limit in this context. In
addition to usual procedures of background and baseline subtraction, the step of
intensity correction relative to the specific experimental setup used for signals
acquisition (optical components, monochromator, CCD,) is indeed necessary.
After the selection of pigments really mixed by painters in the past from our wide
laboratory chromoteque, different specimens were prepared using different and
known proportions.
Measurements were carried out using both a microRaman system equipped with 542
nm and 785 nm laser sources and a portable tool with 542 nm, 633 nm and 785 nm
excitation wavelenghts.
Preliminary results on mixtures show two different behaviours. The spectra of the
first group present well separated peaks allowing the immediate identification of
constituent pigments, multiple convolutions make instead impossible this step for the
second type of signals. The data elaboration requires in this last case, an
appropriate deconvolution procedure in order to isolate the peaks of each pigment.
References
Burrafato G, Calabrese M, Cosentino A, Gueli AM, Troja SO, Zuccarello A. Journal of Raman
Delhaye M et al. in Turrel G. and Corset J. (Editors), Raman Microscopy. Developments and
Applications, Academic Press Inc., San Diego, CA, 1996
Farinella GM, Gallo G., Gueli AM, Stanco F. Communications to SIMAI Congress 2009;
3:211

138
Micro-Raman spectroscopy applied to the investigation of the
concentration of anatase in rutile within TiO2 pigments
Daniela Di Martino, Roberto Lorenzi, Giorgio Spinolo and Alberto Paleari
Dip. Scienza dei Materiali, Universit di Milano Bicocca, via Cozzi 53, I-20125
Milano, ITALY daniela.dimartino@mater.unimib.it
TiO2 is present in nature under three different crystalline forms: anatase, rutile and
brookite, but only the first two types are industrially produced since the last century
[Kampfer 1973]. Nowadays, titanium dioxide is the most widely used white pigment,
though some problems can affect its durability, mainly when applied as coating with
other plastic materials and exposed to the ultraviolet radiation. Indeed, many factors
can contribute to the pigment degradation, like the anatase to rutile ratio [Papliaka et
al., 2010].
On the other side, the debate is still open on the possible use of anatase as a white
pigment before 1920 [Edwards et al., 2006]. A relevant point concerns the
concentration of anatase within the white pigment [Clark et al., 2007]. Therefore, the
concentration of anatase in rutile or other white pigments seems to be of crucial
importance.
In this study we will address the analysis of Raman spectra of mixture of anatase
and rutile pigments, the way to derive their relative concentration, and possible
applications.
References
Clark RJH, Wang Q, Correia A, Journal of Archaeological Science 2007:34; 1787.
Edwards HGM, Nik Hassan NF, Middleton PS, Analytical and Bioanalytical Chemistry 2006:
384; 1356.
Kampfer WA, in Patton TC, Pigment handbook, John Wiley, New York, 1973, Titanium
dioxide chapter 1.
Papliaka ZE, Andrikopoulos KS, Varella EA, Journal of Cultural Heritage 2010: 11; 381.

139
The intriguing case of Silicon crystals unveiled in ancient
mosaic tesserae
Daniela Di Martino1, Anna Galli1,2 and Marco Martini1,3

1
Dip. Scienza dei Materiali, Universit di Milano Bicocca, via Cozzi 53, I-20125
Milano, ITALY daniela.dimartino@mater.unimib.it
2
Istituto di Fotonica e Nanotecnologie-CNR, 3INFN Sezione di Milano-Bicocca, via
Cozzi 53, I-20125 Milano, (Italy).
Pure Silicon, though being a widely diffused element, with an extensive range of
technological applications, is not present in nature: Silicon compounds (like SiO 2 or
SiC) are energetically favoured with respect to metallic Silicon. Thus, only synthetic
routes, providing suitable reducing conditions, allow for the production of metallic
Silicon [Lide, 1997-8]. Actually, in few cases, metallic Silicon was claimed to appear
in terrestrial rocks [Bird and Weathers, 1975, De et al., 1998, Bai et al., 2000, Di
Pierro et al., 2003] or as a consequence of the impact of extraterrestrial materials
such as meteorites. However, the debate is still open on the possible genesis of
metallic Silicon when critical conditions, like high pressures and temperatures, occur.
Here we report a micro-Raman spectroscopic study on ancient mosaic tesserae
belonging to Daphni Monastere (Greece, XI century). The outstanding result
concerns the detection of Silicon nanocrystals within the silica amorphous matrix of
glass mosaics. The occurrence of Silicon inclusions in XI century man artefacts
accounts for the existence of an almost singular site where raw materials containing
metallic Silicon nanocrystals could have been used. It is likely that a singular glass
production site was the origin of all the investigated glass tesserae supporting the
hypothesis of local glass making in contrast with raw materials supplied only from
Middle East or Egypt. A further support to this idea comes from statistical analysis,
Principal Component and Hierarchical Clusters, performed on a number of elements
and compounds.
References
Bai WJ, Robinson PT, Fang QS, Yang JS, Yan BG, Zhang ZM, Hu XF, Zhou MF, Malpas J.
Canadian Mineralogist 2000; 38: 585.
Bird JM, Weathers MS. Earth Planet. Sci. Lett. 1975; 28: 51.
De S, Heaney PJ, Hargraves RB, Vicenzi EP, Taylor PT. Earth Planet. Sci. Lett. 1998; 164:
421.
Di Pierro S, Gnos E, Grobety BH, Armbruster T, Bernasconi SM, Ulmer P. American
Mineralogist 2003; 88: 1817.
Lide DR. Handbook of Chemistry and Physics, Edition 1997-8.

140
New results in the characterization by Raman spectroscopy
of yellow pigments used in ceramic artworks
of the XVI and XVII centuries
Perla Ferrer1, Sergio Ruiz-Moreno1, Alejandro Lpez-Gil1 and

Carmen Sandalinas2
1
Universidad Politcnica de Catalunya, D5, C/ Jordi Girona, 31, 08034 Barcelona
(Spain), Ph. 34934016443, sruiz@tsc.upc.edu, perlafes@hotmail.com,
2
Museo Frederic Mars (ICUB), Plaza de Sant Iu, 5, 08002 Barcelona (Spain).
This investigation is focused on the molecular characterization with Raman

spectroscopy of an important group of yellow pigments whose composition is based
on lead, tin and antimony (among others components). These pigments were
commonly used in Renaissance and/or Baroque polychromed ceramic objects.
Four very ancient and special Italian yellow pigments were acquired from the
Stazione Sperimentale del Vetro, Murano-Venezia (Italy). These reference pigments
have been produced following strict and rigorous manufacturing recipes
corresponding to Venezian fabrication processes for the XVI and XVII centuries. The
molecular characterization of the reference pigments is made with a new Raman
system RMS-320 model of Horiba Jobin Yvon. The results are compared with the
obtained by other authors who investigate the same topic.
The portable characteristic of this optical fiber Raman system allow us the access
into the Museo de Cermica de Barcelona in order to investigate the composition of
the yellow and orange colours of an important collection bellowing to this museum.
Our main objective is to make a comparative analysis between the pigments

employed for the XVI and XVII centuries in ceramic objects from production centers
of Barcelona (Catalonia, Spain), Talavera de la Reina (Spain) an, also, from two
Italian manufacturing centers (Pesaro and Montelupo).
We note the excellent performances that portable Raman spectroscopy offers, in a

direct and non-invasive way, in the analysis of ceramic artworks.
Polychromed plate, XVII century

Polychromed bottle, XVI century
Talavera de la Reina (Spain)
(21.5 cm x 12.5 cm x 7 cm), Pesaro (Italy)
Museo de Cermica de Barcelona
Museo de Cermica de Barcelona

141
Acknowledgements. This work has been supported by CICYT (TEC 2009-07855),
entitled Investigacin y Optimizacin de la Espectroscopia Raman aplicada al
anlisis directo del Patrimonio Artstico, (IRPA). We want to acknowledge to Museo
de Cermica de Barcelona (ICUB) its collaboration in this investigation.
References
Sandalinas C, Ruiz-Moreno S, Lpez-Gil A, Miralles J. Journal of Raman Spectroscopy,
2006; 37: 1146-1153.
Ruiz-Moreno S, R. Prez-Pueyo, Gabaldn A, Soneira M.J, Sandalinas C. Journal Cultural
Heritage, 2003; 4: 309-313.
Sandalinas C, Ruiz-Moreno S, Studies in conservation, 2004, 49: 41-52.
Rosi F., Manuali V., Miliani C., Brunetti B. G., Sgamellotti A., Grygar T, Hradil D, Journal of
Raman Spectroscopy, 2009, 40: 107-111.
Rosi F., Manuali V, Grygar T, Bezdicka P, Brunetti B.G, Sgamellotti A, Burgio L, Seccaronif
C, Miliani C. Journal of Raman Spectroscopy, 2010.

142
Archaeological Iron Age beads from Quinta do Almaraz,
Portugal: A Micro-Raman study
Vivian Filardi,1 Mrcia Vilarigues1,2, and Vnia Muralha2

1
Conservation and Restoration Department, Faculdade de Cincias e
Tecnologia,Universidade Nova de Lisboa, 2829-516, Caparica, Portugal
2
VICARTE (Glass and Ceramics for Art) Research unit, Faculdade de Cincias e
Tecnologia,Universidade Nova de Lisboa, 2829-516, Caparica, Portugal.
solange@fct.unl.pt
An interesting set of archaeological Iron Age glass beads were found in 1987 in
Quinta do Almaraz (Cacilhas), southern bank of the Tagus River. The beads are
beautifully decorated in different colours and seem to have been manufactured
through a technique involving stretching and moulding of the glass on a stick.
Archaeologists believe the beads were brought to this site by Phoenicians,
assumption inferred from the vast ceramic findings in the same site. [Barros et al,
1993]
Raman microscopy (RM) and micro X-ray fluorescence (XRF) were used to
characterize the glass beads by determining their composition and identifying the
materials responsible for the different colours observed. Calcium antimonate was
found to be used as an opacifier, either as the hexagonal CaSb 2O6 and/or the
orthorhombic Ca2Sb2O7, both forms identified by RM. [Gedzeviciute et al, 2009] The
yellow colour shows the Raman signature of a ternary yellow oxide, usually Pb-Sn-
Sb or Pb-Zn-Sb, rather than the traditional Naples Yellow, an interesting finding for
archaeological material. XRF shows that the blue colour is due to a cobalt oxide
dissolved in the glass matrix, and on one sample, cuprite (Cu 2O) is responsible for
the red colour. Other samples are still under investigation. The glass composition will
be determined by XRF, and RM will be used to describe the glass structure and infer
processing temperatures of manufacture. [Prisnloo et al. 2008]
Acknowledgements: We would like to thank Dr. Luis Barros, archaeologist

responsible for the beads collection, for all the information given, and the
Archaeological Museum of Almada (Museu Arqueolgico de Almada).
References
Barros, L., Cardoso, J., Sabrosa, A. "Fencios na margem sul do Tejo: Economia e
integrao cultural do povoado do Almaraz - ALMADA". In Instituto Oriental da
Universidade Nova de Lisboa, Lisboa, Portugal, 1993, p. 143.
Gedzeviciute, V., Welter, N., Schussler, U., Weiss, C. Archaeological and Anthropological
Science 2009; 1: 15.
Prinsloo, L.C., Colomban, Ph., Journal of Raman Spectroscopy 2008; 39: 79.

143
Micro-Raman spectroscopy of a Flemish painting (Virgin and
Child) from the late 15th century
Troels Filtenborg1 and Ole Faurskov Nielsen2

1
National Gallery of Denmark, Slvgade 48-50, 1307 Copenhagen, Denmark
2
Department of Chemistry, University of Copenhagen, 5 Universitetsparken, 2100
Copenhagen, Denmark
A painting of the Virgin and Child in the National Gallery of Denmark collection,
dating from the second half of the fifteenth century, was examined by various
analytical techniques. The painting, on panel, was obviously executed in the
Netherlands and its style pointed to an attribution to one of the masters of the period,
Dieric Bouts, his son Albrecht Bouts, or a painter closely associated or influenced by
them. A number of Netherlandish paintings from this era have in the past been
subjected to technical analysis, meaning that there is a good amount of reference
material.
A further incentive to investigate the materials and technique of the Virgin and Child
was the existence of other, more or less closely related versions of the same image.
In order to clarify the placement of the painting in the interrelation between these
versions as much technical data as possible was desirable, also for the comparison
with documented works by painters of the Bouts circle.
Figure 1. Virgin and Child (National Gallery of Denmark, DEP2) reproduced in a grey scale.
Samples were taken at the three sites marked 1, 2 and 3.

144
NIR-FT-Raman spectra were recorded on a BRUKER RFS100 spectrometer using
near infrared-laser excitation at 1064 nm. The spectral resolution was 4 cm-1. The
instrument was through optical fibres coupled to a NIKON microscope and spectra
were recorded with a 10x objective.
Due to safety reasons the painting could not be brought to the Raman laboratory.
Samples from the painting were taken by careful scratching off a few grains from the
painting with a scalpel at the three sites marked 1, 2 and 3 in Figure 1. Sites 1 and 2
are in the blue part of the painting. A cross section of a sample of the blue paint in
the area of the Virgins cloak showed two separate blue paint layers on top of a
whitish ground layer. An upper layer with a more intense blue colour and a lower
layer with particles of a more greenish hue, mixed with white. Raman spectra of the
upper layer revealed the presence of ultramarine. A tiny portion of the outermost
layer was sampled for micro-Raman spectroscopy, so only pigment particles from
the upper ultramarine layer were present. Most probably the blue pigment mixed with
white in the lower layer is azurite, judged from the colour and morphology of the
pigment particles. A similar two layer pattern was identified by Raman spectroscopy
in several paintings by the Florentine painter Pacino di Bonaguida [Schmidt et al.,
2009]. Ultramarine was a very expensive pigment and to reduce the cost it was often
underpainted with less expensive pigments like azurite. Raman spectra recorded at
sites 1 and 3 showed the presence of lead white. At site 3 this was the only pigment
present. Lead white was also present at the blue coloured site 1 indicating that the
artist used lead white mixed with the blue in various proportions to model the drapery
of the Virgins cloak.
Linseed-oil was a commonly used binder for paintings in Flanders by the second half
of the 15th century, sometimes in combination with egg tempera. Linseed-oil is a
triglyceride with ester bonds to fatty unsaturated acids. Upon drying, the double
bonds are oxidized and a covalent cross-linked, polymerised, strong pattern is
formed [Grehk et al., 2008]. By this very complicated chemical process, involving a
free radical mechanism, the double bonds disappear [Bersani et al., 2003; Grehk et
al., 2008]. Raman spectra at all three sites reveal that linseed-oil might have been
the binder used by the artist. In this context the CH-stretching region from 2800-3000
cm-1 is very important. However, triglycerides with long fatty acid chains show a very
similar pattern in this region and use of binders like walnut oil cannot be excluded.
Egg yolk is very rich in triglycerides and relative band intensities in the region from
1800-1000 cm-1 might indicate that egg yolk has been used, probably in a mixture
with linseed oil.
Acknowledgements. The authors are grateful to Lykke Ryelund, Department of

Chemistry, University of Copenhagen, for recording the Raman spectra.
References
Bersani D, Antonioli G, Lottici PP, Casoli A. Spectrochimica Acta part A 2003; 59: 2409
Grehk TM, Bergher R. Bexell U. Journal of Physics: Conference Series 2008; 100: 012019
Scmidt CM, Walton MS, Trentelman K. Analytical Chemistry 2009 ; 81 : 8513

145
Raman spectroscopy as a tool for garnet analysis and
investigation on samples from different sources
Theodore Ganetsos1,2, Thomas Katsaros1, Susanne Greiff3,

Sonngard Hartmann3
1
Laboratory of Gemstones, Byzantine & Christian Museum, Vas. Sofias 22 Athens,
106 75, Greece
2
T.E.I. of Lamia, 3rd Km. ONR Lamia-Athens, Lamia, 35100, Greece, Tel.
++302231060140, Email: ganetsos@teilam.gr
3
Romisch-Germanisches Zentralmuseum Mainz, Ernst-Ludwig-Platz 2, D-55116
Mainz, Germany
During the Hellenistic period, Garnet was a popular stone for use both as seals and
as decorative inlay in jewellery [Spier 2007]. The Collectors of garnets and minerals
often attach great importance to the provenance or country of origin. [Gubelin Gem
Lab, 2006]. Therefore, the goal of origin determination is to provide the geographic
provenance of a garnet and can be defined as: 1)the attribution of a stone to a
specific type of deposit and 2)the attribution of a stone to a mining area, a
geographic locality, or country. The precious varieties, of Garnets according to Pliny
the Elder, were the Indian, the Garamantic or Carthaginian, the Ethiopia, and the
Alaban-dine. The last were so called because, though found in the Orthosian rocks,
they were worked up (perficiuntur) at Alabandae [King 1867]. This was the sort
called by Theophrastus the Milesian [Caley 1956] both places being in the same
province, Caria (Modern Turkey).The sample from Turkey comes from Alabanda a
site of ancient topography which was described by Pliny the Elder [Table 1].
In this research work we present the identification and the provenance of 22 garnets
from 12 different localities. This is possible because the full range of properties of a
garnet measured and observed in the laboratory reflect the specific conditions of its
genetic background during the natural crystallization process.
We used Raman spectroscopy analysis as a tool which provides even further
information to distinguish garnets from different localities.
Number of Mineral Localities Raman Excitation
Samples Characterisation Wavelength
and Power
Merelani Hills,
2 Grossular (Tsavorite)
Tanzania
5 Grossular Yakutia, Siberia
Santa Eulalia,
5 Grossular
Chihuahua, Mexico
1 Andradite (Melanite) Atlas Mountains,Morocco
1 Andradite (Demantoid) San Benito,
California, USA 785nm
1 Andradite Serifos Island, Greece 120mW
-1
2 Almandine Tyrol, Austria resolution 8cm
1 Almandine Urals, Russia
Alabanda, Aydin Province,
2 Almandine
Turkey
1 Almandine Mali, Africa
1 Almandine (Spessartine) Paros Island, Greece
1 Uvarovite Urals, Russia
Table 1. The table presents the varieties of garnets and the different localities.
This is a light-scattering and non-destructive technique which allows for the

identification of inclusions in garnets by comparing a spectrum to a mineral database
146
for identification of the sample. It shoots a laser beam at the garnet sample and then
measures the weak light emitted to measure the spectrum of the Raman Effect.
Since each specific member of the isomorphous series shows a characteristic
pattern, the Raman Effect can be used as a tool of identification. [Bersani et al.,
2009]. Additionally with the ability to identify and quantify virtually any element we
used XRF analyser as the perfect archaometric analysis tool [Greiff S. Et al., 2006].
Minor and trace elements are often different or incorporated differently in garnets of
the same species but from different localities [Rossman G., 2009] .Thus, they may
provide a readily available tool for determining the locality of origin of garnets. Our
experimental results illustrate this concept.
Otztal, Tyrol, Austria

(red) Santa Eulalia,Chihuahua,
Otztal, Tyrol, Austria Mexico (white)
(dark red-brown) Santa Eulalia,Chihuahua,
Mexico (green)
Yakutia,Siberia
Intensity (Arb. Units)
(green)
200 400 600 800 1000 1200 1400 1600 1800 2000 2200 200 400 600 800 1000 1200 1400 1600 1800 2000 2200
-1
-1
Raman Shift (cm ) Raman Shift (cm )
Fig. 1 a) and b) Raman spectra of garnets from different localities.
Acknowledgements. This work has been financially supported by the T.E.I. of Lamia,
Greece in research cooperation with the Byzantine & Christian Museum, Athens,
Greece and the Rmisch-Germanisches Zentralmuseum, Mainz, Germany.
References
Bersani D, And S., Vignola P., Moltifiori G., Marino I.G., Lottici P.P., Diella V.,
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2009; 73: 484.
Caley R, Theophrastus On Stones, 1956, p.89, 91.
Gubelin Gem Lab, Ltd., The Roots of Origin Determination, 2006, p. 69.
th
Greiff S., Gerick A., Ritz E., Hager T., Junchang Y., 35 International Symposium on
Archaeometry 2005; 11: S4.
Rossman G., Elements 2009; 5: 159.
King C, The Natural History of Gems, 1867: 14.
Spier J, Late antique and Early Christian Gems, 2007, p. 87.
Pliny the Elder, Historia Naturalis, vol. 36, XIII, 62.

147
Surface enhanced Raman spectroscopy of inorganic art
pigments
Sergey Gaponenko1, Elena Klyachkovskaya1, Svetlana Vaschenko1,

Natalia Strekal2, Dmitry Guzatov2, Anna Harbachova1 and
Mikhail Belkov1
1
B.I. Stepanov Institute of Physics NASB, Nezavisimosti Ave. 68, 220072 Minsk
(Belarus), +375 17 284 04 48, s.gaponenko@dragon.bas-net.by
2
Yanka Kupala Grodno State University, Ozheshko str. 22, 230023 Grodno
(Belarus).
Raman spectroscopy is one of the most effective techniques of substances

identification (including the art pigments) owing to the facts that the frequency set of
the Raman spectrum is determined by the structure of the substance under
investigation. However, Raman-based identification of art pigments in a number of
cases is difficult task for researchers because of Raman scattering has very low yield
and therefore it needs large amount of material to be examined. Additionally, since
Raman scattering is rather weak it is readily masked by uncontrollable intrinsic
fluorescence of the analysed probe or other substances presenting in the probe. The
intensity of Raman scattering can be essentially increased if the molecule
(adsorbent) is placed near a metal nanobody where generation of surface plasmons
offers superior enhancement of light--materr interaction resulting in increasing of
Raman scattering by 104 106 times [1] and in certain cases and by 1014 times [2]
(Surface Enhanced Raman Scattering, SERS). Recently a number of papers have
reported successful application of SERS to identify organic art materials [3,4].
However, not only inorganic art pigment but inorganic species in all have not become
the subject of SERS-based examination.
The purpose of the present work is elaboration of surface enhanced Raman
scattering techniques for inorganic art pigments identification. We demonstrate
efficient manifold enhancement of Raman signal using substrates based on colloidal
Ag nanoparticles and Ag- and Au- coated Ge-on-Si nanostructures.
Original ultramarine crystalline particles have the size of the order of 1 m. The
ultramarine suspension that was prepared using ultrasonic disperser has been
deposited on the SERS substrates and dried at room temperature in the horizontal
position. Ultramarine suspension in the same manner was also deposited on the
reference metal-free Ge-on-Si and mica substrates.
The Raman measurements were performed in the backscattering configuration
at room temperature on a Spectra Pro-500i spectrometer (Acton Research, USA)
using the a cw diode-pumped Nd-YAG-laser (532 nm), a holographic filter, a
diffraction grating, and a cooled Si CCD detector.
Original Raman spectrum of ultramarine contains lines at 259 cm-1and 541 cm-1
along with its second harmonic at 1093 cm-1. SERS manifests itself for every line
and additionally gives rise to combinations of original frequencies which is indicative
of promising applications of SERS in inorganic art pigments examination as well as
of strong unharmonicity of vibrations inherent in the particular pigment examined in
our work. These data are summarized in the Figure where reference original Raman
spectrum of ultramarine particles, two reference ultramarine spectra on metal free
substrates as well as reference Raman spectrum of pure mica are presented along
with SERS data for the 4 types of SERS active nanostructures. Notably, ultramarine
lines are not detectable at all when it deposited on reference metal free mica or Ge-
on-Si substrates.
The first SERS-active system is nanosized Ag particles mixed with ultramarine
particles. Ag particles have been extracted from the silver sol by means of drying at
148
the room temperature. The second SERS-active system is juvenile mica surface
coated with silver sol. Silver sol has been prepared via Ag ions reduction with
dextroglucose under heating. According to TEM data silver particles that have been
formed in colloidal solution were 1025nm in size.
The third SERS-active system was Au coated self-assembled Ge-on-Si
nanostructure containing Si-Ge huts of a few tens of nanometers in all dimensions.
Au deposition was performed in vacuum with in situ monitoring by SEM analysis
which confirm continuous Au coating. Unlike previous 2 SERS active systems, the
topology of metal surface was completely defined by the Si-Ge topology.
The fourth SERS-active system is Ag-coated semiconductor self-assembled Ge-
on-Si nanostructures. Here after Ag deposition in vacuum the special annealing was
performed to add additional topological inhomogeneities over those defined by Si-Ge
huts.
Generally, SERS offers 10 to 100 enhancement of Raman signals, different for

different lines and substrates. Taking into account that the micrometer size of
pigment particles exceeds by several orders of the magnitude the SERS-active
volume in the close vicinity of metal nanobodies (approx. (40 nm)3 ) we estimate
average local enhancement to be 10 5 106 times.
Thus surface enhanced Raman spectroscopy can be successfully used for
inorganic art pigments identification. Because of high enhancement factors, the
samples required for SERS could be microscopic in size, of the order of a few
powder grains or crystallites, which can be safely taken from delicate pieces leaving
no visible damage on the objects.
References
1. Kneipp K, Moskovits M and Kneipp H (Eds.), Surface-Enhanced Raman Scattering,

Springer-Verlag, Berlin, GE, 2006.
2. Gaponenko SV and Guzatov DV. Chem. Phys. Lett. 2009; 477: 411414.
3. Chen K, Leona M and Vo-Dinh T. Sensor Review 2007; 27(2): 109120.
4. Whitney AV, Casadio F and Van Duyne RP. Applied Spectrosc. 2007; 61(9): 994-1000.
5. Klyachkovskaya E, Strekal N, Motevich I, Vaschenko S, Harbachova A, Belkov M,
Gaponenko S, Dais Ch, Sigg H and Stoica T. Plasmonics 2011; DOI: 10.1007/s11468-011-
9219-2.

149
Raman spectroscopy as seen from a gemological and
jewelistic point of view
Marco Giarola1, Gino Mariotto1, Marianna Barberio2 and David Aj3

1
University of Verona, Computer Science Department, strada le Grazie, 15 Ca
Vignal 2, 37134 Verona (Italy), Tel. 045-8027975, marco.giarola@univr.it
2
University of Calabria, Department of Physics, Via P. Bucci, 87036 Arcavacata di
Rende, CS (Italy)
3
National Research Council (CNR), Istituto di Chimica Inorganica e delle superfici
(ICIS), Corso Stati Uniti 4, 35127 Padova (Italy) and Scientific Methodologies
Applied to Cultural Heritage (SMATCH), Largo Ugo Bartolomei 5, 00136 Rome
(Italy).
Nondestructive methods, such as optical absorption, luminescence and vibrational

spectroscopies are widely employed for the routine identification of materials used
in works of art and handicraft [Adamo et al., 2005; Adamo et al.,2006; Adamo et al.,
2008].
Moreover the investigation of their inclusions provides unvaluable information
concerning the story of the stuff (mineral or synthetic or treated) a given beautiful
object is made of. Among such materials, gemological species or varieties were the
object of numerous studies by Raman and micro-Raman techniques [Schubnel and
Smith,1992; Bersani and Lottici, 2010].
Our specific approach [Aj et al., 2002; Sodo et al., 2003; Aj, 2008] consists of the
investigation of problems originating in gemological and jewelry laboratories. In the
aim of providing a bridge between different kinds of competencies, we will present
results concerning the presence of uncommon inclusions (among the others, in
diamonds and zoisites), but also the effects of thermal treatments or assemblage
(e.g. for the production of tanzanite and doublets) as well as less intentional effects
during the jewel fabrication.
Moreover, we will show by means of some specific examples, how Raman result can
join, sometimes unexpectedly, to different methods in solving complex gemological
problems, such as characterization of non-surfacial inclusions.
References
Adamo I, Pavese A, Prosperi L, Diella V, Merlini M, Gemmi M, Aj D. Gems & Gemology

2005; 41: 328-339.
Adamo I, Pavese A, Prosperi L, Diella V, Aj D, Dapiaggi M, Mora C, Manavella F, Salusso
F, Giuliano V. J.Gemmology 2006; 30: 215-226.
Adamo I, Pavese A, Prosperi L, Diella V, Aj D, Gatta D, Smith C P. Gems & Gemology
2008;
44: 214-226.
Aj D, Nardone M, Nunziante Cesaro S, Perrone U, Picollo M, Prosperi L, Radicati B,
A.Sodo; Art 2002: Proceedings of the 7th Internat. Conf. Non-Destruct. Testing and
Microanal. for Diagn.and Conserv. Cultural and Environm. Heritage, Antwerp, Belgium, 2-6
june 2002.
Aj D, in Oscar Soriano M C (Editor), Volumen de Actas (Jornadas Internacionales sobre la
Gemologa Scientifica en la Sociedad Actual), Zaragoza, Spain, 2008.
Bersani D, Lottici P P. Anal.Bioanal.Chem. 2006; 397:2631-2646.
Schubnel H.J., Smith D.C.(Editors), La Microsonde Raman en Gemmologie, Revue de
Gemmologie, No. spcial hors srie, Assoc. Franaise Gemmologie, 1992.
Sodo A, Nardone M, Aj D, Pozza G, Bicchieri M. J.Cult.Heritage 4 (2003) 317s-320s.

150
Analysis of Paints of Fors of The Suleyman the
Magnificent in Suleymaniye Mosque
Asl Gokce Gokcay1, Meric Bakiler1, Ahmet Gulec2, Tulay Ugur2

1
Mimar Sinan Fine Art University, Central Research Laboratory, Bomonti, 34380,
Istanbul, (Turkey), +90 212 241 6078, mbakiler@msgsu.edu.tr
2
Istanbul University, Faculty of Letters, Department of Restoration and Conservation
of Artefacts, Vezneciler, 34134, Istanbul, (Turkey), +90 212 440 00 00-15742
The Suleymaniye Mosque was built on the order of Sultan Suleyman the Magnificent
and constructed by the great Ottoman architect Sinan. The construction work began
in 1550 and the mosque was finished in 1557. The Fors is placed at the middle of
chandelier which is hanged on main dome. The quilted turban is look like fors Fors is
represented Suleyman.
The Magnificent who was the 10th sultan of the Ottoman Empire. In this study the
paint layers of this fors of the mosque were investigated by microscope, SEM-EDS
and RAMAN, FTIR spectrometers and simple spot tests analysis. The identification
of pigments used for wooden fors is important for their restoration, conservation,
dating and authentication. The aim of this study was to investigate the number of
layers and the chemical composition of each layer and manufacture techniques of
them. Having these diagnoses, the conservation and restoration remedies were
proposed for the fors.
These analysis were indicated that the original parts of the wood of fors are linden
(Tilia sp.), and some parts were restorated with pine plywood and coated with textile.
The original base layer has lead white as filler and lincead oil as binder. While some
parts of the base layer were painted by white and blue colors, the other parts were
coated with gold leafs over a red clay base layer which has animal glue binder. The
second layer, which probably is 19 th century restoration, has gypsum base and blue
paint all of the surfaces. Parts of the blue paints were also decorated by gold leafs.
Since the wooden parts of the fors have been heavily infected and destroyed by
Anobium Punctatum, before anything else the removing of these insects was
proposed. After the removing of these insects, the surface should be cleaned by
solvents (acetone and alcohol) and non ionic detergent solution. After all these, the
lost part of the fors should be completed by linden and redecorated with lead white
base, blue color and gold leafs regarding to the original material and decoration.
Thus, the original materials will be kept on the wooden fors, the material technology
of it will not be changed, and the new repair materials will not cause any esthetic
problem on the original parts.
Acknowledgements. This work was supported by Prime Ministry State Planning

Organization and Mimar Sinan Fine Art University through the Project No.
2010K121200 and the Project No. 200905 respectively.

151
Surface enhanced Raman scattering (SERS) applied for the
investigation of an Italian cultural heritage canvas
Oana-Mara Gui1,2, Alexandra Falamas3, Lucian Barbu-Tudoran4,

Simona Cinta Pinzaru3, Lelia Ciontea1, Mihaela Aluas3, Belinda Giambra5
and Ioan Sbarciu2
1
Technical University Cluj-Napoca, Faculty of Materials Science and Engineering,
Str. Memorandumului no 28, 400028, Cluj-Napoca, Romania
2
University of Art and Design Cluj-Napoca, Pta. Unirii no 31, 400098, Cluj-Napoca,
Romania
3
Babes-Bolyai University, Faculty of Physics, Str. Kogalniceanu no. 1, 400084, Cluj-
Napoca, Romania
4
Babes-Bolyai University, Electron Microscopy Centre, Str. Clinicilor no. 5-7, 400006,
Cluj-Napoca, Romania
5
Accademia delle Belle Arti e di Restauro Abbazia di San Martino delle Scale
(ABADIR), Piazza Platani no 3, 90046, San Martino delle Scale, Palermo, Italy
A cultural heritage canvas from the early 19 th century, painted by the Vaccaro
brothers for the church of Niscemi, province of Caltanissetta, Sicily, was analysed
using FT-Raman and SERS spectroscopy. The painting, still used in religious rites
related to the Easter mass (la calata da tila), depicts the scene of the Crucifixion
and is executed in a scarce palette, with white, green and blue colours. The aim of
the research was to offer valuable insight into the painting technique, unknown prior
to this study. Due to the sensitivity of the technique, surface enhanced Raman
scattering (SERS) has been applied in order to detect trace amount of pigments that
usually are not resolved by conventional Raman spectroscopy [Jurasekova et al.,
2010]. As aged organic painting materials are
highly fluorescent in normal dispersive Raman
measurement conditions, SERS is usually
employed in artwork diagnosis for the
identification of organic lakes and dyes [Bruni et.
al., 2011]. To the best of our knowledge this is
the first report on SERS investigation on linen
using Ag colloidal nanoparticles.
The investigated canvas, measuring 100 m 2,
was sampled during restoration and 20
fragments (single threads ranging in size
between 0,5 and 3 cm) were collected from
different areas and submitted to spectroscopic
and SEM-EDS analysis. Raman and SERS
spectra of fibres were recorded in a Bruker
Senterra dispersive Raman microscope, using
the 785 nm excitation light of a diode laser.
Samples were subjected to Raman analysis
without any prior preparation. Lazurite was
found in both blue and green coloured areas,
identified by its Raman bands at 546 and 1638
cm-1 (weaker features present at 280 and 1090
cm-1). A sharp Raman band, observed at 1575
Figure 1. Restorers sketch of The cm-1, was attributed to the indole ring vibration of
Crucifixion canvas, with specimen
sampling points indicated in bold. indigo, while three weak intensity bands at 1223,
1310 and 1360 cm-1 were assigned to vibration

152
modes of C-H and N-H groups. Some coloured samples contained traces of lead
white, exhibiting a specific Raman band around 1050 cm -1 and dolomite (identified by
its band at 1096 cm-1). Results were confirmed by SEM-EDS investigations, which
revealed the presence of C, O, Si, S, Al, Ca and traces of Mg, K, Pb, Fe and Cu (the
last two, in a quantity below 0,5%). In this case, the SERS technique allowed
quenching the fluorescence of the linen substrate, and enabled the identification of
both organic and inorganic pigments on the same sample. Moreover, high quality
13
C-NMR signals of colored linen threads were also obtained using a Bruker Avance
DPX 400 NMR Spectrometer, which offered insight into the physico-chemical
properties of both substrate and binding medium.
Vibrational FT-Raman and
ATR-FT-IR spectra from
several samples of uncoloured
single linen threads have been
recorded and the observed
bands assigned to cellulose.
The same samples were
subjected to SERS and for the
first time SERS spectra of
linen fibres are presented. Due
to the SERS effect, vibrations
of the lignin in flax fibres were
enhanced and specific Raman
bands for phenol and aromatic
ring deformations could be
observed between 300 and
1600 cm-1 (see Figure 2): the
Figure 2. SERS spectrum (exc= 785 nm) (black) and FT- aromatic ring deformation at
Raman spectrum (exc= 1064 nm, 1000 scans) (grey) of an 692 cm-1, the aromatic CH
uncolored linen thread showing lignin bands. (*) indicates twisting at 824 cm-1 or the
cellulose bands. The FT-Raman spectrum has been lignin- cellulose complex at
smoothed and shifted upwards for ease of comparison.
1276 cm-1 [Agarwal et. al.,
2009]. Although SERS does not enhance cellulose signals, several bands of the
polysaccharide could also be observed because of the fluorescence quenching: the
(CCC) ring deformations at 435 and 466 cm -1, the (CH2) broad band at ~960 cm-1,
as well as the (COC) glycoside doublet at 1100 cm -1 [Edwards et. al., 2006].
The use of low integration times while showing accurate results demonstrates the
advantages of the SERS technique over FT-Raman investigations of aged natural
fibres. Although further research is still required in understanding how signal ratios
for known ageing markers change when SERS is employed, the scattering effect
enables a more complex diagnosis of historic textiles and canvas supports.
Acknowledgements. This work has been financially supported by the QDOC project,
contract no. POSDRU/107/1.5/S/78534. The support of the Officina della Memoria
and of the Soprintendenza BB.CC.AA. Caltanissetta is gratefully acknowledged.
References
Jurasekova Z., del Puerto E., Bruno G., Garcia-Ramos J.V., Sanchez-Cortes S., Domingo C.,
Journal of Raman Spectroscopy 2010; 41: 1455
Bruni S., Guglielmi V., Pozzi F., Journal of Raman Spectroscopy 2011; 42: 1267
Agarwal U.P., Reiner R.S., Journal of Raman Spectroscopy 2009; 40: 1527.
Edwards H.G.M., Nikhassan N.F., Farwell D.W., Garside P., Wyeth P., Journal of Raman

153
Analysis of Paints of Wooden Separator of Women Part of
Fatih Mosque
Ahmet Gulec1, Mehmet Vedat Kurkcuoglu2, Ozge Boso2

1
Istanbul University, Faculty of Letters, Department of Restoration and Conservation
of Artefacts, Vezneciler, 34134, Istanbul, (Turkey), +90 212 440 00 00-15742,
gulecah@ist.edu.tr
2
Mimar Sinan Fine Art University, Central Research Laboratory, Bomonti, 34380,
Istanbul, (Turkey), +90 212 241 6078
The Fatih Mosque was founded at the one of the hill of Istanbul which had been
destroyed by the earthquake in 1999. In this study the paint layers of wooden
separator (parapets) women part of the mosque were investigated by microscope,
SEM-EDS and RAMAN, FTIR spectrometers and simple spot tests analysis.
The identification of pigments, used for wooden parapets, is important for their
restoration, conservation, dating and authentication. The aim of this study was to
investigate the layers and the chemical composition of each layer and manufacture
techniques of them. Having these diagnoses, the conservation and restoration
remedies were proposed for the parapets.
These analysis were indicated that the wood of parapets are linden (Tilia sp.), and
have three parts which are main structure, wood lath and small door. The main
structure and the wood lath were restored (painted) 5 different periods, the small
door was restored 4 times. The original layer of the main structure and the wood lath
has gray colored base with oil binder and some surfaces of main structure was
decorated by gold leafs with red clay and protein (animal glue) binder, while the door
was totally decorated by silver leafs with red clay and protein (animal glue) binder.
Since the removing the later restoration period layer will cause the loose of the
original layer, it was proposed to keep all the present layers. Simple cleaning with
non ionic detergent solution, to remove the dirt from surface and to complete the
dethatch paint layers with gray oil paint, and gold or silver leafs of regarding to the
original decoration.
Thus, the original materials will be kept on the wooden parapets of the mosques
women part, the material technology of it will not change, and the new repair
materials will not cause any esthetic problem on the original ones.
Acknowledgements. This work was supported by Prime Ministry State Planning

Organization through the Project No. 2010K121200.

154
Scientific investigation on Terra Sigillata found at a vandalic
settlement (A.D. II-III. centuries) in Hungary using Raman
spectroscope
Zsfia Gyalai1, Krisztin Fintor2

1
University of Szeged, Department, of Archaelogy, Egyetem st. 2-6, H-6722 Szeged
(Hungary), gyalaizsofi@citromail.hu
2
University of Szeged, Department of Mineralogy, Geochemistry and Petrology,
Egyetem st. 2-6, H-6722 Szeged (Hungary), Tel. +36 62 544 058, e-mail:
efkrisz@gmail.com
A cooperation program between the Department of Archaeology and the Department

of Mineralogy, Geochemistry and Petrology of the University of Szeged enabled us
to accomplish, during the autumn and spring semester 2010/2011, a scientific
investigation on Terra Sigillata shatters from the archaeological site Garadna By-
passing Road [Csengeri Pusztai, 2008]. The Terra Sigillatas were among the most
demanded and wide-spread articles of the Roman Empire. The occurrence of this
fine pottery beyond the borders of the Empire shows that even the barbaric peoples
couldnt resist their attractive power. Owing to the large-scale demand this pottery
became wide-spread in the Barbaricum, and this is why it can be regarded as a
major find at the archaeological sites of the Roman period. This is why an intensive
investigation of Terra Sigillatas can be regarded as especially important. Application
of natural scientific methods enables us to answer some economic-historical and
manufacturing-technical questions, unanswered to date. In the frame-work of the
current project we endeavored to carry out investigations on Terra Sigillatas from
various aspects, with the help of Raman spectroscope. Apart from analyses
concerning the clay composition, the equipment enabled us to study, by high-
resolution images, the surface, the ornaments and the typical red split of the objects.
Based on archeological investigations of the ornaments of Terra Sigillata samples it
can be determined that the shatters are related to wares were made at
manufactories of Rheinzabern, Westerndorf and Pfaffenhofen.
The Raman microscopic analyses revealed that the 5-7 m thick split coating was
basically made by hematite alone in each studied sample. The body of the different
samples displays very homogenous composition. The most common constituents
are different iron oxides particularly hematite (Fe 2O3) and maghemite (Fe2O3).
Beyond iron oxides quartz, feldspars and micas are the most common components
in each sample. Potassium feldspar is in much higher proportion than plagioclases;
while muscovite is dominant in case of micas biotite only occur very sporadically.
The high mica and the very low plagioclase content distinguish the studied samples
from those originated from Gallic manufactories (Lofrumento et al., 2004). Despite
the very similar main composition the samples of different manufactories exhibit
some characteristic distinctive features. Samples are originated from Pfaffenhofen
contain highest amount of nearly opaque minor (2-4 m) hematite crystals, while
maghemite occur very rarely. Samples from Rheinzabern also contain numerous
minor size hematite grains but the several TiO 2 grain (anatase and rutile) occur in
the body distinguish them from the others. Samples related to Westerndorf contain
the highest amount of maghemite forming elongated greenish brown grains. Minor
hematite grains can be found very rarely while titanite (CaTiSiO 5) grains occur at
many places in these samples.
We think our scientific experiments as shown above are of pioneering character,
considering that investigations on Terra Sigillatas with the help of Raman
spectroscope have not been carried out in Hungary to date, and, on the other hand,

155
because finds of Terra Sigillata from Barbaricum lying outside the eastern border of
the province Pannonia had so far been excluded from the sphare of natural scientific
investigations. The goal of our research has been, first of all, to call attention to the
efficiency of the applied method, to the possibilities offered by the equipment, and, to
encourage Hungarian archaeologists to make use of the method, thus widening the
knowledge available by the application of natural scientific investigation techniques.
References
Csengeri P., Pusztai T. Yearbook of Herman Ott Museum XLVII 2008, p. 89.
Lofrumento C, Zoppi A, Castellucci, EM Journal of Raman Spectroscopy 2004; 35: 650-655.

156
Spectroscopy of Palaeolithic rock paintings from Tito Bustillo
and El Buxu caves, Asturias, Spain.
Antonio Hernanz1, Jose M. Gavira-Vallejo1, Juan F. Ruiz-Lpez2,

Santiago Martn3, ngel Maroto-Valiente4, Rodrigo de Balbn-Behrmann5
and Mario Menndez-Fernndez6
1
Universidad Nacional de Educacin a Distancia (UNED), Departamento de Ciencias
y Tcnicas Fisicoqumicas, Facultad de Ciencias, Paseo de la Senda del Rey 9,
E-28040 Madrid (Spain), Tel. +34 91 3987377, ahernanz@ccia.uned.es,
2
Universidad de Castilla-La Mancha (UCLM) 44, Departamento de Historia, Facultad
de Ciencias de la Educacin y Humanidades, E-16071 Cuenca (Spain)
3
UNED, Departamento de Fsica Matemtica y de Fluidos, Facultad de Ciencias,
Paseo de la Senda del Rey 9, E-28040 Madrid (Spain).
4
UNED, Departamento de Qumica Inorgnica y Qumica Tcnica, Facultad de
Ciencias, Paseo de la Senda del Rey 9, E-28040 Madrid (Spain).
5
Universidad de Alcal de Henares, Departamento de Historia I y Filosofa, Facultad
de Filosofa y Letras, Colegios 2, E-28801 Alcal de Henares, Madrid (Spain).
64
UNED, Departamento de Prehistoria y Arqueologa, Facultad de Geografa e
Historia, Paseo de la Senda del Rey 7, E-28040 Madrid (Spain).
Tito Bustillo and El Buxu caves (Sella Valley, Asturias, Spain) are relevant
archaeological sites containing noteworthy Palaeolithic paintings, Fig. 1. Possible
relationships between the pictorial materials used by the prehistoric artists in both
sites have been investigated. In accordance with the sampling protocol and
experimental methods established in our previous works [Hernanz et al., 2006, 2007,
2008, 2010] samples of red pigment from pictographs of both caves and a red rock
from Tito Bustillo cave have been analysed by Raman microscopy, scanning
electron microscopy coupled with energy dispersive X ray spectroscopy (SEM/EDX),
X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Different
pigment recipes have been found in the samples. Calcite and well crystallised
haematite (-Fe2O3) of a granular size 10 m are always present. Nevertheless,
-quartz, anatase, montmorillonite, amorphous carbon and wstite (Fig. 2) are
additional components detected in some cases. Traces of the elements S, P and Ni,
as well as minerals like -quartz, montmorillonite and wstite suggest probable
relationships among the studied pictographs and both archaeological sites.
Figure 1. A pictograph from Tito Bustillo cave

157
Figure 2. Raman spectrum of a micro particle of wstite (FeO) in a sample of pigment from
the pictograph BPB of El Buxu cave.
Acknowledgements. We gratefully acknowledge financial support from the European

Regional Development Fund (ERDF). We also thank the Consejera de Cultura del
Principado de Asturias for permission to take photographs and samples of the
paintings and substrata of the archaeological sites.
References
Hernanz A, Mas M, Gaviln B, Hernndez B. Journal of Raman Spectroscopy 2006; 37: 492.
Hernanz A, Gavira-Vallejo, JM, Ruiz-Lpez JF. Journal of Raman Spectroscopy 2006; 37:
1054.
Hernanz A, Gavira-Vallejo JM, Ruiz-Lpez JF. Journal of Optoelectronics and Advanced
Materials 2007; 9: 512.
Hernanz A, Gavira-Vallejo JM, Ruiz-Lpez JF, Edwards HGM. Journal of Raman
Hernanz A, Ruiz-Lpez JF, Gavira-Vallejo JM, Martin S, Gavrilenko E. Journal of Raman

158
In situ micro-Raman spectroscopy of prehistoric paintings
from Spanish rock shelters. Part I: Cova dels Rossegadors,
Los Toros - Barranco de las Olivanas and Cueva del To
Modesto
Antonio Hernanz1, Jose M. Gavira-Vallejo1, Juan F. Ruiz-Lpez2,

Egor Gavrilenko3, Ramiro Alloza-Izquierdo4, Ramn Vias-Vallverd5,
Albert Rubio-Mora6,Vicente Baldellou-Martnez7and
Manuel Cals-Gmez1
1
2
3
Instituto Gemolgico Espaol, Alenza 1, E-28003 Madrid, Spain,
4
Laboratorio de Anlisis e Investigacin de Bienes Culturales (LAIBC), Gobierno de
Aragn, Castillo de Capa 10, nave 31, E-50197 Zaragoza (Spain).
5
IPHES, Instituto Catal de Paleoecologia Humana i Evoluci Social, Imperial
Tarraco, 1, E- 43005 Tarragona (Spain).
6
Universidad de Barcelona, Seminari d'Estudis i Recerques Prehistriques (SERP),
Montalegre, 6, E-08001 Barcelona (Spain).
7
Museo de Huesca, Plaza Universidad, 1, E-22002 Huesca (Spain).
Figure 1. Digital reproduction of pictographs from the Los Toros - Barranco de las Olivanas
rock shelter indicating the points from which spectra have been obtained in situ with a
portable Raman microscope.
In the Eastern half of Spain there are around 1,500 open-air rock shelters with
prehistoric paintings in their walls. On 1998, they were included in the UNESCO
World Heritage List under the generic denomination of Rock Art of the Mediterranean
Basin on the Iberian Peninsula. This exceptionally large group of painted rock
shelters is being the object of Raman studies [Hernanz et al., 2006, 2007, 2008,
2010]. In situ Raman spectroscopy has recently been applied for this type of
investigations [Tourni et al., 2011].
The composition, alteration processes and prospects of absolute radiocarbon AMS
14
C dating of paintings from significant shelters of this group have been studied in
situ using a portable Raman microscope.

159
Figure 2. Raman spectrum obtained from a black pictograph of Los Toros - Barranco de las
Olivanas shelter showing the D1 and G (sp3 and sp2 C-C type bonding respectively) bands of
amorphous carbon.
The Cova dels Rossegadors (Pobla de Benifass, Castelln), Los Toros Barranco
de las Olivanas (Fig.1, Tormn, Teruel) and Cueva del To Modesto (Henarejos,
Cuenca) rock shelters have been selected for the present work. Problems
encountered applying in situ micro-Raman spectroscopy for this purpose in
mountainous areas (no power lines, wind, sun light, dust) have been discussed.
Marlstone substrata, patinas and pigments with a large content of clay produce
strong fluorescence radiation that masks the Raman signals even exciting at 785
nm. Calcite, hematite, gypsum, whewellite, weddellite and -quartz have been the
most abundant materials detected. The presence of whewellite, weddellite [Ruiz et
al., 2006; Hernanz et al., 2007, 2008, 2010] and amorphous carbon in some
pictographs is a very promising outlook for absolute AMS 14C dating of these
paintings.
Acknowledgements. This work has been financially supported by the I+D+i project
CTQ2009-12489(BQU) of MICINN (Spain) and the European Regional
Development Fund (ERDF). We also thank the Consejeras de Cultura of the
Comunidades de Castilla La Mancha, Aragn and Valencia for permission to take
photographs and study the paintings of the archaeological sites with the Raman
microscope.
References
1054.
Materials 2007; 9: 512.
Ruiz JF, Mas M, Hernanz A, Rowe MW, Steelman KL, Gavira JM. International Newsletter on
Rock Art (INORA) 2006; 46: 1.
Tourni A, Prinsloo LC, Paris C, Colomban P, Smith B. Journal of Raman Spectroscopy
2011; in press. On line: DOI 10.1002/jrs.2682.

160
ATR-Ftir and Raman spectroscopy analysis for damaged and
restorated old book paper
Rodica-Mariana Ion1,2, Mihaela-Lucia Ion2, Sanda Doncea1,2

1
National Institute of R&D for Chemistry and Petrochemistry ICECHIM, Analytical
Department, 202 Splaiul Independentei 060021-Bucharest (Romania), Tel: +40 021
3163094, rodica_ion2000@yahoo.co.uk
2
Valahia University, Department of Materials Engineering, Mecathronics and
Robotics, Unirii Blvd 18-20, Targoviste (Romania)
The problems of conservation and restoration of the cultural heritage have received
a considerable recent interest, for old books, manuscripts, drawings and prints. The
main reason for the destruction of old paper lies in the oxidation of the cellulose
fibbers, which leads to the paper damaging.
This work deals with a new method of paper consolidation, in the field of Cultural
Heritage conservation. A new method of old book restoration, based on a special
suspension of different nanoparticles, have been presented and discussed in this
paper, exemplified for a Gospel (from a prvate collection).
Fourier-transformed (FTIR) and Raman spectroscopy methods provide the
informations about the molecules present in the artworks, being able to detect both
organic and inorganic compounds, as support or fillers. From these two methods,
FTIR remains in its totally a non destructive one. In the FTIR spectrum of Romanian
Gospel, the so called fingerprint region is between 1000 cm -1 and 1400 cm-1
because this is the region characteristic of the cellulose, which is the main substance
from the paper. In this area the CH2-OH strong absorbance is attributed to the
aromatic rings belonging to lignin, which is present with cellulose in the paper
samples. The peak at 1723 cm-1 indicates the oxidation of the cellulose and the
shoulder near the water absorption at 1648 cm -1, belong to the C = O band, due to
the hydrolysis and oxidation of cellulose. .
The inked areas are more absorbent than blank areas in the range 1750 to 1600 cm-
1
. This increase of absorption could be attributed to the cellulose oxidation process.
Also, the bands from 1450-1350 cm-1 and 1610-1550 cm-1 have been attributed both
to carboxylic salts and to C=O representing a possible way to put into evidence the
carboxylic components. SO2 asymmetric stretching from 670-640 cm-1 and 1690-
1620 cm-1 are proofs for the presence of sulfates in the samples. Despite the
cellulose being the major component of the sample, no strong absorption band
appears in the region (1200-950 cm-1) for the Gospel paper. The low absorption
region (950 to 600 cm-1 and 1900 to 1200 cm-1) of the cellulose corresponds to a low
reflective index, Fig 1.
Hydroxyapatite, [HAp, Ca10(PO4)6(OH)2], as nano-particles dispersions in alcohols
may be applied on paper by spraying or by impregnation. The similar structure of
hydroxyapatite with phosphates which are found in paper as fillers or as impurities of
the fillers led to the definite conclusion that there is a perfect compatibility between
this material and the conservation and restoration stationer.
FTIR spectra of hydroxyapatite synthesized revealed the existence of specific
absorption bands: 3573 - 3570 cm-1 - OH-stretching vibration, 1632-1629 cm-1 -OH
vibration of adsorbed water, 1088 cm-1, 1025 cm-1, 961 cm-1, 629 cm-1 and 598 cm-1 -
PO43-vibration group. A possible mechanism reaction that occurs between the
cellulose fibers and HAp takes place mainly at the primary OH group of cellulose,
which is the most reactive of the three existing, and which has enough energy to
form calcium phosphate cellulose with a free OH group involved in the neutralization
of the paper acidity.

161
Fig. 1: FTIR for cellulose [(-.-.) = pure cellulose) and (__) = degraded cellulose.
In Raman spectra, band height analysis gives more reliable results when partial
overlapping of two Raman bands occurs. Partial overlapping of bands of cellulose
(1094 cm-1) and HAp (1088 cm-1) occurs frequently due to the vicinity of the fibres in
the base paper and the coating. Raman bands are usually narrow. Figure 2 displays
a typical Raman spectrum of a paper coating containing hydroxyapatite. Raman
bands at 709 cm-1 and 1088 cm-1 were assigned to Ca(NO3)2, whereas the Raman
bands at 961 cm-1 and 1025 cm-1 peaks corresponding PO43-vibrations.
Fig.2. Raman spectra of damaged paper (1) and restorated paper (2)
The application of hydroxyapatite for paper restoration allows nanoparticles a deep

penetration into cellulose fibril structure improving its strength, creating a reservoir to
neutralize the papers acidic reaction.
References
Ion RM, Doncea SM, Patent RO 2010
Ion, RM., Ion, ML., Niculescu, VIR., Dumitriu, I, Fierascu, RC., Florea, G, Bercu, C, Serban,
S. Romanian Journal of Physics 2008; 53: 781
Doncea SM, Ion RM, Fierascu RC, Bacalum E, Bunaciu AA, Aboul-Enein HY.
Instrumentation Science & Technology, 2010; 38: 96

162
Micro-Raman spectroscopy of prehistoric paintings from
Remacha rock shelter (Seplveda, Segovia, Spain)
Mercedes Iriarte1, Antonio Hernanz1, Jose M. Gavira-Vallejo1,

Juan F. Ruiz-Lpez2 and Santiago Martn3
1
2
3
UNED, Departamento de Fsica Matemtica y de Fluidos, Facultad de Ciencias,
Paseo de la Senda del Rey 9, E-28040 Madrid (Spain).
Micro-Raman spectroscopy has been used to study prehistoric paintings founded

recently on the walls of an open air rock shelter in a Natural Park called Las Hoces
del Ro Duratn (Seplveda, Spain). This study belongs to a general project made
by our group on prehistoric paintings from the Mediterranean Basin of the Iberian
Peninsula and those from Northern Spain. Micro-samples (1 mm2) of the pigments
and substrata have been extracted from the painting panel of the Remacha rock
shelter (Villaseca, Seplveda) in order to identify its composition, the origin of the
observed colours and authenticate the pictographs.
Figure 1. Removing samples from the Remacha rock shelter (Villaseca.

Seplveda, Spain).
The Raman spectra have been obtained with a Jobin-Yvon Lab-Ram HR-800
Raman microscope using the line 632 nm of a He/Ne laser as exciting source.
Strong fluorescence radiation, probably due to clay materials, masked the Raman
signals from most of the samples. Nevertheless, hematite, whewellite, weddellite,
calcite and dolomite have been detected. The presence of calcium oxalates will
enable the AMS 14C dating of these works of art.

163
Figure 2. Digital reproduction of some pictographs from the Remacha rock shelter, Villaseca,
showing an antropomorph figure.
Acknowledgements. We gratefully acknowledge the European Regional

Development Fund (ERDF) for financial support. We also thank the Consejera de
Cultura of the Comunidad de Castilla-Len for permission to take photographs and
extract micro-samples of the paintings.
References
1054.
Materials 2007; 9: 512.
Ruiz JF, Mas M, Hernanz A, Rowe MW, Steelman KL, Gavira JM. International Newsletter on
Rock Art (INORA) 2006; 46: 1.

164
Spectroscopic characterization of an innovative biological
treatment for corroded metal artefacts
Edith Joseph1, Rocco Mazzeo2, Daniel Job3, Marie Wrle1

1
Laboratory of conservation research, Sammlungszentrum, Swiss national museum,
Lindenmoosstrasse 1, 8910 Affoltern am Albis, Switzerland. Tel. +41 447621389,
edith.joseph@snm.admin.ch
2
Microchemistry and Microscopy Art Diagnostic Laboratory, University of Bologna,
via Guaccimanni 42, 48100 Ravenna, Italy.
3
Laboratory of Microbiology, Institute of Biology, University of Neuchtel, Rue Emile-
Argand 11, 2000 Neuchtel, Switzerland.
Nowadays, organic coatings such as waxes, acrylic resins and corrosion inhibitors
are commonly used for the protection and corrosion inhibition of metal artefacts.
However, research efforts still need to be emphasized through the development of
innovative treatments, which aim at modifying existing corrosion products and
creating more stable and less soluble compounds while maintaining the surfaces
physical appearance. Within the framework of the BAHAMAS project, biological
treatments based on such criteria are being evaluated for the preservation of metal
artefacts. In particular, the capacity of some fungi to precipitate metal oxalates is
exploited for the stabilisation of soluble patinas (sulphates), and/or transformation of
active corrosion products (chlorides). In fact, metal oxalates display a high degree of
insolubility and chemical stability even in acid atmospheres (pH 3), providing the
surface with good protection, as it is the case of copper oxalates, which produce
green compact patinas [Marabelli and Mazzeo, 1993]. We present here the results
so far achieved during the preliminary evaluation on copper/bronze and iron
substrates. The application procedure was also optimized in order to conservators-
restorers make directly use of it.
Properly artificially or naturally aged metal samples with typical occurring corrosion
products, were prepared. The samples are made of copper and iron coupons
exhibiting respectively green and red-orange patina naturally produced during
exposure to the Zrich urban environment. Other bronze, copper and iron coupons
were exposed 6 months to the marine environment of Brest (French Corrosion
Institute), which is characterized for having high chloride atmosphere. For an
extended study, artificial chloride patinas were also produced following literature
[Hayer et al., 2006; Schmidt-Ott, 2009]. Conidies of Beauveria bassiana were
inoculated on a malt-agar delivery system, which was previously spread on the
coupons with a thickness of 2 mm. The formation of metal oxalates was monitored
during the whole duration of treatment of three weeks. All samples surfaces were
documented and fully characterised in order to assess colour, morphology and
composition before and after treatment. A complement of analytical techniques such
as scanner, optical microscopy, X-ray fluorescence (XRF), Raman and Fourier
transform Infrared (FTIR) spectroscopies were used (Figure 1).
A preliminary evaluation of the performances of the treatment was performed on
naturally aged copper roof coupons. Different parameters such as nutrient quantity,
spores concentrations and time of application were assessed through designed
experiments. The homogeneity and thickness of the copper oxalate layer formed
were determined by optical and FTIR microscopies as well as Raman mapping
performed on the surface and cross sections of the copper coupons. The results
showed that the original patina composed of copper sulfates was gradually
transformed into copper oxalates and that the conversion is all but completed on the
surface areas where B. bassiana grew (Figure 2). The experimental protocol
developed for iron was the same as for copper. FTIR analyses showed that dark red
165
crystals aggregated on hyphae presented characteristics absorbance bands at 1366,
1320 and 822 cm-1, which can be attributed to iron oxalates [D'Antonio et al. 2009].
Goethite seemed also to be formed during process. However, their presences were
not confirmed on the coupons surface.
The obtained results permit to select the optimal conditions and establish the best
application procedure for copper artefacts. For iron samples, further tests with spray
application should be performed in order to permit fungi to penetrate the patina
under treatment.This preliminary investigation plays an important role for the
following tasks of the project. In fact, the selected treatments and reference materials
(paraloid, ) will be applied on naturally or artificially aged bronze, copper and iron
standard samples. In order to evaluate their long term corrosion resistance,
monitoring over a 12-months exposure in marine environment as well as after
submission to different cycles of artificial ageing will be performed.
Acknowledgements. This work has been financially supported by the European

Union, within the VII Framework Programme (Contract: BAHAMAS, PIEF-GA-2009-
252759, 2010-2012).
References
Hayez V, Segato T, Hubin A, Terryn H. Journal of Raman Spectroscopy 2006; 37: 1211.
Schmidt-Ott K, Erhaltung von Kulturgtern: das Plasma in der Metallkonservierung-
Mglichkeiten und Grenzen, Collectio archaeologica, Chronos, Zrich, 2009.
D'Antonio MC, Wladimirsky A, Palacios D, Coggiolaa L, Gonzlez-Bar AC, Baran EJ,
Mercader RC. Journal of the Brazilian Chemical Society 2009; 20: 445.
Marabelli M, Mazzeo R. La metallurgia italiana 1993;.85(4): 247.

166
The pigments of the medieval painters in Fribourg :
Investigation of a top quality mural painting from the
Cordeliers Church in Fribourg
Ildiko Katona1, Vincent Serneels1, Peter Vandenabeele2

1
Department of Geosciences, University of Fribourg (Switzerland),
ildiko.katonaserneels@unifr.ch
2
Department of Archaeology, Ghent University (Belgium).
During the 80s, thousands of fragments of mural painting dating back to the late
medieval period (15th century AD) were found during restoration works in the church
of the Cordeliers in Fribourg (Switzerland). For 25 years, they remain unexploited at
the Archaeological Service of Fribourg until their extraordinary esthetic quality was
recognized.
Since 2009, an interdisciplinary team of researchers has been set up and a research
project has been supported by the Swiss National Science Foundation (B.
Pradervand). It includes the reconstruction of the entire scene -20000 fragments-
and the art historical and the technical studies. The technical study aims the
identification of the materials (pigments, binders, supports) and the description of the
painting techniques.
As this major work of art is already fragmented, it offers on exceptional opportunity
for the systematical sampling of the whole painted layer and the production of
numerous small polished sections. On the other hand, the burial of the fragments
under the ground inside the church about 200 years after it has been made, allows a
very good preservation of the very fragile painted layer.
Together with other analytical techniques (XRF, XRD, SEM, optical observation at
various scales and under different lights), Raman Spectroscopy is an efficient
method for the identification of mineral and organic substances used.
The medieval artist, still unidentified, was using a large variety of mineral pigments,
including high quality ones, like red cinnabar, blue azurite, artificial Sn-Pb yellow and
even metallic gold. His technique was highly sophisticated with pigments mixtures for
the production of specific shades and superposition of layers to obtain complex
visual effects.
First mineralogical results on this material will be presented.

167
Applications of Raman spectroscopy on characterisation of
artefacts from semiprecious stones
Thomas Katsaros1, Theodore Ganetsos1,2 and Peter Vandenabeele3

1
Byzantine & Christian Museum, Laboratory of Gemstones, Vas. Sofias 22 Athens,
106 75 (Greece) Tel. +30 2231060140, ganetsos@teilam.gr
2
Technological Educational Institute of Lamia, 3rd Km O.N.R. Lamia-Athens, Lamia,
(Greece)
3
Ghent (Belgium)
In this research work we present the results of analysis of semiprecious stones, as a

part of the I.&D. Passas Foundation Collection Byzantine & Christian Museum. Our
main interest was the analysis on the artefacts made from semiprecious stones
mainly statuettes of goddesses as well as vases.
The art objects studied and presented here are made of nephrite, jadeite [two very
different stones known under the common term jade], [Rawson 1995], lapis lazuli,
sodalite and fluorite. All the artefacts come from China and can be dated from the late
19th early 20th century.
We studied the identification of a group of 43 samples, from which we bring out 15 items
in the present paper. We separated the specific minerals from general categories such
as Jade to Jadeite and Actinolite-Nephrite [Apopei and Buzgar 2010]. A very good
approach for this is the application of Raman Spectroscopy [Vandenabeele 2006].
The separation by mineralogical characterisation, using Raman spectroscopy, of the
Jade artefacts was successful. The different behaviour of Actinolite and Jadeite
under Laser Beam was detected and was interpretive with Raman investigation
[Katsaros et al 2007]. The possibility of the provenance of some Artifacts from well
known mines with Historical context was strong, but we must continue the
characterisation.
650000
600000
550000
500000
450000
400000
350000
300000
250000
Intensity (arb. units)
200000
150000
100000
50000 (Sodalite-Badakshan)
(Lazurite_Afganistan)
15000
exp.BXM_24374
12000 exp.BXM_24355
9000
6000
3000
0
200 400 600 800 1000 1200 1400 1600 1800
-1
Raman shift (cm )
Fig. 1 A comparison between experimental results versus RRUFF data base of sodalite and
Lazurite.

168
For this further study on analysis of the minerals, the application of (chemical
elementary) XRF analysis was used to testify the minor elements and trace elements
which lead us to the chemical profile of their mining.
50000
Jadeite-Burma
45000 Nephrite-MARYLAND
exp.BXM_23968
40000
exp.BXM_23991
35000
30000
Intensity (arb. units)
25000
20000
15000
10000
1600
1400
1200
1000
800
600
400
200
0
200 400 600 800 1000 1200 1400
-1
Raman Shift (cm )
Fig.2 The separation of Nephrite and Jadeite (exp. results and data from bibliography)
The clarification of the specific mineralogical synthesis, of the group of artefacts from
Lapis Lazuli and after that, the separation of the subgroup of Sodalite samples, was
made, without sampling, with Raman spectroscopy. Using XRF data with the
appropriate ratio of elements (such as Cl/Si relative stoichiometric compositions) we
may propose possible sites of provenance for items Jadeite BXM_23991, and
Sodalite BXM_24355, and Fluorite BXM_24624.
Acknowledgements. The authors would like to express their special thanks to the TEI
of Lamia, the Byzantine & Christian Museum and the I. & D. Passas Foundation for
supporting to this research work.
References
Rawson J, in British Museum Press(Editor), Chinese Jade from the Neolithic to the Qing,
London, UK, 1995, p.28.
Apopei AI, Buzgar N. Analele Stiintifice Ale Universitatii Al. I. Cuza lasi Geologie 2010; 56:
57.
Vandenabeele P, Moens L., in Springer Berlin/Heidelberg(Editor), Introducing students to
Raman Spectroscopy in Analytical and Bioanalytical Chemistry, Berlin, Germany, 2006,
p.209
Katsaros Th, Liritzis I, Thompson Tr, Carron K, Cox R., GSA Annual Meeting, Denver,
Colorado 2007; 39: p.574.

169
Raman Characterization of Gemstones from the Collection of
the Byzantine & Christian Museum
Thomas Katsaros1, Eugenia Chalkia1 and Theodore Ganetsos2,1

1
Byzantine & Christian Museum, Vas. Sofias 22, 106 75 Athens (Greece),
Tel. +302107231570, tkatsaros@rhodes.aegean.gr
2
T.E.I. of Lamia, 3rd Km. ONR Lamia-Athens, Lamia, 35100, Greece.
A very significant component of the collection of gold jewellery in the Byzantine

Museum of Athens consists of the Mytilene Treasure from the island of Lesbos.
Despite the importance of the Mytilene Treasure, one of the most significant hoards
of the 7th century from the Aegean area, no previous systematic study has been
dedicated to it since its discovery in 1951, except for brief entries in exhibition
catalogues [Chalkia, 2008]. The presence of Gemstones among the artefacts, set us
the question of their mineralogical identity. We use a portable Raman Spectrometer
(at 785 cm-1) with range 200-2000cm-1. The samples which we study are the
following BXM_875, BXM_872, BXM_178a, BXM_178b, BXM_873a, BXM_873b.
The measurements made in the Laboratory of Byzantine & Christian Museum. The
references of Gemstones in Byzantine literature are many and helpful. [Stocchi
M.,2009]. We study emerald, lapis lazuli and sapphire using Raman Spectroscopy.
This is a light-scattering and non-destructive technique which allows for the
identification by comparing a spectrum to a mineral database of the RRUFF-
Database [Downs R. T., 2006]..
BXM_872_(2)
Emerald-Swat Valley, Pakistan

200 400 600 800 1000 1200 1400 1600 1800 2000 2200
-1
Raman Shift (cm)
Figure 1. Raman spectrum of experimental data in comparison with the bibliography.
We apply Raman spectroscopy to testify 9 stones on the necklace (BXM_872)

(Figure 1). The question was about the identification of these stones if they are real
emeralds or not. Theophrastus of Eressos mentions that exist a kind of false emerald
[Caley, 1956]. In Christian Era Epiphanios of Cyprus is described in his text
emeralds [Epiphanii Cypri, 4 cent.A.D.]. Another interesting reference is the book of
Damigeron (1rst cent. A.D.) which includes a description of emerald [Tahil, 2005]. In
Byzantine era Michael Psellus in his text De Virtutibus Lapidorum made a reference
on emerald. Emerald is now but a general trade de-signation for various green
precious and semi-precious stones and not, in the jewellery trade, the specific term

170
of any gem mineral. The green beryl, excepting in its colour, is the same mineral as
aquamarine. One of the rarest of gems is a flawless emerald-hued beryl [Wodiska
1910]. In accordance to our experimental results: the BXM_872 contains nine
emeralds, the circular amulet BXM_875 is lapis lazuli, the earrings BXM_178a,b with
the blue stones are not sapphires but are possible a kind of glass paste and the
earrings BXM_ 873a,b are glass.
3000
BXM_178B_(2)
BXM_178B_(1)
2500
2000
1500
1000
500
Corundum, Sri Lanka
0
200 400 600 800 1000 1200 1400 1600 1800 2000
-1
Raman Shift (cm )
Figure 2. Raman Spectrometry data in comparison with Rruff data base [Downs R. T., 2006].
As a future work we propose the mineralogical identification of all stones on artefacts

and a further investigation using the X-Ray Fluorescence which will give us relative
concentrations of main chemical elements.
Acknowledgements. The authors would like to express their special thanks to the
T.E.I. of Lamia and the Byzantine & Christian Museum for supporting to this research
work.
References
Stocchi M., The treasury of Saint Peters in the Vatican, Edizioni Capitolo Vaticano, Rome,
Italy, 2009, p.26.
Chalkia E., Catalogue of Byzantine and Christian Museum, The Byzantine Collections,
Athens, Greece, 2008, p.115
Caley R., Theophrastus On Stones, Ed. Ohio Univ. Press, Chicago, USA, 1956, p. 27.
Wodiska J, A Book of Precius Stones, New York, USA, 1910, p.63.
Damigeron, The Virtues of stones, by Patricia Tahil, Edited by Joel Radcliffe, Ars Obscure,
Seattle, USA, 2005, VI, p.14
Pliny the Elder (1rst cent. A.D.) Historia Naturalis XIX, 75.
Spier J, Late Antique & Early Christian Gems, Verlag, Wiesbaden, Germany, 2007, p. 87
Touratsoglou I., Chalkia E., The Kratigos, Mytilene Treasure, Coins and Valuables of the 7th
Century AD, , Athens, Greece, 2008, p.108
Downs R T., 2006 Program and Abstracts of the 19th General Meeting of the International
Mineralogical Association, Kobe, Japan. p.3.

171
Characterisation of 6th century fibulae with gem materials
(cemetery Lajh in Kranj, Slovenia) by means of XRF and
micro-Raman spectroscopy
Sabina Kramar1, Matej Dolenec2 and Judita Lux3

1
Institute for the Protection of Cultural Heritage of Slovenia, Conservation Centre,
Restoration Centre, Poljanska 40, 1000 Ljubljana (Slovenia), Tel. +386 40 693 125,
sabina.kramar@rescen.si
2
University of Ljubljana, Faculty of Natural Sciences and Engineering, Department
of Geology, Akereva 12, 1000 Ljubljana (Slovenia)
3
Institute for the Protection of Cultural Heritage of Slovenia, Preventive Archaeology
Department, Tomieva 7, 4000 Kranj (Slovenia)
The first findings from the Lajh cemetery in Kranj (Slovenia) were discovered at the
end of 19th century and until today almost 800 graves were excavated. The graves
from the Great Migration period (precisely 6 th century) are attributed to the
Romanized indigenous population and also different Germanic tribes as Lombards,
East Goths, Franks, Alamanni Stare, 1980, Knific and Lux 2010. One of the most
characteristic finds of the Lajh cemetery represent fibulae (brooches) which were
part of the female costume. The specific shape and decoration of the fibulae and
type wear characterise different ethnic groups.
Fibulae were often decorated with various gem materials. Among them the red
garnet was the dominant gemstone used in jewels in Europe from 4th till 8th AD. The
peculiar style of decorating metalwork jewel is called cloisonn and actually
originated from the near East and was spread to Western Europe during the Great
Migration period. This jewellery has inlays of thin plates of red and translucent
materials that are fixed to the base of the object using putty or gypsum based
cement Arrhenius, 1985. Some cloisonns could be polychromic (green glass,
ivory, chalcedony, polished rock such as marble) or monochromic for which they
normally used garnet. The analyses of precious artefacts cannot be subjected to
destructive techniques. In order to clarify the nature of the material employed and
evaluate possible provenance, the similar type of ancient jewellery has been
investigated by various non-destructive techniques Farges, 1998, Calligaro et al.,
2002, Smith, 2005.
In this paper several brooches from the Lajh cemetery, are analysed which, based
on their shape, correspond to the S-fibulae, different types of bow fibulae and disc
fibulae. They are decorated with at least two, usually more red gemstones, some of
disc brosches have more than 40 gemstone inlays. In order to determine the
composition of the metal and type of the gem materials, the artefacts were analysed
using X-Ray Fluorescence Spectroscopy (XRF) and micro-Raman Spectroscopy.
Results of XRF analysis of metal artefacts revealed that artefacts were made by
silver gilding, few samples represent gilded billon (Cu-Ag alloy, Zn, Pb, Sn additives)
or consist of leaded bronze.
XRF was used to determine the major elements (Fe, Al, Si, Mg, Ca), specifying the
gem material type and the trace element content (Cr). Results indicate that brooches
were decorated with almandine garnets (Fe-Al-rich garnets) with the chemical
172
formula Fe2Al2(SiO4)3. In addition, the observed Raman spectra with the most
significant band at 918 cm-1 confirmed that all analysed gem materials consisted of
almandine. The almandine variety can be found in Sweden, Austria and Italy Atthill,
1983 but garnet or almandine which was used in early Dark-Age jewellery in north
Europe is thought to come from Bohemia Schoneveld, J. 1993.
The combination of micro-Raman spectroscopy and X-Ray Fluorescence

Spectroscopy has been successfully applied to identify type of the gem materials
and to determine the metal composition of the investigated brooches. Results
obtained contribute to the knowledge of the ancient trading routes.
Acknowledgements. This work has been financially supported by ARRS -

Programme group - P1-0195 - Geochemical and structural processes.
References
Arrhenius, B, in Beck H (Editor), Cloisonn Technik : Reallexikon der Germanischen
Altertumskunde 5, Berlin, New York, 1984, 3034.
Atthill, C. The Macdonald encyclopedia of rocks and minerals, London. 1983, p.608.
Calligaro, T, Colinart S, Poirot J-P, Sudres C. Nuclear Instruments and Methods in Physics
Research B 2002; 189: 320.
Farges, F. American Mineralogist, 1998; 83: 323.
Knific, T. Lux, J. Kranjski zbornik, 2010, 26-36.
Smith, D.C. Spectrocimica Acta Part A, 2005; 61: 2299.
Schoneveld, J. De grote fibula van Wijnaldum, De Vrije Fries, 1993, 73: 7-24.
Stare, V. Catalogi et monographiae, 1980,18, p.136.

173
Raman spectra and elements evaluation of a Tang Dynasty
Buddha
Xianchang Li1,2, Zitong Wu1, Yaliang Cui2, Xiaohua Wang1,Yanjun Liu3,

Hua Tong1, Jiming Hu1
1
Centre of Archaeological Sciences, College of Chemistry and Molecular Sciences,
Wuhan University, Wuhan 430072, China.
2
School of Mathematics and Physics, Anyang Institute of Technology, Anyang
455000, China.
3
Cultural Relics Bureau of Anyang, Anyang 455000, China.
A Tang Dynasty Buddha was studied by the confocal Raman spectra (CRS) and
scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-
EDS). In Figure 1, the bands 100, 135, 151, 290, 347, 371 and 166, 211cm -1 were
respectively attributed to PbO [McCann et al. 1999] and PbCl2 vibrations [Bahfenne
et.al, 2009], the bands 213, 292, 337 and 522 cm -1 were attributed to CuO and Cu 2O
vibrations [McCann et al. 1999]. While the bands 477 and 635 cm-1 could probably
be attributed to SnO2 vibrations because its Raman vibrations were always found at
477, 633 and 745 cm-1 [Rumyantseva et al. 2005]. Furthermore, we also found the
bands for PbCO3, 2CuCO3Cu(OH)2 and CuCO3Cu(OH)2 (not shown here). In
combination with the SEM-EDS analysis (Figure 2), our study showed that the Tang
Dynasty Buddha was composed by Cu-Pb-Sn bronze alloy, and the surface
corrosions were assembled of cupric oxide, cuprous oxide, basic copper carbonate,
massicot, jewellers putty, lead carbonate and lead chloride.
166
135
211
371
151
Intensity(a.u.)
166
100
347
211
292
635
512
477
292
337
215
100 200 300 400 500 600 700 800 900

-1
Raman shift(cm )
Figure 1. Raman spectra of the Figure 2. SEM image and element

Tang Dynasty Buddha distribution of sample interface
Acknowledgements. This work has been financially supported by the National

Natural Science Foundation of China (No. 20705025 and No. 30772058).
References
L. I. McCannK. TrentelmanT. PossleyB. GoldingJournal of Raman Spectroscopy 1999;

30: 121-132.
S. Bahfenne, R. L. Journal of Raman Spectroscopy 2009; 41: 329-333.
M. N. Rumyantseva, A. M. Gaskov, N. Rosman, T. Pagnier, J. R. Morante, Chemistry of
Materials 2005; 17: 893-901.

174
-Raman pigments analysis of a painting with the signature
Picasso
M.R. Lopez-Ramirez1, L.R. Rodriguez-Simn2, Natalia Navas3,

J.C. Otero1, Eloisa Manzano3
1
Department of Physical Chemistry, University of Mlaga, Campus de Teatinos s/n,
E-29071, Mlaga, Spain
2
Department of Paint and Restoration. University of Granada, Avda de Andaluca
s/n, 18071 Granada, Spain
3
Department of Analytical Chemistry, University of Granada, Avda de Fuentenueva
s/n, 18071 Granada, Spain. 34 958243388 emanzano@ugr.es
During the last few years, there has been a growing interest in the scientific analysis
of paintings to authenticate, date and determinate the provenance of artworks.
Particularly, in canvas paintings, it is well known that a complete and unambiguous
characterisation of materials in paintings is often difficult, because of their complex
structure and the heterogeneous mixtures of organic and inorganic components.
The efforts described in this paper are parts of a Research Contract devoted to the
identification of the materials used to manufacture two canvas paintings where there
is a signature "Picasso". In this way, pigments, binding media and varnishes could
be identified and the results could help to obtain valuable historical information as a
means to answer authentication questions of the paintings studied.
Since an important requirement of art analysis is to avoid harm to the precious
artefact during analysis, because an artistic painting cannot be replaced, in situ
Raman microscopy (RMS) is the technique of choice for non-destructive analysis.
Thus, in this paper the authors focus their attention on the application of Raman
microscopy to pigment analysis in the painting Guitar, with a signature Picasso.
The confocal properties of the instrumentation allows the direct performance of
investigation on this easel painting that can be positioned under the microscope
optics of the spectrometer without damaging the work. The Raman spectra in several
blue areas have shown a very similar spectra corresponding to the presence of
phthalocyanine blue pigment, CuC32H16N8, a modern organic pigments first
synthesized in the early twentieth century.
1530
Relative Intensity
747
1186
1006
1342
840
681
143
1143
778
1307
1452
1108
484
592
256
952
500 1000 1500

-1
Wavenumber /cm
Figure 1. In situ Raman spectra of phthalocyanine blue and the optimized geometry of this
molecule.

175
The main Raman bands of phthalocyanine blue are recorded at 681 (m), 747 (s),
1342 (m), 1452 (w) and 1530 (s) cm-1 operating with a Renishaw NIR diode laser
emitting at 785 nm, which agree with published works [Burgio L. et al. 2001, Nadim
C. S. et al. 2009]. The observation of Raman band at 143 (vs) cm-1 in a white area
and also in some light blue samples (with white pigment added to achieve certain
hues) from the painting, may be attributable to titanium dioxide pigment in the
anatase form. Anatase pigment is part of the formulation of ready-mixed house
paints widely used in the artistic production of the first half of the twentieth century
[Gautier G. et al. 2009]. Nevertheless, at the present stage of this study, its presence
is not totally defined and accepted. It will be completely inferred from the results of
the further SEM-EDX elemental analyses.
In addition, future work will focus on the in-depth study of the binding medium and
the type of natural resin present in the varnish. With that aim, mathematical Raman
spectra manipulation such as derivative spectra will be tested [Navas N. et al. 2010].
Acknowledgements. This research has been supported by: UGR: Research Contract
n 2802 through the Results Transfer Office (OTRI) of the University of Granada.
UMA: Ministerio de Ciencia e Innovacin (CTQ2009-08549) and Junta de Andaluca
(FQM-01895).
References
Burgio L., Clark R.J.H. Spectrochimica Acta Part A 2001, 57: 1491-1521.
Nadim C. S., Zumbuehl S., Delavy F., Fritsch A., Kuehnen R. Spectrochimica Acta Part A
2009, 73: 505524
Gautier G., Bezur A., Muir K., Casadio F., Fiedler I. Appl Spectrosc 2009, 63(6): 597-603.
Navas N., Romero-Pastor J., Manzano E., Cardell C. J Raman Spectrosc 2010, 41:1196-
1203.

176
Preliminary FT-Raman and infrared spectroscopic analysis of
some modern Romanian paintings
M.M. Manea1, M. Virgolici1, C.C. Ponta1, O.H. Barbu2,3, I.R. Stanculescu1,4,

P. Bugheanu4, C.D. Negut1,5, M. Cutrubinis1, I.V. Moise1
1
"Horia Hulubei" National Institute of Physics and Nuclear Engineering (IFIN-HH),
IRASM Centre of Technological Irradiations, 407 Atomitilor Str., 077125, Magurele,
Ilfov (Romania), Tel. +40 214042320, mmanea@nipne.ro
2
National University of Arts Bucharest, Department of ConservationRestoration,
010773, Bucharest (Romania)
3
National Museum of Romanian History (MNIR), Centre of Research and Scientific
Investigations, 030026, Bucharest (Romania)
4
University of Bucharest, Faculty of Chemistry, Department of Physical Chemistry,
030018, Bucharest (Romania)
5
University of Bucharest, Department of Atomic and Nuclear Physics, 077125,
Magurele, Ilfov (Romania)
Nicolae Grigorescu (1838 -1907), the first of the founders of modern Romanian
painting, followed by Ion Andreescu and Stefan Luchian, become a symbol for the
young artists generations of the beginning of the XX th century, which tried to identify
and highlight the Romanian spirituality values. N. Grigorescu undertook a
spectacular reborn of the plastic language bringing together the tradition of mural
painting and the impressionist experience.
In the frame of a national research grant (ANCS, PN II program, PD contr.
27/2010) the present work aims to identify pigments used by modern Romanian
painters, and to built spectral databases useful for conservation/restoration purposes
and identification of art forgeries.
The artworks discussed in the present study were analyzed non-destructively with
a Bruker Vertex 70 FT-IR and Raman spectrometer. RAM II module equipped with a
Nd:YAG LASER excitation source of 1064 nm (adjustable power between 1 and 500
mW, with 1 mW resolution) and with a LN2 Ge cooled detector was used for Raman
analysis with a mobile probe. FT-Raman spectra were recorded between 50 and
3500 cm1, with 1000 scans (~30 min) at 4 cm1 resolution.
On another extension of Vertex 70 spectrometer a FT-IR module (650 - 4000 cm-1)
with a MCT detector (LN2 cooled) and a special probe with KBr lined glass fibers
and diamond head optimized for non-contact analysis of flat surfaces was used
complementary. FT-IR spectra were recorded with 2000 scans (~20 min) at 4 cm -1
resolution.
Spectra of historical, modern and contemporary pigments (Kremer Pigmente
GmbH & Co. KG) were used as references. In addition Principal Components
Analysis performed with Statistica 7 software was used for the identification of
pigments and spectral pattern fingerprinting between different creations of the same
artist.
Acknowledgements. Authors are grateful to ANCS, PN II program, PD project

"Fourier Transform Vibrational Spectroscopy Used in Characterization of Painting
Pigments: An Authentication Chance for Romanian Paintings", contr. no. 27/2010;
and DELCROM project, contr. no. 92-086/2008.

177
Raman and XRD characterization of synthetic ceramic
pigments (Co-pyroxenes)
Luciana Mantovani 1, Mario Tribaudino1, Danilo Bersani2,

Pier Paolo Lottici2, Michele Dondi3, Chiara Zanelli3, Geoffrey Bromiley4
1
Dipartimento di Scienze della Terra, Universit degli Studi di Parma, V.le G.P.
Usberti 157a, 43124 Parma, Italy
2
Dipartimento di Fisica, Universit degli Studi di Parma V.le G.P. Usberti 7a, 43124
Parma, Italy
3
CNR-ISTEC, Istituto di Scienza e Tecnologia dei Materiali Ceramici, Faenza
4
School of Geosciences, University of Edinburgh, Edinburgh EH9 3JW
The study of pyroxenes along the join CaCoSi2O6-Co2Si2O6 has an interest in

mineralogy and in ceramic sciences. As for ceramics, Co-bearing silicates can act as
blue to pink pigments. Blue color stems from Co in tetrahedral coordination, like in
CoAl2O4 spinel (blue cobalt), whereas higher coordination drives to a pink hue. In
CaCoSi2O6-Co2Si2O6 pyroxenes the substitution occurs in two different sites M1 and
M2 at different coordination, being M1 a regular octahedron and M2 a distorted
polyhedron with 6-8 fold coordination, and the effect of Co for Ca substitution on the
pyroxene color can therefore be investigated. As for mineralogy the series is an
analogue to the series diopside-enstatite (CaMgSi2O6-Mg2Si2O6) and hedenbergite-
ferrosilite (CaFeSi2O6-Fe2Si2O6) of quadrilateral pyroxenes. The comparison on the
crystal chemistry and phase transitions of the effect of the solid solution of Ca for Co
on the M2 site, vs that of Ca for Mg and for Fe, can provide the basis for a model of
solid solutions in pyroxenes. Preliminary results on the synthesis and
characterization of CaCoSi2O6-Co2Si2O6 pyroxenes are here reported. Previous
experimental data on CaCoSi2O6-Co2Si2O6 pyroxenes are confined to the end
members, CaCoSi2O6 which was synthesized at room pressure, and Co 2Si2O6 which
was synthesized above 3 GPa and 7 GPa in the orthorhombic and monoclinic
polymorphs respectively. In the present study eleven compositions along the series,
at step of 10 mol % of the CaCoSi2O6 component, were synthesized at room and
high pressure. Room pressure syntheses were achieved by calcinations at 1000C
for 12 h of stoichiometric mixtures of the oxides. Combined SEM/EDS, Raman and
XRD investigation gave evidence of an incomplete reaction for the starting materials,
with the presence of residual amorphous silica. Clinopyroxene, with a composition
close to (Ca0.9Co0.1)CoSi2O6, was found in all samples except that with stoichimetric
composition Co2Si2O6, where an assemblage of Co-olivine (Co2SiO4) and silica was
found. Co-olivine was observed in all samples, less in Ca-richer compositions. Co-
ackermanite (Ca2CoSi2O7) was observed between CaCoSi2O6 and
(Ca0.6Co0.4)CoSi2O6. The color changes from pink to blue together with increasing
ackemanite and decreasing olivine.To obtain wider pyroxene solid solution, high
pressure synthesis on the same starting materials was carried out with piston
cylinder apparatus at P=3 GPa and T=1200C, for 4 to 20 h. XRD and Raman
analyses show that between CaCoSi2O6 and Ca0.4Co0.6Si2O6 a clinopyroxene solid
solution is the only phase. In the sample with starting composition Ca 0.2Co0.8Si2O6 we
obtain the coexistence of clinopyroxene, orthopyroxene and quartz, and in Co 2Si2O6
only olivine and quartz, without formation of a pyroxene phase. Cell parameters
follow the same trend with composition previously observed in C2/c pyroxenes along
the series diopside-enstatite and hedembergite-ferrosilite. Changes observed in
Raman spectra may be interpreted as in pyroxenes along the diopside-enstatite.
Single crystal XRD, optical spectroscopy investigations and attempts to synthesize
Co2Si2O6 clinopyroxene by means of a multi-anvil apparatus, are in progress.

178
Combined use of Raman spectroscopy and chemometric to
aged lipidic paint binders discrimination
Eloisa Manzano1, Jos Garca-Atero1, Ana Dominguez2,

Maria Jos Ayora-Caada2, Luis Fermn Capitn-Vallvey1
and Natalia Navas1
1
University of Granada, Analytical Chemistry Department, Avda. Fuentenueva s/n,
18071 Granada (Spain), Tel. +34 958243388, emanzano@ugr.es
2
University of Jaen, Department of Physical and Analytical Chemistry, Paraje Las
Lagunillas B, 23071 Jaen (Spain).
Drying oils are lipid materials frequently used in artistic painting as a binding media
(oil painting). Among them, the most usual drying oil is linseed oil (depending on
period and pictorial technique), being poppy seed and walnut oils also employed.
One important aspect that must be considered when characterising the type of
drying oil in a paint sample is the possible presence of mixtures of different kinds of
drying oils, including that from egg yolk, widely used as binder in mixed techniques
such as tempera grassa, in which egg and drying oil are mixed [Manzano et al.,
2011]. Thus, the characterization of drying oils is a complex task highlight by the
natural and spontaneous ageing process where complicate and unknown process
can be occurs. Also, the drying process is affected by the presence of other
substances such as pigments and chemical driers, including metallic salts [Mills and
White, 2003].
Nowadays multivariate analysis of Raman spectroscopic data is gaining popularity in

the field of Cultural Heritage, particularly to characterise artistic materials including
organic compounds [Nevin et al., 2008; Nevin et al. 2009; Navas et al. 2010]. The
work here presented explores the application of chemometric tools (i.e. Principal
Component Analysis (PCA) and Partial Least Squares Discriminant Analysis (PLS-
DA)) on Raman spectral data to discriminate aged lipid binders in paint model
samples. With that aim, various paint model samples were prepared containing pure
egg yolk, pure linseed oil, pure walnut oil and pure poppy-seed oil, as well as six
binary mixtures of them. These model samples were left to age naturally for six years
at room temperature without controlled ambient conditions and they were further
characterised by Raman spectroscopy. The corresponding Raman spectra were
used to apply PCA in order to test whether spectral differences allowed
discrimination of samples based on their composition and aged stage. Figure 1
shows the results of this multivariate analysis. The first principal component (PC1)
established a clear distinction between samples of pure linseed and poppy seed
(with negative scores) and the rest of the samples. Samples of pure linseed oil and
pure walnut oil showed high positive scores for PC2, whereas poppy seed and egg
yolk were characterized by high negative ones. Binary mixtures showed intermediate
values in the PC2. Looking at the loadings of the corresponding PCs it was also
possible to establish the influence of the different spectral regions on the
discrimination of the samples. The natural groupings within the Raman spectra of the
samples coincided largely with the known class memberships. Based on these
observations, it was concluded that the spectral information was useful to
discriminate between aged samples of different lipid binders.
A supervised technique, PLS-DA, was also applied to generate classification rules
which allow classifying samples of unknown origin. The goal was to identify the
presence of each lipid binders, i. e., egg yolk, linseed oil, poppy seed oil and walnut
179
oil. The best results were obtained for the class egg yolk. This class was modeled
using three latent variables. All samples containing egg yolk were correctly identified,
whereas no false positives from other classes occurred. On the contrary, walnut oil
was the class that exhibit lower specificity. The three validation samples containing
poppy-seed oil were erroneously identified as containing walnut oil. This could be
attributed to the similar fatty acid composition of these two oils. However, the same
did not occur for the poppy seed oil class. Samples containing walnut oil were not
classified as containing poppy-seed. In fact, the specificity for poppy seed class was
good. The major problem with this class was the sensitivity, with two false negatives
for the prediction set. Similar performance was obtained for linseed oil with two false
negatives and one false positive. Despite the size of the sample set was small and
therefore the presented results could not be considered categorical, they clearly
showed the potential of the information contained in the Raman spectra to
discriminate aged drying media in artistic paints.
Figure 1. Scores plot of PCA on Raman spectra of aged, pure and mixed model samples.
L, linseed oil, E, egg yolk, P, poppy-seed oil and W, walnut oil.
The novelty of this work lays on the combined use of Raman spectroscopic data and
chemometric tools such as PCA and PLS-DAD to investigate lipidic binding media.
This is the first attempt to use this approach in the field of cultural heritage and
demonstrates the potential benefits for discriminated fresh and aged lipidic binders
for purposes of conservation and restoration.
Acknowledgements. This work has been financially supported by research groups
FQM-118 and FQM-363 (funds from Cultural and Natural Heritage CEI Project).
References
Manzano E, Rodriguez-Simn LR, Navas N, Checa-Moreno R, Romero-Gmez M, Capitn-
Vallvey LF Talanta doi:10.1016/j.talanta.2011.03.012
Nevin A, Anglos D, Burnstock A, Cather S, Becucci M, Fotakis C, Castellucci E, Journal of
Raman Spectroscopy 2008; 39: 307.
Nevin A, Osticioli L, Anglos D, Burnstock A, Cather S, Castelluci E, Analytical Chemistry
2009; 79: 6143.
Navas N, Romero-Pastor J, Manzano E, Cardell C Journal of Raman Spectroscopy 2010; 41:
1196.
Khn H, in Roy A.(Editor), Artists Pigments: a Handbook of their History and Characteristics,
vol. 2, Oxford University Press, Oxford, UK, 1997, p. 83.

180
Raman, FT-IR and XRF for the characterization and diagnosis
of mortars and concrete degradation processes from XIX
century lighthouses located on the coast of the Basque
Country: The case of Igueldo Lighthouse, San Sebastian
Hctor Morillas1, Olivia Gmez-Laserna1, Maite Maguregui2 and

Juan Manuel Madariaga1
1
Department of Analytical Chemistry, University of the Basque Country, P.O. Box
644, 48080 Bilbao, Basque Country, Spain e-mail: hector.morillas@ehu.es
2
Department of Applied Chemistry, Faculty of Chemistry, University of the Basque
Country, P.O. Box 1072, 20080 Donostia, Basque Country, Spain
Since many years ago, strenuous efforts have been carried out in order to develop
suitable analytical protocols to assess the presence of deterioration products on
buildings and items from the built heritage. These methodologies can be appropriate
to extract relevant information in order to conduct later restoration works (e.g.
selection of restoration building materials similar in composition to those materials
used in the past, designs of cleaning processes that do not affect the aesthetic
appearance of original materials, etc.). Lighthouses, located in various sea routes,
are important items of our immovable cultural heritage or built heritage, including
constructions of great historical, technological and aesthetic value. Few works can
be found in the literature regarding to the characterization of building materials from
historical lighthouses. Besides, among those few works, almost no one refers to the
diagnosis of possible deterioration processes on building materials from lighthouses.
In this work a non-invasive protocol based on the application of Raman, FT-IR and
XRF was applied to characterize and diagnose possible deterioration processes or
pathologies on mortars and concrete from a historical 19 th century (1855 year)
lighthouse located in Igueldo (San Sebastian, Basque Country, North of Spain)
Mortar and cement samples from the lighthouse were analyzed using different
spectroscopic techniques in order to characterize the original composition and decay
products from these materials. For the mineralogical characterization (molecular
speciation) of samples, Raman spectroscopy (portable innoRamTM spectrometer
implementing 785 nm excitation laser, B&WTEKINC.) and complementary
measurements by means of FT-IR spectroscopy (JASCO FT/IR-6300 spectrometer)
using attenuated total reflectance (ATR) sampling (MIRacleTM single reflection ATR,
Pike Technologies) were used. Moreover, elemental composition of samples was
conducted by -energy dispersive-X-ray fluorescence spectroscopy (-EDXRF).
Spectroscopic analyses made on Igueldo Lighthouse mortar samples showed that
the original composition was based on a mixture of calcite (CaCO 3), quartz and other
silicates of different nature (e.g. feldspars). According to historic registers, the
materials used to manufacture these mortars were limestone, sandstone and clays
from unknown origin. Moreover, the original mixture could have included sulphate,
(e.g. calcium sulphate, magnesium sulphate, etc.) and carbonate (sodium carbonate,
barium carbonate, etc.) as additives. An example of this complex mixture can be
seen in the results presented in Figure 1, where the main Raman bands of gypsum
(CaSO42H2O) at 1006 cm-1 and calcite at 1085 cm-1 ; the decaying compound
coquimbite (Fe2(SO4)39H2O) at 1025 cm-1 can also be observed (Fig. 1A). The main
calcium sulphate that it was usually added to the cement paste is gypsum. However,
due to dehydration processes or low purity of gypsum, other less hydrated forms of
calcium sulphate could also be present. Apart from calcium sulphates, magnesium
sulphates were also identified by means of Raman spectroscopy; in this case,
181
epsomite (MgSO47H2O) and hexahydrite (MgSO46H2O) with their main Raman
bands at 986 and 1001 cm-1 respectively were identified. Moreover, natron
(Na2CO310H2O) was also identified by means of Raman spectroscopy at 1067 cm -1.
It is well known that natron has been used since Egyptian times as additive.
Figure 1. Raman spectra of (A) the original composition of the cement showing Raman bands
of quartz (464 cm-1), calcite (1085, 712 and 278 cm-1) and gypsum (1006 cm -1) plus the
decaying coquimbite (1025 cm -1) and (B) sample of the NW wall showing the bands of
thenardite (993 cm-1) and calcite (1085, 712, 280 cm -1).
In some samples, apart from the original components, some decay products other
than coquimbite were also identified. In certain areas of the lighthouse a white
efflorescence was visible, especially in the north-west area of the lighthouse; Raman
analysis made on this efflorescence shown the presence of thenardite (Na 2SO4) (see
Figure 1 B). In all the analyzed efflorescence, it was not possible to identify mirabilite
(Na2SO410H2O), because all the Raman assignations agree quite well with
thenardite Raman spectrum alone. A quite surprising result was the presence of
nitrobarite, Ba(NO3)2 (main Raman band at 1045 cm-1). XRF analysis also revealed
the presence of barium in the samples where nitrobarite was identified. In the
literature, it is well referenced that barite (BaCO 3) was usually added in the paste to
improve the quality of cement. The addition of nitrobarite is not referred, thus its
presence could be attributed to a possible decay product. The formation of
nitrobarite can be explained following a reaction between the barite and a possible
source of nitrates (infiltration waters having ammonium nitrate, impact of
atmospheric NOx, etc.) in an acid medium.
Raman spectroscopy together with additional spectroscopic techniques has been
used with positive results to identify the nature of the original components from
Igueldo Lighthouse cements and mortars. Apart from the original composition, this
technique was useful to identify the presence of possible additive in the cement
paste and also to characterize the nature of possible decay products in the
lighthouse.
Acknowledgements. This work has been financially supported by the project

IMDICOGU (BIA2008-06592), funded by the Spanish MICINN. O. Gmez-Laserna is
acknowledged to the UPV/EHU for her pre-doctoral fellowship.

182
Micro-Raman Spectroscopic Analysis of Inks and Pigments in
Illuminated Medieval Old-Slavonic Manuscripts
Irena Nastova1, Orhideja Grupe1, Biljana Mineva-ukarova1,

Violeta Martinovska2 and Zorica Jakovlevska-Spirovska2
1
Institute of Chemistry, Faculty of Natural Sciences and Mathematics, Ss. Cyril and
Methodius University, POB 162, 1001 Skopje (Republic of Macedonia); tel; ++389-
70-340-220; e-mail: orhideja@pmf.ukim.mk; tel: +389-70-226-787;
biljanam@pmf.ukim.mk
2
National and University Library "St. Kliment Ohridski", Bul. Goce Delev, 6, 1000
Skopje (Republic of Macedonia)
The National and University Library Sv. Kliment

Ohridski in Skopje, Republic of Macedonia, houses rich
collection of old-Slavonic medieval manuscripts, mostly
gospels. Although they have been subjected to
numerous linguistic study, no scientific study has yet
been performed on the pigments and inks used in the
manuscripts. In fact, scientific information on the old-
Slavonic manuscripts, in general, is scarce in the
literature, although old Slavonic translations of the
gospels belong to the group of the oldest translation of
the gospels.
In order to obtain some insight of the technique and
pigments used by medieval illustrators and
calligraphers, we have used micro-Raman spectroscopy
as in situ, non-destructive technique to study Vrutok
four gospels (13-14 century) and Benche four gospels
(16 century). In case of uncertainty in identification of
pigments, XRF and SEM were used.
Vrutok four gospels (Vrutok), dated from the end of 13 or the beginning of the 14th
century, is written on parchment and consists of 157 ff, 18x11,3 cm. It contains
ornaments and inscriptions, which are simpler compared to the Benche. The ink is in
black and red. It seems that the ornaments are drawn with free hand, showing some
irregularities.
Benche four gospels (Benche), dated 16th century, is written on paper, richly
decorated, on 360 ff., 21,5x15 cm. It contains ornaments, watermarks, miniatures
and inscriptions. In each gospel, a miniature devoted to Mathew, Mark, Luka and
John is added, accordingly. The inks used are black, brown and red. The ornaments
are perfectly executed, suggesting the use of models or some type of aid for
drawings.
Both are decorated with ornaments in so called Balkan style characterized with
intertwined rings and floral motifs, although Benche is with more elaborated
decoration. They are written in old-Slavonic language with old Cyrillic alphabet.
The pigments analyses were performed in situ using a LabRAM 300 (Horiba Jobin-
Yvon) micro-Raman spectrometer equipped with a He-Ne laser operating at 5 mW
and 632.8 nm. An Olympus MPlanN microscope with magnification x50 or x100 was
used to focus the laser onto the samples. The backscattered light was dispersed
using 1800 lines/mm grating. The spectral resolution was 34 cm1. To avoid any
damage to the manuscript, laser power was attenuated using different neutral
density filters (D=0.3, D=0.6, D=1. D=2). Acquisition time was varied from 3 to 10 s,
with 5 to 25 scans. Pages were held in place using weights, to avoid loss of focus
183
during the analysis due to the vertical and horizontal vibrations. The precautions
were taken to keep the angle of the open Benche book casing appropriate, to avoid
damage to the casing. The obtained Raman spectra were compared to the reference
database of pigments.
Vrutok text is mainly written in black ink, with letters and inscriptions in red. The
black ink is mixture of iron gall ink with carbon black, the red ink is vermilion. The
pigments identified in the miniature, ornaments and book cover are given in the
Table 1.
Benche text is written in black or brownish ink, at times
very faded, with capitol letters, lines or inscriptions in red.
It is written two century latter than Vrutok one, but there
was only slight change in the used inks. The black and
brown ink was iron gall ink, the red - vermilion. Although
carbon was identified on the surface of the ink, it was
often found over the surfaces of the pages, regardless of
the colour or bare space, suggesting that the carbon is
contaminate, deposited from the ambient, after the text
was written. Much richer palette of pigments, as expected,
was revealed in Benche, compared to Vrutok, (Table 1).
The use of pigments in ornaments compared to paintings
is somewhat different, suggesting that handwriting and
ornamenting on one side and miniatures, on the other,
were done by different persons/painters.
Micro-Raman spectroscopy allowed in situ, non-destructive, rapid and unambiguous
identification of the majority of pigments used in the text, ornamentations and
miniatures in the Vrutok and Benche four gospels. More problematic for identification
were green pigments. Malachite and a mixture of indigo and goethite were easily
detected, while few other green pigments could not be identified. The XRF analysis
of the green pigment from Vrutok revealed presence of copper, but the Raman signal
detected from this pigment could not be related to any, known to us, copper based
green pigment.
Table1. Pigments identified in miniatures and ornaments in Vrutok and Benche four gospels
Benche four gospels Vrutok four gospels

Color Book
Miniatures Ornaments Miniature/Ornaments
cover
Calcite, Gypsum, NA
White Calcite Calcite
Lead white
Realgar/Pararealgar,
Yellow NA Orpiment Goethite
Goethite
Vermilion, Minium,
Red Vermilion Vermilion NA
Red ochre
Blue Indigo Indigo + Carbon black NA Indigo
Indigo + Goethite,
Green Malachite Cu-based green pigment NA
Green earth (?)
Brown Iron gall ink, Goethite Iron gall ink NA NA
Vermilion + Calcite +
Beige NA NA NA
Carbon black + Lead white
Black NA NA Carbon black + Iron gall ink NA

184
The problem of the characterization of Sn-based corrosion
products in bronzes: a Raman approach
Francesca Ospitali1*, Gianfranco Di Lonardo1, Cristina Chiavari 2,

Carla Martini2, Elena Bernardi3, Fabrizio Passarini3 and Luc Robbiola4
1
University of Bologna, Department of Physical and Inorganic Chemistry, Viale
Risorgimento 4, 40136 Bologna (Italy), francesca.ospitali@unibo.it,
2
University of Bologna, Department of SMETEC, Viale Risorgimento 4, 40136
Bologna (Italy),
3
University of Bologna, Department of Industrial Chemistry and Materials, Viale
Risorgimento 4, 40136 Bologna (Italy),
4
Laboratoire TRACES, UMR 5608 CNRS, Universit Toulouse Le Mirail - Maison de
la Recherche, 5, alles Antonio-Machado, 31058 TOULOUSE Cedex 9 (France).
The characterization of corrosion patinas on bronzes is strictly connected and

preliminary to the determination of proper conservation strategies: for instance, the
choice of protective coatings or corrosion inhibitors should be subsequent to the
characterization of the patinas, i.e. the support where they are applied.
Characterization studies give also an important contribute to the comprehension of
the mechanisms of formation of patinas, in particular for outdoor bronzes when the
results are correlated to studies on exposure conditions (the role of environmental
parameters, multi-pollutants, geometries of exposure to the rain) and alloy
composition (the role of alloy elements).
Concerning the last aspect, recent studies highlighted that alloy corrosion behaviour
cannot be assimilated to that of pure metals: in particular, it is demonstrated a
decuprification of the alloy and a relative enrichment of tin, that assumes, together
with its insoluble salts, an important role in the mechanism of formation of patinas.
Thus, from a conservation point of view, the clear characterization of Sn-based
corrosion products becomes fundamental, although quite problematic.
Elemental analytical techniques, like EDS, show only the presence of tin without
information on its structure, whereas molecular or structural characterization
techniques have difficulty in detecting it.
The identification with XRD is often difficult because of the low amount of Sn-based
compounds in the patinas and their scarce crystallinity.
IR micro-spectroscopy is not particularly appropriate because of its poor ability to
detect IR bands of minor compounds, especially when they have bands at the lower
end of the spectral responsivity range of the instrument, as in the case of Sn-based
corrosion products.
Raman micro-spectroscopy is the most suitable among these techniques, thanks to
its high spatial resolution and ability to detect also not-crystalline structures.
Nevertheless, the detection and characterization of Sn-based compounds grown in
patinas is difficult also with Raman micro-spectroscopy, because of the low Raman
scattering power, the uncertain structure and the low crystallinity degree of these
compounds, generally in amorphous states.
The hyphenated system SEM-EDS-Raman SCA that unifies the principal
characteristics of the three different techniques, has been demonstrated a valid
allied in the characterization of Sn-based corrosion products. EP-SEM allows to
obtain morphological information of the patina, EDS probe allows to obtain rapidly a
distribution map of the constitutive elements, in particular the distribution of Sn,
guiding therefore the Raman characterization of the features of interest.

185
This work will illustrate different case-studies where Sn-based corrosion products
grown in bronzes have been identified, examining the implication of the results in the
study of the mechanisms of corrosion. A comparison among bronzes exposed in
different ageing conditions, such as archaeological (i.e. soil) and atmospheric, will be
done.
Acknowledgements. F.O. warmly acknowledges the Department of Physical and

Inorganic Chemistry that always supported her research activity.

186
In-situ characterisation of the coloured materials used in
Elephantine: evolution and permanence from Old Kingdom till
Roman Period.
Sandrine Pags-Camagna1, Dietrich Raue2 and Stephan Seidlmayer3

1
C2RMF-UMR171 CNRS, 14 quai F. Mitterrand, 75001 Paris.
sandrine.pages@culture.gouv.fr
2
Universitt Leipzig, gyptisches Museum - Georg Steindorff, Goethestrae 2 04109
Leipzig
3
Deutsche Archologische Institut, Cairo
Since the first French and German archaeological investigations at the beginning of
the 20th century, and the Egyptian excavations in the 1930s and 1940s, during
which the shrine of Heqaib with its considerable collection of private statues from the
Middle Kingdom was unearthed, there have been 30 campaigns of the German
Archaeological Institute in co-operation with the Swiss Institute for architectural and
archaeological research in Egypt.
According to the traces of settlement dating to the Predynastic Period (as of 3300
BC) and to the oldest sanctuary on the island, the temple of Satet from c. 3200 BC
onwards, the area of settlement was fortified by a city wall. Up to the Graeco-Roman
period the religious centres of the city were continuously renewed and extended.
The main goal of the excavation in Elephantine is to gain a comprehensive picture of
an ancient Egyptian town as a whole. This encompasses living, commercial quarters,
shrines and administrative buildings throughout the duration of their historic
development.
The colours preserved on the various phases of the Temples permit to understand
the evolution through the time of some pigments use. During the excavations of the
houses, raw materials, perfectly dated, were discovered and collected.
A Raman portable spectrometer (HE532 Jobin-Yvon) was taken on the island in
order to distinguish the pigments and precious stones, such as garnet, lapis, ochre,
Egyptian blue, calcite, huntite, etc. The analyses, performed in April 2010 with visible
laser (532 nm) and optical fibre, permitted to propose a chronological evolution of the
materials used for the decoration of the official and private buildings.

187
Evaluation of the restoration of a folding screen belonging to
the Momoyama period.
Sofia Pessanha1, Teresa Isabel Madeira1, Agns LeGac1,2,

Maria Luisa Carvalho1
1
Centro Fisica Atmica da Universidade de Lisboa, Departamento de Fisica, Av.
Prof. Gama Pinto, 2 1649-003 Lisboa, (Portugal), Tel. +351217904776
luisa@cii.fc.ul.pt
2
Departamento de Conservao e Restauro, Faculdade de Cincias e Tecnologia da
Universidade Nova de Lisboa, 2829-516 Monte de Caparica (Portugal)
The Museum Soares dos Reis in Porto owns a precious pair of Japanese golden
folding screens belonging to the early 17 th century Namban genre. As the pieces
manifested structural conservation issues they were subjected to restoration
intervention between 2000 and 2002 in the National Research Institute for Cultural
Properties in Tokyo. According to the restoration report, an unknown substance was
applied to the overall surface, adding a glossy finish, which corresponds to a
restoration work conducted in the western countries. This intervention does not
appear in the Museum reports.
The aim of this work is to determine the materials used in this unknown restoration
work and to understand why these new materials appear in a worse state of
conservation than some of the original ones.
Preliminary, in situ, EDXRF analyses were performed and, right from the beginning
elements such as Cr, Ba and Co appear in the spectra of orange, yellow, brown and
blue areas, accusing the anachronism of the used materials. Nineteen micro-
samples were collected to be analysed with the Xplora Confocal Raman microscope
using the 638 nm laser. Interesting results were obtained for the blue decoration of
one of the houses: while the EDXRF spectrum showed the odd combination of Cr,
Fe, Co, Cu and Zn, the Raman spectra indicated the use of Phthalocyanine blue.
According to the synthesis of this pigment produced in 1936 [1], the restoration could
not be performed before this date.
Acknowledgements. Sofia Pessanha wishes to thank Portuguese Foundation for

Science and Technology for the PhD grant SFRH/BD/60778/2009.
References
1 Burgio L, Clark, R. J. H. Spectrochim. Acta, Part A, 2001, 57, 1491

188
On the utilization of logarithms of eigenvalues to the
discrimination of significant and residual factors
Katja Petzold
University of Freiburg, Institute of Art History, Platz der Universitaet 3 (KG III), 79098
Freiburg i. Br. (Germany), Tel. +49 (0) 7611551231, petzold@uni-freiburg.de
It has been shown previously that target transformation factor analysis (TTFA) as
well as iterative target testing (ITT) are suitable to evaluate multi-component Raman
spectra of paint samples [Petzold, 2008; Petzold 2009]. Unlike factor analytical
approaches that employ normalized data both TTFA and ITT were run using
covariance about the origin. As Raman scattering is very weak covariance matrices
of Raman data may be characterized by eigenvalues smaller than 1. For these
reasons, the number of contributing components cannot be determined by the
means of the eigenvalue-1-criterium.
In order to discriminate significant and residual eigenvalues an indicator function
(IND) has been proposed [Malinowski, 1977]. Most advantageously, the inherent
error of data is taken into account. The imbedded error (IE) decreases until the
number of significant factors is reached. However, regardless of the kind of
spectroscopic data in some cases neither the indicator function nor the imbedded
error function reach a minimum, but steadily decrease. In other cases the decrease
is less equable, but the kink does not signify the correct number of contributing
factors (fig.1). Therefore, the logarithms of eigenvalues were investigated. Three
rules revealed. According to the first rule a large difference between two
neighbouring logarithmic values separates significant factors and factors of lower
importance (fig.2). If the difference equals the differences between this or that
logarithmic eigenvalue pair involved then the line can be drawn here (second rule).
The third rule means that the two groups of factors can be easily discriminated if two
differences, which frame a very small difference, are equal.
Fig. 1: Number of significant factors as indicated applying IND and IE criteria. The Raman spectra set
was modelled with five components (each model mixture contains five different pigments). However,
according to IND (upper graph) and IE (lower graph) only four factors are significant.

189
Fig. 2: Number of factors as indicated applying the log-Test. The same model as in fig.1. The sharp
change in slope signifies the line between significant and residual factors. The upper graph shows the
differences between two neighbouring logarithms of eigenvalues (delta log.), whereas the lower graph
depicts the logarithm of eigenvalue.
The reliableness of the log-Test has been examined using both modelled and real
multi-component Raman spectra sets as well as problems reported in literature. The
log-Test is suggested as complementary to the IND and IE criteria, and is proposed
for further discussion.
Acknowledgements. The author is indebted to the FAZIT Foundation (FAZIT Stiftung

Gemeinntzige Verlagsgesellschaft mbH, Frankfurt a. M.) for their grant and to the
Scientific Society Freiburg (Wissenschaftliche Gesellschaft Freiburg i. Br.) for their
financial support. Additionally, the author would like to thank Mrs Anita Becherer for
recording the Raman spectra.
References
Petzold K, in Vandenabeele P, Moens L. (Editors), GeoRaman 08. 8th International

Conference on Raman Spectroscopy Applied to Earth Sciences - Sensu Latu, June 2nd - 6th,
2008, Ghent, Belgium (Book of Abstracts), Academia Press, Ghent, Belgium, 2008, p. 41.
Petzold K, in Colloquium Spectroscopicum Internationale XXXVI, August 30th - September
3rd, 2009, Budapest, Hungary. Book of Abstracts, Budapest, Hungary, 2009, p. 150.
Malinowski ER. Analytical Chemistry 1977; 49: 606.

190
The XIV century painting in the lunette of Santa Maria del
Prato in Genoa. Investigation on pigments and degradation
products
Rita Pizzone1, Stefano Vassallo1, Paola Parodi1, Paola Traversone2,

Enrico Franceschi3, Dion Nole3, Pietro Baraldi4
1
Superintendance for the Architectural and Landscape Heritage of Liguria.
stefano.vassallo@beniculturali.it
2
Superintendance for the Artistic Historic and Ethnoanthropologic Heritage of Liguria,
3
Department of Chemistry and Industrial Chemistry, University of Genoa,
4
University of Modena and Reggio Emilia, Department of Chemistry, via G. Campi
183, 41125 Modena (Italy).
The restoration of the Madonna Odighitria painted in the lunetta of the portal of
Santa Maria del Portale in Genoa, carried out between june and november 2010,
remains as an important recovering of a rare painted image of the XIV century. The
reason for its interest is rarity and antiquity in the art landscape of Genoa; moreover
it was important to study the degradation phenomena undergone by some colors
applied to the surface with a tempera technique, mainly those based on lead and
copper and in particular the transformation of azurite into copper chloride and copper
oxalate and that of red lead into black plattnerite. The investigations were carried out
in a first step with the techniques of FT-IR, XRF, SEM with EDS, UV VIS
spectrometry, and optical microscopy on stratigraphic samples, and subsequently by
microRaman techniques. The composition and the comparison of the data emerged
enable a clear representation of both the first execution and the present situation to
be traced. A comparison was also made with other degraded paintings of the late
gothic and Renaissance period.
During the restoration a detailed study of the painted surface was carried out in order
to identify whether there were in the past intervention for the recovering of color,
whether there was a preparation of the surface and which painting techniques could
be identified. Due to the time elapsed tempera technique is partly survived,
retouching with mezzo fresco technique having been carried out and repainting of
disappeared areas were exevuted.
The restoration and analytical program was executed with the synergy of the
appropriate Superintendances of the Ministry for Cultural Heritage, the Departments
of Chemistry of the Universities of Genoa and of Modena and Reggio Emilia, and the
Dip.Te.Ris of the University of Genoa.

191
Micro-spectroscopic Raman investigation on the canvas oil
painting Rebecca at the well, of Neapolitan anonymous.
E. Platania*, E. Cazzanelli, G. De Santo, A. Fasanella and M. Castriota
Dipartimento di Fisica, Universit della Calabria, Cubo 31C, Ponte P. Bucci, 87036-
Arcavacata di Rende, Cosenza, Italy; tel.+390984496114,
enzo.cazzanelli@fis.unical.it
In this work, Raman spectroscopy was used to investigate the pigments of the
canvas oil painting Rebecca at the well of a Neapolitan anonymous, property of the
Museo dArte dellOttocento e Novecento (MAON) in Rende (Cosenza), Italy. The
difficulty of the investigation was due to the absence of historical and scientific
documents concerning the painting; moreover, no scientific analysis were performed
previously on it. Art historians ascribe the painting to the XVIII century, taking into
account stylistic and formal studies: scholars agree that the canvas was painted by a
Neapolitan artist. In conclusion, Raman spectroscopy is an excellent probing tool not
only in order to study the pigments composition, but also to investigate the artefact s
history.
Raman spectra were recorded with a Jobin Yvon LabRAM instrument, equipped with
a He-Ne (632.8 nm) laser. Different Olympus objectives (20x, 50x and 100x) were
used to visually explore the painting and to collect the spectra. In this work, only the
spectra obtained with the 50x objective (focal length of 15mm) are shown. The
spectral resolution was about 2 cm-1. The illuminated spot size was about 5 m in
diameter. Neutral filters with different optical densities, 0.3, 0.6, 1, 2, 3 and 4, were
available in order to reduce the impinging laser power and avoid damages to the
painting and pigment modification.
Several problems arose during the investigation: strong fluorescence phenomena
due to the decay of the thick varnish layer; evidence of later corrections for different
areas of the painting. For this reason, the painting was lighted up with a Wood lamp,
which allowed to distinguish the retouched areas from the originals.
In particular, six pigments of the pictorial palette were characterized. The analysis of
the white pigment showed the presence of lead white [Castriota, Cosco et al., 2008,
Castriota, Meduri et al., 2008], commonly known as biacca;. in this case it had a
siccative role for linen oil, used by the artist in this painting. The red pigment has
been identified as red vermilion [Castriota, Cosco et al., 2008; Conti et al.,1993;
Bouchard et al. 2009], a very precious pigment, known also as cinnabar (the
mineral from which the pigment derives). The presence of a so expensive pigment
suggests not only the importance and the richness of the purchaser, but also the
fame of the artist, who was able to buy such material. Moreover, the small extent of
the painting suggests that perhaps the purchaser was an aristocratic, not a cleric,
since in this case he would have preferred huge artefacts to put them in holy places.
The black pigment analysed has been attributed to amorphous carbon[Castriota,
Cosco et al., 2008]. The yellow areas showed the presence of fluorite and silica [
Burgio et al. 2001], and of magnetite, an iron magnetic mineral [Castriota, Meduri et
al., 2008; Sendova et al., 2007], known and used since ancient times. The light blue
areas showed the presence of galena [Burgio et al., 2001]. In some areas of the
painting the presence of blue and green chlorinated phtalocyanine [Clark, 1995;
Clark, 1999; Sakellariou et al., 2004] can be considered an extremely important
discovery. In fact, these pigments, synthesized since 1936, provide evidence about
the paintings restoration during the XX century, which is not documented. The
presence of yellow-orange chrome [Castriota, Cosco et al., 2008; Ortega-Aviles et
al., 2005; Edwards et al., 2005], used since 1809, confirmed the restoration
192
hypothesis. In particular, since this pigment was widely used during the XIX century
and rarely used during the XX century, two restoration interventions can be
supposed: one during the XIX century, and the other one during the XX century.
In conclusion, the micro-Raman diagnostic studies allowed the identification of the
original pigments and of the pigments used in restoration interventions. These
elements are extremely important for the artefacts history.
Acknowledgments: the authors are indebted to the director of MAON, Dr. Antonio
Sicoli, for kindly providing the painting and for the collaboration to the study.
*: present address: Universit di Firenze, Polo Scientifico Sesto Fiorentino,

Dipartimento di Chimica, Via della Lastruccia 3-13, Sesto F.no (FI), Italy
Fig. 1: Canvas oil painting Rebecca at the

well painted by a Neapolitan anonymous,
coming from the MAON museum of Rende Fig. 2: Partial Raman spectrum of Cu
(Cosenza), Italy. phthalocianine, collected from a side
border of the painting.
References
Castriota M. , Cosco V. , Barone T., De Santo G., Carafa P., Cazzanelli E., J. Raman
Spectrosc. 2008, 39, 295.
Castriota M., Meduri E., Barone T., De Santo G., Cazzanelli E., J. Raman Spectrosc.,
2008, 39, 284
Conti A., Cassanelli R., LArte. Critica e Conservazione, Ed. Jaca Book, Milano 1993, p.109.
Bouchard M., Rivenc R., Menke C., LearnerT., Preservation Science, 2009, 6, 27.
Burgio L., Clark R. J. H., Spectrochimica Acta Part A, 2001, 57, 1499.
Sendova M., Zhelyaskov V., Scalera M., Gulliford C., Archaeometry 2007, 49, 655
Clark R. J. H., Journal of Molecular Structure 1995, 347, 417.
Clark R. J. H., Journal of Molecular Structure 1999, 480-481, 15.
Sakellariou K., Miliani C., Morresi A., Ombelli M., J. Raman Spectrosc. 2004, 35, 61
Ortega- Avils M., Vandenabeele P., Tenorio D., Murillo G., Jimenz-Reyes M.,
Gutirrez N., Analytica Chimica Acta 2005, 550, 164.
Edwards H. G. M., Munshi T., J. Anal. Bioanal. Chem. 2005, 382, 1398

193
Investigation and characterisation of selected pieces from a
unique Egyptian collection of Ushabtis
S. Potgieter-Vermaak1,2, G. Mitchell1, M. McLean1, and J.H. Potgieter3,4

1.
Division of Chemistry & Environmental Science, School of Science and the
Environment, Manchester Metropolitan University, Oxford Road, Manchester, M1
5GD, UK.
2.
School of Chemistry, University of the Witwatersrand, Private Bag X3, Wits, 2050,
South Africa.
3.
School of Research, Enterprise and Innovation, Manchester Metropolitan
University, Oxford Road, Manchester, M1 5GD, UK, Tel: +44 161 247 1428,
h.potgeiter@mmu.ac.uk
4.
School of Chemical & Metallurgical Engineering, University of the Witwatersrand,
Private Bag X3, Wits, 2050, South Africa.
Fifty eight Egyptian shabtis held within the Manchester Museum, originally from the
tomb of Horudja (Horuta), are part of a group of approximately 300 excavated from a
flooded tomb in Hawara by British Egyptologist, Sir William Matthew Flinders Petrie
in 1888 [Petrie, 1890]. The shabtis, were found partly submerged in mud and as a
result many of them broke in two during excavation. Shabtis are Egyptian funerary
figurines (generally placed around the sarcophagus inside the tomb) and were
intended to continue the work of the deceased in the afterlife. Thanks to a donation
from Jesse Haworth (a sponsor of Petries excavation) the shabtis have been at the
Manchester Museum for over 100 years. The shabtis are made from Egyptian
faience (a type of ceramic) and they have a characteristic blue or green glaze.
Egyptian faience consists of a crystalline core rich in silica in which the particles are
sintered together [Rehren, 2007]. The blue-green colour of faience artefacts strongly
resembles the semi-precious gems turquoise and lapis lazuli and it is thought that
this likeness increased the popularity of faience in ancient times [La Delfa et al.,
2008; Nicholson, 2009].
In recent years, curators at the museum have developed a growing concern over the
deterioration of the collection. Some shabtis in the collection have lost all or part of
the coloured glaze on the surface and in some other collections a white bloom has
formed over the surface of the shabti. Published papers have suggested that the
bloom formation may be caused by a chemical reaction occurring between the
faience and pollutants in the museum atmosphere, particularly acetic and formic acid
which is emitted by wooden shelving and display cases [Gibson and Watt, 2010]. As
a result curators are keen to use conservation science and further investigations to
help answer some of the unanswered questions relating to museum artefacts and
how to care for them.
Although some authors have conducted studies on blue and green faience, few have
tried to characterise both the core and the glaze. Furthermore, studies have not
been conducted on the Horudja collection. The ushabtis from the tomb of Horudja in
Hawara, the focus of this study, were originally thought to date from the 26 th Dynasty
(664-525 BC). The Horudja ushabtis were discovered standing upright in rows on a
recess within the masonry of the tomb. Moreover, the tomb flooded and caused the
glaze on the ushabtis to discolour from a vibrant blue to white or colourless. The
portion of the ushabti which had been encased in sand and mortar had been given
some protection from the destructive force of the water. On these areas, a small
amount of glaze still remains, even if a little faded. Since donation to the Manchester
194
Museum they have been housed in wooden drawers for a considerable period of
time. The Horudja collection has never been analysed before. Therefore, the core
(and glaze) composition remains unknown and this is the motivation for this study.
During the course of this research, techniques such as scanning electron
microscopy, Raman microscopy and X-ray fluorescence were used to determine the
composition of the glaze and core of faience artefacts. Figure 1 and 2 indicate the
objects of study in this investigation:
Fig. 1 Ushabtis from the tomb of Horudja

Fig. 2 Weathered blue glaze fragment
It was found that the body of the figurines consisted mostly of silica, with a denser
inner core than the outside layer. From the crystal form of the quartz, one can
conclude that the samples investigated in the current work were probably fired at
temperatures mostly around 800 oC, with firing occasionally at higher temperatures
in the region of 900 - 950 oC in the few instances where trydimite have been
detected. Raman spectra on the blue and green coloured faience pieces were
conducted, and revealed that the green colour is mainly due to the presence of
bornite, a Cu5FeS4 type mineral. XRF analysis indicated a reasonable amount of Cu
and S being present. Depending on the area of analysis, the presence of gypsum,
iron oxides, quartz and a carbonate were also detected. The carbonate compound
could also be CuCO3.Cu(OH)2. In the case of the blue colour, a Lapis Lazuli type
aluminosilicate was identified, together with quartz and magnetite. At this stage more
work was required on the material to come to further conclusions as to the best way
to preserve the current collection to prevent further loss of glazed areas and colours.
References
Gibson LT, Watt CM. Corrosion Science 2010; 52: 172

La Delfa S, Formisano V, Ciliberto E. Journal of Cultural Heritage 2008; 9: 113.
Nicholson PT, Faience Technology, UCLA Encyclopaedia of Egyptology, 2009.
Petrie WMF. Kahun, Gurob, and Hawara, Harrison and Sons, London, 1890.
Rehren Th. Journal of Archaeological Science 2007; 35: 1345.
195
Surface-enhanced Raman scattering (SERS) and Raman
study
of red and violet water-colour pigments from an original
Winsor & Newton handbook dating to 1887
Federica Pozzi1,2 , Marco Leona1
1
Department of Scientific Research, The Metropolitan Museum of Art, 1000 Fifth
Avenue, New York, NY 10028 (USA). Tel. +1-2126502724,
federica.pozzi@metmuseum.org
2
Dipartimento di Chimica Inorganica, Metallorganica e Analitica Lamberto
Malatesta, Universit degli Studi di Milano, via G. Venezian 21, 20133 Milano (Italy).
Tel. +39-0250314413, federica.pozzi@unimi.it
The Winsor & Newton company has been one of the main fine art products suppliers
in the world since its establishment in 1832, being responsible for the production of a
wide assortment of materials ranging from oils and pigments to brushes and papers.
All the items manufactured over the years have been indexed in what has become
the most extensive historical archive of the nineteenth century.
Winsor & Newton catalogues, with their collections of swatches showing the results
obtainable with the firms colours, are an important historical and scientific resource,
which affords scholars a precious nsight into the world of artists materials. Such
information can be of utmost importance for interpreting analytical data from actual
paintings in technical studies or authentication efforts. Furthermore, chemical
analysis applied to the study of original art products may also contribute to set up
suitable conservation and restoration approaches, as paint defects as well as the
deterioration degree of pigments in works of art can be deeply characterised and
properly treated by examining actual recipes for a certain material.
In the present study, red and violet tints on drawing paper were examined from a
historical Winsor & Newton handbook of water-colour pigments dating back to 1887.
An appropriate database was thus built, including both surface-enhanced Raman
scattering (SERS) and normal Raman spectra for a wide number of shades.
Scientific analysis of Winsor & Newton colour washes allowed us to deepen our
knowledge about the variety of pigments in use during the modern age. While lakes
prepared from plant and insect dyes, mainly madder and cochineal, are predominant
among the colours offered by Winsor & Newton, some tints based on synthetic dyes
were found as well, often accompanied by commentary on their poor lightfastness.
The pigments here investigated were divided into different classes according to the
observed spectral patterns, and subsequently discussed. The SERS and ordinary
Raman study allowed us to formulate some hypotheses concerning the main
constituents of those shades for which a description is not available in the handbook
(dragons blood and most of the alizarin-based pigments). In addition, we could
correct erroneous indications provided by Winsor & Newton on some tints, as in the
case of violet carmine.

196
Figure 1 - Examples of SERS spectra (exc = 488 nm) of alizarin-based pigments from the
Winsor & Newton handbook: (a) scarlet lake, (b) ruby madder (alizarin), (c) permanent
crimson, (d) violet carmine and (e) neutral tint, compared with (f) reference 10-4 M alizarin
solution.
Figure 2 - Examples of Raman spectra (exc = 488 nm) of alizarin-based pigments from the
Winsor & Newton handbook: (a) scarlet lake, (b) ruby madder (alizarin), (c) permanent
crimson, (d) violet carmine and (e) neutral tint, compared with (f) reference alizarin and (g)
reference madder lake.

197
Raman Microscopy analyses to characterize Nasrid colored
glazed pottery
J. Romero-Pastor1, A. Garca Porras2, R. Van Grieken3,

Sanja Potgieter-Vermaak3 and C. Cardell1
1
University of Granada, Dept. of Mineralogy and Petrology, Science Faculty, Avda
Fuentenueva s/n, E-18071, Granada (Spain).
2
University of Granada, Dept. of Medieval History and Historiographic Sciences and
Techniques, Cartuja Campus, E-18071, Granada (Spain).
3
Micro & Trace Analysis Centre, Dept. Chemistry, Univ. Antwerp, Universiteitsplein
1, B-2610 Antwerp (Belgium).
Pieces of Nasrid pottery from the archaeological sites of Manises and Paterna
(Spain) were analyzed by Raman Microscope (RM) and Scanning Electron
Microscopy-Energy Dispersed Spectroscopy (SEM-EDS) to characterize pigment
composition for this 13th century pottery production. All fragments were decorated
with glazes against a white background with floral decorations in black, green, blue
and/or red. The identification of mineral pigments of the glaze decoration is
challenging. The dissemination of the elements throughout the glaze is different
depending on glaze composition, firing temperature and on the pigment itself
[Guilherme et al., 2011]. However, the high spatial resolution and non-destructive
character of RM allow in-depth characterization of each mineral grain on the glaze
and mapping of more relevant areas such as interfaces between colored regions.
The SEM-EDS analysis of white grazes showed an elemental composition based on
lead, tin, silicon, aluminium, potassium, calcium, sodium, iron and magnesium.
These chemical elements were added as oxides, i.e. PbO, SnO2, SiO2, Al2O3, K2O,
CaO, Na2O, FeO y MgO, respectively. Thus, the glazes were elaborated as tin-
opacified lead glazes with lower alkali contents (Na2O and K2O), Al2O3, CaO, FeO,
and MgO [Perez-Arantegui et al., 1999; Molera et al., 2001].
In particular, some samples showed a white underlayer and blue drawings. The EDS
results of the glaze showed mainly Cu, Cl and Co. According to the RM analysis,
cassiterite, hematite, magnetite and glassy phases were identified. Moreover,
cuprite, cobalt oxide and atacamite were identified only in the blue area. On the
other hand, black and red glazes were also analyzed by RM and SEM-EDS;
pyrolusite and hematite were responsible for these color decorations, respectively.
Acknowledgements. This work has been financially supported by Spanish Science

Ministry Project BHA2003-08671, the Andalusian Research Group RNM-179 and
Flemish Administration for Innovation and Science (BOF UA 2008-2013).
References
Guilherme A, Coroado J, dos Santos JMF, Lhl L, Wolff T, Kanngieger B, Carvalho ML.
Spectrochimica Acta Part B: Atomic Spectroscopy, 2011; In Press.
Perez-Arantegui J, Soto M, Castillo JR. J. Archaeological Science, 1999: 26, 935.
Molera J, Vendrell-Saz M, Prez-Arantegui J. J. Archaeological Science, 2001; 28: 331.

198
Raman as a support in a multianalytical approach to coloured
grounds of gilt stucco surfaces from Hall of Caryatids (Royal
Palace, Milan)
Antonio Sansonetti1, Jana Striova1, Danilo Biondelli1, Irene Aliatis1

1
Istituto per la Conservazione e Valorizzazione dei Beni Culturali , CNR, Via R. Cozzi
53, 20125 Milan (Italy), Tel. +39 0266173342, antonio.sansonetti@icvbc.cnr.it
A microscopic, spectroscopic and elemental analysis of samples coming from some

decorative elements in the Hall of Caryatids, in the Royal Palace of Milan, was
carried out.
The Hall of Caryatids is a 18 th century ballroom and it was the largest in Europe at
the time of its construction; it is located on the first floor of the Royal Palace, built by
the Italian architect Giuseppe Piermarini, on the site of the old theatre burned in
1776. The hall partly survived an heavy bombing in 1943 when it lost the major part
of its neoclassical look, due to a fire started in a close room. As a consequence of
the fire a great part of the ornamental stucco elements, such as columns, frames and
capitals, display a blackening mixed with gilding remnants.
Gilt samples were studied in the form of polished cross sections by optical
microscopy (OM) and classified according to some coloured layers which have been
found as grounds and as likely overpaintings. According to historic sources
Armenian bole (a fine grained natural occurring earth with hematite impurities) was
diffusely employed with the aim to manufacture gildings grounds. The red pigment of
the ground had the aim to warm up the hue of the gold leaf. In the Caryatids Hall,
gold leaves were applied on two different ground layers: the darker layer (on bottom,
directly on the stuccos body) composed of white lead, yellow ochre, red lead binded
with a siccative oil; the lighter coloured one (on top) made by white lead, yellow
ochre and oil. In this paper particular attention is focused on green-bluish layers of
some stuccoes sampled from the columns bases. The use of cold colours in
combination with gold leaves is quite unusual, especially as regards Italian style
ornamental pattern; the hypothesis opened by their revealing regards a possible
reflection of a middle-European 18th century taste, which prefered cold hues to the
warm ones. No evidence of green or blue surfaces is visible at the naked eye, such
as the analytical survey allowed an important virtual reconstruction of the ornamental
pattern of the hall, unthinkable till the present day.
Raman microspectroscopy was performed with two different apparatus: a Renishaw
2000 instrument coupled to a Leica optical microscope using 785 nm and with a
Bruker Senterra instrument equipped with an Olympus BX51 microscope using 785
and 532 nm. Raman measurements revealed Prussian blue, green earths and
chrome yellow as the major responsible for green colour on the cold grounds.
Collected spectra agree with scanning electron microscope analyses (SEM-EDS) on
the same spot areas. The presence of blue and green pigments was confirmed by
micro-infrared spectroscopic (FT-IR) survey. Evidence for organic gilding mordants
(siccative oil) is also revealed.

199
FT-Raman spectroscopy for quantitative analysis of
soluble salts
Maria Laura Santarelli, Elisabetta Petrucci, Daniele Montanaro,

Maria Paola Bracciale, Alessandra Broggi
University of Rome, Department of Chemical Materials and Environment

Engineering, Via Eudossiana 18, 00186 Rome (Italy), Tel. +39 0644585565,
marialaura.santarelli@uniroma1.it
In comparison with other spectroscopic techniques, Raman spectroscopy has not

been widely applied to problems of quantitative analysis. In fact, few literature is
dedicated at quantitative studies. The aim of this paper is to describe new
approaches for using Raman spectroscopy to quantify soluble salts in
efflorescences. Quantitative Raman spectroscopy for this study was conducted using
a 180 scattering geometry MultiRAM FT-Raman spectrometer (Bruker Optik GmbH)
equipped with a diode-pumped Nd:YAG laser operating at 1064 nm, capable of
delivering power to the sample in the range of 0 500 mW. A Michaelson
interferometer and an high-sensitivity, liquid-nitrogen cooled Ge diode detector were
used.
Preliminary experiments were carried out to examine the relationship between the
absolute intensity of the Raman active SO 4= 1 mode (1008 cm-1) and the
spectrometer laser power [Nicolae Buzgar et al., 2009]. Over the range of 0.0 400
mW, the scattering intensity response was measured to be linear with a correlation
of
R2 = 1.
Subsequent quantitative experiments were run with the laser power at a constant set
value, i.e 250 mW. Preliminary experiments were carried out also to examine the
effects of excitation time of the 1064 nm laser [Vickers and Mann, 1991].
Spectral data were analyzed over a range from 98 to 5.000 scans to examine the
effects of heating and instrument drift. Preliminary results indicated that experiments
showed minimal added thermoluminescence background response with additional
number of scans (i.e., beyond 2960 or 30 min. scan). Scans in the range of 98-2960
(or 1-30 min. scan) produced comparable signal-to-noise. It is important to point out
that a consistent background correction method be employed when quantifying the
SO4= 1008 cm-1 peak. The obtained spectra were well defined (i.e., 1008 cm -1 peak
width at half height = 9 cm-1) to allow the selection of 100 cm-1 as the low
wavenumber cutoff point for baseline correction. After this preliminary study a
calibration curve was built for sulfates. A number of mixtures with different
percentages of gypsum mixed with KBr were analyzed. Gypsum content was plotted
versus spectral band intensity of SO4= 1 peak and a line was fitted to the data. For
our particular setup (i.e., solid sample, 494 scans, and invariant laser power at 250
mW), the equation y = 1.0913x 1.0793 described the linear behavior, where y is
the gypsum weight (%w) and x is the 1, background-corrected band intensity at
1008 cm-1 (Fig. 1). The reasonably good correlation (R2 = 0.99) showed the
possibility to evaluate the sulfates content in efflorescences by Raman analysis. The
results obtained with Raman Spectroscopy were compared with the results obtained
by Ionic Chromatography, showing a good correlation.

200
References
Buzgar N., Buzatu A:, Sanislav I. V., ANALELE TIINIFICE ALE UNIVERSITII AL. I.
CUZA IAI, Geologie 2009; Volume LV, nr. 1.
Vickers, T.J., Mann, C.K., 1991. Quantitative analysis by Raman spectroscopy. In: Grasselli,
J.G., Bulkin, B.J. (Eds.), Analytical Raman Spectroscopy. Wiley, New York, pp. 107136.

201
Structures of the synthetic copper complexes: modelisation
and mechanism of the copper linkage with lipidic chains.
Carlotta Santoro, Anne-Solenn Le H, Nadge Lubin-Germain,

Michel Menu, Franois Mirambet and Sandrine Pags-Camagna
C2RMF-UMR171 CNRS, 14 quai F. Mitterrand, 75001 Paris.

sandrine.pages@culture.gouv.fr
Green copper-based pigments verdigris have been widely used as component of oil
painting in the XVth and XVIth centuries due to their transparent green glazes optical
appearance. Unfortunately during the decay process, reactions between this green
pigment and the binding media lead to the darkening or browning of the green
layers, modifying the visual appearance of the painting. As reported in the literature,
copper ions could play a primary reactive role in oxidation processes of drying oil;
thus, the copper chemical environment can undergo local molecular rearrangements,
which, in specific conditions, may lead to a change of the chromatic properties.
Nevertheless, in spite of several studies, recreations and investigations, no
mechanism has been clearly identified to explain this colour change phenomenon.
The understanding of the darkening mechanism observed on those paintings is a
key factor to propose, in the future, new coherent conservation strategies that could
improve the chemical stability of such painting layers for long duration.
A scientific partnership between the C2RMF and the SOSCO laboratory was chosen
to mimic the original copper based inorganic complexes and to investigate the
darkening process.
We have synthesised several specimens of copper soaps, with pure fatty acids with
saturation or not and various carbon chain length, in order to simulate the copper
complexes encountered in green glazes: pure copper pigments and more complex
systems in which the copper pigments are dispersed in oil.
Those samples were characterised for the first time by a complementary set of
techniques coupling structure, environment of the metal ion and molecular: Raman,
FTIR, XRD, UV-visible s, EXAFS and CG-MS. They were employed before and after
tests simulating natural ageing to determine a possible modification of the oxidation
state or the atomic environment of copper ion during the degradation process.
The preliminary results obtained in this study show that the chemical stability of the
main copper complexes resulting from the interaction between the binder and the
pigment could be related to the lability of H 2O molecules inserted in the
crystallographic structure.
The structure of the copper complexes seems to be affected by the synthesis
process and the type of the carbon chain; three types of copper complexes are
generated: monodentate, bidentate and chelate. They could be mixed or major
depending of the thermodynamic conditions.

202
Laser dependent shifting of Raman bands with
phthalocyanine pigments
Nadim C. Scherrer
Bern University of Applied Sciences, Kunsttechnologisches Labor, Fellerstrasse 11,

3027 Bern (Switzerland), Tel. +41 31 8483919, nadim.scherrer@hkb.bfh.ch
The observation started off with difficulties identifying paint samples containing
phthalocyanine green PG7, analysed with 785 nm excitation. The 785 nm laser
tends to show the highest rate of success with pigment analyses from paint samples
and thus is often the first choice. While the spectrum was clearly identifiable as a
phthalocyanine pigment, none of the references would deliver a satisfying match,
neither PG7, PG36, nor any of the PB15s or PB16. Reference spectra of PG7 in the
database, however, were all acquired with 514 nm excitation. Renewed analysis of
the paint sample with the 514 nm laser leads to a spectrum matching the PG7 in the
reference DB. Interestingly, this pigment gives a good response with either 514 nm,
633 nm or 785 nm excitation, yet the spectra differ significantly and thus a PG7
reference spectrum acquired with 514 nm excitation will not match one acquired with
either 633nm or 785nm (Fig. 1). The same was the case with a sample containing
PB16. A further observation was that at high laser power settings, there is visible
alteration at the laser spot (brown), while still spectra of "good quality" are being
collected. Thus, alteration can be induced to the material without being noticed since
a clear spectrum is the result in any case. Applying variable laser settings results in
significant shifts of Raman band positions. Following this observation, the available
phthalocyanine pigment references were re-analysed with sequentially increasing
laser power up until visible alteration was reached. Some pigments were also run in
reverse to control whether the peak shifting is reversible upon reaching the
"overexcited" state with discolouration. Results showed that a) the main band at
1530 cm-1 (PB15) or 1506 cm-1/1538 cm-1 (PG7 at 514 nm/633 nm or 785 nm
respectively) may shift by more than 10 cm-1 to lower wavenumbers with increasing
laser power, and b) the phenomenon is reversible analysing the same spot after
visible alteration with decreasing laser power. This peak shifting related to variable
laser intensity seems to be characteristic to all phthalocyanine pigments. While the
pattern of relative intensities and peak width remains more or less constant with 633
and 785 nm excitation (PG7, PB15), spectra acquired with the 514 nm laser loose in
detail with increasing laser power settings (PG7, PG36, PB16). Browsing the
literature for published Raman spectra of phthalocyanine pigments [Castro,
Vandenabeele et al. 2004; Rosi, Miliani et al. 2004; De Gelder, Vandenabeele et al.
2005; Scherrer, Stefan et al. 2009; Saverwyns 2010] it appears, that the existence of
this phenomenon is easily overseen. The purpose of this contribution is thus to raise
the awareness regarding the sensitivity of phthalocyanines to excessive laser
intensity. The distinction of PB15s based on the position of the main band at or
below 1530 cm-1, as suggested in [Scherrer, Stefan et al. 2009], is thus not possible
and purely a matter of applied laser intensity. It is, however, possible to distinguish a-
(PB15, 15:1, 15:2), B- (PB15:3, PB15:4) and E-crystal (PB15:6) modifications
[Heutz, Bayliss et al. 2000; Scherrer, Stefan et al. 2009; Shaibat, Casabianca et al.
2010]. This is of interest with respect to authentification of paintings since the a-
modifications were marketed in 1935, while the B-modification was discovered
almost twenty years later in 1953 [De Keijzer 2002; Lomax 2005]. The temperature
dependent a->B transition could theoretically lead to products containing both
modifications, even though the transition is observed to occur within a narrow range
of conditions [Heutz, Bayliss et al. 2000; Gaffo, Cordeiro et al. 2010].
203
Fig. 1: Reference spectra of phthalocyanine green PG7 for excitation wavelengths 514nm,
633nm and 785nm with no shift (left). Effect of increasing laser intensity on peak positions
(right). The peak shift is reversible and occurs with all 3 laser sources and seems
characteristic to all phthalocyanine pigments (PG7, PG36, PB15, PB16).
Phthalocyanines have unique physical and chemical properties that have lead to a
broad range of applications far beyond the use as a simple pigment [Singh and
Ravindra 2010]. Explanations for the peculiar peak shifting behaviour of
phthalocyanines under the laser beam are likely related to their unique optical
properties such as reflectivity and dielectric constant as functions of the photon
energy [Singh and Ravindra 2010], rather than a purely temperature related
phenomenon [Heutz, Bayliss et al. 2000; Gaffo, Cordeiro et al. 2010].
References
Castro, K., P. Vandenabeele, et al. Analytical and Bioanalytical Chemistry 2004; 379(4): 674-
683.
De Gelder, J., P. Vandenabeele, et al. Journal of Raman Spectroscopy 2005; 36(11): 1059-
1067.
De Keijzer, M. The history of modern synthetic inorganic and organic artists' pigments.
Contributions to Conservation - Research in Conservation at the Netherlands Institute for
Cultural Heritage (ICN). J. A. Mosk and N. H. Tennent. London, James & James (Science
Publishers) Ltd. 2002: 42-54.
Gaffo, L., M. R. Cordeiro, et al. Journal of Materials Science 2010; 45(5): 1366-1370.
Heutz, S., S. M. Bayliss, et al. Journal of Physical Chemistry B 2000; 104(30): 7124-7129.
Lomax, S. Q. Reviews in conservation 2005;(6): 19-29.
Rosi, F., C. Miliani, et al. Journal of Raman Spectroscopy 2004; 35(8-9): 610-615.
Saverwyns, S. Journal of Raman Spectroscopy 2010; 41(11): 1235-1242.
Scherrer, N. C., Z. Stefan, et al. Spectrochimica Acta Part a-Molecular and Biomolecular
Spectroscopy 2009; 73(3): 505-524.
Shaibat, M. A., L. B. Casabianca, et al. Journal of Physical Chemistry B 2010; 114(13): 4400-
4406.
Singh, P. and N. M. Ravindra Journal of Materials Science 2010; 45(15): 4013-4020.

204
Raman spectroscopic study of copper borate, a green
pigment of the 19th century
Anna Schnemann1, Howell Edwards2, Lisanne Fischer1,

Hartmut Kutzke3
1 State Academy of Art and Design Stuttgart, Am Weissenhof 1, 70191 Stuttgart,

Germany, Tel.: +49/711/28440-262, a.schoenemann@abk-stuttgart.de
2 Department of Chemical and Forensic Sciences, University of Bradford, West
Yorkshire BD7 1DP United Kingdom
3 Museum of Cultural History, University of Oslo, Postboks 6762 St. Olavs plass, N-
0130 Oslo, Norway
The variety of industrial techniques newly developed in the 19 th century led to

innovations in pigment production. In the manufacture of pigments the introduction of
modern technologies such as the performance of precipitation reactions offered new
ways to obtain new compounds used as pigments. Furthermore, procedures in the
production of known, already established pigments were changed to improve yield,
efficiency or quality which influenced properties of the paint. Knowledge about the
manufacturing process of a pigment at different times can be helpful in its analysis
and characterization.
This project focused on the study of little-known pigments in the 19th century which
have been described in historic sources but so far not found in works of art. To
extend our knowledge of the variety of pigments described in sources of the 19th
century, historic recipes were collected and critically reviewed. Selected pigments as
green copper borate were chosen here and experimental work carried out to
reconstruct the manufacturing process. The aim of this study is to obtain information
about conditions for successful pigment preparation taking our synthetics as
reference materials for comprehensive analytical characterization using a
combination of XRD, SEM/EDX, FTIR, and Raman spectroscopic methods.
Copper borate is a green pigment described by Bersch as Kupferborat or

Borkupfergrn and is recommended as an oil paint or paint for porcelain []. It is
obtained by mixing copper sulfate with borax solution. The dried turquoise blue
precipitate is thermally treated at different temperatures resulting in different green
colors.
Raman spectroscopy is a suitable method to characterize different stages in the

manufacture of copper borate and to provide diagnostic analytical discrimination
between copper borates prepared at different temperatures.
The Raman spectrum of the dried precipitate shows a characteristic pattern of two
narrow signals at 866 and 978 cm-1 and a very broad band at 3585 cm-1 , for which
those at 978 and 3585 cm-1 have the highest intensity. After the first stage of heat
treatment an inhomogeneous product is achieved comprising light green particles
mixed with a few of dark green color. In the Raman spectrum of the dark green
particles a pattern of new signals occurs. The most intense new signals were found
at 734 and 1458 cm-1. Further bands with lower intensity were observed at 292, 345,
466, 1153 and 1271 cm-1. Upon further thermal treatment these characteristic
signals of the precipitate decreased significantly, however, those at 734 and 1458
cm-1 are still detectable as weak but broad bands. After very strong thermal
treatment of the copper borate precipitate new characteristic Raman spectral
205
signatures consisting of narrow, very intense signals were obtained with the most
intense maxima at 331 and 469 cm-1.
References
Bersch, J., Lexikon der Farben-Technik, Hartleben Wien, Pest, Leipzig,1902

Nakamoto, K., Infrared and Raman Spectra of Inorganic and Coordination Compounds, Part
A, Wiley Hoboken, New Jersey, 2009

206
Study by micro-Raman and SEM-EDS of mineral series
tremolite-actinolite for the identification of jade
Laura Scrocco1, Paolo Gentile2, Danilo Bersani1 and Pier Paolo Lottici1
1
(Italy)
2
University of Milano-Bicocca, Department of Geological Sciences and
Geotechnologies, Piazzale della Scienza 4, 20126 Milano (Italy).
Jades were used, since ancient times, as jewels and ornaments. In modern
mineralogy the term "jade" refers to two minerals: nephrite, a mineral belonging to the
amphibole group, and jadeite, a species belonging to the pyroxene group [1]. In
particular, nephrite (Ca2(Mg2+,Fe2+)5Si8O22(OH)2) belongs to the series tremolite (Mg-
rich term) - ferroactinolite (Fe-rich term). The criterion for discriminating the members
is provided by the ratio X=Mg/(Mg+Fe2+). For ratio values X0.9 the mineral is
defined tremolite, for values 0.5<X<0.9 the mineral is called actinolite and for values
X<0.5 the mineral is defined ferro-actinolite [2].
The aim of the work is to find a non-destructive method for the identification of the
composition of nephritic jades, based on the Raman spectroscopy.
The method developed is based on the preliminary study of the chemical composition
of some natural samples by means of scanning electron microprobe coupled with
energy dispersive X-ray spectroscopy (SEM-EDS), in order to obtain the values for
their ratio X=Mg/(Mg+Fe2+). The samples used for this preliminary study were six
samples of amphiboles coming from the Alps of Italy and Switzerland.
Raman spectra were then measured on the same spots used for SEM-EDS analysis
and a correlation between the X ratios with the Raman peak positions was obtained.
Figure 1 shows the position of the most intense Raman peak at low frequencies, at ~
670 cm-1, attributed to the Si-O-Si symmetric stretching [3], as a function of the value
of the ratio X=Mg/(Mg+Fe2+).
2+ -1
Fig.1 Correlation between X ratio (Mg/(Mg+Fe )) with the Raman peak 1 (cm )
The results provided by micro-Raman spectroscopy at high frequencies (relative to

the symmetric stretching of OH groups) showed a single peak (A) ~ 3674 cm-1 when
there is substitution of type MgMgMg, a second peak (B) ~ 3657 cm-1 indicates a
207
substitution of type or MgMgFe MgFeMg, the third peak (C) ~ 3646 cm-1 appears in
the presence of substitutions of the type or FeFeMg FeMgFe and fourth peak (D)
~3620 cm-1 in the case of a substitution FeFeFe [4].
Figure 2 shows the normalized areas of the peaks A and D as a function of the X
ratio.
Fig. 2 - Normalized areas of the peaks A and D as a function of the X ratio.
Even if only few points are present, a trend is clearly visible in all the graphs. The use
of the displayed curved allows a first quick identification of the composition of jade
objects of artistic or archaeological interest using only the micro-Raman
spectroscopy.
To test the method, we performed a series of micro-Raman measurements on a jade
bracelet. The analysis has provided for the main peak a wavenumber of 674 cm-1 and
only two high frequencies peaks A (at 3674.9 cm-1 ) and B (at 3660 7 cm-1). The
normalized area for the peak A is nearly 0.7 while peak D is not present. All the
obtained Raman data show that the bracelet has a X ratio near to 0.9, indicating a
composition at the limit between tremolite and actinolite.
References
1. A. Middleton and J. Ambers, Case Study: Analysis of nephrite jade using Raman microscopy
and x-ray fluorescence spectroscopy. In: Edwards HGM, Chalmers JM (eds) Raman
spectroscopy in archaeology and art history. Royal Society of Chemistry Analytical
Spectroscopy Monographs, Cambridge, UK, 23: 403-411.
2. W. A. Deer, R. A. Howie and J. Zussman, An Introduction to the rock forming minerals,
Prentice Hall publisher (1966): 223-231, 242-247.
3. Francesca Casadio, Janet G. Douglas, Katherine T. Faber, Noninvasive methods for the
investigation of ancient Chinese Jades: an integrated analytical approach, Anal Bioanal
Chem (2007) 387: 791-801
4. R. Wang and W.-S. Zhang, Application of Raman spectroscopy in the non-destructive
analyses of ancient Chinese jades, Journal of Raman Spectroscopy (2010), DOI:
10.1002/jrs.2846

208
A Raman spectroscopic study of the paints used by the artist
Stephen Townley Bassett to reproduce San rock art paintings
Aurlie Tourni1,2, Linda C Prinsloo1 and Philippe Colomban2

1
University of Pretoria, Pretoria, Physics Department, South Africa 0002,
prinsloo@up.ac.za
2
UMR7075 CNRS-Universit Pierre-et-Marie-Curie/Paris, Laboratoire de
Dynamique, Interaction et Ractivit, 6, 2 rue Henry-Dunant, 94320 Thiais, France
Stephen Townley Bassett is the third generation in his family to be involved in the
locating and documenting of rock paintings in South Africa. He is a specialist in the
field of Southern African rock paintings and his primary interests lie in the accurate
full colour documentation of the art, as well as research into pigments, paints and
implements used by early hunter-gatherers of the region. His millimetre accurate, life
size recordings are painstakingly rendered with natural pigments and materials
collected in the veld.1
In his own words: Documenting rock art as authentically as possible meant using
only the tools and materials that would have been available to early cave artists. This
required one to try to think as they would have thought. I would need to discard the
tools I was using like pocket-knives, spatulas, plastic and metal containers and
commercially available brushes and begin a kind of experimental archaeology using
only materials I could find in the veld." (Figure 1 a&b). 1
Figure 1: Implements collected in the veldt to use for his paintings (a) and Steve mixing
animal fat into the pigments on his painting stones.
We have previously successfully conducted a Raman spectroscopic study on a rock

art sample in the laboratory2 and performed on-site measurements with a portable
Raman instrument3. In both studies we identified inorganic pigments and alterations

209
products, providing information on both the pigments and conservation state of the
paintings. However, no organic binders or carrying agents were detected and some
of the pigments such as hematite did not give good spectra in the on-site
experiments. Therefore we are using the paints of Stephen Townley Bassett to
initiate a database of all the possible ingredients that might have been used by the
San artists, in order to find the optimum detection technique for each material.
a. b. c.
Figure 2: Example of infrared spectra (a), Raman spectra recorded with 785 nm (b) and
514 nm exciting radiation (c)
The paint samples in the database consist of mixtures of pigment (ochre clay,
thermally treated ostrich egg shell, etc.), different kinds of animal fat (gall, marrow,
etc), hen egg, saliva and water. The samples were analysed with Raman
spectroscopy using different exciting laser lines (514nm, 785nm), as well as infrared
spectroscopy. Also included in the database are spectra of the pure ingredients to
assist in assigning the bands in the spectra of the paint mixtures. In Figure 2 a few
examples of the database entries are shown.
Obviously, each technique gives a partial view of the ingredients. For example, if we
compare the spectra of sample 2B (consisting of red ochre, marrow bone fat and hen
egg): organic phases are very well observed in the infrared spectrum, hematite has
prominent peaks in the spectrum recorded with 785nm excitation and elements of
both are observed in the 514 nm excited spectrum. Aromatic species are very well
detected with red excitation. Fluorescence was a bigger problem with green
excitation than with red. We hope that a combination of the database, the results of
our first on-site expedition and experiments on museum pieces with laboratory
instruments will provide helpful insights to improve our on-site research and provide
guidelines for optimum recording conditions to be used for our next on-site
undertaking.
References
S. Townley Bassett, Rock paintings of South Africa, David Philip, Cape Town, 2001
L.C. Prinsloo, W. Barnard, I. Meiklejohn and K. Hall, J. Raman Spectrosc., 2008; 39, 646.
A. Tourni, L C Prinsloo, C. Paris, P. Colomban and B. Smith, J. Raman Spectrosc. in press

210
Micro-Raman spectroscopy in investigation of Upper
Palaeolithic ferruginous powdered artefacts
Joanna Trbska1, Aleksandra Weseucha-Birczyska2,

Barbara Trybalska3
1
University of Rzeszow, Institute of Archaeology, Hoffmanowej 8, Str, Rzeszow
(Poland); joanna.trabska@archeologia.rzeszow.pl
2
Jagiellonian University, Faculty of Chemistry, Ingardena 8, Str, Krakw (Poland)
3
University of Science and Technology, Mickiewicza Av. 30, Krakw (Poland)
Red ferruginous powders are common micro artefacts at Palaeolithic, especially at

Upper Palaeolithic sites. They occur as loosely dispersed material within
archaeological sediments or are pigments used in parietal paintings and painted
loose stones. Loosely dispersed powders are a subject of this work. They could be
remnants after some common activities (e.g. hide processing) or purposedly
manufactured for medical, cosmetic, painting and sacral use. It can be assumed that
all the mentioned activities may have involved a processus specific for each,
including admixtures of organic and inorganic materials. The latter are expected to
be difficult to determine due to time and post depositional phenomena. Nevetheless,
several attempts have been undertaken: samples from Upper Palaeolithic sites from
Central and Western Europe (Dolni Vestonice, Moravia; Brno II, Moravia; Stadice,
Czech; Goennersgorf, Germany; Monruz, Switzerland) have been examined with the
use of micro-Raman, polarised and scanning microscopy. Size, shape and
composition of powders themselves and surroundings were analysed. Micro-Raman
analyses reveal a complex set of substances, including organic ones.
Some experiments with heated samples were conducted; the samples were
examined with the mentioned methods. Heating history of microartefacts sems to be
possible to reconstruct, again, with the complex use of micro-Raman and scanning
microscopy.

211
Micro-Raman spectroscopy in investigation of white and red
painting layers from Celtic pottery from the Modlniczka site,
Poland
Joanna Trbska1, Aleksandra Weseucha-Birczyska2,

Barbara Trybalska3, Marcin Przybya4
1
University of Rzeszow, Institute of Archaeology, Hoffmanowej 8, Str, Rzeszow
(Poland); joanna.trabska@archeologia.rzeszow.pl
2
Jagiellonian University, Faculty of Chemistry, Ingardena 8, Str, Krakw (Poland)
3
University of Science and Technology, Mickiewicza Av. 30, Krakw (Poland)
4
Private investigator
Celtic pottery is renowned for its sophisticated technology, in reference to

fabric and to painting layers. The ones examined by us represent only two
colours, red and white. Both are thin layered, homogeneous, composed of
very fine grained pigments. Chemical composition of both reveals
unexpectedly elevated concentration of alumina and phosphorus with a very
low amount of calcium. Micro-Raman points at presence of phosphates of
degraded crystal structure. SEM image and micro-Raman reveal a complex
structure of macroscopically homogeneous paint; a suggestion has been put
forward on intentional, technologically complex, process of pigment
manufacturing.
Analogous remarks refer to red painting layer, always thinner than a white
one, very fine grained, homogeneous. Haematite is a colouring agent but
again some alumina phosphorus compounds were detected. The origin of the
latter is being searched for and environment influence has been excluded.

212
Investigation and characterization of porcelain objects,
discovered in Clairefontaine (Belgium), by means of Raman
Spectroscopy.
Jolien Van Pevenage1, Davy Herremans 2, Bart Vekemans1,

Laszlo Vincze1, Peter Vandenabeele2 and Luc Moens1
1
Ghent University, Department of Analytical Chemistry, Krijgslaan 281 S12, B-9000
Ghent (Belgium), Tel. +32 (0)9 264 47 19, Raman@UGent.be
2
Ghent (Belgium).
The porcelain objects, investigated in this project, were found in a latrine of the
Cistercian abbey of Clairefontaine (Belgium). All the ceramics found in this latrine
date mainly from the first half of the 18 th century.
Archaeologists expect on the basis of the shape and the style of the porcelain, that
the objects are Chinese porcelain dating from the first half of the 18 th century. The
aim of this study, at first, is to confirm, support or deny this proposition. Most of these
chronologies have kept up for years and are rarely supported by absolute dating or
determination of the origin.
If the proposition of the archaeologists can be confirmed by spectroscopic research,
it would be interesting to date these porcelain objects. So, the second goal of this
study is to figure out if the porcelain dates from the Ming (1368-1644) or Qing (1644-
1911) period.
In this project, both Raman spectroscopy and X-Ray Fluorescence spectrometry will
be used for the characterization and identification of the samples. Starting with
Raman analyses, lab measurements were executed with a Bruker Senterra R-200L
Raman spectrometer. This spectrometer is equipped with two lasers, a red diode
laser (785nm) and a green Nd:YAG laser (532nm).
In this poster the first results of the Raman analyses are presented.
Acknowledgements. This work is supported by the BELSPO Interuniversity Attraction

Pole Program P6/16 (Belgium).

213
The influence of accelerated degradation over the
discrimination performance between Romanian and Baltic
ambers. FT-Raman spectroscopic characterization
M. Virgolici1, E.S. Teodor2, M.M. Manea1, E.D. Teodor3, I. Petroviciu2,

I.V. Moise1 and C.C. Ponta1
1
"Horia Hulubei" National Institute of Physics and Nuclear Engineering (IFIN-HH),
IRASM Centre of Technological Irradiations, 407 Atomitilor Str., 077125, Magurele,
Ilfov (Romania), Tel. +40 214042320, mmanea@nipne.ro,
2
National Museum of Romanian History, 030026, Bucharest (Romania),
3
National Institute for Biological Sciences (INSB), Centre of Bioanalysis, 296 Spl.
Independenei, 060031, Bucharest (Romania)
In the quest for non-destructive methods useful in tracking the geological origins
of archaeological ambers, Raman spectroscopy was considered for characterization
and fingerprinting purposes [H.G.M. Edwards et al., 1996; R.H. Brody et al., 2001;
W. Winkler et al., 2001; J. Jehlicka et. al., 2004, Teodor et al. 2010].
However, because of extensive degradation of amber beads as a result of
chemical interaction with the archaeological environment, main analytical problem
that arises from here being related with the fact that spectra of archaeological
samples and geological samples are extremely difficult to match even with advanced
multivariate data analysis techniques as Principal Components Analysis or Cluster
analysis [Teodor et al. 2010, Virgolici et al. 2010]. There are two problems to be
solved from here: how Raman spectra of reference geological ambers are changed
after similar ageing and which spectral features can still be clues to attribute the
geological origin of archaeological amber artefacts.
For this purpose artificially degraded amber references in environments with
different humidity and pH were used to check the stability of characteristic spectral
features of Romanite and Baltic ambers in FT-Raman spectrum.
Qualitative (band shifts) and semi-quantitative (peak ratios) modifications were
observed, the influence of different degradation environments being further
discussed.
Romanite (figure 1) is the most affected by the experiment of accelerated
degradation, new peaks appearing at 277 - 290 cm-1, 799 cm-1 ( (COC) / CC
aliphatic chains), 986 cm-1 ( (C-C) aliphatic, aromatic), 1612 - 1617 cm-1, 1637 cm-1
( (C-C) trans-conjugated). Other significant band shifts in Romanite being observed
for (CCO); (S-S) and (CCO); (CH2) and CC aliphatic chains (only for dry
and wet environment), (C=O) (excepting wet and dry environments) vibrations. The
most aggressive environment for Romanite was the dry atmosphere, having as a
result an increase in the peak intensity for 1612 - 1617 cm-1 and 1637 cm-1 ( (C-C)
trans-conjugated) signals; and a simultaneous decrease in the peak intensity for
1454 cm-1 ( (CH2), (CH3)) and 2877 cm-1 ( (C-CH3)) signals.
In comparison Baltic amber suffers significant spectral modifications in acid
environment, having a decrease in peak intensity in the 200 - 1800 cm-1 spectral
region, and it is relatively small affected by the other degradation environments.
The poster focuses on the degradation effects of Romanite and Baltic amber, as
the two raw materials were the most probable sources to be used in the
manufacturing of amber artefacts from Romanian Museum collections [Teodor et al.
2010, Virgolici et al. 2010].

214
Figure 1. FT-Raman spectra of Romanite (spectra numbered from bottom to top): non degraded (1);
and degraded in low acidic wet atmosphere (2), wet atmosphere (3), salty wet atmosphere (4), low
basic wet atmosphere (6), dry atmosphere (7), average spectrum of all degradation atmospheres (5).
Acknowledgements. This work has been financially supported by the ANCS,

ROMANIT project, Contract no. 91-091/2007.
References
H.G.M. Edwards, D.W. Farwell, Spectrochimica Acta Part A 1996; 52:1119
R.H. Brody, H.G.M. Edwards, A.M. Pollard, Spectrochimica Acta Part A 2001; 57:1325
W. Winkler, E.C. Kirchner, A. Asenbaum, M. Musso, J. Raman Spectrosc. 2001; 32: 59
J. Jehlicka, S.E. Jorge Villar, H.G.M. Edwards, J. Raman Spectrosc. 2004; 35: 761
E.S. Teodor, E.D. Teodor, M. Virgolici, M. Manea, G. Truica, S.C. Litescu, Journal of
Archaeological Science 2010; 37: 2386
M. Virgolici, I. Petroviciu, E. Teodor, S. Liescu, M. Manea, C. Ponta, G. Niculescu, C. Sarbu,
A. Medvedovici, Revue Roumaine de Chimie 2010; 55: 349

215
Study of green earth in monochrome mural paintings in the
Tuscany of fifteenth century
Eleonora Vittorini Orgeas1, Cecilia Frosinini2, Carlo Lalli Galliano2

Mariarosa Lanfranchi2, Anna Medori2, Antonella Casoli3, Danilo Bersani1
1
Dipartimento di Fisica, Universit di Parma, V.le G.P. Usberti 7a, 43124 Parma,
Italy
2
Opificio Delle Pietre Dure, V.le Strozzi 1, 50129 Firenze, Italy
3
Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica e Chimica
Fisica, Universit di Parma, V.le G.P. Usberti 17a, 43124 Parma, Italy
The aim of this work is the study of "Stories of Santa Verdiana", a green
monochrome painting, recently restored, present in the chapel of Santa Verdiana,
placed inside a complex which is now the main building of the Faculty of Architecture
of Florence.
Previous investigations indicate that the painting was mostly painted using green
earths. The local origin of the green earth used in the XV century in Tuscany has
been so far assumed on literary sources, but this hypothesis is not supported by
scientifically valid evidence today. We would like to use this case study to evaluate if
the employed green earth could have local origin.
We compare the results obtained on the painting with some of the few historical
samples indicated as a Tuscan standard of green earth: four samples of "bolar green
earth" preserved in the museum of the Academy of Fisiocritici in Siena, collected at
the end of the XIX century.
After that, we concentrated on trade routes attempting to trace the movement of the
pigment, mainly in Italy and in the Mediterranean zone, thanks to testimonies of
Italian merchants who hold the control of trade routes of the XV century in Tuscany.
Samples of green earth taken from the wall painting and the four samples of "bolar
green earth" were analyzed using -Raman spectroscopy, FTIR-ATR and -FT-IR.
tv3-19bell sub.spc: tv3-19bell-oh.spc:
280
100
260
80 240
Ram an In t en s i t y
R am an In t en s i t y
60 220
200
40
180
20
160
1200 1000 800 600 400 200 3200 3300 3400 3500 3600 3700 3800
Raman Shift (cm-1) Raman Shift (cm-1)
Example of Raman spectroscopy analysis on a sample of the wall painting of Santa

Verdiana showing the presence of celadonite.

216
The first conclusion coming from the Raman spectra is that in the samples of the
mural painting of Santa Verdiana in Florence only celadonite is present, without any
evidence of glauconite. No source of celadonite is present in Tuscany, and also the
geological setting doesnt seem favourable to large presence of celadonite.
Raman and FT-IR analysis, supported by previous XRD results, showed that actually
the museum specimens indicated as green earths from Tuscany are not green
earths but are mostly composed by jarosite. So we cannot indicate a local origin for
the green earth used in "Stories of Santa Verdiana".
References
Medori Anna, Storie di Santa Verdiana (sec. XV) nellex convento di S. Verdiana a Firenze.
Studio della tecnica artistica e dello stato di conservazione; Restauro della parete dellaltare;
elaborazione del progetto conservativo globale della cappella., Tesi di Diploma della Scuola
di Alta Formazione dellOpificio delle Pietre Dure di Firenze, 2009.
Ospitali Francesca, Bersani Danilo, Di Lonardo Gianfranco, Lottici Pier Paolo, Green earths:
vibrational and elemental characterization of glauconites, celadonites and historical
pigments, Journal of Raman spectroscopy, 2008.
Feller Robert L., Artists Pigments; a handbook of their history and characteristics, Vol. 1,
Cambridge University Press, 1986.

217
Raman spectroscopy study on ancient glass beads found in
Thailand: Southern Prehistoric Sites
Krit Won-in1, Yatima Thongkam2, Sorapong Pongkrapan1,

Chom Thongleurm3, Sawet Intarasiri 4, Teerasak Kamwanna5 and
Pisutti Dararutana6
1
Kasetsart University, Department of Earth Sciences, Faculty of Science, 10900
Bangkok (Thailand),
2
Silpakorn University, Faculty of Archaeology, 10200 Bangkok (Thailand),
3
Chiang Mai University, Science and Technology Research Institute, 50200 Chiang
Mai (Thailand),
4
Chiang Mai University, Faculty of Science, 50200 Chiang Mai (Thailand),
5
Khon Kaen University, Faculty of Science, 40002 Khon Kaen (Thailand),
6
The Royal Thai Army Chemical department, 10900 Bangkok (Thailand), Tel. +66 8
15531191, pisutti@hotmail.com
Various colors glass beads excavated from prehistoric sites at Southern areas of
Thailand were analyzed non-destructively using Raman spectroscopy and X-ray
fluorescence spectroscopy (SEM-EDS and PIXE) in order to determine the glass
compositions and the glass production technology The Raman spectra and XRF
analysis classified the glasses as both alkali-based and lead-based glass matrices.
The colors were mostly obtained by the additions of transition metal ions.
Consideration of the glass compositions and colorants, it would seem that there was
some production technological relationship between South-East Asia, South Asia,
East Asia and Asia Minor. This information led to gain knowledge of the historic link
of the long distance trade and exchange networks in ancient maritime.
Acknowledgements. This work has been financially supported partly by Faculty of

Science at Kasetsart University and Kasetsart University Research and
Development Institute.

218
Alphabetical list of authors
Abd El Aal, S. 85
Abed-Esfahani, A. 86
Abrams, G. 77
Aceto, M. 3, 9, 38, 86, 88
Agostino, A. 7, 38, 86, 88
Ahmadi, H. 86
Ait Lyazidi, S. 68
Aj, D. 150
Aktan, E. 90, 115
Alesiani, M. 113
Aliatis, I. 199
Alloza-Izquierdo, R. 159
Alonso-Olazabal, A. 91
Aluas M. 152
Ambers, J. 93
Anaf, W. 59
And, S. 95
Angelici, D. 96
Appoloni, C. R. 98
Aramendia, J. 99
Ayora-Caada, M. J. 179
Azzi, G. 101
Baert, K. 10, 20
Bakiler, M. 151
Baldellou-Martnez, V. 159
Baraldi, A. 123
Baraldi, C. 12, 103
Baraldi, P. 9, 12, 88, 103, 105, 106, 107, 191
Barberio, M. 150
Barbieri, M. 105
Barbu, O. H. 177
Barbu-Tudoran, L. 152
Barzagli, E. 38
Beck, L. 46
Belet, A. 120
Belkov, M. 108, 148
Bellot-Gurlet, L. 26, 135

219
Bergamonti, L. 109
Berke, H 14, 111
Bernardi, E. 185
Bersani, D. 9, 28, 101, 109, 110, 114, 123, 127, 129, 178, 207, 216
Bertolotti, G. 113
Berzioli, M. 114
Bezr, A. 116
Bicchieri, M. 71
Bienes, J. J. 91
Biondelli, D. 199
Biondi, A. F. 196
Boitelle, R. 30
Bongiorno, V. 118
Bonjean, D. 77
Bonn, M. 3
Boso, O. 154
Bracciale, M. P. 200
Brambilla, A. 16
Brambilla, L. 107, 131
Broggi, A. 200
Bromiley, G. 178
Bruni, S. 1
Bugheanu, P. 133, 176
Burgio, L. 22
Burlet, C. 77
Buzzini, P. 52
Caffara, R. 118
akar, P. 120
Cals-Gmez, M. 159
Campodonico, S. 118
Caamares, M.V. 121
Canevali, C. 107
Canobbio, E. 9
Cantalejo, P. 42
Cantisani, E. 84
Capel, C. 42
Capelletti, R. 123
Capitn-Vallvey, L. F. 179
Capobianco, G. 127
Cardell, C. 59, 198
Carnasciali, M. M. 118
Carvalho, M. L. 188

220
Casadio, F. 70, 116
Casanova-Gonzlez, E. 18
Casella, A. 123
Casoli, A. 114, 216
Castagneri, G. 7
Castellucci, E. M. 84
Castiglioni, C. 24
Castriota, M. 192
Castro, K. 40, 50, 99
Catarsi, M. 127
atkka, B. 90, 125
Cavalieri, M. 126
Cavazzuti, G. 127
Cazzanelli, E. 192
Ceglia, A. 10, 20
Celona, C. 101
Cerasoli, T. 129
Cesaratto, A. 22
Chalkia, E. 170
Chiavari, C. 185
Cinta Pinzaru S. 152
Cinteza, O. L. 133
Ciontea, L. 152
Civita, F. 38
Coccato, A. 129
Colomban, Ph. 2, 28, 44, 209
Colombini, M. P. 63
Colombo, C. 24, 131
Comelli, D. 16
Conti, C. 24, 81, 131
Conversi, R. 129
Corbiere, T. 14, 111
Cortea, I. 133
Cristache, R. 133
Csermely, D. 109
Cui, Y. 174
Cutrubinis, M. 177
Daher, C. 26, 135

Daly, N. 70
Dararutana, P. 218
Davis, A. 70
Day, J 3

221
de Balbn-Behrmann, R. 157
de Ferri, L. 28
de Groot, S. 30
de Keijzer, M. 30
de Pasquale, A. 9
De Santo, G. 192
De Vincolis, R. 138
De Vries, L. 32
Defeyt, C. 137
del Puerto, E. 68
Deneckere, A. 32
Derbyshire, A. 22
Di Liscia, E. 74
Di Lonardo, G. 185
Di Martino, D. 139, 140
Di Modica, K. 76
Doer, L. 44
Dolenec, M. 172
Domingo, C. 18
Dominguez, A. 179
Domnguez-Bella, S. 42
Doncea, S. 161
Dondi, M. 178
Dovnar-Zapolskaya, E. 62
Edwards, H. 205
El Bakkali, A. 68
Emandi, A. 133
Emandi, I. 133
Er, M. 120
Ercoli, L. 53
Espejo, M. 42
Esquivel, B. 18
Etxebarria, N. 91
Falamas, A. 152
Fasanella, A. 192
Faurskov Nielsen, O. 144
Fenoglio, G. 7, 86, 88
Ferrer, P. 141

222
Ferrugiari, A. 81
Fiedler, I. 115
Filardi, V. 143
Filtenborg, T. 144
Fintor, K. 155
Fischer, L. 205
Fontana, D. 138
Franceschi, E. 191
Fratini, T. 84
Freguglia, G. 103
Freisinger, E. 14
Fremout, W. 33
Frosinini, C. 216
Fumo, A. 126
Galli, A. 140
Gamberini, M. C. 103
Gamillscheg, E. 88
Ganetsos, T. 152, 168, 170
Gaponenko, S. 148
Garca Ibez de Opakua, A. 99
Garca Porras, A. 198
Garca-Atero, J. 178
Garzanti, E. 95
Gast, N. 35
Gautier, G. 116
Gavira-Vallejo, J. M. 157, 159, 163
Gavrilenko, E. 159
Gebhard, R. 35
Gediga, B. 48
Gentile, P. 107, 207
Giambra, B. 152
Giarola, M. 150
Gilg, H. A. 35
Giordano, V. 7
Goemaere, E. 77
Goidanich, L. 106
Gokce Gokcay, A. 151
Gktrk, E. H. 44
Gmez-Laserna, O. 181
Gomez-Nubla, L. 99
Gonzles Vidal, J. J. 37
Grazzi, F. 38

223
Greco, M. 24, 131
Greeneltech, N. 70
Greiff, S. 146
Grupe, O. 183
Gueli, A. M. 138
Gui, O. M. 152
Gulec, A. 151, 154
Guzatov, D. 148
Gyalai, Z. 155
Haddad, M. 68
Halac, B. 74
Harbachova, A. 108, 148
Hartmann, S. 146
Herm, C. 55
Hernndez, V. 42
Hernanz, A. 157, 159, 163
Herremans, D. 213
Hofmann, H. 88
Horemans, B. 59
Hu, J. 174
Hunger, K. 79
Hutter, J. 14
Iannaccone, R. 38
Intarasiri, S. 218
Ion, M. L. 161
Ion, R. M. 161
Irazola, M. 40
Iriarte, M. 163
Jakovlevska-Spirovska, Z. 183
Job, D. 165
Jorge-Villar, S. 42
Joseph, E. 165
Jungels, C. 77
Jussiani, E. I. 98

224
K
Kamwanna, T. 219
Karampelas, S. 79
Katona, I. 167
Katsaros, T. 146, 168, 170
Kiris, V. 62
Krmz, B. 44
Klyachkovskaya, E. 108, 148
Knuutinen, U. 50
Kontozova, V. 59
Kosec, T. 65
Kramar, S. 172
Kurkcuoglu, M. V. 154
Kutzke, H. 205
Lahlil, S. 46
Lalli Galliano, C. 216
Lancelot, E. 47
Lanfranchi, M. 216
Lanz, H. 79
Laue, S. 83
Le H, A. S. 26, 135, 202
Lebon, M. 46
LeGac, A. 187
Leona, M. 61, 196
Li, X. 174
Linstaedter, J. 42
Liu, Y. 174
Lluveras, A. 63
Lo Giudice, A. 96
Lofrumento, C. 84, 126
Lopes, F. 98
Lpez-Gil, A. 141
Lopez-Ramirez, M. R. 175
Lorenzi, R. 139
Lottici, P. P. 28, 101, 109, 113, 114, 123, 129, 178, 207
Lubin-Germain, N. 202
Lucejko, J. J. 107
Lux, J. 172
Lycke, S. 137
ydba-Kopczyska, B. I. 48

225
M
Ma, Q. 14, 111

Madariaga, J. M. 40, 50, 99, 181
Madeira, T. I. 188
Maguregui, M. 40, 50, 181
Maier, M. 74
Malcherek, T. 113
Manea, M. M. 177, 214
Mantovani, L. 178
Manzano, E. 175, 179
Mariotto, G. 150
Maroto-Valiente, A. 157
Martn, S. 157, 163
Martnez, S. 121
Martinez-Arkarazo, I. 40, 50
Martini, C. 185
Martini, M. 140
Martinovska, V. 183
Massonnet, G. 52
Mazzeo, R. 165
McLean, M. 184
Medianero, J. 42
Medori, A. 216
Megna, B. 53
Melo, M. J. 57
Melquiades, F. L. 98
Menndez-Fernndez, M. 157
Menu, M. 46, 202
Menzel, J. 55
Mercangz, Z. 44
Mercuri, G. 127
Meulebroeck, W. 10, 20
Miguel, C. 57
Mineva-ukarova, B. 63, 183
Minoli, D. 101
Mirambet, F. 202
Mitchell, G. 193
Modugno, F. 107
Moens, L. 6, 32, 76, 213
Moise, I. V. 176, 214
Montanaro, D. 200
Montejo, M. 66
Morillas, H. 181
Mortazavi, M. 86
Mousavi, J. 86

226
Muehlethaler, C. 52
Muir, K. 116
Muralha, V. 143
Muralha, V. S. F. 57
Murelaga, X. 91
Nastova, I. 63, 183

Navas, N. 175, 179
Negut, C. D. 175
Nevin, A. 16
Nole, D. 191
Nys, K. 10, 20
Olivares, M. 40, 91
Ortega, L. 91
Ospitali, F. 185
Osticioli, I. 16
Otero, J. O. 175
Pags-Camagna, S. 187, 202

Paleari, A. 139
Pan, L. 14
Parellada, C. I. 98
Paris, C. 26, 135
Parodi, P. 191
Passarini, F. 186
Passmore, E. 93
Pereira, F. C. 198
Prez-Pueyo, R. 37
Pessanha, S. 188
Petroviciu, I. 214
Petrucci, E. 200
Petrullo, S. 12
Petzold, K. 189
Piccardo, P. 118
Picollo, M. 38
Pimenta, V. 135
Pirson, S. 77
227
Pizzone, R. 191
Plassard, F. 546
Platania, E. 192
Pongkrapan, S. 218
Ponta, C. C. 177, 214
Portmann, A. 14
Possenti, E. 24
Potgieter, J. H. 194
Potgieter-Vermaak, S. 59, 194, 198
Pozzi, F. 61, 196
Pratesi, G. 96
Prencipe, M. 4
Prieto-Taboada, N. 99
Prinsloo, L. C. 209
Przybya, M. 212
Raikov, S. 62
Ramos, J. 42
Raue, D. 187
Re, A. 96
Realini, M. 24, 131
Regert, M. 26
Reiche, I. 46
Reinoso, M. 74
Ricci, G. 71
Ricci, M. 84, 126
Ricci, M. A. 71
Riedo, C. 107
Rizzo, G. 53
Robeva ukovska, L. 63
Robbiola, L. 185
Rochut, S. 135
Rodriguez-Simn, L. R. 175
Roldn, L. M. 18
Romero-Pastor, J. 198
Ropret, P. 65
Rousselire, H. 46
Rubio-Mora, A. 159
Ruiz-Lpez, J. F. 157, 159, 163
Ruiz-Moreno, S. 37, 141
Ruvalcaba-Sil, J. L. 18

228
S
Sachanbiski, M. 48
Salvemini, F. 38
Salvioli-Mariani, E. 127
Snchez, A. 66
Sanchez-Cortes, S. 68, 121
Sandalinas, C. 141
Sansonetti, A. 199
Santarelli, M. L. 200
Santoro, C. 202
Santos-Vasquez, V. 18
Sanz Lpez de Heredia, A. 99
Sarmiento, A. 91
Saverwyns, S. 33
Sbarciu, I. 152
Schatz, G. 70
Scherrer, N. C. 203
Schiavon, E. 9
Schluetter, F. 83
Schlter, J. 113
Schmahl, W. 35
Schnemann, A. 205
Scrocco, L. 207
Seferolu, Z. 90, 125
Seidlmayer, S. 187
Serneels, V. 167
Shah, N. 70
Simon, G. 28
Simpson, St J. 93
Sodo, A. 71
Soneira, M J. 37
Spinolo, G. 139
Stanculescu, I. R. 177
Stark, R. 35
Stella, G. 138
Strekal, N. 148
Striova, J. 131, 199
Strivay, D. 137
Tagliapietra, R. 73
Teodor, E. D. 214
Teodor, E. S. 214

229
Terryn, H. 10, 20
Thienpont, H. 10, 20
Thongkam, Y. 218
Thongleurm, C. 218
Tinti, A. 106
Tomasini, E. 74
Tommasini, M. 81
Tong, H. 174
Tourni, A. 209
Trbska, J. 211, 212
Traversone, P. 191
Tribaudino, M. 178
Troja, S. O. 138
Trojsi, G. 12
Trybalska, B. 211, 212
Tun, J. 66
Ugur, T. 151
Valentini, G. 16
Valley, N. 70
van Bommel, M. R. 30
Van de Voorde, L. 76
Van Duyne, R. P. 70
Van Grieken, R. 59, 198
Van Pevenage, J. 76, 213
Vanbrabant, Y. 77
Vandenabeele, P. 16, 32, 76, 137, 167, 168, 213
Vandevijvere, M. 76
Varetto, M. 7
Varone, A. 12
Vaschenko, S. 148
Vassallo, S. 191
Vega, D. 99
Vekemans, B. 31, 76, 213
Vermeij, L. O. E. S. 30
Verri, G. 93
Vezzalini, M. G. 28
Vignali, F. 114
Vignaud, C. 46
230
Vilarigues, M. 143
Vias-Vallverd, R. 159
Vincze, L. 32, 76, 213
Virgolici, M. 177, 214
Vittorini Orgeas, E. 216
Wang, X. 174
Wei, C. 35
Weniger, G. 42
Weseucha-Birczyska, A. 211, 212
Wijnberg, L. 137
Wild, F. 14, 111
Won-in, K. 218
Wrle, M. 79, 165
Wouters, H. 10, 20
Wu, Z. 174
Yin, X. 13
Zancan, G. 127
Zanelli, C. 178
Zanichelli, G. 9
Zannini, P. 9, 88, 105, 106
Zerbi, G. 24, 81, 131
Zhang, Z. 14, 111
Ziemann, M. A. 83
Zoppi, A. 84
Zoppi, M. 38
Zuccarello, A. R. 138
Zuluaga, M. C. 91

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L. Teerlinc vermilion Orpiment, red lead and

I. Oliver Red lead Hematite, goethite, red lead,

P. Oliver Red lead Hematite, goethite, red lead,

J. Hoskin Red lead Hematite, goethite, red lead,

Table 1 Most common pigments mixtures

20 (orange cr) material is the

Derbyshire A. and Withnall R. Journal of Raman Spectroscopy 1999; 37: 185.