Synchrotron radiation and neutrons in art and - Ipanema

Transcription

9 >12 sept. 2014 Musée du Louvre, Paris
Synchrotron radiation and neutrons
in art and archaeology Conference
Conférence Rayonnement synchrotron
et neutrons pour l’art et l’archéologie
Invited speakers
Orateurs invités
Matthias Alfeld
Emilie Chalmin
Catherine Dejoie
Trinitat Pradell
Ritimukta Sarangi
Marco Stampanoni
Public session
Wednesday
September 10,
afternoon
Louvre auditorium
Session publique
10 septembre
après-midi
Auditorium du Louvre
Uwe Bergmann
Robert van Langh
Philippe Sciau
International
scientific committee
Comité scientifique
international
Annemie Adriaens
Loïc Bertrand
Joris Dik
Koen Janssens
Apurva Metha
Jennifer Mass
Martin Radtke
Ina Reiche
Jean Susini
Josefina Pérez-Arantegui
Robert van Langh
www.sr2a-2014.org
9 >12 sept. 2014 Musée du Louvre, Paris
Synchrotron radiation and neutrons
in art and archaeology Conference
Conférence Rayonnement synchrotron
et neutrons pour l’art et l’archéologie
EDITO / ÉDITO
Synchrotron radiation and neutrons in art and archaeology Conference
Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie
Le musée du Louvre est l’œuvre d’hommes passionnés,
collectionneurs, artistes, conservateurs, chercheurs, ... qui en
ont forgé l’âme. C’est un musée vivant. Ouvert à partir d’une
collection royale patiemment rassemblée depuis François Ier
au début du XVIe siècle, le musée est l’héritier du siècle des
Lumières et le fils de la Révolution ; il a d’emblée cette mission
de musée universel, s’adressant à un public universel.
Les collections du musée couvrent un large panorama
chronologique, géographique et matériel : les objets les
plus anciens appartiennent au département des Antiquités
orientales, les plus récents sont des dessins contemporains
conservés aux Arts Graphiques ; les collections s’étendent
de l'Amérique aux frontières de l'Inde et de la Chine.
« Assurer l’étude scientifique des collections » et « concourir (...)
à la recherche » sont deux missions fondamentales assignées
au musée du Louvre aux côtés de la conservation et l’accueil
des publics dans le décret de sa création en établissement
public, en 1992.
Connaître au mieux les œuvres de nos collections,
les hommes qui les ont créées, les techniques qui les ont
mises en forme, découvrir les innovations et les influences
des artisans et des artistes, enquêter sur les parcours des
œuvres de la fouille au musée – pour les pièces archéologiques - ou depuis leur création, leur passage d’une
collection d’amateur à un autre, mettre en relation les
sources archivistiques et documentaires, les analyses physico-chimiques, et le regard sur l’œuvre, ... c’est le travail
quotidien des chercheurs du Louvre.
Cette recherche modifie parfois fondamentalement la
présentation même des œuvres du musée ; elle amène le
public à découvrir ou redécouvrir un artiste, une culture,
une époque, grâce notamment aux quelque quarante expositions ou actualités des salles au Louvre ou hors les murs.
Avec la trentaine de publications d’ouvrages scientifiques
(catalogues raisonnés, catalogues d’expositions, monographies), les colloques et conférences consacrés à l’archéologie
et à l’histoire de l’art, le résultat de cette recherche est largement diffusé auprès de tous.
Depuis 2010, nous publions La Recherche au musée du
Louvre, bulletin annuel de la recherche qui a pour objectif
de recenser tous les projets et études menés au musée du
Louvre. Il informe sur les nouvelles acquisitions de chaque
département, développe les principales restaurations
et présente les nouveaux espaces muséographiques.
Il reprend les temps forts des expositions in situ et hors les
murs et propose un annuaire des acteurs de la recherche.
A l’instar des grandes institutions de recherche, le musée
du Louvre s’est doté depuis 2011 d’un Conseil scientifique
constitué de membres éminents de la recherche en archéologie et histoire de l'art, issus des universités et des
musées nationaux et internationaux, ainsi que d'acteurs
du musée, afin de bénéficier d’un regard extérieur sur sa
politique de recherche.
Le développement de projets de recherche, en lien avec
les institutions de recherche du Ministère de la Culture
et du Ministère de l’Enseignement supérieur et de la
Recherche, fait partie de nos priorités. Souhaitant s’impliquer dans les nouveaux développements technologiques
associés aux recherches menées sur les collections,
le musée du Louvre s’est associé aux sept laboratoires du
CNRS, du ministère de la Culture et du MNHN (IPANEMA
à SOLEIL, C2RMF, LAMS, département de préhistoire du
MNHN, LAPA, LRMH, CRCC) et à la Fondation des Sciences
du Patrimoine pour accueillir dans ses murs la conférence
internationale du Synchrotron radiation and neutrons in
art and archaeology 2014.
Jean-Luc MARTINEZ
Président - directeur du musée du Louvre
3
EDITO / ÉDITO
The Louvre owes its existence to the many passionate
collectors, artists, curators and researchers who have given
the museum its heart and soul. The museum is a living
entity. Born out of a royal collection patiently assembled
since the early 16th century reign of Francis I, it is heir to the
Age of Enlightenment and a child of the French Revolution.
From the very outset, the Louvre was intended as a universal
museum open to all.
Its collections cover vast expanses of time and space, and a
wide array of works: the oldest items are to be found in the
Department of Near Eastern Antiquities and the most recent
are contemporary drawings housed in the Department
of Prints and Drawings. The collections span continents,
stretching from America to the borders of India and China.
Along with conservation and visitor reception, the 1992
decree that conferred on the Louvre the status of public
institution charged the museum with two other core
missions: “ensuring scientific study of the collections” and
“promoting ... research”. Every day, the Louvre’s research team
works to gain a deeper understanding of the pieces in our
collections, of their creators and of the techniques employed
in the creation process. Every day, they gain insight into
what influenced craftspeople and artists, and how they
innovated in turn; they trace the trajectories of pieces from
their excavation (in the case of archaeological artefacts)
or from their creation to their arrival at the museum, and
from one connoisseur’s collection to another. Every day,
our researchers make connections between archival and
documentary sources, physicochemical analyses, and the
way artworks are interpreted from an art history perspective.
In some instances, research radically changes the very presentation of the museum’s artworks, allowing the public to
discover or rediscover an artist, a culture, or a time period
through some forty exhibitions and events taking place inside and outside museum walls. Research findings are made
widely available through some thirty scientific publications
(catalogues raisonnés, exhibition catalogues, monographs),
as well as symposia and lectures dedicated to archaeology
and art history.
In 2010, we published the first edition of La Recherche
au musée du Louvre (“Research at the Musée du Louvre”),
an annual bulletin that inventories all projects and studies
carried out at the Musée du Louvre. The bulletin provides
updates on new acquisitions for every department, gives a
detailed presentation of main conservation works, and introduces new exhibition spaces. It also contains a summary of
onsite and offsite exhibition highlights, as well as a directory
of research specialists.
In 2011, following the example of leading research institutes,
the Musée du Louvre set up a Scientific Council comprising,
on the one hand, eminent figures in archaeological and art
history research, from universities as well as national and
international museums; and on the other hand, museum
stakeholders, who provide a welcome outside perspective
on the Louvre’s research policy.
Developing research projects in collaboration with the research institutes of the French Ministry of Culture and of the
French Ministry of Higher Education and Research is one of
our priorities. Always eager to be involved in new technological developments associated with research carried out on
its collections, the Musée du Louvre hosts within its walls the
2014 edition of the International Conference on Synchrotron
Radiation and Neutrons in Art and Archaeology. For the occasion, the museum has partnered with seven laboratories
from the National Centre for Scientific Research (CNRS), the
Ministry of Culture, and the National Museum of Natural
History (MNHN) – IPANEMA at SOLEIL, C2RMF, LAMS, MNHN
Prehistory Department, LAPA, LRMH, CRCC – as well as the
Foundation for Cultural Heritage Sciences.
Jean-Luc MARTINEZ
President - Director of the Musée du Louvre
4
EDITO / ÉDITO
Bienvenue !
Depuis 2005, la conférence internationale sur le Rayonnement synchrotron et neutrons pour l’art et l’archéologie
(SR2A) réunit scientifiques et professionnels des matériaux
anciens du monde entier en leur offrant une occasion
unique de partager leur expertise et leur expérience,
ce pour répondre à un double objectif : dresser un état de
l’art des méthodes avancées d’étude du patrimoine culturel
et de l’archéologie ; encourager les synergies entre physique,
sciences naturelles, sciences humaines et sciences sociales,
en impliquant notamment les équipes des sciences
de conservation.
Après le musée Van Gogh à Amsterdam en 2010 et
le Metropolitan Museum of Art de New-York en 2012, cette
sixième édition se tient cette année au cœur de la ville de
Paris, dans l’environnement exceptionnel du musée du Louvre.
Pendant trois jours, la conférence réunira près de 300 personnes venues des quatre coins du monde : archéologues,
scientifiques en conservation, conservateurs, scientifiques
ayant l’expérience des techniques sur grands instruments
et d’autres techniques d’analyse, étudiants, historiens
de l’art, restaurateurs, gestionnaires de patrimoine culturel,
utilisateurs potentiels des synchrotrons, etc.
Conservation et altération, Processus et chaînes opératoires,
Nouvelles méthodes et processus analytiques, Paléontologie et paléo-environnements. À une semaine des Journées
européennes du Patrimoine, nous avons souhaité inclure
une composante inédite à cet événement en organisant
une session spéciale destinée à faire découvrir au public
du musée du Louvre la richesse des méthodes synchrotron et
neutrons pour l’étude du patrimoine culturel et archéologique.
Autre innovation, des visites d’étude, associant conservateurs
du musée et spécialistes des méthodes synchrotron, sont
organisées au Louvre.
Les méthodes synchrotron et neutron sont en plein
développement pour l’étude des objets patrimoniaux.
Les conférences, tables rondes et séances de posters sont
ainsi programmées autour de quatre sessions thématiques
qui réuniront des conférenciers de notoriété internationale :
L’événement a suscité un très vif intérêt puisque nous avons
reçu plus d’une centaine de résumés provenant de 23 pays
différents situés sur quatre continents (Amérique, Europe,
Asie, Océanie). Les contributions à la conférence seront
publiées dans un numéro spécial de la revue internationale
Journal of Analytical Atomic Spectrometry, en accès libre
après la conférence pour leur assurer une plus large diffusion.
Le Comité local d’organisation du SR2A tient tout particulièrement à remercier les partenaires de cette sixième
édition dont la disponibilité, le soutien et les conseils feront,
je l’espère, de cet événement une réussite. Je pense aux
laboratoires franciliens et au musée du Louvre, organisateurs
de l’événement, ainsi qu’aux structures partenaires qui nous
ont apporté leur soutien, à savoir le CNRS, le ministère de
la Culture et de la Communication, le Muséum national
d’histoire naturelle, la Fondation des Sciences du Patrimoine,
la Région Ile-de-France et le Synchrotron SOLEIL.
Nous vous souhaitons un très instructif et agréable moment !
Loïc BERTRAND
Comité local d’organisation du SR2A
5
EDITO / ÉDITO
Welcome!
Since 2005, the International Conference on Synchrotron
radiation and neutrons in art and archaeology (SR2A) brings
together scientists and specialists of historical materials from
all over the world, offering them an unprecedented opportunity to meet and share their expertise and experience
with two aims: to review progress in advanced methods
for the study of cultural heritage; and to encourage
synergies between Physics, Natural Science, Humanities
and Social sciences, involving teams from Conservation
science in particular.
After the Van Gogh Museum in Amsterdam in 2010 and
the Metropolitan Museum of Art in New-York in 2012,
this sixth meeting is held this year at the heart of Paris,
in the exceptional venue of the Louvre. Over three days,
the conference will gather nearly 300 people from all over
the world: archaeologists, conservation scientists, conservators, researchers with experience in large-scale research
facilities and other analytical techniques, art historians,
curators, cultural heritage managers, students, potential users
of synchrotrons, etc.
Conservation and alteration, Processes and chaînes opératoires, New methods and analytical processes, Paleontology
and palaeo-environments. A week before the European
Heritage Days, we wanted to include a brand new component in the event, a special session to introduce the Louvre’s
visitors to the richness of methods employing synchrotron
and neutron radiation for the investigation of artistic and
archaeological materials and artifacts. Study visits are another innovation, bringing together curators and specialists
in synchrotron methods at the Musée du Louvre.
Synchrotron and neutron methods are developing fast
for the study of historical artefacts. The seminars, roundtable discussions and poster sessions will be scheduled
around four themed sessions involving world-class speakers:
The event has attracted great interest, and we have received
over a hundred abstracts from 23 countries on four continents (America, Europe, Asia and Australia). Contributions to
the Conference will be published in a special issue of Journal
of Analytical Atomic Spectrometry, which will be made freely
available after the Conference to ensure the widest audience.
The SR2A Local Organizing Committee is very grateful to
the partners of this sixth event, whose responsiveness,
support and advice will, I hope, make it a success. I think
in particular of the Ile-de-France laboratories and the Musée du Louvre that organised the event, and the partner
institutions who have given their support: the CNRS,
the ministry of Culture and Communication, the National
Museum of Natural History, the Fondation des Sciences du
Patrimoine, the Ile-de-France region and Synchrotron SOLEIL.
We wish you a very instructive and pleasant moment!
Loïc BERTRAND
SR2A Local Organizing Committee
6
CONTENTS / TABLE DES MATIÈRES
SESSION PLANNING / AGENDA DES SESSIONS
p. 9
DETAILED PLANNING / AGENDA DÉTAILLÉ
p. 10
INVITED SPEAKERS / ORATEURS INVITÉS
p. 14
SIDE EVENTS / ÉVÉNEMENTS SATELLITES
p. 15
ABSTRACTS FOR ORAL PRESENTATIONS / RÉSUMÉS DES PRÉSENTATIONS ORALES
p. 17
ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS
p. 101
PARTNERS / PARTENAIRES
p. 200
COMMITTEES / COMITÉS
p. 201
MUSÉE DU LOUVRE PLAN / PLAN DU MUSÉE DU LOUVRE
p. 202
ITINERARY FROM THE MUSÉE DU LOUVRE TO THE MUSÉE D’ORSAY
ITINÉRAIRE DU MUSÉE DU LOUVRE AU MUSÉE D’ORSAY
p. 204
PROCEEDINGS / ACTES
p. 205
AUTHOR INDEX / INDEX DES AUTEURS
p. 206
7
SESSION PLANNING / AGENDA DES SESSIONS
SESSION PLANNING
AGENDA DES SESSIONS
9 Sept. 2014
18:30 > 20:30
Welcome reception and preliminary registration C2RMF, Palais du Louvre
10 Sept. 2014
9:00 > 10:00
Registration and Official opening
10:00 > 11:50
CONSERVATION AND ALTERATION I
13:40 > 15:00
NEW METHODS AND ANALYTICAL PROCESSES I
15:30 > 16:30
PROCESSES AND CHAÎNES OPÉRATOIRES I
17:00 > 20:00
POSTER SESSION (Salle des 80)
PUBLIC SESSION
11 Sept. 2014
09:30 > 11:00
NEW METHODS AND ANALYTICAL PROCESSES II
11:30 > 14:40
CONSERVATION AND ALTERATION II
14:40 > 16:00
PALAEONTOLOGY AND PALAEOENVIRONMENTS I
16:30 > 17:40
PALAEONTOLOGY AND PALAEOENVIRONMENTS II
20:30 > 22:30
Conference dinner
12 Sept. 2014
09:30 > 10:20
PROCESSES AND CHAÎNES OPÉRATOIRES II
10:20 > 14:40
CONSERVATION AND ALTERATION III
14:40 > 15:40
NEW METHODS AND ANALYTICAL PROCESSES III
15:40 > 16:40
Round table: global methodology
16:40 > 17:00
Conference prizes and closure
17:00 > 19:00
Study visits (Louvre Museum)
9
DETAILED PLANNING
AGENDA DÉTAILLÉ
From Tuesday 09 September 2014 at 18:30 to Friday 12 September 2014 at 19:00 (CET)
9 Sept. 2014
Welcome reception and preliminary registration
18:30 > 20:30
Centre de recherche et de restauration des musées de France
(14, quai François Mitterrand, palais du Louvre, Porte des Lions, 75001 Paris)
10 Sept. 2014 | Musée du Louvre (Auditorium)
08:45
Recommended arrival time at the Richelieu ‘group entrance’
09:00
Museum Opens (Access through the Richelieu ‘group entrance’)
Registration
09:00 > 09:30
Official Opening
09:30 > 10:00
CONSERVATION AND ALTERATION I SESSION
10:00 > 10:30
O-01
Investigation of historical paintings by X-ray techniques
10:30 > 10:50
O-02
Synchrotron studies of the migration of lead soaps in old master
paintings and model systems
Invited Speaker: Matthias Alfeld, Deutsches Elektronen-Synchrotron DESY, Hamburg, Germany
Speaker: Annelies van Loon, Van’t Hoff Institute for Molecular Sciences / Paint Studies,
University of Amsterdam, Amsterdam, The Netherlands
10:50 > 11:10
O-03
Neutron radiography for the quantitative analysis of water uptake
and swelling of painting canvases and preparation layers
Speaker: Roel Hendrickx, Swiss Institute for Art Research, Kunsttechnologie Department,
Zürich, Switzerland
11:10 > 11:30
O-04
Non-invasive in situ spectroscopic techniques and synchrotron
radiation-based X-ray methods to examine the state of conservation
of chrome yellow
Speaker: Letizia Monico, CNR-ISTM/Centre Smaart and Antwerp University, Chemistry
Department, Perugia, Italy
11:30 > 11:50
O-05
SR-XRD analysis of bole layers in popular and erudite
Portuguese gilded baroque retables
Speaker: Carolina Barata, Universidade de Aveiro, Geosciences Department, Geobiotec Research Unit,
Aveiro, Portugal
Lunch (On Your Own)
12:00 > 13:40
NEW METHODS AND ANALYTICAL PROCESSES I SESSION
13:40 > 14:00
O-06
Detection of platinum in gold with D²XRF
14:00 > 14:20
O-07
Spectroscopic pulsed neutron imaging and its application to metal
cultural heritage
Speaker: Martin Radtke, BAM Federal Institute For Materials Research and Testing, Analytical Chemistry,
Berlin, Germany
Speaker: Yoshinori Shiota, Nagoya University, Graduate School of Engineering, Nagoya, Japan
14:20 > 14:40
O-08
A scanning nano-XRF study of a 19th century daguerreotype photograph
14:40 > 15:00
O-09
In-situ time-lapse X-ray diffraction of silver corrosion
15:00 > 15:30
10
Speaker: Edward Vicenzi, Smithsonian Institution, Museum Conservation Institute, Suitland, USA
Speaker: Rosie Grayburn, Universiteit Gent, Department of Analytical Chemistry, Gent, Belgium
Break
SUITE
PROCESSES AND CHAÎNES OPÉRATOIRES I SESSION
15:30 > 15:50
O-10
Non-invasive characterization of two Japanese swords
from the Wallace collection
Speaker: Elisa Barzagli, ISC-CNR and University of Firenze, Sesto Fiorentino (Firenze), Italy
15:50 > 16:10
O-11
Reducing manufacturing conditions of medieval blue glass revealed
by µ-XANES
Speaker: Myrtille Hunault, Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie,
Université Pierre et Marie Curie, Paris, France
16:10 > 16:30
O-12
Pablo Picasso’s The Blue Room (1901): an intensive technical investigation
of a blue period painting
Speaker: Jennifer Mass, Winterthur Museum, Scientific Research and Analysis Laboratory, Winterthur, USA
16:30 > 17:00
Break
NB: Last admission to Musée du Louvre at 19:00
17:00 > 20:00
POSTER SESSION (salle des 80)
in parallel to PUBLIC SESSION
O-13
X-ray fluorescence imaging: from Archimedes to Archaeopteryx
and beyond
Invited Speaker: Uwe Bergmann, SLAC National Accelerator Laboratory, California, USA
O-14
What have we learned from Neutron Transmission Radiography
and Time-of-Flight Neutron Diffraction on Renaissance bronzes?
Invited Speaker: Robert van Langh, Rijksmuseum Amsterdam, Amsterdam, The Netherlands
O-15
How to use the hierarchical heterogeneous structure of ancient ceramics
to trace their firing protocol
Invited Speaker: Philippe Sciau, CNRS, CEMES, Toulouse, France
20:00
Adjourn
21:30
Museum Closes (Extended Hours for Wednesday)
08:45
09:00
Museum Opens (Access through the Richelieu ‘group entrance’)
09:30 > 10:00
O-16
Role of S K-edge X-ray absorption spectroscopy in conservation efforts
of the Mary Rose
Invited Speaker: Ritimukta Sarangi, SLAC National Accelerator Laboratory, California, USA
NEW METHODS AND ANALYTICAL PROCESSES II SESSION
10:00 > 10:20
O-17
Combined structural analysis of ancient ill-ordered carbon-based
cosmetics and inks
Speaker: Pauline Martinetto, CNRS–UJF, Institut Néel Département MCMF, Grenoble, France
10:20 > 10:40
O-18
X-ray powder diffraction mapping and tomography for analysis
of (degraded) paint layer systems
Speaker: Frederik Vanmeert, University of Antwerp, Chemistry - Axes Research Group, Antwerp, Belgium
10:40 > 11:00
O-19
Virtual X-ray reading (VXR) of ancient administrative handwritten documents
Speaker: Fauzia Albertin, École Polytechnique Fédérale de Lausanne, Lausanne, Switzerland
Break
11:00 > 11:30
CONSERVATION AND ALTERATION II SESSION
11:30 > 11:50
O-20
Degradation mechanisms of reinforcement iron rebars in monuments:
influence of porosity on the formation of corrosion products studied
by X-ray tomography
Speaker: Mathieu Jacot-Guillarmod, Bern University of Applied Sciences, Bern, Switzerland
11
11:50 > 12:10
O-21
SUITE
De Colorando Auro: revealing different surface treatments of the silver
gilded statuettes of a 13th century shrine using XANES
Speaker: Amandine Crabbé, Vrije Universiteit Brussel, Brussels, Belgium
12:10 > 12:30
O-22
Degradation mechanisms of reinforced concrete monuments study
of initial corrosion processes in chlorinated environments
Speaker: Sophie Grousset, CNRS-CEA, NIMBE-SIS2M/LAPA, Gif-sur-Yvette, France
12:30 > 14:10
Lunch (On Your Own)
13:00 > 14:00
Book signing session in the Louvre Bookshop
14:10 > 14:40
O-23
Synchrotron radiation for ancient and historical materials
Invited Speaker: Marco Stampanoni, Paul Scherrer Institut - ETH Zürich, Swiss Light Source,
Institute for Biomedical Engineering, Zürich, Switzerland
PALAEONTOLOGY AND PALAEO-ENVIRONMENTS I SESSION
14:40 > 15:00
O-24
Conservation of lignitized pyritic woods in the light of synchrotron
measurements
Speaker: Giliane Odin, Muséum National d’Histoire Naturelle, Paris, France
15:00 > 15:20
O-25
When photons meet fossils: the chemistry of ancient life
15:20 > 15:40
O-26
Fossilization and diagenesis in the Djebel Oum Tkout Lagerstätte (upper
Cretaceous, Morocco): insights from rare earth elements microscale spectroscopy
Speaker: Nicholas Edwards, University of Manchester, School of Earth, Atmospheric
and Environmental Sciences, Manchester, UK
Speaker: Pierre Gueriau, Muséum National d’Histoire Naturelle, Paris, France
15:40 > 16:00
O-27
Remnants of life: integrated geochemical methods for the analysis
of exceptionally preserved specimens
Speaker: Roy Wogelius, University of Manchester, School of Earth, Atmospheric and Environmental
Sciences, Manchester, UK
Break
16:00 > 16:30
PALAEONTOLOGY AND PALAEO-ENVIRONMENTS II SESSION
16:30 > 16:50
O-28
Confocal X-ray fluorescence and the biogenic uptake of strontium
in colonial Antigua
Speaker: Treena Swanston, University of Saskatchewan, Anatomy and Cell Biology, Saskatoon, Canada
16:50 > 17:10
O-29
Pigment preservation in Egyptian mummified tissues
17:10 > 17:40
O-30
Rock art pigments: alteration and weathering processes in caves
and open sites
Speaker: Bart van Dongen, University of Manchester, School of Earth, Atmospheric
and Environmental Sciences, Manchester, UK
Invited Speaker: Emilie Chalmin, Université de Savoie, CISM-EDYTEM, Le Bourget-du-Lac, France
17:40
Adjourn
18:00
Museum Closes
Conference dinner at the Musée d’Orsay
(entrance includes access to museum before the dinner)
20:30
08:45
09:00
Museum Opens
09:30 > 10:00
O-31
Materials, techniques and conservation of 15th to 19th centuries
stain glass “grisailles”
Invited Speaker: Trinitat Pradell, Universitat Politecnica de Catalunya, Fisica, Castelldefels, Spain
12
SUITE
PROCESSES AND CHAÎNES OPÉRATOIRES II SESSION
10:00 > 10:20
O-32
Deciphering ancient ceramic firing conditions through replication
Speaker: Ilaria Cianchetta, Getty Conservation Institute, Los Angeles, USA
CONSERVATION AND ALTERATION III SESSION
10:20 > 10:40
O-33
Difference between sub-microscopic and macroscopic preservation
states of marine archaeological elephant tusks revealed by micro-SAXS/
WAXS analysis
Speaker: Marie Albéric, Laboratoire d’Archéologie Moléculaire et Structurale, Ivry-sur-Seine, France
10:40 > 11:00
O-34
The use of synchrotron radiation for the analysis of the distribution
of additives in ABS design objects and model samples
Speaker: Daniela Saviello, Politecnico di Milano, Dipartimento di Chimica Materiali e Ingegneria
Chimica, Milano, Italy
Break
11:00 > 11:30
11:30 > 11:50
O-35
X-ray spectroscopic characterization of sulfur compounds in marine
archaeological wood
Speaker: Magnus Sandström, Stockholm University, Department of Materials and Environmental
Chemistry, Stockholm, Sweden
11:50 > 12:10
O-36
Synchrotron X-ray scattering of ethylene vinyl acetate copolymer based
art conservation adhesives: elucidation of morphological differences
Speaker: Chris McGlinchey, The Museum of Modern Art, New York, USA
12:10 > 12:30
O-37
Optimization of an ammonium oxalate treatment for the protection
of monumental limestone and marble surfaces
Speaker: Domagoj Mudronja, Croatian Conservation Institute, Natural Science Laboratory, Zagreb, Croatia
Lunch (On Your Own)
12:00 > 13:40
14:10 > 14:40
O-38
Learning from the past: the formation process of rare ε-Fe2O3
in the ancient black-glazed Jian (Tenmoku) wares
Invited Speaker: Catherine Dejoie, ETH Zurich, Laboratory of Crystallography, Zürich, Switzerland
NEW METHODS AND ANALYTICAL PROCESSES III SESSION
14:40 > 15:00
O-39
Synchrotron laminography for micrometer-scale three-dimensional
region-of-interest imaging of flat artwork
Speaker: Lukas Helfen, Karlsruhe Institute of Technology, Institute for Photon Science and Synchrotron
Radiation, Karlsruhe, Germany
15:00 > 15:20
O-40
Combined synchrotron-based micro-spectroscopic analyses of painting
thin-sections
Speaker: Émeline Pouyet, ESRF, Grenoble, France
15:20 > 15:40
O-41
New developments and opportunities in synchrotron ultraviolet
luminescence microscopy
Speaker: Matthieu Réfrégiers, Synchrotron SOLEIL, Gif-sur-Yvette, France
ROUND TABLE, CONFERENCE CLOSURE AND STUDY VISITS
15:40 > 16:40
Round Table: global methodology
16:40 > 17:00
Conference prizes and Closure
17:00 > 19:00
Study visits at the Musée du Louvre
19:00
Adjourn
21:30
Museum Closes (Extended Hours for Friday)
13
INVITED SPEAKERS
ORATEURS INVITÉS
Matthias Alfeld
DESY,
Hamburg, Germany
Uwe Bergmann
LCLS,
Stanford, USA
Emilie Chalmin
EDYTEM,
Le Bourget du Lac, France
Trinitat Pradell
Universitat Politècnica de Catalunya,
Castelldefels, Spain
Catherine Dejoie
ETH Zurich,
Switzerland
Ritimukta Sarangi
SLAC,
Stanford, USA
Philippe Sciau
CEMES,
Toulouse, France
Marco Stampanoni
Swiss Light Source,
Villigen, Switzerland
Robert van Langh
Rijksmuseum Amsterdam,
The Netherlands
14
SIDE EVENTS / ÉVÉNEMENTS SATELLITES
SIDE EVENTS
ÉVÉNEMENTS SATELLITES
In addition to oral presentations and the poster session,
the event includes several social events:
A Welcome event to provide the participants with
information about the Conference and offer them the
opportunity to meet over a glass of wine;
A Dinner prepared by chef Yann Landureau,
on Thursday, September 11, in the restaurant
of the prestigious Musée d’Orsay, classified as a
historical monument. It will be preceded by a visit
to the Museum;
A Public session to introduce the Louvre’s visitors to
the richness of methods employing synchrotron and
neutron radiation for the investigation of artistic and
archaeological materials and artifacts;
Study visits organised with the Musée du Louvre
will associate a curator and an analytical scientist
with a group of participants to the conference who
will discuss about research on an artefact from
the Louvre collection;
A Stand with books for young and old in connection
with the themes on which the Conference focuses in
the Louvre bookshop.
En parallèle des présentations orales et de la session
poster, la sixième édition du SR2A comprend plusieurs
événements :
Un accueil de bienvenue pour délivrer aux
participants des informations sur la conférence
et leur permettre de se rencontrer autour d’un verre ;
Un dîner, élaboré par le chef Yann Landureau,
le jeudi 11 septembre dans le restaurant du prestigieux musée d’Orsay, classé Monument historique.
Il sera précédé d’une visite du musée ;
Une session publique pour faire découvrir au public
du musée du Louvre la richesse des méthodes
synchrotron et neutrons pour l’étude du patrimoine
culturel et archéologique ;
Des visites d’étude organisées au musée du Louvre
où un conservateur et un scientifique discuteront de
l’avancée de la recherche sur un objet de la collection
du Louvre avec un groupe de participants ;
Un stand présentant des ouvrages pour petits
et grands en lien avec les thématiques abordées lors
de la conférence est présent au sein de la librairie
du musée du Louvre.
15
ABSTRACTS
FOR ORAL
PRESENTATIONS
RÉSUMÉS
DES PRÉSENTATIONS
ORALES
17
ABSTRACTS FOR ORAL PRESENTATIONS
RÉSUMÉS DES PRÉSENTATIONS ORALES
NOTES
18
O-01
10 sept. 2014
10:00 > 10:30
Matthias Alfeld1
1
Deutsches Elektronen-Synchrotron DESY, 22607, Hamburg, Germany
Investigation
of historical paintings
by X-ray techniques
The use of synchrotron radiation (SR) based techniques
for the analysis of historical paintings and other cultural
heritage objects has undergone a steep increase in the
last 10-15 years [1]. Paintings are investigated on different length scales: the better part of a painting’s surface
can be investigated in a non-destructive fashion by scanning macro-XRF (MA-XRF) with a lateral resolution of a few
hundred micrometers, while small samples taken from a
painting are often studied at a sub-micrometer length scale.
The macroscopic investigation of paintings by MA-XRF allows
the study of surface and sub-surface paint layers, which may
visualize changes of concept (pentimenti) and discarded
and overpainted works [2]. The study of paint samples aims
in general at the identification of pigments and their degradation process by techniques such as scanning micro-XRF,
XRD and XANES [3, 4].
While no technique of same effort was found to provide results comparable to that of SR based ones for small samples,
mobile, X-ray tube based MA-XRF scanners provide results
only slightly inferior to SR instruments. Mature in-house built
scanners [5], as well as commercial instruments [6], allow for
the investigation of large areas (several thousands of square
centimeters) in a few hours. They also permit the investiga-
tion of historical paintings too large to be investigated at a
SR source. Given the comparably low effort of these in-situ
investigations with mobile scanners, MA-XRF can also be
used in studies of more routine naature, e.g. those aimed at
supporting the planning of conservation treatments.
In this contribution the development and perspective
of scanning macro-XRF for the investigation of historical
paintings will be discussed. Further, it will be shown how
the capabilities of beamline P06 at DESY can contribute to
the investigation of samples taken from historical paintings.
With its state-of-the-art KB mirror system and the highly sensitive Maia detector system [7] the beamline allows for a fast
acquisition of elemental distribution images by micro-XRF
with dwell times of a few milliseconds per pixel and a lateral
resolution in the sub-micrometer range. It also allows for
a fast acquisition of large stacks of elemental distribution
images with variable primary energy for XANES imaging
as well as for XRF tomography. Microscopic X-ray diffraction
imaging and tomography is also feasible.
Finally, the value of advanced data evaluation procedures,
such as non-negative matrix approximation, for the interpretation of data sets obtained from historical paintings will
be discussed [8].
Bibliography
[1] L. Bertrand, et al., Appl. Phys. A: Mater. Sci. Process. 106 (2012) 377-396.
[2] M. Alfeld, J.A.C. Broekaert, Spectrochim. Acta, Part B 88 (2013) 211-230.
[3] L. Monico, et al., Anal. Chem. 83 (2011) 1214-1223.
[4] F. Da Pieve, et al., Phys. Rev. Lett. 111 (2013) 208302.
[5] M. Alfeld, et al., J. Anal. At. Spectrom. 26 (2011) 899-909.
[6] M. Alfeld, et al., J. Anal. At. Spectrom. 28 (2013) 760-767.
[7] R. Kirkham, et al., AIP Conf. Proc. 1234 (2010) 240-243.
[8] M. Alfeld, et al., IOP Conf. Ser. (submitted).
19
NOTES
20
O-02
10 sept. 2014
10:30 > 10:50
Synchrotron studies
of the migration
of lead soaps in old
master paintings
and model systems
If and how lead soaps migrate in aged oil paintings are two
important and challenging questions. The formation of leadrich surface deposits and lead soap aggregates that affect
many Old Master paintings indicates that lead soaps (reaction
products of lead-containing pigments and fatty acids from
the oil medium) are mobile and that they may travel through
the paint. Previous SEM-EDX studies have shown lead-rich
deposition bands and finely dispersed lead-rich particles in
the paint medium and at layer interfaces that are not confined
to pigment particles [1, 2]. This paper discusses the application
of synchrotron-based analyses, with FTIR and X-ray techniques,
to obtain structural information about the various lead compounds present and their spatial distribution in the paint layers
at the micro-scale.
We selected a coherent corpus of samples from a traditional
oil painting by Rembrandt van Rijn, Homer, 1663 (Mauritshuis) and an original painted ceiling dating from c.1650
(Johan de Witthuis, The Hague). The results of analyses were
Bibliography
[1] Keune, K., van Loon, A., Boon, J., 2011, ‘SEM backscattered-electron images
of paint cross-sections as information source for the presence of the lead
white pigment and lead-related degradation and migration phenomena
in oil paintings’, Microscopy and Microanalysis Vol 17, Issue 5: 696-701.
[2] Van Loon, A., Noble, P., Boon, J., 2012, ‘The formation of complex crusts
in oil paints containing lead white and smalt: dissolution, depletion,
diffusion, deposition’, in Historical Technology, Materials and Conservation:
SEM and Microanalysis, ed. N. Meeks, C. Cartwright, A. Meek, A. Mongiatti,
London, The British Museum/Archetype: 207-209.
[3] Osmond, G., Boon, J.J., Puskar, L., Drennan, J., 2012, ‘Metal stearate
distributions in modern artists’ oil paints: surface and cross-sectional
investigation of reference paint films using conventional and synchrotron
infrared microspectroscopy’, Applied Spectroscopy Vol 66, Number 10:
1136-1144.
Annelies van Loon1 - Katrien Keune1 - Mathieu Thoury2
Joen Hermans1 - Christophe Sandt3 - Solenn Réguer4
Petria Noble5 - Klaas Jan van den Berg6 - Alysia Sawicka7
Aviva Burnstock7 - Loïc Bertrand2
University of Amsterdam, Van ‘t Hoff Institute for Molecular Sciences / PAinT,
1098 XH, Amsterdam, Netherlands
2
Ipanema, 91192, Gif sur Yvette, France
3
Synchrotron SOLEIL, SMIS beamline, 91192, Gif sur Yvette, France
4
Synchrotron SOLEIL, Diffabs beamline, 91192, Gif sur Yvette, France
5
Royal Picture Gallery Mauritshuis, Paintings Conservation Studio, 2501 CM,
The Hague, Netherlands
6
Cultural Heritage Agency of the Netherlands, Research and Knowledge
Centre, 1071 ZC, Amsterdam, Netherlands
7
The Courtauld Institute of Art, Conservation and Technology, WC2R ORN,
London, United Kingdom
1
compared with data from 16 replica paint films constructed to
simulate the lead soap migration and aggregation processes.
Synchrotron experiments were carried out at Synchrotron
SOLEIL near Paris, at the SMIS and Diffabs beamlines, which
allowed performing FTIR, XRF, XRD and XANES (Pb L3-edge)
respectively. Methodology was optimized to prepare polished cross-sections, using micromesh polishing cloth (dry),
and 2 to 6 µm thick thin-sections, using ultra-microtome,
allowing measurements in reflection and transmission modes.
Areas of interest were identified through pre-characterization
on a bench-top FTIR imaging microscope.
In Rembrandt’s Homer, the dark passages of paint are disfigured by the presence of a whitish insoluble surface crust rich
in lead. A similar surface crust was observed on the surface
of dark paints of the painted ceiling in the Johan de Witthuis.
This unique case-study is of significance as it survives unvarnished and the lead salts have developed on the surface
for centuries. Samples from both cases show comparable
layer build-ups, composed of one or more medium-rich,
overlying dark paint layers on top of a lead white-containing
preparatory layer, that acts as the source of the lead to form
lead soaps. Lead soaps were measured with both FTIR and
XANES throughout the entire multi-layer paint build-up,
which supports our hypothesis of their mobility. The high
signal-to-noise ratios of the FTIR spectra allowed us to observe
pronounced differences in the carboxylate profiles of the
paint layers and reference samples of pure lead soap crystals.
This points to different chemical environments of the lead
carboxylate group, and is comparable to observations on zinc
soap distributions in modern oil paint layers [3]. These results
will be further discussed in the paper, as they provide important clues about the mechanisms regarding the formation and
migration of lead soaps in aged oil paintings.
21
NOTES
22
O-03
10 sept. 2014
10:50 > 11:10
Roel Hendrickx1 - Ester S.B. Ferreira1 - Jaap J. Boon1
Anders Kaestner2
1
SIK-ISEA, Kunsttechnologie, CH-8032, Zürich, Switzerland
PSI, ICON beamline, CH-5232, Villingen, Switzerland
Neutron radiography
for the quantitative
analysis of water
uptake and swelling
of painting canvases
and preparation layers
2
This contribution concentrates on the moisture uptake of
painting canvases and preparation layers. Many chemical
reactions and material transport phenomena in paint layers
lead to changes in surface appearance and to deformations
or mechanical stresses in paintings. These chemical reactions
and material mobility are linked to or driven by the presence of
moisture. It is our goal to elucidate and quantify the water mobility and storage in the paint multiplex using historically accurate replicas of known paintings and original painting samples.
The focus is on materials used in late 19th century and early 20th
century painting, which have been characterised in previous
work using synchrotron X-ray tomography and SEM [1,2],
in the context of the study of the early oeuvre of the Swiss
painter Cuno Amiet (1868-1963). It appears that the ground
layers, which were usually handmade in the cases under
study and are mostly composed of animal glue and chalk,
have an important number of pores in the capillary range [1].
The glue itself is known to have a pronounced hygroscopic
behaviour [3].
Neutron radiography is very well suited to follow up the water
uptake of these complex layered systems because of the high
attenuation of water molecules, which leads to a relatively high
contrast in the images of humid materials when compared
to the surrounding materials. In collaboration with SIK-ISEA,
AMOLF, has developed a moisture reaction chamber which
is relatively transparent for neutrons and which can hold a
1 cm2 sample of primed canvas and in which a high relative
humidity can be generated during a dynamic water uptake experiment [4]. Experiments are executed in the ICON beamline
at PSI, Switzerland. The resulting images are 2D arrays of 16 bit
grey values, 2048×2048 pixels with a resolution of about 14
micron/pixel. Comparison of the images in humid condition
(taken every 100 seconds for a period up to 10 hours) to those
of the dry state, allows the assessment of the evolution of
the quantity of moisture. An important challenge is to take
into account the movement of the sample and its changing
shape. A methodology for a quantitative analysis is proposed
using Matlab for image processing. This involves a specific
segmentation of the image with a morphological reconstruction, which allows to use relative distance to the edges in the
analysis, rather than fixed points.
The first results confirm the hypothesis that water transport is
governed by diffusion and increases linearly with the square
root of time. The experimental method itself is shown to be
feasible and versatile. A new set of experimental data is currently being investigated. Further analyses currently under
study include the variation of several parameters such as the
coarseness of the weave, the preparation method of the sizing
and the presence and composition of a ground layer.
Bibliography
[1] Gervais, C., Boon, J.J., Marone, F., and Ferreira, E.S.B. (2013). Characterization
of porosity in a 19th century painting ground by synchrotron radiation
X-ray tomography. Appl. Phys. - Mater. Sci. Process. 111, 31–38.
[2] SIK-ISEA (in preparation for publication). Technologische Forschungen
zur Malerei von Cuno Amiet (1883–1914), Zürich: Scheidegger & Spiess.
[3] Mecklenburg, M.F. (2007). Determining the Acceptable Ranges of Relative
Humidity And Temperature in Museums and Galleries. Part 1. Structural
response to Relative Humidity, Unpublished report, Maryland:
Smithsonian Museum Conservation Institute.
[4] Boon, J.J., Eijkel, G., Cerjak, I., Ferreira, E.S.B., Gervais, C., and Kaestner,
A. (2012). Monitoring Water Uptake and Proton Exchange in Painted
Canvas Model Systems by Neutron Radiography in a Perfusion Mini
Reaction Chamber. Poster presentation at the Conference on Synchrotron
Radiation in Art and Archaeology SR2A 2012, New York.
23
NOTES
24
O-04
10 sept. 2014
11:10 > 11:30
Non-invasive in situ
spectroscopic techniques
and synchrotron
radiation-based X-ray
methods to examine
the state of conservation
of chrome yellow
pigments in Van Gogh’s
Sunflowers
Ongoing technical examination aims to appraise the current
condition of Vincent van Gogh’s Vase with Sunflowers (Arles,
January 1890), now in the collection of the Van Gogh Museum
in Amsterdam, with a view to possible conservation and restoration treatment.
This paper focuses on one aspect of the research involving color
change due to the alteration of certain types of the chrome
yellow paints used by the artist.
A methodological approach based on the combination of
non-invasive spectroscopic methods and advanced synchrotron
radiation (SR)-based X-ray investigations now provides direct
evidence for the fact that the darkening of some chrome yellow
paint areas in Vase with Sunflowers may in part be ascribed to
a reduction process of the original chromate.
Bibliography
[1] Monico L, Janssens K, Miliani C, Brunetti BG, Vagnini M, Vanmeert F,
Falkenberg G, Abakumov A, Lu Y, Tian H, Verbeeck J, Radepont M, Cotte M,
Hendriks E, Geldof M, van der Loeff L, Salvant J, Menu M. Anal. Chem. 2013,
85, 851-859.
[2] Monico L, Van der Snickt G, Janssens K, De Nolf W, Miliani C, Verbeeck J, Tian
H, Tan H, Dik J, Radepont M, Cotte M. Anal. Chem. 2011, 83,1214-1223.
[3] Monico L, Janssens K, Miliani C, Van der Snickt G, Brunetti BG, Cestelli Guidi M,
Radepont M, Cotte M. Anal. Chem. 2013, 85, 860-867.
[4] Geldof M, Megens L, Salvant J. Van Gogh’s palette in Arles, Saint-Rémy
and Auvers-sur-Oise, in Vellekoop M, Geldof M, Hendriks E, Jansen L,
de Tagle A (eds). Van Gogh’s Studio Practice, Amsterdam, 238-255.
[5] Monico L, Van der Snickt G, Janssens K, De Nolf W, Miliani C, Dik J, Radepont
M, Hendriks E, Geldof M, Cotte M. Anal. Chem. 2011, 83, 1224-1231.
[6] Tan H, Tian H, Verbeeck J, Monico L, Janssens K, Van Tendeloo G. Angew.
Chem. Int. Edit. 2013, 52, 11360–11363.
Letizia Monico1 - Koen Janssens2 - Costanza Miliani1
Ella Hendriks3 - Frederik Vanmeert2 - Geert van der Snickt2
Muriel Geldof4 - Luc Megens4 - Marine Cotte5
Brunetto Giovanni Brunetti1
CNR-ISTM/Centre SMAArt, Chemistry Department, Perugia University - Via Elce di
Sotto 8, I-06123, Perugia, Italy
2
Antwerp University, Chemistry Department - Groenenborgerlaan 171, B-2020,
Antwerpen, Belgium
3
Van Gogh Museum, Conservation Department - Paulus Potterstraat 7, 1070 AJ, Amsterdam,
The Netherlands
4
Heritage Agency of the Netherlands (RCE), Hobbemastraat 22, 1070 AJ, Amsterdam,
The Netherlands
5
ESRF, X-ray and FTIR Microspectroscopy Beamline ID21 - Avenue des Martyrs 71, F-38000,
Grenoble, France
1
In keeping with our previous studies [1], preliminary non-invasive
in situ Raman, reflection mid-FTIR investigations and MA-XRF
scanning analysis of this painting revealed that Van Gogh made
effective use of different ready-manufactured varieties of the
chrome yellow pigment, including the more light-stable PbCrO4
as well as the S-rich PbCr1-xSxO4 (x~0.5), variety that is known for
its high tendency to undergo photo-reduction.[2,3]
Depending on the shade investigated, these different forms of
chrome yellow were found present alone or in mixtures with
each other, or with other pigments, such as zinc white, vermilion,
emerald green and minium. In some orange tones the “ chrome
orange ” pigment was also identified. These mixtures were frequently applied by Van Gogh in his later works.[4]
Similar results were also obtained by laboratory FTIR, Raman
and SEM-EDX investigations as well as SR µ-XRD analysis
of related paint samples.
Cr K-edge µ-XANES and µ-XRF analysis of a selection of micro-samples taken from the most representative chrome
yellow-paint areas of the painting provided a detailed characterization of the distribution of the Cr species within the paint layers.
In those samples containing the pigment in the PbCr1-xSxO4 form,
we found an amount of 40-100 % Cr(III) species in the non-original varnish layer and/or at the paint surface in close contact with
it. The concentration of reduced Cr decreases with depth in the
bright yellow paint down to values of about 15 %.
Based on these results we consider it reasonable to pose that the
darker Cr(III)-based compounds originated through reduction of
the original chromate pigment.
This agrees with the alteration mechanism previously observed in darkened chrome yellow samples taken from other
paintings by Van Gogh, such as Bank of the Seine (Van Gogh
Museum) and Falling leaves (Les Alyscamps) (Kröller-Müller
Museum, Otterlo) [5,6].
This paper will present detailed information about the chemical composition and conservation state of the chrome
yellow paint areas in the Amsterdam version of Vase with
Sunflowers, discussing results gained through a combined
used of non-invasive and laboratory analytical techniques
as well as SR-based X-ray methods.
25
NOTES
26
O-05
10 sept. 2014
11:30 > 11:50
Carolina Barata1 - Carolina Barata2 - Fernando Rocha1
Antonio João Cruz3 - Antonio João Cruz4
Slavka Andrejkovičova1 - Solenn Réguer5
SR-XRD analysis
of bole layers
in popular and erudite
Portuguese gilded
Baroque retables
1
Very little is known about the materials and techniques
used in Portuguese gilded retables from the Baroque.
The studies based on a scientific approach are very scarce [1]
and focused particularly on works with erudite features and
on the characterization of the superficial gold leaf.
Although the thin gold leaf is what stands out on gilded
retables, its appearance is conditioned by the layer which
lies immediately beneath it, which is usually described as
the bole layer, essentially composed of clay minerals agglutinated in a proteinaceous glue. The bole contribution to
the final effect derives mainly from its colour and its texture,
parameters that depend on its mineralogical composition.
The bole has usually red or yellow tones and traditionally
is designated as Armenian bole, in accordance with the
origin where it is supposed to be obtained the material
of best quality (Armenia). However it was frequently adulterated due to its high cost [2]. Furthermore, it is known
that the bole was also extracted in other regions, namely
in Portugal where good quality boles were obtained [3].
The high consumption of boles in the Baroque period was
mainly due to the fact that they were healing clays administered mainly orally as antacids, gastrointestinal protectors
and antidiarrhoeaics [4].
In order to clarify the origins of the boles used in Portuguese retables and to understand the differences between
materials used in works with different artistic quality,
microsamples collected from two different groups of erudite and popular gilded retables, respectively belonging to
the city of Oporto and its rural surroundings, were selected
for elemental and mineralogical characterization. These
samples show a bole layer with a thickness of 30 µm in
average, but its minute size do not allow the use of regular
micro-XRD equipment for phase identification. For this
reason it was necessary to use SR-XRD, performed with a
six circles diffractometer at the DIFFABS beam line at SOLEIL
Synchrotron, on 34 samples previously analysed through
SEM-EDS [5]. The analysis was performed in reflection mode
since the samples are very friable and do not allow the preparation of thin layers for transmission mode. Considering
that it is intended to clarify the origin of the materials and,
more specifically, if the boles have Portuguese origin or
not, four Portuguese references with known composition
and provenance were also analysed.
The results, which are presented in the communication, suggest that boles of the erudite and the popular retables have
similar composition, both qualitative and quantitative. Most
boles are mainly composed of kaolinite (usually the predominant clay mineral), illite and smectite and feldspars, quartz
and gypsum as well. This composition is consistent with
the composition of the common red Portuguese clays [6]
and is also similar to the composition of most geophagic materials [7].
Bibliography
[1] Cardoso, I.P.; Infocus. 2006. 41 (4), 64-86.
[2] Cruz, A.J.; Artis. 2009, 7-8, 385-405.
[3] Biringuccio, V.; The Pirotechnia, Dover Publications: New York, 1990, 117;
Costa, E. M.; A Natural History of Fossils, London, 1757, 20; Hill, J.; A history
of the materia medica, editora: London, 1751, 188-189.
[4] Gomes, C.; Silva, J.; Minerals and Human Health: benefits and risks.
C. Gomes e J. Silva: Aveiro, 2006, XI-XII.
[5] Barata, C.; Cruz, A. J.; Rocha, F.; I Encontro Luso Brasileiro de Conservação
e Restauro, UCP/CITAR: Porto, 2012, 40-50.
[6] Gomes, C.; Argilas: aplicações na indústria. C. Gomes: Aveiro, 2002, 251-255.
[7] Wilson, M.J.; Journal of Chemical Ecology. 2003. 29 (7), 1525-1547;
Carretero, M.I.; Pozo, M.; Applied Clay Science. 2010. 47, 171-181.
Universidade de Aveiro, Geosciences Department, Geobiotec Research
Unit, 3810-193, Aveiro, Portugal
2
Universidade Católica Potuguesa, Conservation Department, 4169-005,
Porto, Portugal
3
Instituto Politécnico de Tomar, Conservation Department, 2300-313,
Tomar, Portugal
4
Hercules, Research Unit, 7000-809, Évora, Portugal
5
Synchrotron SOLEIL, Diffabs, 91190, Saint-Aubin, France
27
NOTES
28
O-06
10 sept. 2014
13:40 > 14:00
Martin Radtke1 - Günter Buzanich1 - Uwe Reinholz1
Heinrich Riesemeier1 - Oliver Scharf2 - Maria Guerra3
BAM Federal Institute For Materials Research And Testing, 1.3 Analytical
Chemistry, 12489, Berlin, Germany
2
IfG Institute For Scientific Instruments GmbH, 12489, Berlin, Germany
3
ArchAm - UMR 8096 CNRS - Univ. Paris 1 Pantheon-Sorbonne, 92023, Nanterre
Cedex, France
1
Detection of platinum
in gold with D²XRF
The only realistic chance for non-destructive gold provenance is the determination of the trace element pattern.
Among the most characteristic elements of gold are Sn, Pd
and Pt kept in the metal along the metallurgical process [1].
The non destructive determination of Pt with energy dispersive X-ray fluorescence is especially challenging because
the weak fluorescence lines of the Pt traces are overlapping
with the strong Au fluorescence or, depending on the excitation energy, the Au Raman scattering [2]. To resolve peak
overlaps the use of a wavelength dispersive system (WDX)
is mandatory.
While the much better energy resolution of a WDX is a clear
advantage, there are as well drawbacks. Compared to an
energy dispersive system the measurement time is higher,
because each element must be measured separately and
the efficiency is restricted due to the used slits which are
defining the geometry in traditional WDX systems.
These disadvantages can be overcome, by using several
detection channels in parallel and more sophisticated
geometries like the Rowland circle. Here we describe a
new approach, that is based on a flat crystal geometry for
wavelength dispersion and an additionally energy dispersive
system for detection, the so-called Double Dispersive X-Ray
Fluorescence (D2XRF).
While even with a simple SDD detector the detection limit
can be lowered significantly, the full advantage of this
set-up can be achieved by using an array detector like the
Color X-ray Camera (CXC) [3]. In this case no collimating elements are necessary and a high efficient detection scheme
is realized. Depending on the set-up, a whole energy region of around 1000 eV can be measured simultaneously,
which is an additional benefit. We carried out measurements
on various gold standards with known Pt concentrations.
We could demonstrate the highly reliable conversion
between measured count rates and Pt concentrations and
lowered with this setup the detection limit for platinum
in gold to less than 1 ppm in 1000 s, which is the best value
reached for non destructive analysis.
Bibliography
[1] Provenance Determination of Archaeological Metal Objects Ernst Pernicka
01/2014; ISBN: 978-1-4614-9017-3 In book: Archaeometallurgy in Global
Perspective. Methods and Syntheses, Chapter: Provenance Determination
of Archaeological Metal Objects, Publisher: Springer, Editors: B.W. Roberts,
C. Thornton, 239-268
[2] M. Radtke, I. Reiche, U. Reinholz, H. Riesemeier, M. F. Guerra, Beyond the
Great Wall: gold of the silk roads and the first empire of the steppes.
Analytical Chemistry, 85,2013, 1650-1656
[3] O. Scharf, S. Ihle, I. Ordavo, V. Arkadiev, A. Bjeoumikhov, S. Bjeoumikhova,
G. Buzanich, R. Gubzhokov, A. Gunther, R. Hartmann, M. Kuhbacher,
M. Lang, N. Langhoff, A. Liebel, M. Radtke, U. Reinholz, H. Riesemeier,
H. Soltau, L. Struder, A. F. Thunemann, R. Wedell, Compact pnCCD-Based
X-ray Camera with High Spatial and Energy Resolution: A Color X-ray
Camera. Anal Chem 2011, 83. 2532-2538, DOI: Doi 10.1021/Ac102811p..
29
NOTES
30
O-07
10 sept. 2014
14:00 > 14:20
Yoshinori Shiota1 - Takashi Kamiyama2 - Syota
Nagashima2 - Sasiphan Khaweerat3 - Yoshiaki Kiyanagi1
Nagoya University, Graduate School of Engineering, 464-8603, Furo-Cho,
Chikusa-Ku, Japan
2
Hokkaido University, Faculty of Engineering, 060-8628, Kita-13 Nishi-8, Kita-Ku,
Sapporo, Japan
3
Thailand Institute of Nuclear Technology, Nuclear Science, 10900, 16 Vibhavadi
Rangsit, Chatuchak, Bangkok
1
Spectroscopic pulsed
neutron imaging
and its application
to metal cultural
heritage
In research on precious cultural heritage, non-destructive
measurement of its material structure is one of important
technique to investigate age, region, material composition
and production technology. The spectroscopic pulsed
neutron imaging technique offers non-destructive method
to reveal internal crystallographic structure and elemental
distribution in bulk metal, due to the high penetration
of neutron beam.
At a pulsed neutron source, the neutron energy can be analyzed by using time-of-flight method and the transmission
spectra with specific Bragg-edges of a crystalline material
are obtained from transmission measurement. We have
developed quantitative evaluation technique of microstructural information such as crystal lattice plane spacing,
crystallographic texture, crystallite size and crystalline phase
by analyzing the Bragg-edges [1]. Spectroscopic analysis
of the Bragg-edges is performed by using the RITS code that
is based on the Rietveld theory [2]. In addition, the application
Bibliography
[1] Y. Kiyanagi, H. Sato, T. Kamiyama and T. Shinohara, J. Phys. Conf. Ser. 340
(2012) 012010.
[2] H. Sato, T. Kamiyama and Y. Kiyanagi, Mater. Trans. 52 (2011) 1294-1302.
[3] Y. Kiyanagi, N. Ayukawa, Y. Shiota, K. Kino, T. Sato, H. Sato, T. Kamiyama,
F. Grazzi, A. Scherillo, S. Uno and A. S. Tremsin, Application of a pulsed
neutron transmission method to a cultural heritage study,1st International
Conference on Neutron Imaging and Neutron Methods in Archaeology
and Cultural Heritage Research (NINMACH 2013), Munchen, Germany,
September, 2013.
[4] Y. Shiota, T. Sato, H. Hasemi, A. S. Tremsin, T. Kamiyama and Y. Kiyanagi,
Non-destructive Measurement of Microstructural Factor of Japanese Sword
by using Neutron Transmission Spectroscopy, The international conference
on “ the Beginnings of the Use of Metals and Alloys ” (BUMA VIII), Nara,
Japan, September, 2013
of the technique coupled with a position sensitive neutron detector is possible to obtain microstructural information depending on the position of a bulk material
with one neutron transmission imaging measurement.
Sometimes elemental composition in the material obtained
from resonance absorption or activation analysis provides
significant information.
The spatial distributions are useful in order to investigate
mechanical properties, working process, elastoplastic deformation and composite phase characteristics in the metal
materials. As a result, the method was used for our metal
cultural heritages analysis [3,4]. After Japanese swords were
measured as a traditional transmission imaging, they were
evaluated distributions of martensite steel phase, crystallite
size and texture. Such a microstructural factor is due to steel
material and production technology. Besides, the method
was introduced to the analysis of some authentic Thai coins
produced during A.D.1874-1919.
In this study, we will introduce the principle of the spectroscopic pulsed neutron imaging and the results on Japanese
swords and coins. In the Japanese swords, the differences of
microstructural factors were observed among swords produced in different region and age. Meanwhile, the analysis of
Thai coins shows slightly differences in the crystallographic
structure varied by date of production.
This work was partially supported by a Grant-in-Aid for
Scientific Research (S) from Japan Society for the Promotion
of Science (No. 23226018).
31
NOTE
NOTES
32
O-08
10 sept. 2014
14:20 > 14:40
Edward Vicenzi1 - Benjamin Stripe2 - Volker Rose2
1
2
Smithsonian Institution, Museum Conservation Institute, 20746, Suitland, USA
Advanced Photon Source, Argonne National Laboratory, 60439, Lemont, USA
A scanning nano-XRF
study of a 19th century
daguerreotype
photograph
Nanoscale structures on the surface and near surface of
daguerreotype photographs have been characterized
by nano-X-ray fluorescence spectrometry (nano-XRF).
The examined features include photo contrast-inducing
nanoparticles, a gilding layer, and sulphide corrosion within
19th century photographic images.
In 1839, the daguerreotype photographic process was first
presented to the scientific community in France. The technology spread rapidly and was widely used around the globe
until roughly 1860. Image formation can be generalized in
four steps:
1) exposing silver-plated copper to an iodine vapor,
2) further exposing the sensitized plate to visible light within
a camera,
3) development of an image after the plate is treated with
heated mercury vapor, and finally
4) deposition of a gold gilding layer [1].
Bibliography
[1] Y. Kiyanagi, H. Sato, T. Kamiyama and T. Shinohara, J. Phys. Conf. Ser. 340
(2012) 012010.
[2] H. Sato, T. Kamiyama and Y. Kiyanagi, Mater. Trans. 52 (2011) 1294-1302.
[3] Y. Kiyanagi, N. Ayukawa, Y. Shiota, K. Kino, T. Sato, H. Sato, T. Kamiyama,
F. Grazzi, A. Scherillo, S. Uno and A. S. Tremsin, Application of a pulsed
neutron transmission method to a cultural heritage study,1st International
Conference on Neutron Imaging and Neutron Methods in Archaeology
and Cultural Heritage Research (NINMACH 2013), Munchen, Germany,
September, 2013.
[4] Y. Shiota, T. Sato, H. Hasemi, A. S. Tremsin, T. Kamiyama and Y. Kiyanagi,
Non-destructive Measurement of Microstructural Factor of Japanese Sword
by using Neutron Transmission Spectroscopy, The international conference
on “ the Beginnings of the Use of Metals and Alloys ” (BUMA VIII), Nara,
Japan, September, 2013
Some microanalytical information has been derived from
scanning electron microscopy-based studies of daguerreotypes [e.g. 2]. However, given the scale of the particles,
detailed microchemical analysis of image-forming nanoparticles requires sample preparation that involves feature
removal from the object followed by thinning of material to
minimize particle/photon scattering. Such sample preparation technology has only been widely available in the past
decade via focused ion beam (FIB) microscopy. This effort
seeks to determine the elemental make-up of nanoparticles
as well as the protective nanofilm that coats daguerreotypes
by way of synchrotron nano-XRF imaging and analysis. Additionally, this study aims to produce the first quantitative
chemical measurements of 19th century daguerreotype
nanostructures using a standards-based methodology.
The hard X-ray nanoprobe at Argonne National Laboratory’s
Advanced Photon Source was used to collect scanning
fluorescence X-ray images with a 10 keV incident beam.
Focusing zone plate optics produced a 30 nm X-ray probe,
rastered relative to the specimen, to collect hyperspectral
nano-XRF images using a four element silicon drift EDS
detection system [4,5]. Nano-XRF images and spectra were
processed using a package of software routines designed
specifically for XRF data sets [6].
Nano-XRF imagery reveal nanoparticle cores are nearly
completely encapsulated by the Au gilding layer, instead
of simply being coated only on upper surfaces. Fitting and
quantification of the nano-XRF spectra for daguerreotype
particles and gilding layers establishes that sulphur is an
important player with regard to the chemistry of the interior
of daguerreotype HgAg nanoparticles and it is not restricted
to the atmosphere/object interface.
33
NOTES
34
O-09
10 sept. 2014
14:40 > 15:00
Rosie Grayburn1 - Rita Wiesinger2 - Mark Dowsett3
Paul Thompson4 - Manfred Schreiner2 - Annemie Adriaens1
Universiteit Gent, Department of Analytical Chemistry, 9000, Gent, Belgium
Academy of Fine Arts, Institute of Science And Technology, 1010, Vienna, Austria
3
University of Warwick, Department of Physics, CV4 7AL, Coventry, United Kingdom
4
European Synchrotron Radiation Facility, XMaS (BM28), 38000, Grenoble, France
1
In-situ time-lapse
X-ray diffraction
of silver corrosion
2
Several heritage systems have been studied using stateof-the-art synchrotron techniques [1–4] developed by the
Electrochemistry and Surface Analysis (ESA) group at Universiteit Gent, Belgium, and the Analytical Science Projects
(ASP) group at Warwick University, UK. In this presentation
we show how the eCell [5] (and associated control software)
can be used to study the time-lapse corrosion of pure silver
by anthropogenic gases alongside newly designed equipment for analysis of multiple samples. This work was carried
out on the XMaS [6] beamline at the European Synchrotron
Radiation Facility, Grenoble.
The cultural heritage value of silver is documented in
museum collections across the globe. However, the silver
surface is not as chemically stable as that of other precious
metals, and is susceptible to corrosion by gases such as H2S
and O3. In order to study the initial corrosion of silver in the
presence of these gases, a customized gas-mixing set-up
(designed by the Institute of Science and Technology,
Academy of Fine Arts, Vienna) delivered the required humidity and gas concentration to the cell under turbulent
flow conditions to the silver sample surface placed under
the X-ray transparent Kapton window.
The design of the experiment meant that pressurised gases
could be used as source gases with minimal safety concerns
in the hutch. The eCell itself was not kept above atmospheric
pressure as the gases flowed through the cell from the top
(sample height) to the base, and the effluent was extracted
at low outlet velocity (max. 1 L min-1) using the vacuum line
in the hutch. The hydrogen sulphide source gas contained
10 ppm H2S in synthetic air. This was diluted to 500 ppb
using synthetic gas in the gas-mixing manifold. The ozone
was generated by running synthetic air through an ozone
generator. The concentrations of both the source gas and
output gas were well below the safety limits and presented
no danger to the users.
The time-lapse XRD data shows that when pure silver is
exposed to 500 ppb H2S, 500 ppb O3 and RH >50 % crystalline corrosion products start to form after only 30 minutes
of gas flow. Silver sulfide, silver oxides, intermediates and
mixed species formed over the duration of the experiment. The data can start to give us an idea as to the exact
mechanism of degradation by this gas mixture as we track
the transformation from one crystalline species to another.
In addition a carousel sample changer (EVA Surface Analysis,
UK) accessory was designed to study multiple pre-corroded
silver samples using SR-XRD. Grooves in the carousel surface
allow low angles of diffraction to be measured.
The data we have collected using the eCell/gas flow set up
at XMaS introduces a set of highly useful tools for scientists
who wish to study time-lapse gaseous corrosion at ambient
temperature and pressure.
Bibliography
[1] R. Grayburn, M. Dowsett, M. De Keersmaecker, E. Westenbrink,
J. A. Covington, J. B. Crawford, M. Hand, D. Walker, P. A. Thomas, D. Banerjee,
and A. Adriaens, Corrosion Science, 2014, 82, 280–289.
[2] M. Dowsett, A. Adriaens, C. Martin, and L. Bouchenoire, Analytical
Chemistry, 2012, 84, 4866–4872.
[3] A. Adriaens, M. Dowsett, K. Leyssens, and B. Van Gasse, Analytical and
Bioanalytical Chemistry, 2007, 387, 861–8.
[4] M. Dowsett, A. Adriaens, B. Schotte, G. Jones, and L. Bouchenoire, Surface
and Interface Analysis, 2009, 41, 565–572.
[5] M. G. Dowsett and A. Adriaens, Analytical Chemistry, 2006, 78, 3360–5.
[6] S. D. Brown, L. Bouchenoire, D. Bowyer, J. Kervin, D. Laundy, M. J. Longfield,
D. Mannix, D. F. Paul, a. Stunault, P. Thompson, M. J. Cooper, C. a. Lucas, and
W. G. Stirling, Journal of Synchrotron Radiation, 2001, 8, 1172–1181.
35
NOTES
36
O-10
10 sept. 2014
15:30 > 15:50
Elisa Barzagli1 - Francesco Grazzi1 - Alan Williams2
David Edge2 - Antonella Scherillo3 - Marco Zoppi1
Istituto Dei Sistemi Complessi, CNR, research, 50019, Firenze, Italy
The Wallace Collection, Museum and Conservation, W1U 3BN, London,
United Kingdom
3
Science and Technology Facility Council, ISIS Facility, research, OX11 0QX, Didcot,
United Kingdom
1
Non-invasive
characterization of two
Japanese swords from
the Wallace collection
2
The metallurgy of historical combat weapons (swords,
in particular) is one of the most interesting topics of archaeometallurgy because they were manufactured using the
highest quality materials and the most advanced technology
available throughout the ages [1,2].
In order to achieve a good level of characterization of metal
artifacts, by traditional analytical methods, a destructive approach is usually necessary. However, this method is strictly
forbidden for well conserved museum exhibits. Neutron
techniques have already been demonstrated to be among
the most suitable methods to characterize qualitatively
and quantitatively the composition and the microstructural
properties of metal artifacts in a non-destructive way [3-5].
Ancient Japanese swords represent one of the best examples
in this field. Hence, they are one of the most interesting
classes of artifacts that can be studied in order to better
understand the evolution of metallurgy [6,7].
All the Japanese swords, so far investigated by neutron
diffraction, have shown distinctive inner structures and
manufacturing procedures [4,5,8,9]. These procedures have
been refined across the years starting from the Koto period
(X-XVI century), in different ways, by five schools of swordsmithing, each aiming to provide what was believed to be
the optimum mechanical characteristics for each part of
the blade, according to its function [6,10]
The work presented is part of a long-term project aimed at
the characterization of the processing techniques in different
traditions and their evolution over time.
Samples object of this work are two blades, with different
shape and characteristics, belonging to the collection of
arms and armour of the Wallace Collection (London, UK):
1) a long sword (Tachi) of the 15th Century (Koto period belonging to the Yamato Tradition). The Tachi is a long sword
used by horsemen, that needed to be hard enough to
cut armours and elastic enough to sustain a hard impact.
2) a long knife (Tanto) or double edged straight sword used
mainly as a piercing weapon. It is dated to the 17th century
(Shinto period).
The measurements were carried out using the diffractometer
INES (Italian Neutron Experimental Station) at the ISIS spallation neutron source (UK).
The investigation focused on the characterization of the
quantitative phase composition and of the microstructural
properties.
The results showed differentiation of the carbon content and
the microstructure in the different parts of the two blades.
The characteristics are in agreement with the data found in
the literature: high hardness in the edge, and high resilience
in the back.
The good quality of the results obtained is combined with
the privilege of being able to analyze objects belonging to
one of the best collections of arms and armour in Europe.
Bibliography
[1] A. Williams, The knight and the blast furnace, Brill, Leiden (2003).
[2] V. F. Buchwald, Iron and steel in ancient times, Historisk-filosofiske Skrifter
29, The Royal Danish Academy of Sciences and Letters (2005).
[3] F. Grazzi et al., J. Anal. At. Spectrom. 27, 293 (2012).
[4] F. Grazzi et al., J. Anal. At. Spectrom. 26, 1030 (2011)
[5] F. Grazzi et al., Anal. Bioanal. Chem. 400,1493 (2011).
[6] K. Nagayama, The Connoisseur’s Book of Japanese Swords, Kodansha
International, Tokyo (1997).
[7] M. Chkashige, Oriental Alchemy, Samuel Weiser press, New York (1974).
[8] F. Grazzi et al., Mater. Sci. Forum 65, 167 (2010).
[9] F. Grazzi et al., La Metall. Italiana, 5/2011, 13 (2011).
[10] L. Kapp, H. Kapp, and Y. Yoshihara, The Craft of the Japanese Sword,
Kodansha International, Tokyo (1998).
37
NOTES
38
O-11
10 sept. 2014
15:50 > 16:10
Myrtille Hunault1 - Fanny Bauchau2 - Claudine Loisel2
Michel Herold3 - Matthew Newville4 - Georges Calas1
University Pierre and Marie Curie, Paris 6, IMPMC, 75252, Paris Cedex 5, France
Museum National d’Histoire Naturelle, CRC-LRMH, 77420, Champs-Sur-Marne, France
3
University Paris Sorbonne, Centre Andre Chastel, 75004, Paris, France
4
University of Chicago, Advanced Photon Source, GSECARS, 60409, Argonne, Il, USA
1
Reducing
manufacturing
conditions of medieval
blue glass revealed
by µ-XANES
2
Transition metal ions are widely used as colorant in glass
manufacturing. In the Middle Age, glassmakers were able to
control the glass production conditions in order to obtain a
wide range of colors. The blue color relies on the presence of
Co2+, Fe2+ and Cu2+. The main blue colorant is Co2+, which only
occurs in this oxidation state in the glass. On the contrary,
Fe, Cu and Mn can happen in several oxidation states. These
elements can interact in their redox equilibriums, which
influences the glass color. The oxidation state is also sensitive to the temperature and to the oxygen partial pressure
of the furnace. The exact processing conditions have been
investigated according to ancient textbooks but suffer from
terseness and their impact on final glass color is not yet
understood.
In the framework of the study of the 13th century stained
glass color of the Sainte-Chapelle of Paris, four contemporary samples dating from 12th-13th centuries were analyzed
with synchrotron radiations. As a comparison, for each
sample, a fragment was re-melted at 1200°C in air. K-edge
micro-XANES was performed at the beamline 13-ID-E at the
Advanced Photon Source (Chicago, IL, USA) to determine
the oxidation state of Mn, Fe and Cu. The measurement
was performed across the glass thickness and compared to
the re-melted glass fragment. The results revealed that the
four ancient glasses are reduced compared to the re-melted
equivalent glass. In ancient glasses, Mn is mainly present
as Mn2+, Fe as Fe2+ and Cu as Cu+, whereas more oxidizing
melting conditions favor Fe3+ and Cu2+. Potential variations
of the oxidation state inside the glass thickness could not be
observed suggesting that it may occur at lower scale than
the micro-XANES analysis sensitivity. Altogether, this shows
that the partial pressure of oxygen in medieval furnaces was
lower than in air (0.21 atm).
These results inform us on the sensitivity of the blue color to
the relative coloring role of each species and the influence
of the glass processing. The correlation with the optical absorption signature of these glasses provides a starting point
for further analyses and interpretations of the color of the
Sainte-Chapelle stained glass windows.
Bibliography
[1] M. Schvoerer, Conserv. Restaur. Vitr. Actes Journées Détudes Cent. Int. Vitr.
(1993) 131.
[2] B. Cochain, D.R. Neuville, D. de Ligny, J. Roux, F. Baudelet, E. Strukelj, P. Richet,
J. Phys. Conf. Ser. 190 (2009) 012182.
[3] L. Grodecki, Comptes-Rendus Séances Académie Inscriptions Belles-Lettres
120 (1976) 345.
[4] K. Boulanger, M. Hérold, Le vitrail et les traités du Moyen Âge à nos Jours:
Actes du XXIIIe colloque international du Corpus Vitrearum Tours 3-7 Juillet
2006, Peter Lang, 2008.
[5] J.-M. Bettembourg, (n.d.).
[6] C.B. Azzoni, Peridico Miner. 71 (2002) 73.
[7] M. Hunault, G. Calas, J. Am. Ceram. Soc. (2013).
[8] G. Calas, J. Petiau, Solid State Commun. 48 (1983) 625.
[9] M. Wilke, F. Farges, G.M. Partzsch, C. Schmidt, H. Behrens, Am. Miner. 92
(2007) 44.
[10] F. Farges, M.-P. Etcheverry, A. Scheidegger, D. Grolimund, Appl. Geochem.
21 (2006) 1715.
[11] G.E. Brown, F. Farges, G. Calas, Rev. Miner. 32 (1995) 317.
[12] M.-H. Chopinet et al. C. R. Chimie 5 (2002)
39
NOTES
40
O-12
10 sept. 2014
16:10 > 16:30
Jennifer Mass1 - Arthur Woll2 - Alyssa Hull3 - Patricia Favero4
Adam Finnefrock5 - Robin Kirkham6 - Anthony Kuczewski7
Catherine Matsen1 - Gareth Moorhead6 - Chris Ryan6
Pablo Picasso’s The
Blue Room (1901):
an intensive technical
investigation of a blue
period painting
1
Pablo Picasso’s 1901 painting, The Blue Room, in The Phillips
Collection, Washington, DC, is considered a major turning
point in this artist’s work during a seminal year in his stylistic
development. With The Blue Room and other works, Picasso
transitioned into his Blue Period, abandoning earlier colorful
depictions of belle époque nightlife in fin-de-siècle Paris for
a more subdued, primarily blue palette that would continue
to dominate his paintings into 1904.
Despite extensive research into various aspects of Pablo
Picasso’s working methods and materials, and detailed
analyses of a handful of his later paintings, comprehensive
technical analysis of a work from the Blue Period, and of one
of Picasso’s reused canvases, has not been carried out. The
Blue Room has been known for several years to have another
painting, a portrait, beneath the presentation surface, also
thought to have been carried out in 1901. It is well known
that Picasso reused his canvases, one major example of
which is the Art Institute of Chicago’s Blue Period painting
The Old Guitarist (1903-4), which has been shown to have at
least three different hidden figures.
Here we describe initial results of a comprehensive analysis of
The Blue Room. We describe combined results from portable
X-ray fluorescence (XRF), Raman spectroscopy, FTIR, and
scanning electron microscopy X-ray microanalysis, along
with synchrotron-radiation (SR) based XRF mapping of the
entire painting. The SR-XRF maps were obtained at the Cornell High Energy Synchrotron Source using a new version of
the 384-sensor Maia detector. The goals of this measurement
were to determine the elemental distribution of the combined painting, and the feasibility of distinguishing features
of the presentation surface and buried works in this and
other, similar Picasso works of the same period. Due to the
high concentration of zinc throughout the painting, as well
as Picasso’s use of a lead-based ground, the painting was
scanned in its entirety twice: once with an incident energy
of 12.6 keV to excite mercury L-edge fluorescence but not
lead, and a second time with an energy of 9.37 keV, below
the zinc K edge. Both scans were performed with a pixel
size of 0.2×0.2 mm2, and took approximately 11 hours to
complete. Despite the thickness of zinc and barium—based
fillers and similarity in composition between the two images,
several features of the buried portrait are distinguishable in
the XRF maps, which are assisting the ongoing curatorial
work on this painting.
Questions addressed will include: what palette and painting
methods did Picasso use for the two works? What is the relationship between the two palettes? Were the works painted
wet-into-wet? The combination of the cross-section studies,
molecular analyses, and XRF imaging provide a wealth of
new information about this important work.
Winterthur Museum, Conservation Department, 19735, Winterthur, USA
Cornell University, Cornell High Energy Synchrotron Source, 14853, Ithaca, USA
3
University of Delaware, Department of Chemistry, 19716, Newark, USA
4
The Phillips Collection, Conservation Department, 20009, Washington DC, USA
5
Janssen R&D, 19002, Spring House, USA
6
CSIRO, Materials Science and Engineering, 3168, Clayton, Australia
2
41
NOTES
42
O-13
10 sept. 2014
17:00 > 20:00
Uwe Bergmann1
1
SLAC National Accelerator Laboratory, LCLS, 94025, Menlo Park, USA
X-ray fluorescence
imaging:
from Archimedes
to Archaeopteryx
and beyond
In an attempt to uncover the hidden writings in the
Archimedes Palimpsest some years ago the technique
of rapid-scan X-ray fluorescence (XRF) was developed at
the Stanford Synchrotron Radiation Lightsource. After its
successful application in that project, XRF has been refined
over the last years, leading to numerous new studies
of large objects of cultural, archaeological and paleontological importance.
In the field of cultural heritage we will present examples including the imaging of a leaf from a seventh-century Qur’an
palimpsest and a section of the original score of the opera
Médée believed to be over-painted by its composer Luigi
Cherubini. Other examples presented include the recent
discovery of soft-tissue residue in fossils of Archaeopteryx,
as well as the work that has successfully resolved the remnants of pigment in Confuciusornis sanctus, a 120-millionyear-old fossil of the oldest documented bird with a fully
derived avian beak.
Bibliography
[1] Bergmann, et al, Chemical mapping of paleontological and archeological
artifacts with synchrotron X-rays, Annual Review of Analytical Chemistry,
5, 361-389 (2012)
[1] Bergmann U., Chapter 6, Imaging with X-ray Fluorescence
in ‘The Archimedes Palimpsest’, Vol. 1 Netz R, Noel W, Wilson N, Tchernetska
N, eds., Cambridge University Press, (2011)
[1] Bergmann, U; Morton, RW; Manning, PL; Sellers, WI; Farrar, S; Huntley, KG;
Wogelius, RA; and Larson, P; Archaeopteryx feathers and bone chemistry
fully revealed via synchrotron imaging, Proc Natl Acad Sci, 107, (20)
9060-9065 (2010)
[1] Manning, et al, Synchrotron-based chemical imaging reveals plumage
patterns in a 150 million year old early bird, Anal. At. Spectrom., 28,
1024–1030 (2013)
[1] Sadeghi, B; Bergmann, U; The Codex of a Companion of the Prophet
and the Qur’an of the Prophet, Arabica, 57/4-5, 343-436, (2010)
[1] Wogelius, et al, Trace metals as biomarkers for Eumelanin Pigment
in the Fossil Record, Science, 333, 1622-1626 (2011)
43
NOTES
44
O-14
10 sept. 2014
17:00 > 20:00
Robert van Langh1
1
Rijksmuseum, museum, 1071 XX, Amsterdam, The Netherlands
What have
we learned from
Neutron Transmission
Radiography
and Time-of-Flight
Neutron Diffraction on
Renaissance bronzes?
In November 2005 the Rijksmuseum showed 13 different
neutron tomographic reconstructions of Renaissance
bronzes during an exhibition at the Daniel Katz Gallery in
London. Within art history the project was widely perceived
as a project where science can truly bring new information
within the authentication of art objects.
In 2010 a continuation of the project took place where
12 bronzes more were studied at the PSI installation for
neutron tomography at the beam line NEUTRA located
at the spallation neutron source SINQ. The setup consists
on a quasi-parallel beam with up to 40 cm annual diameter directed to the object of interest. Behind the object,
the transmitted beam is detected with a two-dimensio-
Bibliography
[1] Langh, R. van, E. Lehmann, S. Hartmann, A. Kaestner, and F. Scholten,
‘The study of bronze statuettes with the help of neutron imaging
techniques’, Analytical Bioanalytical Chemistry 395 (2009), pp. 1949-1959.
[2] Langh, R. van, A. Pappot, S. Creange, L. Megens, and I. Joosten, ‘The effect
of surface changes in heat treated bronze samples analyzed by x-ray
fluorescence spectometry’, Metal 2010, ICOM-CC metal working group.
Charleston 2010, pp. 204-209.
[3] Langh, R. van, L. Bartoli, J.R. Santisteban, and D. Visser, ‘Casting technology
of Renaissance bronze statuettes: the use of TOF-neutron diffraction
for studying afterwork of Renaissance casting techniques’, Journal of Analytical Atomic Spectrometry 26, no. 5 (2011), pp. 892-898.
[4] Langh, R. van, et al., ‘New Insights of alloy compositions by studying
Renaissance bronze statuettes by combined neutron imaging
and neutron diffraction techniques’, Journal of Analytical Atomic
Spectrometry 26, no. 5 (2011), pp. 949-958.
nal neutron sensitive device, based on a highly sensitive
CCD-camera looking via a mirror onto a scintillation screen.
About 300 single projections of the object are needed for
one tomography run, where the object is rotated around
its vertical axis in steps from 0° to 180°.
A reconstruction algorithm calculates from these 2D projection data the 3D volume matrix, which can be forwarded for
further analysis to the visualisation tools, where animation,
slices and segmentation can be obtained.
Using the data from neutron imaging, neutron diffraction
was used to analyse the inside of the sculptures based
on the apparent difference of attenuation shown in the
neutron images. The neutron diffraction experiments were
executed at Engin-X the neutron diffractor of ISIS, Science
and Technologies Facilities Council at the Rutherford
Appleton Laboratory in Oxfordshire. The data revealed
completely new insights in the manufacturing of Renaissance bronzes.
During the presentation various insights into the bronze
sculpture will be given and put in an art historical context
and it will show that collaboration between scientists,
curators and conservators is essential for obtaining results
that are reliable for the authentication of works of art.
45
NOTES
46
O-15
10 sept. 2014
17:00 > 20:00
Philippe Sciau1
1
CNRS, CEMES, 31055, Toulouse, France
How to use
the hierarchical
heterogeneous
structure of ancient
ceramics to trace
their firing protocol
In archaeological investigations, ceramics are one of the advance technological products. Not only are they identifying
markers, but often also indicator of technological prowess of
a civilization and/or an archaeological period. Consequently,
they have been a major focus of archaeometric research
from the beginning of the field in the 1950s. Among the
investigation fields, the manufacturing process held and still
holds an important place and in particular the identification
of the firing protocol. A whole study includes the study of
firing structure survey found during the excavations, the
physico-chemical analyses of ceramic fragments, experimental firings and making replications, but unfortunately
in many cases the firing structures were not identified or
the conservation state was not enough to deduce from them
information concerning the firing process. Also, the physico-chemical study of sherds is often the best way to obtain
information concerning the manufacturing process. Through
the example of the black and/or red high gloss coatings
of Greek and Roman potteries, we will try to show how to
deduce precise information using synchrotron facilities and
other advanced materials science investigation techniques.
The approach used the heterogeneous and complexity
of these artifacts. It is based both on a multi-scale analysis
and a decomposition in sub systems of materials. From the
confrontation of the results obtained for each sub-system
and at different scales, we will show how the various steps of
firing protocol can be traced as well as information concerning the raw materials used in the manufacturing process.
47
NOTES
48
O-16
11 sept. 2014
09:30 > 10:00
Eleanor Schofield1,2 - Ritimukta Sarangi1
1
2
Role of S K-edge
X-ray Absorption
Spectroscopy in
Conservation Efforts
of the Mary Rose
Sulfuric acid production is a pervasive problem in wooden
archeological artefacts and has been shown to significantly
damage these cultural heritage relics. The problem is aggravated in the case of waterlogged wooden artefacts, in which
sulfur accumulation is accelerated due to the presence of
sulfur metabolizing bacteria. Finding a common solution
to all waterlogged wood acidification is impossible due to
the variation in the type of wood, acidification and extent
of damage. In this study a treatment plan for the sulfur
rich wood of the Mary Rose is developed based on alkaline
The Mary Rose Trust, HM Naval Base, PO13LX, Portsmouth, UK
SLAC National Accelerator Laboratory, Stanford University, 94025, Menlo Park, USA
earth metal carbonates. The efficacy of the treatment plan
is followed with S K-edge X-ray absorption spectroscopy,
which is an excellent tool for the determination and differentiation of the different types of sulfur species present in the
wooden artefacts. It is observed that the treatment is successful in converting the dangerous low-valent sulfur species in
the wooden artefacts into more benign forms of sulfur,
in the process neutralizing the formed acid. The benefits
and limitations of this treatment plan will be addressed.
Bibliography
[1] Eleanor J. Schofield, Ritimukta Sarangi, Apurva Mehta, A. Mark Jones, Fred J.
W. Mosselmans, and Alan V. Chadwick, Materials Today, 2011, 14, 354-358
49
NOTES
50
O-17
11 sept. 2014
10:00 > 10:20
Pauline Martinetto1 - Sophie Cersoy1 - Pierre Bordet1
Jean-Louis Hodeau1 - Elsa van Eslande2 - Philippe Walter2
1
Univ. Grenoble Alpes, CNRS-UJF, Institut Néel, 38000, Grenoble, France
Sorbonne Universités, CNRS-Univ Paris 06, LAMS, 75000, Paris, France
Combined structural
analysis of ancient
ill-ordered carbon-based
cosmetics and inks
2
Carbon black materials are easy to get by combustion of
organic matter and were thus often used since prehistory,
as pigments or drawing, writing, dyeing materials or even
as cosmetics components. Black carbon-based powders
from the roman site of Pompeii were analyzed. The six
analyzed samples come from ink and cosmetic containers
made of bronze or glass. Ancient recipes as well as preliminary studies in laboratory revealed the complexity of
these precious materials containing both ill-ordered phases
(mostly carbonaceous ones) and well-crystallized ones.
Diffraction patterns thus show diffuse scattering signatures
(broad oscillations from non-graphitic carbon) with Bragg
reflections superimposed.
DSCT experiments requiring moving the sample with a
precise translation - rotation system and involving data
acquisitions of few hours per sample, enabled us to localize
and extract the signal of the various phases present. These
first promising results are being completed by micro-beam
data collected on Diffabs at SOLEIL, as some heterogeneities
within the sample seems to be a few dozen microns in size.
The treatment of data acquired at thirty increasing 2theta positions to reach a high Q-range has been achieved.
Assessment of the weight proportion of each crystallized
phase in the archaeological samples using Rietveld refinements was first achieved. PDF calculations were compared
with structural models taking into account the presence and
proportion of each crystallized phase obtained in the previous step. For the amorphous part, differences with graphite
structure could be visualized and proved to be relevant for
short range order arrangements. Other models mentioned in
literature (turbostratic piles and/or curved-graphitic-sheets)
are still under tests.
Moreover quantitative comparison of the PDF of references
and archaeological samples, combined with Raman spectroscopy analysis performed in the laboratory, enabled to
discriminate carbon blacks according to their starting material (e.g. soot, peach black...). Additionally the size of the
coherent graphitic domains of the carbon black structures
may be estimated by both techniques between 5 to 15 Å
according to the samples.
Therefore the following two-steps strategy involving
non-destructive techniques and analysis of reference
carbon-based materials was chosen and set up on D2Am
beamline at ESRF:
1- Selective extraction of the total scattering signal of each
phase present using X-ray Diffraction Scattering- Computed
tomography (DSCT) and
2- Structural characterization of amorphous phases by Pair
Distribution Function (PDF) analysis using X-ray scattering
data collected on a wide 2 theta-range with a good statistic.
Bibliography
[1] M. Alvarez-Murga, et al., Journal of Applied Crystallography, 2011.
[2] P. Bleuet P., et al., Nature Materials, 2008.
[3] H.G.M. Edwards, et al., Journal of Molecular Structure, 2000.
[4] T. Egami, et al., ‘Underneath the Bragg peaks’, Pergamon, Oxford, England,
2003.
[5] A.C. Ferrari, et al., Physical Review B, 2000.
[6] R.E Franklin, Acta Crystallographica, 1950.
[7] L. Hawelek, et al., Philosophical Magasine, 2007.
[8] A. Varichon, ‘Couleurs: Pigments et teintures dans les mains des peuples’,
Seuil, 2005.
[9] B.E Warren, Journal of Physical Chemistry, 1934.
51
NOTES
52
O-18
11 sept. 2014
10:20 > 10:40
Frederik Vanmeert1 - Koen Janssens1 - Matthias Alfeld2
Gerald Falkenberg2 - Geert van der Snickt1 - Wout de Nolf1
University of Antwerp, Department of Chemistry, AXES Research Group,
2020, Antwerp, Belgium
2
DESY, PETRA-III, P06 Beamline, 22607, Hamburg, Germany
1
X-ray powder
diffraction mapping
and tomography for
analysis of (degraded)
paint layer systems
X-ray powder diffraction is a general method for highly
specific phase identification and quantitative analysis.
When employed with synchrotron micro beams in two-dimensional scanning mode, it allows for quantitative
mapping of the crystalline phases present in complex,
heterogeneous materials [1].
A variant of scanning SR-XRPD is XRPD tomography [2]
where the sample under investigation is rotated along one
axis and translated along a second axis perpendicular to
the first. This method allows to record phase maps in virtual
planes inside the sample under investigation without the
need for physically sectioning the material. The elimination
of the physical sectioning step has the advantage that the
integrity of (brittle or fragile) samples [3] is preserved while
also any contamination or phase transformations due
to sample preparation are avoided.
In this paper we describe the results of examining several paint
layer systems by means of conventional 2D scanning XRPD
and by means of XRPD tomography using a (sub) microscopic X-ray beam (0.4×0.4 μm2) of 21 keV energy, produced at
PETRA-III beamline P06 and compare the results critically.
The paint multilayer systems to be discussed as examples
originate on the one hand from 15th C. panel paintings by
H. Memling; their complexity, sometimes involving more
than 10 individual layers of different thicknesses and strongly
different compositions reflects the extensive craftmanship
of this ‘Flemish primitive’ painter. In some cases, the original
complexity of the stratigraphy has been increased further
due to the formation of degradation products. As such,
these paint layer systems are a challenge and interesting
test case for analysis by XRPD mapping and tomography.
Stratigraphically more simple paint layer systems can on
the other hand be found is paintings by the late 19th C.
painter V. Van Gogh. These sample materials, however, often
contain traces of (ongoing) degradation processes that
have given rise to the in situ formation of layered systems
of primary and secondary phases. Analysis of these systems
by highly-specific methods such as XRPD mapping and
tomography allows to extract information on the nature of
the alteration mechanisms involved and experimentally test
some hypotheses. The case of the alteration of red lead will
be treated as an example.
Bibliography
[1] De Nolf W., Vanmeert F. and Janssens K., XRDUA: crystalline phase
distribution maps by 2D-scanning and tomographic μXRPD, J. Appl. Cryst.,
in press (2014).
[2] Álvarez-Murga, M., Bleuet, P. & Hodeau, J. L. Diffraction/scattering
computed tomography for three-dimensional characterization
of multi-phase crystalline and amorphous materials, J. of Appl. Cryst.
45 (2012) 1109-1124.
[3] Artioli G., Dalconi M.C., Parisatto M., Valentini L., Voltolini M., Ferrari G., 3D
imaging of complex materials: the case of cement, Int. J. Mat. Res.103
(2012) 145-150.
53
NOTES
54
O-19
11 sept. 2014
10:40 > 11:00
Fauzia Albertin1 - Alberto Astolfo2 - Marco Stampanoni2
Eva Peccenini3 - Yeukuang Hwu4 - Frederic Kaplan5
Giorgio Margaritondo1
Virtual X-ray reading
(VXR) of ancient
administrative
handwritten
documents
1
The study of ancient documents is too often confined
to specimens of high artistic value or to official writings.
Yet, a wealth of information is often stored in administrative
records such as ship records, notary papers, work contract,
tax declaration, commercial transactions or demographic accounts. One of the best examples is the Venice Time Machine
project that targets a massive digitization and information
extraction program of Venetian archives. The Archivio di Stato
in Venice holds about 80 kms of archival documents spanning
over ten centuries and documenting every aspect of Venetian
Mediterranean Empire. If unlocked and transformed in a digital
information system, this information could change significantly
our understanding of European history.
We are exploring new ways to facilitate and speed up this
broad task, exploiting X-ray techniques, notably those based
on synchrotron light. Specifically, we plan to use X-ray tomography to computer-extract page-by-page information from sets
of projection images. The raw data can be obtained without
opening or manipulating the bounded administrative registers,
reducing the risk of damage and accelerating the process.
We present here positive tests of this approach. First,
we systematically analyzed the ink composition of a sample
of Italian handwritings spanning over several centuries.
Then, we performed X-ray imaging with different contrast
mechanisms (absorption, scattering and refraction) using
the differential phase contrast (DPC) mode of the TOMCAT beamline of the Swiss Light Source (SLS). Finally, we
selected cases of high contrast to perform tomographic
reconstruction and demonstrate page-by-page handwriting recognition.
The experiments concerned both black inks from different
centuries and red ink from the 15th century. For the majority of the specimens, we found in the ink areas heavy or
medium-heavy elements such as Fe, Ca, Hg, Cu and Zn.
This eliminates a major question about our approach,
since the documentation on the nature of inks for ancient
administrative records is quite scarce. As a byproduct,
the approach can produce valuable information on the
ink-substrate interaction with the objective to understand
and prevent corrosion and deterioration.
École Polytechnique Fédérale de Lausanne (EPFL), Faculté des Sciences
de Base, CH-1015, Lausanne, Switzerland
2
ETHZ and Paul Scherrer Institut (PSI), Institute for Biomedical Engineering,
CH-8092, Zürich, Switzerland
3
University of Ferrara, Department of Physics and Earth Sciences
and Laboratory Teknehub, IT-44122, Ferrara, Italy
4
Academia Sinica, Institute of Physics, TW-11529, Taipei City, Taiwan
5
École Polytechnique Fédérale de Lausanne (EPFL), Laboratoire
d’humanités digitales, CH-1015, Lausanne, Switzerland
55
NOTES
56
O-20
11 sept. 2014
11:30 > 11:50
Degradation
mechanisms
of reinforcement iron
rebars in monuments:
influence of porosity
on the formation
of corrosion products
studied by X-ray
tomography
Gothic cathedrals have been building thanks to metallic reinforcement metallic chains and rebars. These elements can be
embedded in lime, mortar or hydraulic binders and corrode
in contact with these media. The mechanical resistance of
the metallic elements is affected by the corrosion processes
endangering the structure. In order to assess the possible
damage and establish a reliable conservation diagnosis the
knowledge of the corrosion mechanisms is required. In previous studies [1,2] the formation of a corrosion layer constituted of iron oxide and oxi-hydroxides has been characterized. Besides, elementary iron is detected in a micrometer to
millimeter zone in the binder, heterogeneously distributed
and can locally reach concentration of few tenth wt %.
This zone of the corrosion system is called the transformed
medium. Mappings on samples prepared on cross section
reveal that the distribution could correspond to the migration of iron along the cracks formed in the medium, at
the interface with the corrosion products. The presence of
these cracks partially filled with corrosion products raise
questions: are these cracks present at the beginning when
Mathieu Jacot-Guillarmod1 - Claire Gervais1
Olivier Rozenbaum2 - Valerie L’ Hostis3 - Philippe Dillmann4
Delphine Neff4
Bern University of Applied Sciences, 3027, Bern, Switzerland
Institut des Sciences de la Terre d’Orléans, CNRS-BRGM-Université
d’Orléans, 7327, Orléans, France
3
Laboratoire d’ Etudes du Comportement des Bétons et des Argiles,
CEA Saclay, 91191, Gif Sur Yvette, France
4
LAPA; NIMBE-SIS2M UMR 3299 and IRAMAT UMR 5060, CNRS/CEA Saclay,
91191, Gif Sur Yvette, France
1
2
the bars are embedded in the binder or do they form due
to the mechanical constraints induced by the precipitation
of the corrosion layer?
To answer to these questions this study focuses on samples
of corroded bars sampled with the adjacent binder.
Samples come from the north tower of Orléans’ cathedral and
from Saint Sulpice church dated from the XVIIIth century. In order to investigate the transformed medium and the distribution of the corrosion products and of the porosity in it samples
of 2×2 mm² have been prepared for X-ray tomography.
Acquisitions were realized on a laboratory set-up and under
synchrotron radiation on ID19 at the ESRF. Laboratory system enabled voxel sizes between 2 and 4 µm while images
obtained at the ESRF were acquired with a 0.7 µm voxel size.
The collected tomography images were filtered by an inverse
scale space method and the corrosion products, porosity
and binder were segmented by a local Otsu thresholding
procedure. Visualized analysis of the segmented images
reveals that corrosion products and porosity form two
highly connected and percolating networks. These two
networks are linked together and tend to be continuous,
which agrees with the hypothesis of a gradual filling of the
porosity network by the corrosion products. Their connectivity, shape, tortuosity, and their spatial distribution were
further characterized and quantified by means of chord distribution functions, Betti numbers and diffusion simulations.
This procedure combining image processing and simulations
was found particularly powerful to investigate the corrosion
process and its relationship to porosity.
Bibliography
[1] W.-J. Chitty et al, Corrosion Sci., 47 (2005) 1555-1581.
[2] A. Demoulin et al, Corrosion Sci., 52 (2010) 3168-3179.
57
NOTES
58
O-21
11 sept. 2014
11:50 > 12:10
Amandine C. Crabbé1 - Marie-Angélique Languille2
Cristian Mocuta3 - Helena J. M. Wouters4 - Herman Terryn1
Isabelle Vandendael1
De Colorando Auro:
revealing different
surface treatments
of the silver gilded
statuettes of
a 13th century shrine
using XANES
1
In 2005 the Holy Lady Shrine of Huy, Belgium (13th century
masterpiece of Mosan art [1]) went to the Royal Institute for
Cultural Heritage (IRPA) for its third restoration. In order to
restore the gilded silver statuettes of the shrine, it is of major importance to acquire knowledge about which surface
treatments these statuettes might have undergone during
their history. In previous publications we demonstrated
that it is possible to modify the surface colour of a 24 carat
gilding on a silver substrate by applying interpreted medieval recipes [2-4] on model samples. In order to characterise
both the treated model samples and the statuettes from
the shrine, a non-destructive and non-invasive surface analytical technique is needed. We analysed both the model
samples treated in the lab and the real historical samples
chemically with XANES. This communication presents a
short overview of the research project focussing particularly
on the chemical characterisation of our model samples and
the historical samples performed with XANES.
Depending on the applied recipe the colour modified model
samples present variations in the copper concentration or
deposition of iron in the top layer of the gilding. The oxidation state and geometry of these two chemical signatures is
determined using XANES, enabling us to differentiate colour
treated surfaces from untreated surfaces on model samples [5].
The XANES analyses of the historical samples reveal the
presence of iron and copper at their surfaces implying that
some colouring treatments might have been applied to
them. Finally, some differences in chemical composition are
detected between the statuettes of the apostles and the
Christ, indicating that different statuettes might have been
treated differently by the metal craftsmen.
Bibliography
VUB, SURF, 1050, Brussels, Belgium
CNRS, IPANEMA, 91192, Saint Aubin, France
3
Synchrotron SOLEIL, DiffAbs, 91192, Saint Aubin, France
4
KIK-IRPA, Laboratory, 1000, Brussles, Belgium
2
In conclusion, XANES proves to be a very useful tool to reveal
the chemical state of iron and copper at the surface of the
historical samples, leading to some important recommendations for future restorations of the shrine. The analysis of
more historical samples with XANES and a continuation of
the characterisation of the copper K-edges should allow
determining which recipes might have been applied to the
statuettes of the Holy Lady Shrine of Huy.
[1] D. Robert, J.-P. Sosson, D. thomas Goorieckx, L. Maes, L. Masschelein-Kleiner
in Bulletin de l’Institut Royal du Patrimoine Artistique 12 (1970) 5-85
[2] A. Crabbé, I.Vandendael., H. Wouters, G. Dewanckel, O. Steenhaut,
H. Terryn, in Surface and Interface Analysis 40 (2008), 469-473.
[3] A. C. Crabbé, G. Dewanckel in Archives des Bibliothèque de Belgique
94 (2011) 1581-1591.
[4] A. C. Crabbé, I. Vandendael, G. Dewanckel, H. Terryn, H. J. M. Wouters,
in Surface Engineering 40 (2013) 159-163.
[5] A. C. Crabbé, M.-A. Languille, I. Vandendael, J. Hammons, M. G. Silly,
G. Dewanckel, H. Terryn, H. J. M. Wouters, in Applied Physics A (2013) 39-46.
59
NOTES
60
O-22
11 sept. 2014
12:10 > 12:30
Florian Kergourlay1 - Sophie Grousset2 - Jean-Louis Gallias1
Delphine Neff2 - Solenn Réguer3 - Albert Noumowe1
Philippe Dillmann2
Degradation
mechanisms
of reinforced concrete
monuments study
of initial corrosion
processes in chlorinated
environments
1
Since the Antiquity, monuments have been reinforced by the
use of steel bars or reinforcements embedded in binders such
as lime mortar or cement concrete. The understanding of corrosion mechanisms of these reinforcements at a microscopic
scale is therefore a crucial step to set up more efficient conservation treatments. The initial alkaline conditions within most
of the binders allow the formation of passive and protective
layer at the surface of the metal, slowing corrosion rates.
However, a decrease of the interstitial solution pH because of
the natural binder carbonation or the penetration of aggressive chemical species as chloride ions from the environment
to the steel surface can lead to the destabilization of the
passive layer with a significant increase of the kinetics. These
processes imply formation of corrosion products that can
generate cracks and binder spalling by high tensile stresses.
This is strongly linked to the way Fe ions will migrate in
the porous network of the binder or precipitate locally.
Besides, it is known that corrosion induced by chloride leads to
a random pit formation [1]. However, the exact initial mechanisms are not completely understood at microscopic scale.
To better understand the first stages of corrosion processes
in chlorinated environments a four step experimental metho-
dology has been carried out to (I) determine the corrosion
pattern formed in the early stages and (II) monitor the ferrous
species transport within the binder porous system.
The first step consisted in the design of a dedicated cell
replicating the binder / iron (steel bar or archaeological
iron reinforcement) system allowing in situ analysis during
the corrosion processes. Before and after the in-situ experiments, characterizations of the system were performed
thanks to complementary multi-scale tools including optical
and scanning electron microscopy (OM and SEM), Energy
Dispersive and micro-Raman Spectroscopies (EDS and µRS).
Then, the in situ elementary and structural evolution of the
corrosion system were monitored thanks to X-ray diffraction
and fluorescence mapping under synchrotron microbeam
(µSXRD and µSXRF) realized on the DiffAbs beamline at
SOLEIL synchrotron.
Firstly, it has been underlined that corrosion processes are initiated at the metal/cement interface flaws such as porosities
or pre-existing cracks. Secondly, thanks to the in situ approach
the formation of a transcient Fe(II)-Fe(III) corrosion product,
the green rust [2,3] and its evolution on several days have
been observed for the first time. Finally, the XRF monitoring
of the ferrous transport has shown a fast penetration into the
paste on several millimeters in a few hours.
These results would provide a better understanding of chloride induced corrosion processes helping to evaluate reinforced concrete durability and hereafter upgrading modeling.
Bibliography
University de Cergy-Pontoise, Laboratoire de Mécanique et Matériaux
du Génie Civil, F-95000, Cergy-Pontoise, France
2
CNRS-CEA, NIMBE-SIS2M/LAPA, 91191, Gif/Yvette, France
3
Synchrotron SOLEIL, Diffabs, 91190, Saint-Aubin, France
[1] D. Jones, Prentice Hall, 1996
[2] P. Refait et al, Corrosion Science, 40, 1547-1560, 1998
[3] K.K. Sagoe-Crentsil et al, Cement and Concrete Research, 23(4),
785-791, 1993
61
NOTES
62
O-23
11 sept. 2014
14:10 > 14:40
Marco Stampanoni1
1
Paul Scherrer Institute, Swiss Light Source, 5232, Villigen, Switzerland
Synchrotron-radiation
for ancient and
historical materials
Due to its exceptional properties in term of high photon flux,
small source size and low divergence, synchrotron radiation
has been increasingly used for a plethora of investigations
assessing the physico-chemical properties of materials.
The non-invasive character of such probe makes it particularly
suited for the study of ancient, unique and historical materials.
This principle is at the basis of tomographic microscopy
investigations which aim at revealing the microscopic
structure of samples by exploiting the contrast generated
either by their X-ray absorption or their induced phase
shift. Fine tunability of the probe energy is another key
feature of synchrotron radiation, which enables high sensitive chemical spectroscopic investigations. In my talk I
will review the most relevant X-ray techniques applied
nowadays for the study of ancient and historical materials.
I will discuss in particular tomographic applications by
presenting existing methods, discussing their limits and
introducing emerging approaches.
Bibliography
[1] L. Bertrand et al., Development and trends in synchrotron studies
of ancient historical materials, Physics Reports 519 (2), 2012
[2] C. Gervais et al., Characterization of porosity in a 19th century painting
ground by synchrotron radiation X-ray tomography, Applied Physics
A 111 (1), 2013
63
NOTES
64
O-24
11 sept. 2014
14:40 > 15:00
Giliane Pauline Odin1 - Véronique Rouchon1
Frederick Vanmeert2 - Koen Janssens2 - François Farges3
Delphine Vantelon4
Conservation
of lignitized pyritic
woods in the light
of synchrotron
measurements
1
Because of simultaneous presence of oxygen, water,
reduced carbon and sulfur species (such as pyrite), lignitized woods are highly susceptible to oxidize after their
excavation, which often results in distorting significantly
the specimen. To improve their conservation, we have
experienced some conservator’s methods such as water
washing and slow drying under plastics, in order to evaluate
their efficiency and potential side effects.
For a reason so far unknown, sulfones were poorly present
even though expected as oxidation products. Carbon-XAS
measurements demonstrate the presence of aromatic,
carboxylic and alkyl carbons, but no change could be
highlighted during treatments.
Lignitized pyritic woods coming from Angeac-Charente
(Charentes, France, 130 Ma) and Rivecourt (Oise, France,
60 Ma) were submitted to several drying (with different
oxygen and humidity levels) or washing (in pure water
or 1 % hydrogen peroxide) treatments. We then monitored
their oxidation on LUCIA and TEMPO beamlines (SOLEIL)
by XAS, XPS and XANES measurements, to enhance the
mechanism awareness.
These experiments showed that reduced sulfur is not only
present as pyrite but also as organic sulfides. Sulfur K-edge
XANES spectra were modeled satisfactorily, considering
a mixture of pyrite and dibenzothiophene, a compound
known to be present in bitumen. The oxidation of sulfur
compounds products sulfoxides, sulfites and sulfates.
MNHN, CRC, 75005, Paris, France
University of Antwerp, Department of Chemistry, B-2020, Antwerp, Belgium
3
MNHN, IMPMC, 75005, Paris, France
4
SOLEIL, LUCIA, 91190, Saint Aubin, France
2
Washing treatments in water has no significant effect on
sulfur speciation, even after five months. Sulfates are nevertheless released in the bath, pointing out a decrease of
sulfur content. In peroxide hydrogen solution, this release
is stronger and sulfates are identified in both woods and
solution. Comparison of drying protocols shows that oxidation largely depends on humidity and to a lesser extent
on oxygen: in dry air, sulfur is mostly present in its reduced
form. In wet air, sulfates grow within the first days of exposure, after which, no more is produced.
These data incline conservative protocol towards fast conditioning of the samples, in humidity controlled environment
rather than anoxic ones. These conclusions are noticeable
as the control of humidity is easier and cheaper to achieve
than that of oxygen.
65
NOTES
66
O-25
11 sept. 2014
15:00 > 15:20
Nicholas Edwards1 - Phillip Manning1 - Victoria Egerton1
William Sellers2 - Uwe Bergmann3 - Roy Wogelius1
University of Manchester, School of Earth, Atmospheric and Environmental
Sciences, M13 9PL, Manchester, UK
2
University of Manchester, Faculty of Life Sciences, M13 9PL, Manchester, UK
3
SLAC National Accelerator Laboratory, Linac Coherent Light Source, 94025,
Menlo Park, USA
1
When photons meet
fossils: the chemistry
of ancient life
It was generally perceived by the palaeontological community that “ soft-tissue ” fossils (such as plants, skin, fur, feathers)
are little more than highly altered and/or replicated traces
of the living organisms. Indeed, such soft-tissues degrade
rapidly in most environments and so it was believed that
their preservation over tens and hundreds of millions of
years could only be the result of a unique combination of
post-mortem bio- and geochemical processes that altered
their composition into something that could be preserved.
Consequently, it was also believed that any chemical analysis of these fossil tissues would reveal little useful information about the original organism, let alone something as
distant as their original biochemistry. However, many recent
studies on a range of fossil tissues have shown that remnants of the original biochemistry may well be preserved.
One avenue of research, currently being led by the University of Manchester (UK), is the use of chemical imaging
techniques to identify and map the chemical inventory
of fossil tissues in-situ within their geological matrices.
Three primary non-destructive techniques: Synchrotron
X-ray Fluorescence imaging, X-ray Absorption Spectroscopy
and Fourier Transform Infrared Spectroscopy imaging have
shown that remnants of both the trace metal (organometallic) and organic (protein) inventory within soft-tissue fossils
may be preserved, detected and mapped within discrete
biological structures over entire organisms after hundreds of
millions of years. Key results from this work include the identification of remnant skin protein and dental chemistry in
50 million year old reptile fossils [1,2], and the identification
and imaging of the metallome (bioaccumulated metals) in
1) 50 million year old plant material [3] and
2) feathers up to 150 million years old [4,5].
Bibliography
[1] N. P. Edwards, H. E. Barden, B. E. van Dongen, P. L. Manning, P. L. Larson,
U. Bergmann, W. Sellers and R. A. Wogelius, Proc. R. Soc. London, Ser. B,
2011, 278, 3209–3218.
[2] N. P. Edwards, R. A. Wogelius, U. Bergmann, P. L. Larson, W. I. Sellers
and P. L. Manning, Appl. Phys. A, 2013, 111(1), 147–155.
[3] N. P. Edwards, P. L. Manning, U. Bergmann, P. L. Larson, B. E. van Dongen,
W. I. Sellers, S. M. Webb, D. Sokaras, R. Alonso-Mori, K. Ignatyev, H. E. Barden,
A. van Veelen, J. Anné, V. M. Egerton and R. A. Wogelius, Metallomics, 2014,
6, 774-782.
[4] P. L. Manning, N. P. Edwards, R. A. Wogelius, U. Bergmann, H. E. Barden,
P. L. Larson, D. Schwarz-Wings, V. M. Egerton, D. Sokaras, R. A. Mori
and W. I. Sellers, J. Anal. At. Spectrom., 2013, 28, 1024–1030.
[5] R. A. Wogelius, P. L. Manning, H. E. Barden, N. P. Edwards, S. M. Webb,
W. I. Sellers, K. G. Taylor, P. L. Larson, P. Dodson, H. You, L. Da-qing
and U. Bergmann, Science, 2011, 333, 1622–1626.
67
NOTES
68
O-26
11 sept. 2014
15:20 > 15:40
Pierre Gueriau1 - Loïc Bertrand2,3
Muséum national d’Histoire naturelle, CR2P UMR 7207, 75005, Paris, France
SOLEIL synchrotron, 91192, Gif-Sur-Yvette, France
3
IPANEMA USR 3461, 91192, Gif-Sur-Yvette, France
1
2
Fossilization and
diagenesis in the
Djebel Oum Tkout
Lagerstätte (upper
Cretaceous, Morocco):
insights from rare earth
elements microscale
spectroscopy
Recent studies using Synchrotron-based X-ray fluorescence
scanning approaches shed light on the chemistry of fossilized plant and animal remains [1-5]. They particularly focused on organics and metal distributions (at minor-to-trace
levels) but other trace elements such as strontium and rare
earth elements (REEs), which are used in palaeoenvironmental and taphonomic studies, can also be easily mapped using
this technique [6]. We will show that the distributions of
these trace elements are informative at histological scales in
well-preserved fossils from the Upper Cretaceous of Morocco.
Presence of strontium, yttrium and REEs is attributed to their
long-term isomorphous substitution within bone bioapatite and the authigenic apatite that replicated soft-tissues.
Furthermore, we will discuss about the speciation and preferential incorporation of the more informative elements,
studied using microscopic X-ray absorption near edge spectroscopy (XANES) and UV-Visible luminescence spectroscopy, which provide relevant information on the microscale
fossilization, diagenetic and preservation conditions in this
exceptional fossil locality.
Bibliography
[1] Bergmann U et al. (2010) Archaeopteryx feathers and bone chemistry fully
revealed via synchrotron imaging. Proceedings of the National Academy
of Sciences of the USA 107: 9060-9065.
[2] Wogelius R et al. (2011) Trace metals as biomarkers for eumelanin pigment
in the fossil record. Science 333: 1622-1626.
[3] Edwards N et al. (2011) Infrared mapping resolves soft tissue preservation
in 50 million year-old reptile skin. Proceedings of the Royal Society B:
Biological Sciences 278: 3209-3218.
[4] Edwards N et al. (2013) Mapping prehistoric ghosts in the synchrotron.
Applied Physics A 111: 147-155.
[5] Edwards N et al. (2014) Leaf metallome preserved over 50 million years.
Metallomics 6: 774-782.
[6] Gueriau P et al. (2014) Trace elemental imaging of rare earth elements
discriminates tissues at microscale in flat fossils. PLoS One 9(1): e86946.
69
NOTES
70
O-27
11 sept. 2014
15:40 > 16:00
Remnants of life:
integrated geochemical
methods for the analysis
of exceptionally
preserved specimens
Recently published research has shown that the chemical
residue of biochemical processes can, under exceptional
circumstances, be preserved in-situ even in samples that
have been buried over long periods of geological time [1-4].
Soft tissue chemistry can now be resolved even after over
150 million years of aging [2]. Analysis of such specimens
presents a number of obstacles. Along with the difficulties
inherent in analyzing minute quantities of remaining material, such objects are typically rare and valuable hence
destructive sampling is often precluded. Furthermore,
a range of geochemical processes may alter the specimen
in unpredictable ways. Specimen size may make it impossible to use standard techniques that require high vacuum.
Therefore, new analytical methods have been developed to
make chemical analysis of large fossil specimens possible. In
this talk we will show how synchrotron methods can serve
as a spearhead in leading the analysis of such challenging
material [3]. However, given the complex nature of the
analytical problem, it is almost always necessary to combine
Roy Wogelius1 - Nicholas Edwards1 - Arjen van Veelen1
Victoria Egerton1 - Jennifer Anne1 - William Sellers2
Uwe Bergmann3 - Roberto Alonso-Mori4
Konstantin Ignatyev5 - Phillip Manning1
University of Manchester, SEAES, M13 9PL, Manchester, UK
University of Manchester, FLS, M13 9PL, Manchester, UK
3
SLAC Nat. Acc. Lab., LCLS, 94025, Menlo Park, USA
4
SLAC Nat. Acc. Lab., SSRL, 94025, Menlo Park, USA
5
Diamond Light Source, I18, OX11 0DE, Didcot, UK
1
2
several different techniques in order to fully constrain the
chemistry [1-4]. We will discuss the application of several
complementary methods to the analysis of a range of fossils
including bone and soft tissue. In particular, we show how
advances in synchrotron rapid scanning X-ray fluorescence,
microfocus imaging, X-ray absorption spectroscopy, and
infra-red mapping can be combined for the study of the
distribution of organometallic complexes within residual
organic-rich regions of large specimens. We will also show
how these methods can be used to select small regions for
pinpoint destructive analysis in order to maximize chemical results but minimize damage to precious material and
how overprinting geochemical processes may be resolved
via thorough analysis of the embedding matrix. Examples
involving different biological tissues (skin, hair, feathers,
bone, leaves) from a range of locations and ages will be discussed within the context of analytical approach, specimen
constraints, desired data, and final outcome. Special attention will be given to the resolution of pigment patterns [1,2].
Bibliography
[1] Wogelius et al. (2011) “ Trace metals as biomarkers for eumelanin pigment
in the fossil record, ” Science 333, 1622-1626.
[2] Manning et al. (2013) “ Synchrotron-based chemical imaging reveals
plumage patterns in a 150 million year old early bird, ” J. Anal. At. Spectrom.
28, 1024-1030.
[3] Bergmann U., Manning P.L and Wogelius R.A. (2012) “ Chemical mapping
of Paleontological and Archeological Artifacts with Synchrotron X-Rays, ”
Ann. Rev. Anal. Chem. 5, 361-389.
[4] Edwards et al. (2014) “ Leaf metallome preserved over 50 million years ,”
Metallomics 6, 774-782.
71
NOTES
72
O-28
11 sept. 2014
16:30 > 16:50
Treena Swanston1 - Tamara Varney2 - Ian Coulthard3
Reg Murphy4, David Cooper1
University of Saskatchewan, Department of Anatomy & Cell Biology, S7N 5E5,
Saskatoon, Canada
2
Lakehead University, Department of Anthropology, P7B 5E1, Thunder Bay, Canada
3
Canadian Light Source, Experimental Facilities Division, S7N 2V3, Saskatoon, Canada
4
National Parks Antigua, Heritage Resources, P7B 5E1, St. John’s, Antigua, W.I.
1
Confocal X-ray
fluorescence and
the biogenic uptake
of strontium
in colonial Antigua
Strontium (Sr) is a non-essential trace element with
properties similar to calcium. Trace element analyses
in the past have included Sr as an element of interest
because its presence within modern bone is directly
related to the diet of that individual. Until recently, it
was difficult to determine whether Sr in archaeological samples was a result of biogenic uptake or diagenesis. Confocal X-ray fluorescence is a valuable technique for differentiating between these two modes.
This technique was utilized at the Advanced Photon Source
on Beamline 20-ID where we analyzed samples from mul-
tiple individuals associated with the Royal Naval Cemetery
(1793-1822) in Antigua plus a sample from a pre-European
contact site (Muddy Bay) as part of a larger project with the
goal of identifying the social determinants of lead poisoning.
Two of the samples indicating differential strontium uptake
during bone remodelling events were from individuals with
European ancestry as determined by the cranial features.
In this paper we will discuss the advantages of using
synchrotron radiation to identify the biogenic uptake of
strontium, which suggests geographic and/or seasonal variation of the Royal Naval expeditions during colonial times.
Bibliography
[1] Swanston, T., Varney, T., Coulthard, I., Feng, R., Bewer, B., Murphy, R., Hennig,
C., Cooper, D. 2012. Element localization in archaeological bone using
synchrotron radiation x-ray fluorescence: Identification of biogenic uptake.
Journal of Archaeological Science 39(7):2409-2413.
73
NOTES
74
O-29
11 sept. 2014
16:50 > 17:10
Pigment preservation
in Egyptian mummified
tissues
The image we have of ancient Egyptians mostly comes from
how they depicted themselves in brightly coloured tomb
paintings. Men and women are illustrated with jet-black hair.
Mummified remains however tell a different story, the hair
found almost always appear to have a reddish-brown colour
and the same is true for animal remains. This uniformity of
colour has been attributed to partial oxidation of melanin
pigments [1,2] although red dyes may also have been applied [3]. Our international research effort has recently developed the ability to non-destructively image, analyse and
quantify chemical residues within palaeontological samples
with unprecedented speed and sensitivity. The work undertaken by a team from the University of Manchester, working
at both Stanford Synchrotron Radiation Lightsource and
the Diamond Lightsource, has demonstrated that pigment
chemistry can survive thousands or even millions of years.
Detailed chemical analysis indicates we have the capability
to non-destructively detect, map and quantity pigment
chemistry and reconstruct possible patterns within fossil/
sub-fossil tissue for the very first time [4,5].
Bart van Dongen1 - Natalie Mccreesh1 - Holly Barden1
Campbell Price2 - Tristan Lowe3 - Nicholas Edwards1
Jennifer Anne1 - Victoria Egerton1 - Phillip Manning1
Roy Wogelius1
Science and Williamson Research Centre for Molecular Environmental
Science, M13 9PL, Manchester, United Kingdom
2
University of Manchester, Manchester Museum, M13 9PL, Manchester,
United Kingdom
3
University of Manchester, Henry Mosley X-Ray Imaging Facility, M13 9PL,
Manchester, United Kingdom
1
Here we apply state-of-the-art synchrotron-based imaging
and spectroscopy to analyse a sample of mummified hair
encased in a ball of clay from the New Kingdom (c. 1295 B.C),
opened by Egyptologists a century ago [6] and currently
part of the Egyptology collection held at The Manchester
Museum (University of Manchester). Although having the
same reddish-brown colour as most Egyptian mummified
material, we identify original pigment composition and
discuss the impact of mummification on possible pigment
preservation. Our approach provides a unique opportunity
to study the effects of preservation methods widely applied
in antiquity with the potential to reconstruct the pigmentation of a suite of mummified tissue types. Our ultimate goal
is to begin to restore the colour of Ancient Egypt.
Bibliography
[1] Brothwell, D. and R. Spearman, (1963), The hair of earlier peoples, in Science
in Archaeology: a Comprehensive Survey of Progress and Research.,
D. Brothwell and E. Higgs, Editors. Thames & Hudson: London. p. 427-436.
[2] Hrdy, D.B., (1978), American Journal of Physical Anthropology, 49, 277-282.
[3] Fletcher, J., (2002), The Ostracon 13 2-8.
[4] Bergmann, U., R.W. Morton, P.L. Manning, W.I. Sellers, S. Farrar, K.G. Huntley,
R.A. Wogelius, and P. Larson, (2010), Proceedings of the National Academy
of Sciences, 107, 9060-9065.
[5] Edwards, N.P., P.L. Manning, U. Bergmann, P. Larson, B.E. van Dongen,
W. Sellers, S.M. Webb, D. Sokaras, R. Alonso-Mori, K. Ignatyev, H. Barden,
A. van Veelen, J. Anne, V.M. Egerton, and R.A. Wogelius, (2014), Metallomics,
6, 774-782.
[6] Crompton, W.M., (1916), The Journal of Egyptian Archaeology, 3, 128.
75
NOTES
76
O-30
11 sept. 2014
17:10 > 17:40
Émilie Chalmin1
1
Université de Savoie, CISM-EDYTEM, 73376, Le Bourget Du Lac, France
Rock art pigments:
alteration
and weathering
processes in caves
and open sites
Prehistoric rock art is one of the most ancient arts currently
known thanks to its preservation in limestone caves in SW
Europe and in open sites (South of Africa, Tassili, Australia...);
however, this art is threatened by numerous alteration and
weathering phenomena. These phenomena could lead
to the damage or the total disappearance of the paints.
Environmental parameters, meteorological and anthropic
effects could be involved in these processes.
Understanding these phenomena involving physico-chemical and/or biological processes is essential to preserve
our cultural heritage and requires specific methodological
development adapted to the complex, delicate and precious samples. The use of synchrotron-based methods is
now well known to answer to this problematic of mixture
of phases, heterogeneity of these kinds of samples. Through
examples of rock art studies in France and Australia, the
investigation of natural and biosynthetic samples by means
of combined laboratory and synchrotron methods enables
to reach 3 processes:
The first example is coming from Jawoyn rock art, in Arnhem
Land (North Australia) considered as the most ancient rock
Bibliography
[1] David, B., Geneste, J.-M., Whear, R. L. et al. (2011). Australian Archaeology
73: 73.
[2] David, B., Barker, B., Petchey, F. et al. (2013). Journal of Archaeological
Science 40(5): 2493-2501.
[3] Chalmin E., Castets G., Delannoy J.J. et al. (submitted) coédition ERAUL
(université de Liège) - Service géologique de Belgique
[4] Allemand, L. & Bahn, P. G. (2005). Nature 433(7028): 800-800.
[5] Bastian, F., Jurado, V., Novakova, A. et al. (2010). Microbiology 156(3):
644-652.
[6] Hoerlé, S., Konik, S. & Chalmin, E. (2011). Karstologia 58: 29-40.
[7] Chalmin, E., Sansot, E., Orial, G. et al. (2008). X-Ray Spectrometry 37: 424-434.
[8] Chalmin, E. & Reiche, I. (2013). Microscopy and Microanalysis 19: 1523-1534.
art of the Australia due to archaeological and geomorphological studies, which reveal the presence of the first
humans on the Australian continent (45-5000 years BP)[1,2].
However, in the absence of radiometric dates relating to the
art (paintings, rock crusts), our aims are:
(I) to systematically assess whether the painting could have
been done ~ 40,000 years ago and
(II) to characterize the painting matter. Due to the rock
substrate weathering and the very thin layer of remaining
pigment, the characterization is particularly challenging
and enables to understand the weathering process [3].
Secondly, the Lascaux cave, well known for the impact of the
biocide treatment [4,5], is also threatened by the presence
of vermiculation, small aggregates of particles, bound by a
matrix of clay and precipitated calcite and often found in
karstic environments. New vermiculations were reported
in some spots nearby paints. A protocol was proposed in
order to understand the formation mechanisms of vermiculations, in order to prevent any impact of this phenomenon
on rock art [6].
Finally, a peculiar study case concerns calcium carbonate
formations in caves such as Large cave of Arcy-sur-Cure
(Yonne), where the prehistoric figures are completely masked by a white opaque calcite layer [7]. The role of the bacteria in the sensitive equilibrium of the cave environment
seems to be non-negligible [5]. In the case of the Large cave,
we attempt to determine if bacteria are playing a role in this
opaque calcite layer supposed to be due to biomineralization. Two questions are addressed (i) Is it possible to find one
or several biogenic tracers in the natural neoformed calcite
phases? And (ii) can we find such biogenic tracers in natural
white opaque calcite from the Large cave and get clues on
the role of bacteria in their formation [8]?
77
NOTES
78
O-31
12 sept. 2014
09:30 > 10:00
Trinitat Pradell1 - Gloria Molina1 - Sonia Murcia2
Judit Molera3
Universitat Politècnica de Catalunya, Dpt. Física, 08860, Castelldefels, Spain
Univrsidad de Valencia, 3Instituto de Ciencia de los Materiales,
46980, Paterna, Spain
3
Universitat de Vic, Escola Politècnica Superior, 08500, Vic, Spain
1
Materials,
techniques
and conservation
of 15th to 19th centuries
stain glass “ grisailles ”
2
A grisaille is a brown-blackish paint applied onto the inner
surface of stain glass to draw the contours and details of the
figures and generate shades and volumes in the faces, hair,
hands and clothing. Grisailles were traditionally made of
finely ground oxides of iron but also of copper, zinc, lead or
manganese mixed with lead ground glass, Arabic gum and a
medium such as vinegar or urine and fixed onto the flat glass
by firing. The lead glass is known to have a lower melting
temperature than the window glass softening temperature
and therefore, can be fixed without affecting its stability.
Grisailles are consequently a mixture of unreacted substances, crystalline and amorphous compounds produced
during firing but also resulting from their weathering and
aging. Grisailles were applied between the 13th century
(Gothic) and the first half of the 16th century (Renaissance)
together with yellow stains on either transparent or coloured
bulk glass and also later with enamels and plaqué glass.
During the second half of the 16th century the new religious
Calvinism Iconoclasm and the Reformation in the North
of Europe but also the Trento Council in the Catholic
Church resulted in a mass destruction of stain glass and
its substitution by transparent glass in Religious buildings
and, consequently in a progressive loss of old stained glass
techniques. Stain glass was rediscovered in the 19th century
all over Europe becoming a fundamental decorative element of the new esthetic movements; in this period stain
glass also incorporated technical innovations and a general
reformulation of the materials used, that seems to have
negatively influenced its stability. However, the micrometric
layer structure of the grisailles (typical layer thicknesses vary
between 10 and 100 µm) together with the low amount
and diverse nature of the compounds (pigment particles,
crystalline and amorphous reaction compounds, aging
and weathering compounds) have limited their identification. The high brilliance, collimation, energy selection and
monochromacity of the SR beam are ideal to obtain 2D
micro-XRD maps from thin cross sections of the grisailles.
XRD-patterns with a high signal to noise ratio and angular
resolution were obtained using a 20 µm × 20 µm spot size,
28 kV energy and a CCD camera, SX165 (Rayonix) area detector in MDPD beamline at Alba-Cells. The analyses are complemented with SEM-EDX analyses of the cross sections of
the grisailles. A selection of grisailles from several cathedrals
in Spain (Avila, Burgos, Alcalá de Henares, Segovia) a dating
from 15th to the 19th century and belonging to several master
glaziers are studied. Changes in the methods of production
and materials in the different historical periods are obtained
and also related to the conservation state of late materials.
79
NOTES
80
O-32
12 sept. 2014
10:00 > 10:20
Ilaria Cianchetta1 - Karen Trentelman1 - Brendan Foran2
Marc Walton3 - Apurva Mehta4
The Getty Conservation Institute, 1200 Getty Center Dr., 90049, Los Angeles, USA
The Aerospace Corporation, 2350 E. El Segundo Blvd., 90245-4691, El Segundo, USA
3
Art Institute of Chicago, 111 S Michigan Ave., 60603, Chicago, USA
4
SLAC National Accelerator Laboratory, 2575 Sand Hill Road, 94025-7015, Menlo Park, USA
1
Deciphering ancient
ceramic firing
conditions through
replication
2
The decorated ceramics produced in ancient Athens from
the 6th through the 4th centuries BCE, also known as Attic
pottery, are considered a benchmark technological achievement of the pre-industrial world. The iconic black-figure
vessels (black figures painted on red reserve), and the later,
more refined, red-figure vessels (figures left in reserve on
a black background), demonstrate a sophisticated control
of particle morphology, porosity and firing conditions.
Both techniques achieved the production of smooth
and glossy black surfaces layers – called black gloss – by
alternating the high-temperature kiln between oxidative
and reductive environments during firing. Areas painted
with a refined slip turned from red (due to the presence of
Fe3+ compounds: hematite, α-Fe2O3 and maghemite, γ -Fe2O3)
to black (Fe2+ iron compounds: magnetite, Fe3O4, hercynite,
FeAl2O4) depending on the atmospheric condition of each
stage. Although a basic understanding of their production
has been developed [1], details regarding the painting and
firing schemes employed are still not completely understood
In order to understand the technological foundations of
Athenian pottery production [2,3], we have examined each
step of the black gloss production individually to understand
the role of thermodynamics and kinetics in controlling the
overall process. This presentation will focus on the effects
of firing conditions on the density and color of the gloss
produced. Over 50 replicate samples were painted with
refined illitic clay and fired using a three-stage (oxidation-reduction-oxidation) firing protocol, systematically varying the
temperature, and duration of the stages. The resulting gloss
samples ranged in color from bright red to deep black, as
well as “ misfired ” samples in which both red and black gloss
is formed, all similar in appearance to examples found on
ancient Athenian pottery. The body and slip of the samples
were characterized by colorimetry, ICPMS, micro-XRF and
XANES to determine the chemistry, color and mineralogy
of the gloss. Statistical analysisof the data indicate that the
temperature and duration of each of the oxidative steps –
the first and third stages in the canonical three step firing
sequence– is critical for controlling the color and the density
of the glosses produced.
In order to understand the state of black gloss production
technology and how it evolved over four centuries - from
the Corinthian production of the 7th century BC, through the
Athenian production of the 6th and 5th century BC, ending
with Faliscan and Apulian production of the 4th century BC we examined and analyzed the color and mineralogy of 25
original Greek and Italian sherds belonging to the collection
of the J. Paul Getty Museum. This materials characterization
approach is beginning to provide very detailed glimpses
into not only how this benchmark technology evolved, but
also the variations in the production processes practiced by
contemporary workshops.
Bibliography
[1] J.V. Noble, The technique of Attic vase painting, American Journal of
Archaelogy 64, (1960) 307-313
[2] M. S. Walton E. Dohene, K. Trentelman, G. Chiari, J. Maish, A. Buxbaum
Characterization of coral red slips on greek attic pottery, Archaeometry 51,
3, (2009) 383–396
[3] M. Walton, K. Trentelman, M. Cummings, G. Poretti, J. Maish, D. Saunders,
B. Foran, M. Brodie, A. Mehta, Material Evidence for Multiple Firings
of Ancient Athenian Red-Figure Pottery, Journal of American Ceramic
Society 96, 7, (2013) 2031–2035
81
NOTES
82
O-33
12 sept. 2014
10:20 > 10:40
Marie Albéric1,2 - Aurélien Gourrier3,4
Wolfgang Wagermaier2 - Peter Fratzl2 - Ina Reiche1,5
Sorbonne Universités, Laboratoire d’archéologie Moléculaire et Structurale
(LAMS), UMR 8220 CNRS UPMC, 75005, Paris, France
2
Max Planck Institute of Colloids and Interfaces, Research Campus - GOLM
Biomaterials Department, 14424, Potsdam, Germany
3
UMR 5588 CNRS Université Grenoble Alpes, Laboratoire Interdisciplinaire
de Physique (LIPHY), 38000, Grenoble, France
4
European Synchrotron Radiation Facility, Grenoble, FRANCE5 BESSY II;
Helmholtz-Zentrum Berlin für Materialien und Energie, 14476, Berlin, Germany
5
Rathgen-Forschungslabor, Staatliche Museen zu Berlin, 14059, Berlin, Germany
1
Difference between
sub-microscopic
and macroscopic
preservation states of
marine archaeological
elephant tusks revealed
by micro-SAXS/WAXS
analysis
Elephant ivory used to manufacture art objects from prehistoric to contemporary times is a biological nano-composite
material subjected to complex physico-chemical alteration
mechanisms occurring over time [1,2]. Ivory, the dentin part
of elephant tusks is composed of an organic collagen-based
matrix at 20 % with embedded Mg-rich carbonated hydroxyapatite (HAP) at 70 wt. % and 10 % water. It presents
a highly hierarchical structure [3]. The proper conservation
of valuable ivory artefacts needs the understanding of
the mechanisms responsible for structural modifications,
including the HAP crystal size, organization and collagen
fiber orientation.
Micro-SAXS/WAXS profiling [4,5] performed under synchrotron radiation at the MySpot beamline (BESSY II, Berlin)
allowed us to characterize the structural features of three elephant tusks recovered from a 17th century Dutch shipwreck
in Brittany seawaters. By comparison to modern elephant
tusks, the structural changes have been identified and linked to different mechanisms, which slightly varies from one
tusk to another depending on the very specific local marine
environment of each tusk. The most surprising result is that
the macroscopical preservation states of the surfaces do
not always reflect the microscopical preservation states of
the inner parts. This shows the importance of studying the
entire material at different levels of organization to better
understand the alterations occurring in ivory from marine
environment and to propose conservation treatments well
suited for archeological ivory objects from seawaters.
Bibliography
[1] Lafontaine, R. H., Wood, P. A., 1982. The stabilization of Ivory against
relative humidity fluctuations. Studies in Conservation 27, 109-117.
[2] Godfrey, I. M., Ghisalberti, E. L., Beng, E. W., Byrne, L. T. and Richardson,
G. W., 2002. The analysis of ivory from a marine environment.
Studies of Conservation 47, 29–45.
[3] Su, X.W., and Cui, F.Z., 1999. Hierarchical structure of ivory: from nanometer
to centimeter. Materials Science and Engineering C 7, 19-29.
[4] Wess, T.J., Drakoopoulos, M., Snigirev, A., Wouters, J., Paris, O., Fratzl, P., Collins,
M., Hiller, J., Nielsen, K., 2001. The use of small angle X-ray diffraction studies
for the analysis of structural features in archaeological samples.
Archaeometry 43, 117–129.
[5] Gourrier, A., Bunk, O., Müller, K. Reiche, I., 2011. Artificially heated bone at
low temperatures: a quantitative scanning-small-angle X-ray scattering
imaging study of the mineral particle size. Archeoscience, 35, 191-199
83
NOTES
84
O-34
12 sept. 2014
10:40 > 11:00
The use
of synchrotron
radiation for
the analysis of
the distribution
of additives in ABS
design objects
and model samples
Acrylonitrile Butadiene Styrene (ABS)-based plastics are found
in numerous design objects in museums collections and are
widely used today for the excellent mechanical, chemical,
and physical properties. However, ABS is susceptible to
photo-oxidative degradation and this instability often leads
to the loss of properties, chemical modifications, worsening
of mechanical performance and color changes, mainly
yellowing [1]. This is particularly tricky for the conservation of
historical objects and there are currently no ethical methods
to reverse the yellow appearance. The assessment of the
role of additives in polymers degradation is a critical point
for the conservation and preservation of artefacts made in
plastics. Natural polymers, organic additives and inorganic
colorants are usually found in historical ABS; these materials
are heterogeneously distributed in plastics and are present as
microscopic inclusions, requiring spatially resolved analysis for
their complete characterization.
SR-Fourier Transform Infrared Spectroscopy (SR-FTIR) analyses
were carried out on historical design objects at the ID21
beamline of the European Synchrotron Facility (ESRF). Combining high spatial resolution with high signal to noise ratio
Daniela Saviello1 - Austin Nevin2 - Émeline Pouyet3
V. Capogrosso4 - S. Bellei2 - A. Cesaratto4 - Sara Goidanich1
Lucia Toniolo1 - Marine Cotte3
Politecnico di Milano – Dipartimento di Chimica Materiali e Ingegneria
Chimica, Via Luigi Mancinelli 7, 20131, Milano, Italy
2
Consiglio Nazionale delle Ricerche – Istituto di Fotonica e Nanotecnologie
(CNR-IFN), Dipartimento di Fisica, Politecnico di Milano, Piazza L. Da Vinci 32, 20139,
Milano, Italy
3
European Synchrotron Radiation Facility, rue Jules Horowitz 6, F-38000, Grenoble, France
4
Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy
5
LAMS (Laboratoire d’Archéologie Moléculaire et Structurale) UMR-8220,
3 rue Galilée 94200 Ivry-sur-Seine, France
1
spectra, this study allowed comprehensive analysis, providing
2D images associated with molecular information about the
polymer composition and the presence of additives. It allowed
the identification of protein-based additives as microscopic
inclusions in the objects samples. SR-µFTIR analyses were
also carried out on artificially-aged ABS model samples. The
reactive molecular groups and degradation products were
identified and mapped in a superficial layer of a few tens of
microns [2,3].
Some of the aged model samples had been treated with optical brighteners and agar gel in order to improve the appearance of yellowed ABS. As a matter of fact, the yellowing of the
polymer was reduced in this way and at our knowledge this is
the first approach that does not involve the use of aggressive
products. In this work, SR based µ-FTIR will allow mapping
the distribution of such added chemicals and evaluating the
chemical modifications in the polymeric blend following the
treatment, a key issue in the assessment of treated samples.
In a historical object analyzed, microscopic inclusions containing Cd and S were identified through preliminary SEM
analyses. SR-based μ-FTIR, µ-XANES and µ-XRF spectroscopies
will be soon used to map traces of such Cd-based pigments
in thin sections. While CdS-based are well-known as colorants
and stabilizers in ABS used in the past, there are now significant
concerns regarding the leaching of toxic Cd ions from plastics.
In the context of the degradation and stability of historical
plastics, it is not clear if Cd-based colorants improve long-term
stability of ABS to photo-oxidation or if CdS based colorants
present on the surface of the objects are sensitive to oxidation
and formation of CdSO4 and other salts.
Bibliography
[1] Bokria et al. Polymer 2002, 43, 11: 3239–3246;
[2] Nevin, et al. Report on work at ID21 ESRF
[3] E. Pouyet et al., Analytica Chimica Acta, 822, 51-59 (2014)
85
NOTES
86
O-35
12 sept. 2014
11:30 > 11:50
Farideh Jalilehvand1 - Magnus Sandström2
Yvonne Fors3 - Vicki Richards4
University of Calgary, Department of Chemistry, T2N 1N4, Calgary, Canada
Stockholm University, Department of Materials and Environmental
Chemistry, 10691, Stockholm, Sweden
3
Department of Conservation, University of Gothenburg, 41320, Göteborg, Sweden
4
Western Australian Museum, Shipwreck Galleries, 6160, Fremantle, Australia
1
X-ray spectroscopic
characterization
of sulfur compounds
in marine
archaeological wood
Conservation of marine archaeological wood from historical shipwrecks increasingly relies on modern analytical
techniques to obtain insights into improving specifically
designed treatments [1]. Synchrotron radiation plays an
important role in allowing characterization of many types
of sulfur and iron compounds accumulated in the wood on
the seabed, which is important in assessing the long-term
detrimental processes associated with their post treatment.
Generally, the incorporated sulfur compounds originate from
hydrogen sulfide produced by sulfate-reducing bacteria in
wood buried under the seabed [2-4]. Analyses of the amount
and speciation of the sulfur compounds can be performed
by X-ray spectroscopic methods, in particular sulfur K-edge
XANES (X-ray Absorption Near Edge Structure), combined
with elemental analyses by scanning X-ray fluorescence
(XRF) of wood cores. By fitting normalized sulfur K-edge
XANES spectra of structurally known sulfur compounds as
models to spectra of wood samples, the relative amounts
Bibliography
[1] Y. Fors, F. Jalilehvand, M. Sandström, Analytical Aspects of Waterlogged
Wood in Historical Shipwrecks, Anal. Sci., 2011, 27, 785-792.
[2]. Y. Fors, T. Nilsson, E. D. Risberg, M. Sandström and P. Torssander, Sulfur
accumulation in pine wood (Pinus sylvestris) induced by bacteria
in simulated seabed environment: implications for marine-archaeological
wood and fossil fuels, Int. Biodeterior. Biodegrad., 2008, 62, 336-347.
[3] Y. Fors, F. Jalilehvand, E. Damian Risberg, C. Björdal, E. Phillips, M. Sandström,
Sulfur and iron analyses of marine archaeological wood in shipwrecks from
the Baltic Sea and Scandinavian waters, J. Arch. Sci. 2012, 39, 2521-2532.
[4] Y. Fors, H. Grudd, A. Rindby, F. Jalilehvand, M. Sandström, I. Cato,
L. Bornmalm, Sulfur and iron accumulation in three marine-archaeological
shipwrecks in the Baltic Sea: The Ghost, the Crown and the Sword, Sci. Rep.
2014, 4, 4222; DOI:10.1038/srep04222.
2
of different types of functional sulfur groups are evaluated,
while the total sulfur and iron concentrations are obtained
by calibrating their X-ray fluorescence in XRF experiments.
High resolution X-ray spectromicroscopy at the sulfur K-edge
shows that organically bound sulfur (mainly thiols, disulfides)
accumulates in lignin-rich parts of the wood cell walls. Of
special interest for the conservation treatment regime are,
however, the iron sulfides including pyrite, which form in
the presence of corroding iron objects. The iron sulfides
are subsequently easily oxidised at post treatment under
atmospheric conditions with high humidity. Sulfur K-edge
XANES spectra often show iron sulfides to be present in
treated museum artefacts affected by acidity problems and
formation of iron sulfate salts. Laboratory experiments show
that some types of the unstable iron sulfides formed within
the wood are coupled to bacterial activity and resemble
ferredoxin-type iron-sulfur clusters [2]. Samples from PEG
treated timbers from shipwrecks displayed in museums
worldwide, (e.g. the Batavia, Australia, the Mary Rose, UK, the
Skuldelev Viking ships, Denmark, the Vasa, Sweden) will be
compared with timber samples recovered from the seabed
(e.g. from the Pandora, Australia, the Mary Rose, UK, the Ghost
ship and Kronan, Sweden) to discuss the effects of various
conservation treatments.
87
NOTES
88
O-36
12 sept. 2014
11:50 > 12:10
Chris McGlinchey1 - Felisa Berenguer2 - Kevin G. Yager3
Rebecca Ploeger4 - René de la Rie5
The Museum of Modern Art, 11 West 53Rd St, 10019, New York, Ny, USA
IPANEMA, L’Orme des Merisiers, 91192, Saint Aubin, Gif-Sur-Yvette, France
3
Center for Functional Nanomaterials - BNL, P.o. Box 5000 Bldg. 735, 11973, Upton, Ny, USA
4
Art Conservation Dept. Buffalo State College, 1300 Elmwood Dr, 14222, Buffalo, NY, USA
5
Art Conservation Dept. University Of Amsterdam, PO Box 19268, 1000 GG,
Amsterdam, The Netherlands
1
Synchrotron X-ray
scattering
of ethylene vinyl
acetate copolymer
based art conservation
adhesives: elucidation
of morphological
differences
The ethylene vinyl acetate copolymer based art conservation
adhesives BEVA 371 and BEVA 371b are dry to the touch at
room temperature and become highly tacky soft solids capable of adhesion between 60 and 65 ºC, the recommended
activation temperature for both adhesives. These two formulations have the same semicrystalline components (two
ethylene vinyl acetate (EVA) copolymers and paraffin wax) but
have different low molecular weight additives (amorphous
ketone resins). Recent published findings (Ploeger 2014)
have found that the formulations vary in tack below the recommended activation temperature: 371 begins to develop
some tack above 45 ºC while 371b achieves tack more abruptly between 55 and 60 ºC. This is significant because 371,
the original formulation, is no longer available yet having
gradual tack development can sometimes be exploited by
conservators if the object is temperature sensitive or a weaker adhesive bond is desired. Small angle X-ray scattering
(SAXS) studies help reveal the structural differences that are
likely responsible for the change in activation properties.
These studies carried out at the SWING beamline at SOLEIL indicate the ketone resins influence the ability of the
2
polyethylene component of the copolymer to recrystallize
upon cooling. Pure EVA copolymers at 20 ºC indicate a crystal
structure (peak at Q ~ 0.055 nm–1) that is nearly eliminated in
formulation 371, but retained in 371b. This indicates that the
polyethylene phase is mostly amorphous in 371 at room temperature which helps explain the gradual tack development
as the material is heated. When heated to 65 ºC both show
a peak at Q ~ 0.03 nm–1 but in formulation 371b it is much
stronger, indicating greater crystallinity. Formulation 371,
examined by wide angle X-ray diffraction at beamline X27C
at Brookhaven National Lab, exhibited diffraction peaks
corresponding to the -CH2- (orthorhombic) unit cell, which
were retained at the activation temperature, 65 ºC. Polarized
light microscopy at 65 ºC also shows a weak crystal structure
evenly dispersed throughout the material in both formulations and helps explain why neither acts as free-flowing
liquid at the recommended activation temperature. The
findings demonstrate that SAXS is a useful tool to study
resin-copolymer compatibility for this class of adhesives and
may help guide the development of future formulations
when specific activation properties are desired.
89
NOTES
90
O-37
12 sept. 2014
12:10 > 12:30
Domagoj Mudronja1 - Frederik Vanmeert2
Kevin Hellemans2 - Stjepko Fazinic3 - Darko Tibljas4
Koen Janssens2
Optimization of
an ammonium oxalate
treatment for
the protection of
monumental limestone
and marble surfaces
1
Stone samples have been treated with two application methods (poultice and brushing) using a solution of ammonium
oxalate (AmOx) and varying treatment time. Limestone and
marble model samples with different porosity were selected,
and attention was specifically focused to study brushing
treatment, which is economically more feasible on large
surfaces than the poultice method for creating an acid-resistant calcium oxalate (CaOx) layer. The distribution/contrast
between calcite and the two Ca-oxalate forms (weddellite
and whewellite) on treated stone samples was visualized using
synchrotron-based micro analytical techniques (SR-µXRD
in transmission geometry with 10.5 × 6.5 µm2 (hor. × vert.)
probe size and SR-µFTIR with 10×10 µm2 probe size). SR-µXRD
provided information on the layer thickness of the two oxalate
forms while SR-µFTIR was used to visualize the distribution of
calcium oxalate on the stone surface.
SR-µXRD results of two brushing treatments (1 and 3 hours
treatment time) on two different stones showed that on the
less porous (2 %) Carrara marble there is only a small difference
between the shorter and longer treatment. The oxalate layer
thickness, consisting of both weddellite and whewellite,
is between 30 and 40 µm. The measured diffraction intensity
of both calcium oxalates is approximately the same for both
treatments. On the more porous (7 %) Veselje limestone the
difference between the shorter and longer brushing treatment is more visible. The thickness of the weddellite layer is
approximately the same for both treatment times (roughly
50 µm). Whewellite reaches a depth of around 400 µm with
the 3h treatment compared to 150 µm for the 1h treatment.
The measured intensity of both calcium oxalates is higher on
stones treated with the longer treatment time.
SR-µFTIR comparison of the CaOx distribution on surfaces
treated by brushing on two model stones showed that on
a less porous Carrara marble there is no difference between
shorter and longer treatments. This difference is more visible
on more porous Veselje limestone, as the surface of the stones
after longer brushing treatments shows a higher coverage
with oxalate. It seems that on the less porous stone after 1 h of
brushing treatment the layer of CaOx is more homogeneous, so
there is no more CaCO3 left on the surface to react with AmOx.
On the more porous stone after one hour of treatment, there is
still some CaCO3 on the surface that reacts during subsequent
application of AmOx.
Both analytical methods confirmed that on less porous stones
(<2 %) there is actually no difference between different application methods and treatment times, since a protective
CaOx layer has been homogeneously formed after 1 hour of
brushing or ten hours of poultice treatment. Stones that are
more porous need a longer brushing treatment to create
a similar CaOx layer.
Bibliography
[1] De Nolf, W., Janssens, K., Surface and Interface Analysis, 2010, 42, 411
[2] Doherty, B., Pamplona, M., Selvaggi, R., Milliani, C., Matteini, M., Sgamellotti,
A., Brunetti, B., Applied Surface Science, 2007, 253, 4477
[3] Doherty, B., Pamplona, M., Matteini, M., Sgamellotti, A., Brunetti, B., Journal
of Cultural Heritage, 2007, 8, 186
[4] Mairani, A., Matteini, M., Rizzi, M., OPD Restauro, 2000, 12, 146
[5] Matteini, M., Moles, A., Lanterna, G., Nepoti, M.R., International Symposium II:
The Oxalate Films in the Conservation of Works of Art, 1996, 425
[6] Matteini, M., Conservation Science in Cultural Heritage, 2008, 13
[7] Mudronja, D., Vanmeert, F., Hellemans, K., Fazinic, S., Janssens, K., Tibljas,
D., Rogosic, M., Jakovljevic, S. Applied physics. A, Materials science
& processing, 2013, 111, 108
[8] Pinna, D., Salvadori, B., Porcinai, S., Construction and Building Materials,
2011, 25, 2723
[9] Vanmeert, F., Mudronja, D., Fazinic, S., Janssens, K., Tibljas, D., X-ray
spectrometry, 2013, 42, 256
Croatian Conservation Institute, Government research institute, 10000, Zagreb,
Croatia
2
University of Antwerp, Government University, 2610, Antwerp, Belgium
3
Rudjer Boskovic Institute, Government Research Institute, 10000, Zagreb, Croatia
4
Institute for Mineralogy and Petrology, Government University, Zagreb, Croatia
91
NOTES
92
O-38
12 sept. 2014
14:10 > 14:40
Catherine Dejoie1 - Philippe Sciau2 - Weidong Li3
Laure Noe2 - Apurva Mehta4 - Kai Chen5 - Hongjie Luo6
Martin Kunz7 - Nobumichi Tamura7 - Zhi Liu7
Learning from
the past: the formation
process of rare ε-Fe2O3
in the ancient
black-glazed Jian
(Tenmoku) wares
1
Ancient Jian wares are famous for their lustrous black glaze
that exhibits unique colored patterns [1,2]. Some striking
examples include the brownish colored « Hare’s Fur » (HF)
strips and the silvery « Oil Spot » (OS) patterns. The Black
glazed “ Jian ware ”, also known in Japan as “ Temmoku ware ”,
was mainly produced in Jian Kiln located in Jianyang of Fujian
Province. The surface patterns of the Jian wares such as Hare’s
Fur and Oil Spot are believed to originate from the crystallization of iron oxides. It is currently believed that hematite
(α-Fe2O3) crystals are formed on the HF surface and mixtures
of magnetite (Fe3O4) and hematite crystals are precipitated
on the OS surface [3]. However few mineralogical studies
have been carried out to confirm this theory. To reveal the
crystallographic nature of the iron oxides and their formation
mechanism, we have investigated the microstructure and
local chemical composition of ancient Jian bowl samples
through a combination of X-ray based and electron based
characterization techniques. For the first time, we identified
the presence of ε-Fe2O3, a rare metastable polymorph of
Fe2O3 with unique magnetic properties [4], in both HF and
OS samples. The micro-XRD results also indicate that there are
differences between ε-Fe2O3 crystallites in the HF sample and
the OS sample. The ε-Fe2O3crystallites in HF are nanometer
size and randomly oriented, while the ε-Fe2O3 crystallites in
the OS sample grow to larger micron size with a dentritic texture. This is a direct indication that the firing conditions of ceramics significantly affect the formation of iron oxide crystals.
OS firing conditions are clearly more favorable to the formation and stabilization of ε-Fe2O3 crystallites of larger size,
which are significantly larger than nano-sized ε-Fe2O3 crystals
that can be synthesized today. These results shed new lights
on the actual mechanisms and kinetics of polymorphous
transitions of Fe2O3. Deciphering technologies behind the
fabrication of ancient Jian wares has the potential to provide
new pathways for the industrial synthesis of the metastable
ε-Fe2O3 phase.
ETH Zurich, Lab. of Crystallography, 8093, Zurich, Switzerland
CEMES, 31055, Toulouse, France
3
Chinese Academy of Sciences, Shanghai Institute of Ceramics, 200050,
Shanghai, China
4
Stanford Synchrotron Radiation Lightsource, 94025, Menlo Park, USA
5
Xi’an Jiaotong University, Center for Advancing Materials Performance from
the Nanoscale, 710049, Xi’An, China
6
Shanghai University, 200436, Shanghai, China
7
Lawrence Berkeley National Lab, Advanced Light Source, 94720, Berkeley, USA
2
Bibliography
[1] Wu, M. P. S. Black-glazed Jian ware and tea drinking in the Song Dynasty.
Vol. 29 22-31 (Orientations, 1998).
[2] Li, W., Luo, H., Li, J., Li, J. & Guo, J. Studies on the microstructure of the
black-glazed bowl sherds excavated from the Jian kiln site of ancient China.
Ceramics International 34, 1473-1480, doi:http://dx.doi.org/10.1016/j.
ceramint.2007.04.004 (2008).
[3] Wood, N. Chinese glazes: their origins, chemistry and recreation.
(Univ of Pennsylvania Press, 1999).
[4] Tronc, E., Chanéac, C. & Jolivet, J. P. Structural and Magnetic Characterization
of ε -Fe2O3. Journal of Solid State Chemistry 139, 93-104, doi:
http://dx.doi.org/10.1006/jssc.1998.7817 (1998).
93
NOTES
94
O-39
12 sept. 2014
14:40 > 15:00
Lukas Helfen1 - Peter Reischig2 - Arie Wallert3 - Joris Dik4
Tilo Baumbach2
ESRF, ID19, 38000, Grenoble, France
KIT, IPS, 76021, Karlsruhe, Germany
3
Rijksmuseum, Restoration and Research, 1070 DN, Amsterdam, The Netherlands
4
TU Delft, 3mE, 2628 CD, Delft, The Netherlands
1
Synchrotron
laminography
for µm-scale
three-dimensional
region-of-interest
imaging of flat artwork
2
Synchrotron laminography is presented as a non-destructive
tool to obtain three-dimensional (3D) information about
paintings and other flat artwork. Information on the genesis
and decay of historical paintings usually lies hidden under
the paint surface. Traditional methods for the study of hidden
paint layers (like radiography and different microscopy techniques) have shortcomings in the lack of depth information /
separation and destructiveness. Confocal methods (e.g.
based on X-ray fluorescence) are restricted to investigate
rather limited 3D regions due to the dwell time required at
each scanning point.
We will point out the potential of synchrotron laminography for
3D region-of-interest imaging of flat artwork. Synchrotron laminography, initially developed for the non-destructive high-resolution imaging in microelectronics and microsystem technology [1],
allows one to zoom with varying spatial resolution into the
paint layer system and to image more representative parts of
a painting. It has recently been shown to yield complementary
information about paint stratigraphy and substructure on mockup specimens [2-4]. Additionally, we will present first results
obtained at the ESRF X-ray imaging beamline ID19 on historical
masterpieces from G. Metsu and F. Hals.
Bibliography
[1] L. Helfen, T. Baumbach, P. Mikulik, D. Kiel, P. Pernot, P. Cloetens and
J. Baruchel: “ High-Resolution Three-Dimensional Imaging of Flat Objects
by Synchrotron-Radiation Computed Laminography ”, Appl. Phys. Lett.
86, 071915 (2005).
[2] K. Krug, L. Porra, P. Coan, G. Tauber, A. Wallert, J. Dik, A. Coerdt, A. Bravin,
M. Elyyan, L. Helfen, and T. Baumbach, “ Relics in Medieval Altarpieces?
Combining X-ray tomographic, laminographic and Phase-Contrast
Imaging to Visualize Thin Organic Objects in Paintings“, J. Synchr. Rad.
15, 55-61 (2008)
[3] J. Dik, P. Reischig, K. Krug, A. Wallert, A. Coerdt, L. Helfen and T. Baumbach,
“ Three-dimensional Imaging of Paint Layers and Paint Substructures
with Synchrotron Radiation Computed µ-Laminography ”, Journal of
the American Institute of Conservation, 48 (3), 185-197 (2009)
[4] P. Reischig, L. Helfen, A. Wallert, T. Baumbach, J. Dik, “ Non-invasive,
three-dimensional X-ray imaging of paint layers ”, Appl. Phys. A. 111,
983-995 (2013)
95
NOTES
96
O-40
12 sept. 2014
15:00 > 15:20
Émeline Pouyet1 - Marine Cotte2 - Barbara Fayard3
Anna Lluveras-Tenorio4 - Jennifer Mass5
Daniela Saviello6 - Austin Nevin7 - Philippe Sciau8
Combined
synchrotron-based
micro-spectroscopic
analyses of painting
thin-sections
1
The complex and heterogeneous structure of paint samples
compromises their chemical characterization. Spectral-imaging techniques, combining microscopy and spectroscopy,
are very well suited to achieve full 2D chemical descriptions of
fragment sections. Both the composition and the stratigraphy
of the multilayered complex mixtures in samples are probed.
Access to a multi-modal and non-invasive platform able to
perform both X-ray and FTIR micro spectroscopies is very
promising for the characterization of painting samples. In this
context, user communities are pushing towards an improved
and easier combination of these techniques [1]. For successful
application of both FTIR and X-ray analysis it is necessary to
improve i) sample preparation and ii) instrumental capabilities.
Indeed, the full exploitation of both micro-FTIR and X-ray
techniques through transmission measurements can open
new avenues for hyper-spectral characterization of historical
paintings. The most standard sample preparation approaches
will be discussed and the related possible analytical and
chemical interferences will be illustrated and solved using
two examples [2]:
I) asian historical leanly bound gilded sculpture fragments, and
II) samples from polymeric design objects from the 1960’s.
The first set of samples shows complex multi-step gilding
techniques based on the use of saponified oil as a mordant.
The polymer samples present a degraded surface due to
photo-oxidation processes, which could be studied analyzing
artificially aged model samples. These results could not have
been obtained without the development of dedicated sample
preparation.
The development of new micro-spectroscopy tools for improving and diversifying the capabilities imaging beamlines
are also in progress. In particular, a new micro-spectroscopy
tool based on a 2D full-field XANES set-up was developed at
ID21, ESRF, combining XAS with full-field X-ray microscopy [3].
In this set-up a series of radiographies are acquired over
millimetric field of view (up to 2 mm2) with sub-micron resolution (down to 0.3×0.3 µm2), while scanning the energy
of the incoming beam around the absorption edge of the
element of interest. Millions of XAS spectra are thus acquired
within few minutes in low dose configuration. This technique
is therefore very well-suited for the 2D study of multilayered and heterogeneous samples such as artistic materials.
The new XANES full-field imaging end-station will be introduced and its capabilities will be illustrated with the first experiments carried out on historical painting samples. As long
as samples can be prepared as thin-sections of micrometric
thickness, the set-up is largely applicable to a broad range
of materials, and successful analyses will be presented on
samples from ancient glasses, papers and ceramics [4].
Bibliography
[1] M. Cotte et al., Journal of Analytical Atomic Spectrometry, 23,
p. 820-828 (2008)
[2] E. Pouyet et al., Analytica Chimica Acta, 822, 51-59 (2014)
[3] B. Fayard et al., Journal of Physics: Conference Series, 25i (2013)
[4] F. Meirer et al., Journal of Analytical Atomic Spectrometry., 28,
1870-1883 (2013)
European Synchrotron Radiation Facility, 38000, Grenoble, France
LAMS UMR-8220, 94200, Ivry-Sur-Seine, France
3
Laboratoire de Physique des Solides, 91405, Orsay, France
4
Department of Chemistry and Industrial Chemistry, 56100, Pisa, Italy
5
Scientific Research and Analysis Laboratory, Conservation Department,
19735, Winthertur, USA
6
Politecnico di Milano, Dipartimento di Chimica Materiali e Ingegneria
Chimica, 20133, Milano, Italy
7
Consiglio Nazionale delle Ricerche, Dipartimento di Fisica, 20133, Milano, Italy
8
CEMES, 31055, Toulouse, France
2
97
NOTES
98
O-41
12 sept. 2014
15:20 > 15:40
Matthieu Réfrégiers1 - Mathieu Thoury1,2
Bertrand Cinquin1 - Frederic Jamme1
1
Synchrotron SOLEIL, DISCO, 91192, Gif Sur Yvette, France
IPANEMA, DISCO & IPANEMA, 91192, Gif Sur Yvette, France
New developments
and opportunities
in synchrotron
ultraviolet
luminescence
microscopy
2
Use of synchrotron deep ultraviolet (DUV, below 350 nm) for
exciting luminescence opens up new possibilities in historical
samples studies because, it does not need external specific
probes or labeling, but instead allows taking profit of the intrinsic
properties of the materials studied.
It is possible to track at the same time, semi-conductors localization and embeding biomaterials.
We have developed two DUV fluorescence microscopes set-up
for luminescence coupled to a synchrotron beamline, providing
fine tunable excitation from 200 to 600 nm and full spectrum
acquired on each point of the image, to study DUV excited
fluorescence emitted from nanovolumes directly inside complex
samples. In addition, to record full field UV luminescence images,
a full field DUV microscope with only one transmission optic has
been installed on the DISCO beamline imaging branch. Due to
diffraction limit the lateral resolution is always increased when
looking in the UV range allowing nanometric spatial resolution.
New developments are underway on the beamline for better
flexibility: UV monophotonic excitation does present real spectral excitation, paving the way to excitation imaging for better
selectivity of the chromophores. Moreover, we are installing a
semi structured illumination scheme in order to perform HiLo
microscopy for full-resolution optically sectioned images of
thick samples.
Bibliography
[1] Giuliani, F. Jamme, V.Rouam, F. Wien, J.L. Giorgetta, B. Lagarde,
O. Chubar, S. Bac, I. Yao,S. Rey, C. Herbeaux, J.L Marlats, D. Zerbib, F. Polack
and M. Réfrégiers, J. Synchrotron Rad. 2009, 16: 835- 841.
[2] Jamme, F., Villette, S., Giuliani, A., Rouam, V., Wien, F., Lagarde, B., & Refregiers,
M. Microscopy and Microanalysis, 2010, 16(5): 507-514.
[3] Tawil, G., Jamme, F. Réfrégiers, M., Viksø-Nielsen, A., Colonna, P., & Buléon,
A. Analytical Chemistry, 2011, 83(3): 989–993.
[4] Jamme, F., Kascakova, S., Villette, S., Allouche, F., Pallu, S., Rouam, V.,
& Refregiers, M. Biology of the Cell, 2013, 105(4): 277–288.
[5] Zubkovs, V., Jamme, F., Kascakova, S., Chiappini, F., Le Naour, A., & Refregiers,
M. Analyst, on line first
[6] Thoury, M., Echard, J. P., Réfregiers, M., Berrie, B., Nevin, A., Jamme, F.,
& Bertrand, L. Analytical Chemistry, 2011, 83(5): 1737–1745.
[7] Mertz, J. Nature Methods, 2011, 8(10): 811-819.
99
ABSTRACTS
FOR POSTERS
RÉSUMÉS
DES POSTERS
101
P-01
Rouge/Red
10 sept. 2014 17:00 > 20:00
Eleanor Cato1 - Jaap J. Boon1 - Camelia Borca2
Daniel Grolimund2 - Luca Quaroni2 - Ester S. B. Ferreira1
1
SIK-ISEA, Art technology, 8032, Zurich, Switzerland
Paul Scherrer Institute, Synchrotron radiation, 5232, Villigen, Switzerland
Characterisation,
distribution and origin
of mixed Tutton salt
efflorescence in early
20th century degraded
cadmium yellow paint
in the oeuvre of
Cuno Amiet (1868-1963)
2
A total of 70 paintings by the Swiss artist Cuno Amiet (1868-1963)
were examined within the context of a technological study of
his early oeuvre from 1883-1914. Several paintings exhibit surface efflorescence on the cadmium yellow containing paint.
Cuno Amiet used cadmium yellow as such or in pigment mixtures in paintings throughout the period studied but it is the
dominant yellow in his palette after 1908. Particularly interesting
is his work from 1913. While preparing a series of paintings for
a Kunsthaus Zürich commission, he extensively used light cadmium yellow - a CdS/ZnS pigment with significant amounts of
cadmium carbonate and cadmium oxalate. Four of the 8 paintings from this series were studied and the examination of the
remaining four is planned. All exhibit a similar formation of a Zn
and Cd containing efflorescence despite different ownerships
and conservation histories. We infer that the original pigment
quality or paint mixture is a determining factor in the reactivity.
A multistep analytical approach was developed involving X-ray
tomography (XTM) followed by production of a suitable target
cross section for study by light microscopy and SEM-EDX,
and finally the subsequent preparation of a thin section for
micro-XRF and micro-XRD (approx. 35 micron thickness) and
micro-FTIR by polishing down to 5 microns. The 3D rendering
of the different phases obtained from on the XTM data demonstrate that the crystalline efflorescence was present in different
depths of the sample and is not only a surface phenomenon.
The efflorescent growth is the physical cause of the delamination
of the paint layer. The analysis of this crystalline efflorescence
by FTIR indicates the presence of Tutton salts as an ammonium
sulphate double salt of zinc and/or cadmium. Comparison
with synthesised references shows that the FTIR spectroscopy
can’t discriminate between Cd(NH4)2(SO4)2 and Zn(NH4)2(SO4)2.
However, the synthesised double salts produce different XRD
patterns. The high spatial resolution of the micro-XRF and
micro-XRD setup at the microXAS beamline at PSI enabled the
mapping of the two phases in the thin section. The micro-XRF
map shows that the crystals are rich in cadmium and zinc with
different distributions. The micro XRD detected the presence
of both Cd(NH4)(SO4) and Zn(NH4)(SO4) when comparing their
XRD patterns with those of synthesised reference materials
using XRDUA software. The origin of the ammonium sulphate
will be discussed in light of the pigment manufacture literature
contemporary to the painting and the collective results of
Amiet’s 1913 painting series. Cd(NH4)(SO4) efflorescence has
been detected before in a 1921 painting by James Ensor [1]
but its origin remained unclear and was thought to be possibly
associated with conservation treatments.
Bibliography
[1] Van der Snickt, G., J. Dik, et al. (2009). « Characterization of a Degraded
Cadmium Yellow (CdS) Pigment in an Oil Painting by Means of Synchrotron
Radiation Based X-ray Techniques. » Analytical Chemistry 81(7): 2600-2610.
103
P-02
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10 sept. 2014 17:00 > 20:00
Characterisation
of silver pre-Roman
coins from Northern
Italy with
neutron-based
techniques
During the last two years, several pre-Roman coins from northern
Italy have been analysed thanks to neutron-based techniques
such as neutron diffraction (ND) and prompt gamma activation
analysis (PGAA). This coinage is a collection of several series of
silver coins, called drachmas, produced by different Celtic and
non-Celtic tribes settled in northern Italy between the 4th and
the 1st century B.C. They are all characterized by the imitation of
the lion depicted on Massalia’s heavy drachm, whose different
styles have been used by numismatists to group them in typologies. Many issues still remain unsolved, such as chronology,
attributions and relationships within the emissions [1-2].
To provide new data for this study, a selection of specimens
coming from different hoards and museum collections, representative of different emissions, has been analyzed with
non-destructive neutron based techniques, which allowed the
problem of the silver surface enrichment [3] to be overcome.
We performed time-of-flight neutron diffraction measurements
Bibliography
[1] Pautasso, A., 1966. Le monete preromane dell’Italia settentrionale,
Sibrium, 7: 1-162.
[2] Arslan, E.A., 1995. La monetazione celtica cisalpina. Un nuovo
quadro generale, Sibrium, 22: 179-215.
[3] Beck, L., Bosonnet, S., Réveillon, S., Eliot, D., Pilon, F., 2004. Silver surface
enrichment of silver-copper alloys: a limitation for the analysis of ancient
silver coins by surface techniques, Nuclear Instruments and Methods
in Physics Research B, 226: 153-162.
[4] Grazzi, F., Celli, M., Siano, S., Zoppi, M., 2007. Preliminary results of the Italian
neutron experimental station INES at ISIS: Archaeometric applications,
Il Nuovo Cimento C, 30: 59-65.
[5] Arslan, E.A., 1991-1992. Le monete padane preromane a Budapest,
Numizmatikai Közlöny, XC-XCI: 9-33.
[6] Révay, Zs., Belgya, T., Kasztovszky, Zs., Weil, J.L., Molnár, G.L., 2004.
Cold neutron PGAA facility at Budapest, Nuclear Instruments
and Methods in Physics Research B, 213: 385-388.
104
Jacopo Corsi1 - Alessandro Lo Giudice1
Alessandro Re1 - Angelo Agostino2 - Antonella Scherillo3
Francesco Grazzi4 - Zsolt Kasztovszky5 - Boglarka Maroti5
Laszlo Szentmiklosi5 - Federico Barello6
Università di Torino and INFN, Dipartimento di Fisica, Via Giuria 1, 10125, Torino, Italy
Università di Torino, Dipartimento di Chimica, Via Giuria 7, 10125, Torino, Italy
3
STFC, Rutherford Appleton Laboratory, ISIS facility, OX11 0QX, Chilton-Didcot, United Kingdom
4
ISC-CNR, Via Madonna del Piano 10, 50019, Sesto Fiorentino, Italy
5
Hungarian Academy of Sciences, Centre for Energy Research, Konkoly-Thege
Miklós út 29-33, H-1121, Budapest, Hungary
6
Soprintendenza per i Beni Archeologici del Piemonte e M.A.E., Piazza S. Giovanni 2,
10122, Torino, Italy
1
2
with the INES diffractometer [4] at the ISIS facility (Rutherford
Appleton Laboratory, UK) on coins coming from the Biandrate
(NO), Casale Monferrato (AL) and Serra Riccò (GE) hoards and
from some numismatics collections in Turin. The analysis of diffraction patterns has been carried out with the GSAS software to
determine phase weight fractions through Rietveld refinement.
Otherpre-Romanscoins,keptattheHungarianNationalMuseum[5],
have been measured at the PGAA station [6] of the Budapest
Neutron Centre. The possibility to analyse these coins has been
a unique chance, because of the richness of the collection and
the presence of several typologies not previously analysed.
The results obtained on around 100 coins show a clear silver
debasement occurring among the first and latter drachmas
emissions, due to inflation processes which can be related with
the increasing economic power of the Roman republic in the
Po valley. The silver loss can be also used to establish a relative
chronology between the different emissions, in agreement
with the few dating data available from archaeological research.
These results are also providing new fundamental elements for
the study of metrological relationships with the contemporary
Roman republican currency. Finally, a comparison between ND
and PGAA measurements will be presented, providing results
both on standards and coins, in order to combine the results
obtained with the two techniques.
Acknowledgements:
This project has been supported by the Cooperation Agreement no. 06/20018 between CNR and STFC. The financial
support by CHARISMA Grant Agreement n. 228330 is gratefully acknowledged. We kindly acknowledge Dr. M. Torbágyi
for the loan of coins of the Hungarian National Museum
and Dr. A. Guerrini for those from the Armeria Reale in Turin.
P-03
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10 sept. 2014 17:00 > 20:00
Milene Gil1 - Jose Antonio Pestana2 - Luis Dias1
Lucia Tobias1 - Ana Cardoso1 - Catarina Miguel1
Jose Mirão1 - Antonio Candeias1
Analytical
characterisation
of gilding techniques
in secco 16th century
murals at the Convent
of Christ
(Tomar, Portugal)
1
A combined analytical approach has been adopted for the
study of the gilded decorations, presumably from the 16th
century, of the Convent of Christ Charola in Tomar. The main
goal was to compare the gilded materials and techniques
used in six murals pannels with angels. Thirteen microsamples
from the clothes, bases and frames paint layers were collected
in order to attest originality and contemporaneity.
The analytical setup comprised optical microscopy (normal
and UV light), electron scanning microscopy coupled with
X-ray spectrometry (SEM-EDS) and Fourier transform infrared
microspectroscopy (micro-FTIR). Preliminary results showed
that leaves of pure gold were used in the angels clothes while
gold-silver alloys (with traces of Cu content) were found in the
decorative base and frames. The gold leaves thicknesses range
from 40 to 147 nm. The high lead content in the layer immediatly below the leaves in all the samples analysed appoint
to an oil gilding, over mordant. In only one sample, a tin leaf
was found below the gold leaf corresponding to a previous
decoration with gilt leather.
Acknowledgments
The authors wish to acknowledge the Fundação para
a Ciência e Tecnologia for financial support (Pós-doc
grant SFRH/BPD/63552/2009) and projects ONFINARTS
(PTDC/EAT-HAT/115692/2009) and PRIM’ART (PTDC/CPCEAT/4769/2012), funded by FCT/MEC and co-funded by
Fundo Europeu de Desenvolvimento Regional (FEDER)
through the program COMPETE.
HERCULES Laboratory, 7000-809, Évora, Portugal
105
P-04
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10 sept. 2014 17:00 > 20:00
Prayoon Songsiriritthigul1 - Markus Kleine2
Josef Hormes3
Institute of Science, Suranaree University of Technology, Korat, Thailand
Glasmalerei Peters Gmbh, Paderborn, Germany
3
Center for Advanced Microstructures and Devices (Camd), Louisiana State
University, Baton Rouge, USA
1
106
Corrosion products
from window 116
of the Cathedral of
Chartres: a combined
study using X-ray
fluorescence and X-ray
absorption near edge
structure spectroscopy
2
The corrosion of glass is a very complex process as it depends
on external conditions (e.g. micro-climate, pollution) as well
as on the composition of the glass (color, content of potassium etc.). While the basic mechanisms of the degradation
process are known, there are still some open questions that
have be answered for finding the “ best ” method for cleaning and protecting historic glass. The Chartres Cathedral
(UNESCO World Heritage Site) is famous for its stained glass
windows. The majority of the windows (about 150 out of
the 176) were made and installed between 1205 and 1240.
The samples for this investigation were taken from one
of the clerestory windows (window 116) of the cathedral
(dated to the period 1228–31) that was recently restored at
the Glasmalerei Peters in Paderborn. By using a spatula six
corrosion samples were taken from differently colored fields
of the window. The corrosion products had different colors
(from beige to dark brown) and varied in their structure
between powdery and flaky. Experiments were carried out
at Beamline 8 at the Synchrotron Light Research Institute
(SLRI) in Korat (Thailand). Fluorescence was excited using
monochromatic radiation of 10 keV and detected using a
13-element Ge-detector. For the assignment of elements
and a rough calibration of fluorescence intensities NIST standard glass samples (NIST 610 and NIST 612) were measured.
The fluorescence spectra of all 6 samples are dominated by
the signals from 5 elements: Ca, Mn, Fe, Cu, and Zn with a
very clear additional signal from sulfur. There are unexpectedly strong variations in the Ca/K – ratio between the samples
indicating that the leaching process is strongly influenced
by the other constituents of the glass. Based on the Mn/Fe
ratio one can distinguish at least two groups of samples: for
samples coming from “ blue ” glasses, the Mn/Fe-ratio is < 1;
for samples from yellow/skin colored and reddish samples
the Mn/Fe ratio is ~ 1. Also the sample coming from a
green field of the window has a Mn/Fe ratio < 1, but here
the general fluorescence pattern is changed by very strong
Cu Kα and Cu Kβ lines. The K-XANES spectra that have been
recorded for the major elements indicate that in opposition
to general expectation not all elements in the corrosion layer
are present just as sulfates.
P-05
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10 sept. 2014 17:00 > 20:00
Early 18th c.
arsenic pigments
in the old and new
worlds: tracking the
transformation and
migration of arsenic
sulfide pigments in
a Dutch golden age
still-life and new
England polychromed
chest on stand
Arsenic sulfide pigments orpiment (As2S3) and realgar (As4S4),
are well known to shift color under exposure to visible light.
Realgar undergoes photo-induced polymorphism and turns bright yellow (pararealgar) to colorless (As2O3, arsenolite), whereas
orpiment photo-oxidizes and becomes colorless (arsenolite).
Here we report on this transformation as well as the characterization of the reaction products and their mobilities, based
on investigation of two works of art from the early 18th century:
Still life with five apricots by Adriaen Coorte (1704) (Royal
Picture Gallery Mauritshuis, The Hague, The Netherlands) and
an colonial American polychromed chest on stand attributed to
Charles Guillam painted in Saybrook, Connecticut c. 1710-1727
(Winterthur Museum, Wintherthur, USA).
Katrien Keune2 - Jennifer Mass1 - Florian Meirer3
Carol Pottash4 - Annelies van Loon4 - Alyssa Hull5
Apurva Mehta6 - Arthur Woll7 - Robert Gordon8
Adam Finnefrock9 - Émeline Pouyet10 - Marine Cotte10
University of Amsterdam, Faculty of Science, 1090 GD, Amsterdam, Netherlands
3
Utrecht University, Inorganic Chemistry and Catalysis, 3584 CG, Utrecht, Netherlands
4
Mauritshuis, Conservation, 2517 HV, The Hague, Netherlands
5
6
SLAC National Accelerator Laboratory, Stanford Synchrotron Radiation
Lightsource, 94025, Menlo Park, USA
7
Cornell University, Cornell High Energy Synchrotron Source, 14853, Ithaca, USA
8
Advanced Photon Source, Pacific Northwest Consortium, 60439, Argonne, USA
9
Janssen R&D, 19002, Spring House, USA
10
ESRF, 38043, Grenoble, France
1
2
Microspectroscopy was carried out at ESRF ID21 and at an X-ray
microprobe at SSRL, supplemented by light microscopy, infrared
spectroscopy, backscattered electron microscopy with X-ray microanalysis and Raman microspectroscopy. Confocal microspectroscopy was carried out at APS. This presentation will focus on
results from X-ray microspectroscopy: X-ray fluorescence mode
(XRF scanning) allowed precise mapping of local elemental distribution, while X-ray Near-Edge Absorption Structure (XANES) in
combination with multi-energy XRF mode allowed identification
and mapping of the gross chemical speciation.
The As maps for both the Saybrook and Coorte samples show
a diffuse distribution, the arsenic photoalteration products
have thus been mobilized and moved throughout the paint’s
thickness. XRF maps with the X-ray incidence energy over the
most species sensitive region of the As K edge, separated by
1 eV from 11867 to 11877, clearly indicate the presence of multiple As species. The Coorte contains still intact AsSx species as
well as oxidized As species, while Saybrook contains oxidized
As species only. Confocal XRF of the As species in the Coorte
ground layer confirmed that only oxidized species are present.
Comparison of the Coorte XANES spectra and their prinicipal
components with published spectra and As reference compounds were carried out. These analysis suggest As2S3 (most
reduced), Ca3(AsO4)2 (most oxidized), and As2O3 can adequately
represent the majority of the As speciation in the sample. The
arsenate and arsenite products are very mobile. The arsenate
species seems to have reacted with the gypsum (CaSO4) in the
paint layer and the chalk (CaCO3) in the ground layer. As2O3 has
accumulated at the interface between paint and ground layer.
The Saybrook cross-section shows that almost all of the As in
the paint layer has been fully oxidized to Pb3(AsO4)2, where the
lead is derived from a lead white-based ground layer. At the
moment, it is not clear whether arsenates are formed directly
from the photo-oxidized arsenic sulfide or by the oxidation of
the As2O3. These results will be elaborated and further discussed
with respect to the preservation of the works in question.
107
P-06
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10 sept. 2014 17:00 > 20:00
Synchrotron-based
imaging fossilised
dinosaur skin
Integument colour is controlled by both the chemical and
structural characteristics of a material, whether it is skin, hair,
feathers or any other biological tissue. Colour is crucial in the
evolution of species through multiple selective advantages
that might include camouflage or display. The combination
of morphology (structural) and biomarkers (chemical) has
been used to infer colour and pigment patterns in a range
of extant and extinct organisms, including iconic fossils
such as Archaeopteryx [1]. Melanin is the most widely used
pigment in vertebrates and consists of several covalently
linked indoles and is considered an unusually large polymer
compared to most natural pigments. The sheer size and complexity of these molecules determines their precise structure
and physical properties and also controls their bonding to
other components (e.g. proteins, metal ions) [2]. Here we
analyse two key specimens of fossilised dinosaur skin using
non-destructive chemical analysis in order to investigate the
potential for pigment preservation in the integument; one
sample from an embryonic sauropod dinosaur (~90 million
years old) and the other skin from a mummified hadrosaur
dinosaur (~66 million years old). Synchrotron Rapid Scanning
X-ray Fluorescence is combined with X-ray Absorption Near
Bibliography
[1] Manning, P. L., Edwards, N. P., Wogelius, R. A., Barden, H., Larson, P. L.,
et al. 2013. Synchrotron-based chemical imaging reveals plumage patterns
in a 150 million year old bird, RSC, Journal of Analytical Atomic Spectrometry,
28(7), 1024-1030.
[2] Wogelius, R. A., Manning, P. L. Larson, P. L., Barden, H., Edwards, N. P.,
et al. 2011. Trace metals as biomarkers for eumelanin pigment
in the fossil record, Science, 333(6049), 1622-1626.
[3] Manning, P. L., Morris, P. M., McMahon, A., Jones, E., Gize, A., et al. 2009.
Preserved soft-tissue structures and organic molecules in a mummified
hadrosaur dinosaur from the Hell Creek Formation, North Dakota (USA).
Proceedings of the Royal Society Series B., 276 (1672), 3429-3437.
[4] Manning, P. L., Wogelius, R.A., Dongen, B.E. van., Lyson, T.R., Bergmann, U.,
et al. 2013. The role of skin pigment and biochemistry in the exceptional
preservation of hadrosaur skin. In Eberth, D. A., and Evans, D. C. (eds),
Indiana University Press, in press.
108
Phillip Manning1 - Roy Wogelius1 - Nicholas Edwards1
William Sellers1 - Bart van Dongen1 - Sam Webb2
Victoria Egerton1 - Rodolfo Coria3 - Tristan Lowe1
Uwe Bergmann2
University of Manchester, ML39PL, Manchester, UK
Slac National Accelerator Laboratory, 94025, Menlo Park, USA
3
Conicet – Universidad Nacional De Río Negro, 00000, Plaza Huincal, Argentina
1
2
Edge Structure spectroscopy to provide detailed information
on the trace-metal inventory and oxidation state of elements
within these fossils, and demonstrates that organically derived
endogenous compounds are present. The results support
earlier work that showed both structure and macromolecular
composition of dinosaur skin can be conserved for over 66
million years [3]. Additional infrared spectroscopy mapping
indicates the presence of key functional groups within the
skin of both samples, indicative of the breakdown products (amide groups) from endogenous structural proteins
(comparable to keratin) [4]. When combined with the results
from the synchrotron-based imaging in this study we show
clear evidence for the presence of Cu-O/Cu-N complexation, indicative of endogenous pigments still being present
within discrete biological tissue samples from exceptionally
preserved fossil integument. The trace-metal coordinated
biochemistry of melanin-type pigments in dinosaur skin potentially played key roles both in life and death. Melanin, rich
in trace-metals, functioned as a ‘natural-biocide’ protecting key
soft-tissues in life. The very same trace-metals inhibited the
natural processes of decay after death, resulting in rare and
remarkable fossils that display soft tissue structures.
P-07
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10 sept. 2014 17:00 > 20:00
Mirta Santos1 - Margarida Nunes1 - Catia Relvas1
Marta Manso2 - Maria Luisa Carvalho2 - Ana Teresa Caldeira1
Francisca Figueira3 - Teresa Ferreira1
Analytical
and microbiological
studies on paper
exhibiting foxing
1
Foxing spots emerge on paper as stains of reddish-brown,
brown or yellowish color, generally of small dimensions,
with sharp or irregular edges, most of which, when excited
with UV light, show fluorescence [1]. Despite the formation
mechanisms of foxed areas have been studied since 1930,
there are still no conclusive results. Metal contamination,
fungi and moisture condensation processes are suggested
as possible causes of foxing [2]. Metals found in foxing
spots, may arise either from the papermaking process or
from airborne dust, include potassium, iron, tin, copper,
copper–mercury or copper–zinc or brass [2,3].
In this study a contribution on the formation of foxing stains
on papers from 18th and the 20th century will be presented.
Fluorescence of foxing stains under ultraviolet light was
registered as a first indication of permanent change in the
cellulose and indication on degradation by metal-induced
oxidation or fungal digestion. Elemental mapping under
micro-EDXRF spectrometry was carried out to identify any
possible metal contamination on the spot and surrounding
areas. VP-SEM/EDS analysis took into account fibers state
of conservation and it permitted to distinguish different
typologies of the foxing stains. Additionally, VP-SEM/EDS
contribute to estimate the fillers used in the papermaking
process. Micro-XRD, ATR-FT-IR and micro-Raman studies
were develop to complete the study of the fillers and sizing
materials used in paper production and to evaluate the
degradation status of cellulose fibers in the foxing stains.
ICP-MS analyses were carried out in order to estimate the
total amount of metals in the foxing stains and compare
it with unstained areas. Biological colonization was also
studied in order to evaluate the possible influence of biotic
attack in foxing.
Laboratório HERCULES & CQE, Universidade de Évora, Largo Marquês
de Marialva 8, 7000-804, Évora, Portugal
2
Centro de Física Atómica da Universidade de Lisboa, Av. Professor Gama Pinto 2,
1649-003, Lisboa, Portugal
3
Laboratório José Figueiredo, Direção Geral do Património Cultural,
Rua das Janelas Verdes 37, 1249-018, Lisboa, Portugal
Bibliography
[1] M. Bicchieri, S. Ronconi, F.P. Romano, L. Pappalardo, M. Corsi, G. Cristoforetti,
S. Legnaioli, V. Palleschi, A. Salvetti, E. Tognoni, Study of foxing stains on paper
by chemical methods, infrared spectroscopy, micro-X-ray fluorescence
spectrometry and laser induced breakdown spectroscopy, Spectrochimica
Acta Part B: Atomic Spectroscopy, 57, 2002, 1235-1249.
[2] Soyeon Choi Foxing on Paper: A Literature Review, Journal of the American
Institute for Conservation, 46, 2007, 137-152.
[3] M. Manso, S. Pessanha, F. Figueira, S. Valadas, A. Guilherme, M. Afonso,
A. C. Rocha, M. J. Oliveira, I. Ribeiro, M. L. Carvalho, Characterisation of foxing
stains in eighteenth to nineteenth century drawings using non-destructive
techniques, Analytical and Bioanalytical Chemistry, 395, 2009, 2029–2036.
109
P-08
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10 sept. 2014 17:00 > 20:00
Gold in ancient Egypt:
studies on provenance
& corrosion
The multi-disciplinary project CNRS PICS 5995 intends to
provide with science-based techniques new evidence on
the technologies used in the Egyptian workshops producing
gold work during the Bronze Age, and to shed more light
on the origin of the gold [1,2]. This project also revealed:
(1) the presence of surface atmospheric corrosions; and
(2) the almost continuous use of placer gold in all types
of objects except gold foils, detected by the presence of
whitish platinum group element (PGE) inclusions.
In this work 20 gold foils from the excavations of John Garstang
at Abydos, on behalf of the Liverpool Institute of Archaeology,
were analysed to identify the corrosion products found on the
foils and the metal composition. As would be expected from
the earlier work, no whitish PGE inclusions could be observed
on the foils. The use of placer gold can only be detected by the
presence of Pt in gold. The foils from Abydos were analysed by
SEM-EDS, by µ-PIXE with 3 MeV proton beam, and by µ-XRF
using a M4 Tornado. To determine the Pt contents, we used the
Double Dispersive X-ray Fluorescence (D2 XRF) setup recently
developed in the BAMline at BESSY [3].
Bibliography
[1] Troalen, L.G., Guerra, M.F., Tate, J., Manley, B.: Technological study of gold
jewellery pieces dating from Middle to New Kingdom in Egypt,
ArchéoScience 33, 111–119 (2009)
[2] Miniaci, G., La Niece, S., Guerra, M.F., Hacke, M.: Analytical study of first royal
Egyptian heart-scarab, Sobekemsaf, British Museum Technical Research
Bulletin 7, 53–60 (2013)
[3] See the communication by Radtke M., G. Buzanich, U. Reinholz, H. Riesemeier,
O. Scharf, M. F. Guerra: Detection of platinum in gold with D2 XRF.
110
Isabel Tissot1 - Lore Troalen2 - Marta Manso1
Matthew Ponting3 - Ian Shaw3 - Martin Radtke4
Uwe Reinholz4 - Maria Luisa Carvalho1
Maria Filomena Guerra5
Centro de Física Atómica da Universidade de Lisboa, Av. Prof. Gama Pinto 2,
2
National Museums Scotland, 242 West Granton Road, EH5 1JA, Edinburgh, UK
3
Garstang Museum, University of Liverpool, 12-14 Abercromby Square, L69 7WZ,
Liverpool, UK
4
BAM FIMRT, Richard-Willstaetter-Strasse 11, 12489, Berlin, Germany
5
ArchAm - UMR 8096 CNRS, MAE, 21 allée de l’Université, 92023, Nanterre, France
1
The results obtained show that the composition of the
Egyptian gold foils from Abydos is typical of placer gold
with Ag ranging between 0.2 and 14 % and Cu from 05
and 1.5 %. Contrary to expectation, the presence of Pt could
be detected in all the analysed foils but at contents that
could only be determined by D2XRF, which evidences the
use of placer gold for their manufacture.
For the study of the corrosion products found on the Egyptian gold foils, several ternary and binary gold alloys were
produced and artificially aged in a corrosive environment
containing high concentrations of S2-. The results obtained
for the artificially aged coatings and for the corroded
Egyptian gold foils were compared. We could show the
presence on the corroded surfaces of different corrosion
phases revealed by the heterogeneous distribution of Ag, Cu,
in spite of the homogeneous distribution of S which can be
associated to a strong adsorption on the metallic surface
and to the presence of early corrosion stages.
P-09
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10 sept. 2014 17:00 > 20:00
Octaviana Marincas1 - Daniel Timpu2
1
2
Recent studies
of the alterations of
historic mural painting
restoration. Results
from two churches
(XIXth century) located
in Iasi - Romania
At the end of the XIXth century, the king of Romania Carol
the Ist invited the french architect André Lecomte du
Noüy to restore five important churches from the country.
Two of them are located in Iasi. One of them have been
totally reconstructed and the other one have been partially changed. The original indoor mural painting have
been removed and a new decoration have been applied.
Bibliography
[1] C. Gervais, M.-A. Languille, S. Réguer, M. Gillet, S. Pelletier, C. Garnier,
E. Vicenzi, and L. Bertrand. Why Does Prussian Blue Fade? Understanding
the Role(s) of the Substrate. J. Anal. At. Spectrom., 28(10), 1600-1609, Oct 2013.
[2] L. Robinet, M. Spring, and S. Pagès-Camagna. Vibrational spectroscopy
correlated with elemental analysis for the investigation of smalt pigment
and its alteration in paintings. Anal. Methods, 18(5):4628–4638, Sept 2013.
[3] C. Gervais, M.-A. Languille, S. Reguer, M. Gillet, E. P. Vicenzi, S. Chagnot,
F. Baudelet, and L. Bertrand. “ Live ” Prussian blue fading by time-resolved
X-ray absorption spectroscopy. Appl. Phys. A, 111(1):15–22, Apr 2013.
[4] J. K. Delaney, P. Ricciardi, L. D. Glinsman, M. Facini, M. Thoury, M. Palmer
and E. R. de la Rie. Use of imaging spectroscopy, fiber optic reflectance
spectroscopy and X-ray fluorescence to map and identify pigments
in illuminated manuscripts. Stud. Cons., Jan 2013.
[5] Jonynaitė, J. Senvaitienė, J. Kiuberis, A. Kareiva, R. Juškėnas, R. Ramanauskas,
XRD characterization of cobalt-based historical pigments and glazes,
chemija. 2009. vol. 20. No. 1. P. 10–18
[6] B. Constantinescu, R. Bugoi, E. Pantos, D. Popovici, Phase and chemical
composition analysis of pigments used in CuCuteni Neolithic painted
ceramics, Documenta Praehistorica XXXIV (2007) p. 281-288
[7] M. Bacci, M. Picollo, G. Trumpy, M. Tsukada and D. Kunzelman, Non-Invasive
Identification of White Pigments on 20th-Century Oil Paintings by Using
Fiber Optic Reflectance Spectroscopy, Journal of the American Institute
for Conservation, Vol. 46, No. 1 (Spring, 2007), pp.27-37
[8] D. Erhardt, C. S. Tumosa, M. F. Mecklenburg, Long-Term Chemical
and Physical Processes in Oil Paint Films, Studies in Conservation, Vol. 50,
No. 2 (2005), pp. 143-150
[9] L. F. Capitan-Vallvey, E. Manzano, V. J. Medina Florez, A Study of the Materials
in the Mural Paintings at the ‘Corral del Carbon’ in Granada, Spain, Studies
in Conservation, Vol. 39, No. 2 (May, 1994), pp. 87-99
University of Arts George Enescu, Univ. Lecturer, 700451, Iasi, Romania
Institute of Macromolecular Chemistry Petru Poni, Senior Researcher,
Iasi, Romania
Today the state of conservation requires urgent mural painting restoration. Samples have been collected and analyzed
in order to establish the painting technique, the morphology of alterations, and the state of conservation. Different
imaging and analytical techniques like optical microscopy,
SEM-EDX, FTIR spectrometry and X ray diffraction have been
used. The obtained results have made possible to identify the
technique and materials that have been used. Samples have
been collected from the zones where specific deteriorations
occured. Explanations on the causes of the specific deteriorations could be established. Thus the results are useful for
the future mural painting restoration projects.
111
P-10
Rouge/Red
10 sept. 2014 17:00 > 20:00
Jennifer Mass1 - Émeline Pouyet2 - Florian Meirer3
Marine Cotte2 - Apurva Mehta4 - Alyssa Hull5 - Erich
Uffelman6 - Barbara Buckley7 - Frederik Vanmeert8
Cadmium carbonate’s
role in the synthesis
and alteration of
cadmium yellow paints:
evidence from the
works of Henri Matisse
and Edvard Munch
1
Cadmium carbonate (CdCO3) has for several years been
identified in the altered cadmium yellow (CdS) paints found
in Impressionist, early modernist, and post-Impressionist
works. When concentrated at the surface of the paint layer,
CdCO3 appears to result from the photo-alteration of CdS,
likely through a CdSO4-containing phase. However, in other
cases no clear stratigraphy is present and CdCO3 is distributed
throughout the paint layer. This is significant because CdCO3
is highly insoluble (Ksp = 1.0 ×10-12), and if it formed solely
due to photo-alteration it would not be expected to migrate
away from the painting’s surface. In cadmium yellow paints in
works such as Edvard Munch’s c. 1910 The Scream (The Munch
Museum, Oslo), Plahter et al. have proposed that CdCO3 is
present because it was used in the indirect wet process synthesis of CdS (e.g., the reaction of CdCO3 and Na2S) [1]. Thus,
the CdCO3 would be a residual starting reagent rather than a
photo-alteration product. The identification of CdCO3 in the
unaltered cadmium yellow paints of early modernist works
such as Pablo Picasso’s The Blue Room (The Phillips Collection,
1901) and Henri Matisse’s Flower Piece (The Barnes Foundation,
1906) supports the Plahter interpretation.
To address this question of CdCO3’s role, a flake of apparently
non-degraded cadmium yellow paint was removed from
Henri Matisse’s Flower Piece to study the CdCO3 distribution
both as a function of depth in the paint layer and in individual
pigment particles. X-ray microspectroscopy and microdiffraction were respectively carried out at ESRF ID21 and Petra III,
supplemented by light microscopy, backscattered electron
microscopy with X-ray microanalysis, and Fourier transform
infrared spectroscopy. This presentation will focus on results
from X-ray microspectroscopy: µX-ray fluorescence (XRF
scanning) allowed precise mapping of local elemental distribution, and Full Field X-ray Near-Edge Absorption Structure
(FF-XANES) [2] allowed for mapping the chemical speciation
using the Cd-L3 and S-K edges.
Bibliography
[1] Plahter, U. and Topalova-Casadiego, B. Cadmium Yellow in « The Scream »
painted by Edward Munch. The National Gallery Technical Bulletin
30th Anniversary Conference, London, Archetype, 2011.
[2] Fayard, B., et al., The new ID21 XANES full-field end-station at ESRF.
Journal of Physics: Conference Series, 2013. 425(19): p. 192001.
112
ESRF, ID21, 38043, Grenoble, France
3
Utrecht University, Inorganic Chemistry and Catalysis, 3584 CG, Utrecht, Netherlands
4
Stanford University, SSRL, 94025, Menlo Park, USA
5
6
Washington and Lee University, Department of Chemistry, 24450, Lexington, USA
7
The Barnes Foundation, Conservation Department, 19130, Philadelphia, USA
8
University of Antwerp, Department of Chemistry, 2020, Antwerp, Belgium
2
FF-XANES imaging of a 15 µm thin section at the Cd-L3 edge
revealed the presence of three Cd-based phases: CdS, CdSO4,
and CdCO3. The CdSO4 was concentrated on only one surface
of the sample, suggesting its role as a photo-alteration product
rather than a synthesis starting material. CdCO3 comprised
the bulk of the individual pigment particles, suggesting that
it is a synthesis starting reagent and not a photo-alteration
product. CdS was concentrated on the surface of these
CdCO3 particles. CdSO4 was surrounding some of the CdCO3
particles, suggesting the beginnings of photo-oxidation of
the thin CdS coating.
P-11
Rouge/Red
10 sept. 2014 17:00 > 20:00
Mehdi Moini1 - Christopher Rollman1 - Loïc Bertrand2
George Washington University, Academic, 20007, Washington, USA
SOLEIL Synchrotron Facility, 91192, Gif-sur-yvette, France
3
IPANEMA, 91192, Gif-sur-yvette, France
1
2
Impact of synchrotron
X-ray irradiation
on proteinaceous
specimens
Synchrotron radiation (SR) has become a preferred technique for the analysis of a wide range of archeological
samples, artwork, and museum specimens. While SR is
called a “non-destructive” technique, its effect on proteinaceous art objects has not been fully investigated at the
molecular level. To investigate the molecular level effects
of X-ray on proteinaceous specimens, samples ranging
from amino acids to proteinaceous objects such as silk,
wool, parchment, and rabbit glue were irradiated by synchrotron X-ray. Specimens were irradiated with two X-ray
energies (8 keV and 22 keV) and two photon fluxes (focused or unfocused) under various lengths of time. At the
macroscopic level, color change, brittleness, and solubility
enhancement were observed for several samples within
100 s of X-ray irradiation. In addition, significant molecular
level modifications were observed with free amino acids as
well as with proteinaceous specimens. Aspartic acid (Asp),
wool, parchment, and rabbit skin glue showed increased
racemization upon increasing X-ray irradiation time with
rabbit skin glue showing the greatest increase in D-Asp.
However, silk, cystine, and asparagine (Asn) did not show
signs of racemization at the irradiation times studied. In
addition to Asp racemization, parchment and rabbit skin
glue also showed racemization of isoleucine (Ile) and
phenylalanine (Phe) after 100 s of X-ray irradiation using a
focused beam. In general, focused and low energy (8 keV)
beams induced more damage than unfocused and higher
energy (22 keV) beams. The results demonstrate that X-ray
radiation can induce significant molecular level damage
after a few seconds of X-ray irradiation.
Bibliography
[1] Dating Human Bone; Is Racemization Dating Species Specific? Mehdi
Moini, Christopher Rollman, and Christine France, Anal Chem. 2013, 85,
11211-5.
[2] Dating Silk and other Innovations in Mass Spectrometry, Mary Ballard,
Christine France, Caroline Solazzo, and Mehdi Moini, TSG Post prints
Volume 21, 2013
[3] Moini, M., Klauenberg, K., Ballard, M. “ Dating Silk By Capillary Electrophoresis
Mass Spectrometry ”, Anal Chem. 2011, 83, 7577-7581.
[4] Araki, N, Moini, M. “ Age Estimation of Museum’s Wool Textiles from Ovis
aries using Deamidation Rates Utilizing MALDI TOF MS ” Rapid Commun.
Mass Spectrom. 2011, 25, 3396-3400.
113
P-12
Rouge/Red
10 sept. 2014 17:00 > 20:00
Letizia Monico1 - Koen Janssens2 - Matthias Alfeld3
Frederik Vanmeert2 - Marine Cotte4 - Gerald Falkenberg3
Chris Ryan5 - Daryl Howard6 - Costanza Miliani1
Cr K-edge full spectral
XANES imaging
of alteration process
in chrome yellow
pigments by means
of the Maia X-ray
detector
1
During the last decade, synchrotron radiation (SR)-based micro
X-ray fluorescence (µ-XRF) and X-ray absorption near edge
structure (XANES) methods (in point analysis or mapping
mode) has been succesfully used for the study of the degradation pathways of artists’ pigments due to their valuable
capabilities to provide information at the microscale level on
the valence states of the same metal and on the distribution
of the secondary compounds [1].
Nowadays, technological research perspectives are driven
by the need for shorter dwell times, not only to render the
2D or 3D mappings of large areas more feasible but also to
overcome problems due to beam induced damage to sample
materials.
In this regard, “ fast ” detectors are providing valuable solutions due to their capabilities of process high count rates
that result from an XRF signal collected in an extended solid
angle without significant dead time. The Maia X-ray detector
[developed by CSIRO (Australia) and the Brookhaven National
Laboratory (USA)] [4], installed at the Australian Synchrotron
X-ray fluorescence microscopy (XFM) beamline and at the
Hard X-ray micro/nano-probe beamline P06 of DESY falls into
this category. This system already has found application in the
painting conservation field [5].
In this context, Cr K-edge µ-XANES and µ-XRF experiments
conducted at the X-ray and FTIR Microspectroscopy beamline
ID21 of ESRF allowed us to elucidate that the darkening
phenomenon of the originally bright chrome yellow paint
(PbCrO 4, PbCr 1-xS xO 4) in a number of Vincent van Gogh
paintings and in a series of photochemical aged paint micro-samples is ascribable to a reduction reaction from Cr(VI)
to Cr(III) and that this process is related to the crystalline structure and the chemical composition of the pigment itself [2-3].
Bibliography
[1] M. Cotte, J. Susini, J. Dik, K. Janssens, Acc. Chem. Res. 43, 705 (2010).
[2] L. Monico, G. Van der Snickt, K. Janssens, W. De Nolf, C. Miliani, J. Dik,
M. Radepont, E. Hendriks, M. Geldof, M. Cotte, Anal. Chem. 83, 1224 (2011).
[3] L. Monico, K. Janssens, C. Miliani, G. Van der Snickt, B. G. Brunetti,
M. Cestelli Guidi, M. Radepont, M. Cotte, Anal. Chem. 85, 851 (2013).
[4] C. G. Ryan, D. P. Siddons, R. Kirkham, Z. Y. Li, M. D. de Jonge, D. J. Paterson,
A. Kuczewski, D. L. Howard, P. A. Dunn, G. Falkenberg, U. Boesenberg,
G. De Geronimo, L. A. Fisher, A. Halfpenny, M. J. Lintern, E. Lombi, K. A. Dyl,
M. Jensen, G. F. Moorhead, J. S. Cleverley, R. M. Hough, B. Godel, S. J. Barnes,
S. A. James, K. M. Spiers, M. Alfeld, G. Wellenreuther, Z. Vukmanovic, S. Borg,
J. Phys.: Conf. Ser. 499, 012002 (2014).
[5] D. L. Howard, M. D. de Jonge, D. Lau, D. Hay, M. Varcoe-Cocks, C. G. Ryan,
R. Kirkham, G. Moorhead, D. J. Paterson, D. Thurrowgood, Anal. Chem. 84,
3278 (2012).
114
CNR-ISTM/Centre Smaart, Chemistry Department - Via Elce Di Sotto 8, I-06123,
Perugia, Italy
2
Antwerp University, Chemistry Department - Groenenborgerlaan 171, B-2020,
Antwerpen, Belgium
3
DESY, Hard X-Ray Micro/Nanoprobe Beamline P06 - Notkestraße 85, D-22607,
Hamburg, Germany
4
ESRF, X-Ray And Ftir Microspectroscopy Beamline ID21 - Avenue des Martyrs 71,
F-38000, Grenoble, France
5
CSIRO, Earth Sciences and Resource Engineering - 26 Dick Perry Avenue, WA 6151,
Kensington, Australia
6
Australian Synchrotron, X-Ray Fluorescence Microscopy Beamline Blackburn Road, Vic 3168, Clayton, Australia
In the present paper, the advantages and drawbacks of the
latest generation of X-ray semiconductor type detectors that
are implemented at the ID21, XFM and P06 beamlines in the
specific context of SR-based XANES/XRF imaging of Cr-based
painting materials, will be discussed.
For this purpose, recently obtained results at these three SR
stations from a series of photochemical aged paint model
samples and micro-samples taken from several Van Gogh
paintings, such as for example Falling leaves (Kröller-Müller
Museum, Otterlo) and The Bedroom (Van Gogh Museum,
Amsterdam), will be presented.
P-13
Rouge/Red
10 sept. 2014 17:00 > 20:00
Katharina Müller1 - Marie Albéric1 - Andreas Staude2
Heinrich Riesemeier2 - Ina Reiche1,3
Laboratoire d’Archéologie Moléculaire et Structurale, UPMC - UMR 8220
CNRS, 75005, Paris, France
2
Bundesanstalt für Materialforschung und -prüfung, 12205, Berlin, Germany
3
1
Application of microCT
for archaeological
ivory identification
and a better
comprehension
of its alteration
phenomena
Human and animal bones and teeth play an important role
as precious key witnesses of ancient societies. Amongst them
ivory, the dentine part of animal tusks, can be considered as
a very precious biomaterial, which continuously was used
for the manufacture of excellent objects at least since the
Palaeolithic period. Ivory is a complex nano-composite material possessing a specific structure, highly organised from
the macro- to the nano-scale and not yet fully understood.
Archaeological ivory is even more complex due to alteration
processes occurring over time. Non-destructive investigations of modern and archaeological ivory artefacts by micro
X-ray tomography (microCT) contribute to a better comprehension of the structural organisation of the material and of
structural alteration phenomena. Furthermore, characteristic
features of the ivory structure can be used for the identification of ivory used as raw material for ancient objects.
This is a key point in archaeological interpretations as the
choice of material may depend either on the availability, the
production techniques or the context in which the objects
were used. The characteristic morphological features of ivory
Bibliography
[1] Reiche, Müller, Staude, A., J. Goebbels, H; Riesemeier, Journal of Analytical
Atomic Spectrometry, 26, 1802-1812.
[2] C. Vercoutère, K. Müller, L. Chiotti, R. Nespoulet, A. Staude, H. Riesemeier
and I. Reiche 2011, ArcheoSciences, 35, 259-271. (2012).
visible at macroscale, the so-called Schreger pattern, allow a
quite straightforward ivory identification for objects of adequate size. But surface treatments, decorations or diagenetic
alterations lead to the disappearing of these characteristic
patterns and make the application of more sophisticated
methods necessary.
The potential of microCT for the study of bone materials
has been shown in numerous works ranging from anatomic
studies to biomedical research on pathologies and bone
implants. MicroCT allows the three-dimensional (3D) study
of morphological features with a high spatial resolution in
the micrometer range. MicroCT setups installed at synchrotron sources provide even higher spatial resolution (< 1 µm),
needed to image the specific characteristics of the ivory
microstructure (tubules of about 2 µm in diameter).
By microCT analysis we were able to identify the raw materials
used for the manufacture of a bishop’s crozier (15th century,
Cathedral of Angers, France) and of Palaeolithic beads
from three archaeological key-sites in Southwest-France
(the rock shelters Pataud, Le Blot and Les Peyrugues) [1].
The results emphasized the exceptional status of this type of
beads also in regard to the choice of raw material and gave
possible hints to the manufacturing procedure [2]. Furthermore, microCT allowed new insights into microstructural
features of ivory as well as the evaluation of the preservation
state of archaeological ivory objects coming from different
site conditions (rock shelters, marine environments) and
of different ages (middle age to Paleolithic). Characteristic
alteration phenomena observed are the increase of porosity,
the formation of fissures or cracks and inclusions.
115
P-14
Rouge/Red
10 sept. 2014 17:00 > 20:00
Gert Nuyts1 - Simone Cagno2 - Koen Janssens3
University of Antwerp, PHD Student, B-2020, Antwerp, Belgium
Norwegian University of Life Sciences, Researcher, N-1432, AS, Norway
3
University of Antwerp, Professor, B-2020, Antwerp, Belgium
1
2
Micro-XANES study
on Mn browning:
identification
of the formed Mn
compounds
Under influence of environmental conditions, historical glass,
especially non-durable mediaeval glass, can undergo corrosion.
This is a complex process governed by several factors and
involving various transformations. One of the most disfiguring
corrosion phenomena is the formation of dark-coloured Mn
enrichments or stains that reduce glass transparency and
can cause macroscopic browning/blackening of the glass
surface. As described elsewhere in more detail by Schalm
et al. [1], Mn-stains can be formed during glass corrosion
when a Mn source is present. It can originate e.g. from the
groundwater surrounding a buried glass fragment. However
historical glass often contains a small amount of Mn, which
can either be deliberately added as decolourising agent (in
the form of pyrolusite, MnO2) or present as an impurity of the
raw materials (e.g. wood ash). [2] In unaltered bulk glass Mn is
mainly present as Mn(II), and a minor fraction as Mn(III), due to
its stability during the glass production. Previous studies have
suggested the presence of MnO2 in the Mn stains [1], and a
hypothesis for its formation was proposed: in the presence of
water and oxygen, Mn(II) and/or Mn(III) ions can be oxidised
to higher oxidation states, giving rise to, e.g., insoluble MnO2
from which the Mn stains are formed[1,3,4]. In addition to
pyrolusite (MnO2), Watkinson et al. [5] suggested the presence
of several dark black/brown coloured Mn bearing minerals
leading to the discolouration phenomena, however without
Bibliography
[1] O. Schalm, K. Proost, K. De Vis, S.Cagno, K. Janssens, F. Mees, P. Jacobs
and J. Caen, Archaeometry, 2011, 53(1), p:103-122.
[2] R. Newton and S. Davison, Conservation of glass, 1997, Oxford: Butterworth
Heinemann.
[3] A. Domenech- Carbo, M.T. Domenech-Carbo, and L. Osete-Cortina,
Electroanalysis, 2001, 13(11), p:927-935.
[4] S. Cagno, G. Nuyts, S. Bugani, K. De Vis, O. Schalm, J. Caen, L. Helfen,
M. Cotte, P. Reischig and K. Janssens, 2011, 26, p:2442-2451.
[5] D. Watkinson, L. Weber and K. Anheuser, Archaeometry, 2005, 47, p:69-82.
116
giving proof of their presence. We have employed microscopic XANES spectroscopy in an attempt to identify the
Mn-compounds present in Mn-stains found in historically
corroded glass samples. For this purpose several glass fragments were analysed that originate from an excavation at a
former Franciscan friary and are dated to the 14th century, all
of which contain Mn (0.5-1.6 wt %; expressed as MnO). Glass
fragments, visually showing Mn browning, were cut, polished
and their composition was determined via SEM-EDX analysis.
Similar cross-sections were analysed at beamline ID21 at the
ESRF, Grenoble, France. Prior to XANES analysis, elemental
distribution maps were recorded to localise the Mn stains.
XANES spectra were recorded at different points across the
stains and linear combination fitting was performed on these
unknown spectra, expressing the latter as a combination of
series of Mn reference spectra. The expected presence of
pyrolusite (MnO2) was not observed, while the best fits were
obtained using a fitting model including Mn2O3 and hollandite
(black/gray Mn-bearing mineral BaMn(IV,II)8O16). This suggests
that the model by Schalm et al. [1] where an oxidation to MnO2
needs to be refined as (a) Mn is not completely oxidised to
+IV while (b) not only pyrolusite is formed. It appears that
the blackening of the glass can also be caused by other dark
coloured Mn-bearing minerals such as hollandite or related
compounds/minerals with varying Mn(IV):Mn(II) ratios.
P-15
Rouge/Red
10 sept. 2014 17:00 > 20:00
Giliane Pauline Odin1 - Véronique Rouchon1
Frederick Vanmeert2 - Koen Janssens2 - François Farges3
Delphine Vantelon4
S-XANES study of
Autunian pyritic fossils:
influence of organic
matter on degradations
1
The collections of the Muséum national d’Histoire naturelle
(MNHN, Paris, France) and the Muséum d’Histoire naturelle d’Autun (MHNA, Autun, France) include many fossils
preserved within Autunian shale. They contain unstable
sulfur compounds, such as pyrite, whose oxidation results in
efflorescence, mainly related to iron sulfates [1].
S-XANES measurements were performed on artificially aged
shale and collection specimens (LUCIA, SOLEIL). On these ones,
spectra show a different speciation of the sulfur between the
shale and the fossil itself. The shale contains oxidized sulfur
species (mostly sulfates) whereas the organic matter of the fossil is composed of reduced species as organic sulfides, which
may reflect the future potentiality of the fossil to oxidize. On
artificially aged shale, the efflorescence of sulfates is promoted
by the increase of temperature and humidity, giving spectra
very similar to those of collection specimens. Gypsum (calcium
sulfate dihydrate) is the major crystalline phase growing on
the shale, whereas iron sulfates mainly crystallize around
fragments of organic matter. These observations suggest a
possible link between the presence of organic matter and
the formation of iron sulfates. Complementary ageing are
currently performed in order to validate this hypothesis.
To understand the key factors of the degradation, newly
excavated shale samples were collected in the Autunian of
the Autun Basin, place of origin of the damaged specimens.
They were artificially aged at 50 % or 80 % relative humidity
(RH) and at 40°C or 90°C, in order to reproduce the alterations
observed on specimens [2]. A special attention was paid on
a currently excavated fossiliferous level called “ the Muse
Fishes Layer ”, which contains pyritic fishes (actinopterygians
attributed to Aeduella).
MNHN, CRC, 75005, Paris, France
University of Antwerp, Department of Chemistry, B-2020, Antwerp, Belgium
3
MNHN, IMPMC, 75005, Paris, France
4
SOLEIL, LUCIA, 91190, Saint Aubin, France
2
Bibliography
[1] Rouchon V. et al., 2012. Raman and FTIR spectroscopy applied
to the conservation report of paleontological collections: identification
of Raman and FTIR signatures of several iron sulfate species such as ferrinatrite
and sideronatrite. Journal of Raman Spectroscopy, 43, 1265-1274.
[2] Odin G. P. et al., 2014. Accelerated ageing of shale of palaeontological interest:
Impact of temperature conditions. Annales de Paléontologie, in press.
117
P-16
Rouge/Red
10 sept. 2014 17:00 > 20:00
Identification,
analysis of the building
stones used
in the historical period
and quantification
of decay
and deterioration:
Comparative study
of a substituted
antique stone with
restored stone using
SEM and XRD technique
The process of identification of the material, including the
stones used in construction, is the first step in any architectural
conservation and restoration project. The process of identification and classification of stone involves many different
techniques, like Physical examination, thin section analysis, chemical investigations, electron microscopy, X ray diffraction etc.
These investigation forms the crucial backbone of information
for deciding the strategy for conservation and restoration plan
and further treatment. This information is also useful in understanding the cause and methods of decay and deterioration.
A group of state listed monument of the mediaeval temple
architecture in Nagari style was selected for understanding
the nature of decay and deterioration and evolving an appropriate methodology. These are situated in Mandi, Himachal
Pradesh, a northern Himalayan state of India. These temples
were completely destroyed in major earthquake of 1905 and
the restoration work was carried out at intermittent stages. As
per the practice of the time, locally available stone of similar
quality from the same live quarry Thus Trilokinath temple along
118
Janbade Prafulla Tarachand1
1
Chandigarh College of Architecture, Sector 12, 160012, Chandigarh, India
with Ardhanareswar temple provides the opportunity to study
the medieval stone against the stone from the restored work
and fresh sample from the quarry. The thin sections, chemical
analysis along with SEM analysis and X-ray diffraction analysis
were used to understand the character and mineralogical composition of the stone along with various properties of the stones.
The pro-conservation situation demands an appropriate
mechanism for meaningful understanding of the materials for
managing treatments & conservation activities in historic cities
and monuments.
Surface Area based approach to quantification of the stone
decay model: case study of Trilokeenath temple, Mandi, India
The documentation for the conservation and restoration project
remains most crucial stage as lot of decision making are based
on the accuracy and authenticity of it. The documentation
provides the professional a framework to analysis and logical
decisions. The policy makers and fund allotters face a different
dilemma. They don’t have the clues to decide how much to
give whom? To avoid this kind of confusion and uncertainty, it is
required that a streamlined and standard scale of measurement
is evolved to decide the severity of the decay and damage in the
given heritage structure. There have several model proposed for
the quantification of the decay and deterioration of the stone
monuments like the fitzner and zezza. These models are either
over simplified or too complicated.
We have tried to bring the balance by using the simple method
for the classification of the damage categories and used simple
area calculations methods for the quantification of the decay
and damage. The preliminary application of the proposed model to the Trilokeenath temple, Mandi, India has been tried for
its appropriateness. The pro-conservation situation demands
an appropriate mechanism for meaningful understanding,
of the extent and degree of the damage objectively, of the
each monument and also each part of the monuments. This
helps in the rationality in resource allocation. This paper tries to
identify those techniques and methods and analyze them for
conservation aspects. The analysis is qualitative and attempt
has been made to quantify it and thus making it objective and
not liable to subjective interpretations, this could be the first
step towards the goal of having explicitly described strategy for
future course of suitable actions in use for conservation project.
P-17
Rouge/Red
10 sept. 2014 17:00 > 20:00
Determination
of the alteration
mechanism
of green copper based
pigments by a multianalytical approach
Among the various painting materials used during the XVth
and XVIth centuries, some green copper-based pigments
as verdigris and resinate have been widely used for their
transparent and pure green tones. Unfortunately chromatic
modifications like browning or darkening can be observed
on those green painted layers. The understanding of the
degradation process is the key factor to evaluate potential
evolution of the damages through time.
Despite several previous studies pursued on this question
during the last 20 years, the mechanism responsible for
the darkening of green copper-based pigments remains
unknown. Several contradictory hypotheses were formulated: oxidation of binders due to a high chemical reactivity
of copper when present in the form of verdigris or resinate,
poor stability with other pigments, reduction of Cu(II),
formation of inorganic copper oxides, effects of outer SO2
and NO2 pollutants, diffusion of copper ions from verdigris
by fatty and resin acids, variation in the hydration of Cu
complex [1-3]. Up to now, no clear and definite explanation
of the degradation process has been proposed and the
debate remains still unsolved.
Bibliography
[1] Altavilla C., Ciliberto E., Appl. Phys.A, 83, 699-703 (2006).
[2] Gunn M., Chottard G., RivièreE., Girerd J., Chottard J.-C, Studies in Conservation,
47, 1, 12-23 ( 2002).
[3] Ioakimoglou E., Boyatzis S., Argitis P., Fostiridou A., Papapanagiotou K.,
Yannovits N., Chem. Mater., 11, 2013-2022 (1999).
[4] Santoro C., Zarkout K., Le Hô A.-S., Mirambet F., Gourier D., Binet L.,
Pagès-Camagna S., Reguer S., Mirabaud S., Le Du Y., Griesmar P.,
Lubin-Germain N., Menu M., Appl. Phys.A, 114, 637, (2014)
Solenn Réguer1 - Carlotta Santoro2 - Anne-Solenn Le Hô3
François Mirambet3 - Sandrine Pagés-Camagna3
Didier Gourier4 - Laurent Binet4 - Karim Zarkout3
Sigrid Mirabaud5 - Nadège Lubin-Germain2 - Michel Menu3
SOLEIL Synchrotron, L’orme des Merisiers, BP 48, 91192, Gif Sur Yvette Cedex, France
SOSCO, EA 4505 CNRS – Université de Cergy-Pontoise, 95011, Cergy-Pontoise, France
3
C2RMF - IRCP UMR8247, Research department, 75001, Paris, France
4
IRCP UMR8247 - C2RMF, Chimie ParisTech, 75231, Paris cedex 05, France
5
INP, Restoration department, 93210, Saint Denis la Paline, France
1
2
To better understand the degradation process, the present
approach is based on the comparison of data collected
on both model samples simulating the ancient paintings
and real samples issued from Old masters paintings.
Model samples have undergone artificial ageing (RH, T,
light) to reproduce the color change effect. They were
characterised before and after accelerated ageing tests by
a complementary set of analytical investigation techniques
as UV-visible, EPR and SEM-EDS [4]. Among them, X-ray absorption spectroscopy was realized on the DiffAbs beamline
at SOLEIL synchrotron.
The darkening is clearly promoted by the unsaturation
degree of the siccative oil. XANES experiments have demonstrated that incorporation of copper acetate or resinate pigments in the linseed oil binder and the following
accelerated ageing induces a rearrangement of the bridge
binuclear structure of the copper atoms generally observed
for the pure pigments. The chromatic change has been
evidenced and characterized by UV-visible spectroscopy.
Moreover EPR experiments allowed us to demonstrate
that incorporation of copper acetate in oil favours the
monomeric copper-carboxylate structure due to the lability of Cu-carboxylate ligand bonds. Nevertheless, it is not
responsible for the browning mechanism. The formation of
Cu(I) in the copper complexes of the pigment/oil system is
considered. It could be initiated by ambient light absorption
through LMCT leading to the reduction of Cu(II) into Cu(I)
and a drastic change in the optical properties. The partially
decarboxylated Cu(I)-Cu(I) pairs are thought to react with
oxygen, promoting the formation of copper bridged by
peroxide bonds and a darkening of samples.
119
P-18
Rouge/Red
10 sept. 2014 17:00 > 20:00
Nati Salvado1 - Salvador Buti1 - Gianfelice Cinque2
Jordi Juanhuix3 - Carme Clemente4 - Victoria Beltran1
Trinitat Pradell5
Synchrotron radiation
based techniques
for the study of altered
metal foil coatings
in Baroque altarpieces
Universitat Politècnica de Catalunya, Departament d’Enginyeria Química,
08800, Vilanova i la Geltrú, Spain
2
Diamond Light Source, Miriam Beamline, OX11 0DE, Chilton-Didcot, UK
3
CELLS-A LBA Synchrotron, Xaloc Beamline, 08290, Cerdanyola del Vallès, Spain
4
Escola d’Art i Disseny, Diputació de Tarragona, 43500, Tortosa, Spain
5
Universitat Politècnica de Catalunya, Departament de Física i Enginyeria
Nuclear, 08860, Castelldefels, Spain
Baroque artists applied metal foils on altarpieces to produce
colourful sparkling and shining light effects. Additionally,
pigments or dyes were mixed with oils and resins and
applied over the silver or gold foils to create also colour
shades. However, the effect intended by the artist appears
distorted by the alterations occurred over the years resulting from the chemical reactions among the materials
themselves and with the environment. Besides, these
processes are favoured by the environmental conditions
in which the materials are kept. The silver foil itself reacts
with the environment through the micro fissures open in
the organic protection coatings producing silver sulphides
and chlorides, which, while crystallizing, produce themselves stresses that enlarge the cracks resulting in a gradual
loss of the metal layer. Generally speaking, the metal foils
coatings become fragile and more vulnerable making their
restoration more complex and risky. The study of the reactivity and stability of the metal foils, coating layers and the
adhesives which fix the foils onto the ground layers (often
a bole) is essential to define restoration strategies.
The samples extracted are very complex, to the original
materials (bole, adhesives, metal foils, resins, drying oils,
pigments/dyes, fillers and binders), reaction, weathering
and aging compounds (i.e. metal carboxylates and oxalates)
we have to add those materials incorporated by historical
restorations and dirtiness. Furthermore, those substances are
present in variable concentrations, and often in extremely
low concentrations. Finally, the location and distribution of
the reaction and aging substances in the different layers is
also important and consequently, homogenizing and dissolving the samples is not adequate since this valuable information is lost. Synchrotron radiation based micro-sensitive
techniques such as µFTIR, µXRD and µXRF,are outstanding
to overcome the difficulties involved in the analysis.
Bibliography
[1] N.Salvadó, S. Butí, A. Labrador, G. Cinque, H. Emerich and T. Pradell, SR-XRD
and SR-FTIR study of the alteration of Silver foils in Medieval paintings,
Anal.Bional.Chem, 399, 9 (2011) 3041-3052
[2] I.C.A. Sandu, M.H. de Sá, M.C. Pereira, Ancient ‘gilded’ art objects
from European cultural heritage: A review on different scales
of chraracterization, Surf. Interface Anal. 43, (2011), 1134-1151
[3] N. Salvadó, S. Butí, J. Nicholson, A. Labrador, H. Emerich and T. Pradell;
Identification of reaction compounds in micrometric layers from 15th
century Gothic paintings using combined SR-XRD and SR-FT-IR, Talanta,
79-2, (2009), 419-428.
120
1
The cathedral of Tortosa, a few kilometres inland from the
mouth of the Ebro river in Catalonia, contains a set of Baroque
altarpieces made over a prolonged period of about one hundred years, the oldest dating 1671 and the newest, 1775.
During this extended period the materials used and the
techniques employed changed and those changes are manifested in the aging and alteration processes undergone
by the artworks. The nature, reactivity and alterations of
the green, red and amber protective coatings are studied.
P-19
Rouge/Red
10 sept. 2014 17:00 > 20:00
Evaluation
of the atmospheric
plasma afterglow
cleaning performance
of tarnished
silver-copper
surfaces by means
of synchrotron X-ray
photoelectron
microscopy
Silver sulphide compounds are rather easily reduced to metallic silver when they are treated with an atmospheric plasma
afterglow obtained from a gas mixture of 5 vol % H2 in He.
Therefore, it is a promising technique for the cleaning of tarnished silver objects, especially silver in combination with other
materials such as gelatin (e.g., photographic glass negatives)
or organic fibers (e.g., silver threads in textiles). However,
most historical silver objects are alloyed with a small amount
of copper (e.g., Sterling silver contains 92.5 w % Ag and
7.5 w % Cu) and this copper appears to oxidize preferentially
during the sulphidation process. The resulting black sulphide
layer is composed of complex mixtures of Cu-rich and Ag-rich
sulphides. Unfortunately, with the current plasma technoloBibliography
[1] Graedel T.E., Franey J.P., Gualtieri G.J., Kammlott G.W., Malm D.L.,
On the mechanism of silver and copper sulfidation by atmospheric H2S
and OCS, Corrosion Science, 25(12) (1985) 1163-1180
[2] Hayez V., Franquet A., Hubin A., Terryn H., XPS study of the atmospheric
corrosion of copper alloys of archaeological interest, Surface and Interface
analysis, 36 (2004) 876-879
[3] Patelli A., Favaro M., Simon S., Storme P., Scopece P., Kamenova V.,
Kamenarov Z., Lorenzon A., De Voeght F., PANNA Project – Plasma
and Nano for New Age Soft Conservation. Development of a Full-Life
Protocol for the Conservation of Cultural Heritage, in Progress in Cultural
Heritage Preservation, Lecture Notes in Computer Science, Springer,
Heidelberg, Volume 7616, 2012, pp 793-800
Olivier Schalm1 - Patrick Storme1 - Vitaliy Feyer2
Amandine Crabbé3 - Stefano Voltolina4
Alessandro Patelli4 - Herman Terryn3
University of Antwerp, Conservation Studies, 2000, Antwerp, Belgium
Peter Grünberg Institute, Research Center Jülich, 52425, Jülich, Germany
3
Vrije Universiteit Brussel, Research Group of Electrochemical and Surface
Engineering, 1050, Brussels, Belgium
4
Veneto Nanotech, Nano Fabrication Facility, 30175, Venezia-Marghera, Italy
1
2
gies the Cu-rich sulfides are almost impossible to remove.
Therefore, atmospheric plasma afterglows are able to remove
the black tarnish layer from some silver objects while visually
similar tarnish layers on other objects cannot be removed at
all, making the cleaning behaviour unpredictable.
In order to understand this difference in cleaning behaviour,
the surface of polished and sulphidized pure silver (Ag999),
sterling silver (Ag925) and copper coupons (Cu999) before
and after plasma treatment were characterized at the µm-level
using optical microscopy and scanning electron microscopy.
The analyses showed that for all metals the morphology of the
upper surface was transformed during the afterglow treatment,
but due to a lack of depth resolution it was not possible to
obtain chemical information from the surface layer. For an in
depth investigation, we used photoelectron microscopy at
the NanoESCA beamline of the Elettra synchrotron. The set-up
includes a non-magnetic, electrostatic photoelectron emission
microscope (PEEM) and a double-pass hemispherical analyser,
allowing the mapping of core-level photoemission signatures
with the lateral resolution of about 100 nm.
This investigation has shown that atmospheric plasma treatments on sulphidized Ag999, Ag925 and Cu999 were able to
reduce some corrosion compounds. The surface of sulphidized Ag999 consisted of a granular layer of sulphide particles.
The XPS analyses suggested the presence of a monosulphide
layer covered by a layer rich in polysulphides. The afterglow
was able to reduce all the polysulphide S-S bonds and most
of the monosulphides. The resulting surface consisted of
a porous aggregate of metallic silver particles with on top
some isolated monosulphide Ag2S particles. At a µm-level,
the sulphidized Ag925 comprised Cu-rich sulphide islands.
However, this microstructure could not be observed with
XPS, due to the presence of a thin but homogeneous Ag2S
top layer. The afterglow was able to reduce this Ag2S film into
metallic silver. For sulphidized Cu999, the afterglow was able
to transform some sulphide compounds, resulting in a thin
metallic Cu film on top of the surface.
121
P-20
Rouge/Red
10 sept. 2014 17:00 > 20:00
Eleanor Schofield1 - Mark Jones1 - Alan Chadwick2
1
2
Mary Rose Trust, Charity, PO1 3LX, Portsmouth, United Kingdom
University of Kent, University, CT2 7NZ, Canterbury, United Kingdom
Oxidation
of problematic sulfur
within Mary Rose
timbers as a function
of drying time
The Mary Rose, currently based in Portsmouth Historic
Dockyard, has been undergoing conservation since its
excavation in 1982. The Tudor ship sank in 1545 off the
south coast of England during confrontation with the
invading French fleet. The starboard side was covered in
protective silt whilst the portside gradually eroded away.
The burial environment, with limited Oxygen, reduced the
activity of traditional wood eroding bacteria. However,
it also promoted the activity of sulfur reducing bacteria,
which reacted with sulfate ions in the seawater to produce
reduced sulfur compounds. These gradually diffused into
the wood, often reacting with iron ions available from
122
corroded artefacts or fixtures. Since excavation, the ship
has been kept wet with water and various concentrations
of Polyethylene Glycol, a polymer used to gradually replace
the water within the wood to ensure mechanical stability
upon drying. In April 2013 the sprays were turned off and
the ship is now drying under environmentally controlled
conditions. Sulfur X-ray Absorption Spectroscopy has been
used to determine the change in sulfur speciation as a
function of drying time and depth into the timbers of the
Mary Rose hull. This is the first time sulfur development
has been measured real-time as function of air-drying.
Initial results will be presented here.
P-21
Rouge/Red
10 sept. 2014 17:00 > 20:00
Alicja Rafalska-Łasocha1 - Marta Grzesiak-Nowak2 Dominika Sarkowicz3 - Wiesław Łasocha1,2
Jagiellonian University, Faculty of Chemistry, Kraków, Poland
Institute of Catalysis And Surface Chemistry Pas, Kraków, Poland
3
National Museum in Krakow, Poland
1
Investigation
of historic pigments
and painting materials
in works
by Henryk Siemiradzki
2
Antiquity and Bible were the main inspiration for Henryk
Siemiradzki (1843-1902). His paintings depict scenes from
Greco-Roman world e.g. Roman Orgy in the Time of Caesars
(1872) and from the life of first Christians e.g. Christian
Dirce (1897). Siemiradzki’s works show also scenes from
everyday life of ancient people, beautiful landscapes and
portraits. Exact knowledge of the chemical composition of
pigments used by Henryk Siemiradzki − one of best Polish
artists − is important for enrichment of the data concerning
his workshop and is also useful in conservation and preservation of his works representing mainly Academic art [1].
At the beginning of this study the components of several
powdery pigments (which belong now to the collection of
the National Museum in Krakow) inherited from Siemiradzki
were examined and compared with the results obtained
by XRF analysis.
In the second part of this project samples taken from Siemiradzki paintings: The Ruins of the Roman villa, A Scene from the
life of the first Christians, Portrait of Son Leos and Self-Portrait
with a Palette were investigated by means of XRPD with
the use X-rays from laboratory and synchrotron sources.
We wanted to identify brown pigment in the first painting
and blue pigments in last three paintings. The obtained
results show that the brown paint contained the mixture of
red, white and yellow pigments while blue paints contained
iron cobalt aluminum oxide (FeCoAlO4) or artificial ultramarine
(Na7Al6Si6O24S3) or Prussian blue Fe4[Fe(CN)6]3 with some admixtures of other painting materials.
X-ray powder diffraction measurements were carried out in
DESY Hamburg or at Faculty of Chemistry Jagiellonian University with the use of X’PERT PRO MPD diffractometer, Cu Kα
radiation, 40 kV and 30 mA, a graphite monochromator and
PIXCEL PSD detector. The phase analysis was performed with
the use of PDF4+ database. The obtained results with comparison to XRF analysis will be presented during the conference.
Bibliography
[1] Blak H., Małkiewicz B., Wojtałowa E., Malarstwo polskie XIX w. Katalog
zbiorów pod redakcją Zofii Gołubiew, Kraków 2001.
123
P-22
Rouge/Red
10 sept. 2014 17:00 > 20:00
Methodology
in practice: workshop
on sample preparation
for FTIR analysis
at IPANEMA - SOLEIL
synchrotron
In the framework of the networking activities of the CHARISMA European project (funded under FP7, GA no. 228330,
www.charismaproject.eu) an innovative initiative was
co-organized by IPANEMA and the National Gallery London,
to foster collaborative exchange of knowledge on scientific
methods applied to cultural heritage within the consortium,
and to communicate the outcomes of this work externally,
with the objective of raising standards more generally across
this research area. The workshop Sample preparation and
analytical methodology for synchrotron FTIR microscopy,
was held at the IPANEMA laboratory, SOLEIL synchrotron,
5-6 July 2012, with three associated days of beamtime on
the SMIS synchrotron FTIR beamline. This was formulated as
a practical ‘hands on’ counterpart to a survey and literature
review on sample methodology and preparation practices.
Coupling a ‘hands-on’ workshop – where participants with
various levels of expertise on differing topics could exchange
ideas – with experimental time, where the same participants actually worked together on a pre-selected corpus of
samples, was a valuable and fruitful event.
The workshop brought together a small number of scientists who had specific expertise in this area. It proved to
be a stimulating forum for a direct exchange of ideas and
knowledge, through working together very closely in a
practical way, discussing hints and tips, and learning from
each other’s experience. It served as a pretext for concen-
Bibliography
[1] Blak H., Małkiewicz B., Wojtałowa E., Malarstwo polskie XIX w. Katalog
zbiorów pod redakcją Zofii Gołubiew, Kraków 2001.
124
Mathieu Thoury1,2 - Marika Spring3 - Loïc Bertrand1,2
Serge Cohen1 - Marie-Angélique Languille1
Alessandra Vichi1,2
IPANEMA, F-91192, Gif-Sur-Yvette Cedex, France
SOLEIL Synchrotron, F-91192, Gif-Sur-Yvette Cedex, France
3
Scientific Department, National Gallery, Trafalgar Square, WC2N 5Dn London, UK
1
2
trated effort on this aspect of analytical methodology,
which can sometimes be neglected, with habitual practice
being continued without an assessment of whether it is
adequate. In fact sample preparation is far from routine,
and can have a strong influence on the quality of the data
and results and has become more important with the advent
of new chemical imaging techniques.
Those based on FTIR are of special interest because over
the last two or three years several of the institutions within
CHARISMA have acquired imaging or mapping systems.
They are therefore keen to re-assess and refine their protocols, to achieve a more sophisticated understanding of
the factors influencing their analyses with these systems,
and to evaluate the place of FTIR imaging/mapping within
the examination of individual cross-sections with multiple
complementary analytical techniques. A range of samples
were prepared in different ways and the effect on FTIR
analysis in various modes was tested: transmission, reflectance, transflectance or ATR – in the lab or on the beamline.
The experiments explored included different embedding
media and systems, improving polishing techniques with
both traditional and new methods (e.g. argon ion polishing,
through the Ilion+ kindly loaned by Gatan) and microtomy,
either to make thin sections (for transmission and transflectance FTIR) or for ‘resurfacing’ of thick sections. This poster will
present the main observations and conclusions of this work.
P-23
Bleu/Blue
10 sept. 2014 17:00 > 20:00
David Agyeman-Budu1 - Arthur Woll2
Sanjukta Choudhury3 - Ian Coulthard4 - Robert Gordon5
Emil Hallin4
Fabrication of spoked
channel arrays for 3D
micro confocal X-ray
fluorescence
1
We report the development and practical demonstration of
spoked channel arrays (SCAs), a novel X-ray collection optic
for confocal X-ray fluorescence microscopy (CXRF). The optic
consists of micron-scale, lithographically-fabricated arrays
of collimating channels, all directed towards a single source
position. In contrast to polycapillaries, SCAs exhibit nearly
energy-independent resolution and collection efficiency.
For example, a nearly energy-independent depth resolution
below 2 microns has been achieved from 3-10 keV, degrading slightly to 3±0.5 microns at 1.7 keV. Our original SCA
design, described in Ref. 1, exhibited limited working distance and efficiency. An improved design [2] has effectively
solved both limitations, resulting in a practical optic that has
now been used for a wide range of art and archaeological
applications. In particular, we have employed 1 µm and 7 µm
optics at APS beamline 20-ID-B for confocal XRF mapping
and XAFS of an 11th century stained glass sample from the
Paderborn Cathedral, a paint sample from an 18th century
oil painting by Adriaen de Coorte and most recently, an archaeological bone sample excavated from a cemetery near
English Harbor, Antigua. Here, we report key details required
to design and fabricate SCAs, including limitations imposed
by the substrate material and factors that determine useful
channel dimensions. The optics reported in refs. 1-2 were
fabricated from silicon, and were thus expected to operate
well only below about 12 keV. Recently, we have fabricated
new optics from germanium, which should operate well
up to 30 keV. In addition, we are currently fabricating SCAs
with channel widths up to 50 μm, which we may be suitable
for use in non-synchrotron based CXRF systems.
Department of Materials Science and Engineering, Cornell University,
14853, Ithaca, USA
2
Cornell High Energy Synchrotron Source, Cornell University, 14853, Ithaca, USA
3
Geol. Sciences, University of Saskatchewan, SK S7N 5E2, Saskatoon, Canada
4
Canadian Light Source, Canadian Light Source, SK S7N 2V3, Saskatoon, Canada
5
PNCSRF, Aps Sector 20, 60439, Argonne, USA
Bibliography
[1] A. R. Woll, D. Agyeman-Budu, D. H. Bilderback, D. Dale, A. Y. Kazimirov,
M. Pfeifer, T. Plautz, T. Szebenyi, and G. Untracht, in SPIE Optics
and Photonics 2012, edited by S. Goto, C. Morowe, and A.M. Khounsary
(SPIE, San Diego, CA, 2012), 8502, 85020K-85021-85014 (2012).
[2] Arthur R. Woll, David Agyeman-Budu, Sanjukta Choudhury, Ian Coulthard,
Adam C. Finnefrock, Robert Gordon, Emil Hallin, and Jennifer Mass,
« Lithographically-fabricated channel arrays for confocal X-ray fluorescence
microscopy and XAFS, » Journal of Physics: Conference Series 493,
012028 (2014).
125
P-24
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Bone physiology
through particle
physics
Most palaeontological studies that use synchrotron techniques apply tomographic methods in order to obtain fine
morphological details that cannot be distinguished using
conventional CT scanning. However, there is considerably
more information to be gleaned from fossil material
through the sensitivity and tunability of a synchrotron
light source. Most notably, the use of fine scale compositional mapping and the quantification of trace elements
can be critical for resolving key biochemical structures
and thereby improve our understanding of biological
processes and pathways [1,2]. For example, the processes
behind bone remodeling and healing recapitulate bone
development. Thus the ability to determine trace element patterns associated with such processes can lead
to a better understanding of bone development within
different vertebrate groups, and perhaps may even help
uncover details about the evolutionary development of
the skeleton.
Bibliography
[1] U. Bergmann, P. L. Manning and R. A. Wogelius. Annu. Rev. Anal. Chem.,
2012, 5, 361-89. DOI:10.1146/annurev-anchem-062011-143019
[2] U. Bergmann, R.W. Morton, P.L. Manning, W.I. Sellers, S. Farrar, K.G. Huntley,
R.A. Wogelius & P. Larson. Proc. Natl. Acad. Sci. U.S.A, 2010,107(20),
9060-9065.
[3] M.B. Goodwin, P.G. Grant, G. Bench, & P. Holyrod. Palaeogeogr.
Palaeoclimatol. Palaeoecol., 2007, 23, 458-476.
[4] S. Gomez, R. Rizzo, M. Pozzi-Mucelli, E. Bonucci, & F. Vittur. Bone, 1999,
25(1), 33-38.
126
Jennifer Anne1 - Roy Wogelius1 - Nicholas Edwards1
Arjen van Veelen1 - Victoria Egerton1 - William Sellers2
Uwe Bergmann3 - Dimosthenis Sokaras4
Konstantin Ignatyev5 - Phillip Manning1
Science, M13 9PL, Manchester, UK
2
University of Manchester, Faculty of Life Sciences, M13 9PL, Manchester, UK
3
SLAC National Accelerator Laboratory, Linac Coherent Light Source, 94025,
Menlo Park, USA
4
Lightsource, 94025, Menlo Park, USA
5
Diamond Light Source, OX11 0DE, Didcot, UK
1
In this study we focus on mapping and quantifying trace
elements that are crucial for the maintenance and repair
of bone within both extant and extinct organisms by using
a combination of Synchrotron Rapid Scanning-X-ray Fluorescence (SRS-XRF) and microfocus elemental mapping.
Zinc was found to be differentially distributed within: 1] the
fracture callus of a large carnivorous dinosaur (Allosaurus
fragilis: ~146 million years old), 2] the secondary osteons of
an extinct dugong (Metaxytherium sp.: ~17 million years
old), and 3] within the plexiform tissue of an extinct hyena
(Crocuta crocuta spelaea: ~40 thousand years old). These
tissues all consist of actively remodeling or ossifying bone
at the time of death. The distributions and concentrations of
zinc match those found in modern tissues from comparable
species [3]. As zinc is crucial for the ossification and mineralization of bone [4], we propose that zinc may be used as
a biomarker for active ossification within the fossil record.
P-25
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Tomography
for cultural heritage
at Synchrotron SOLEIL
In the past decade, synchrotron-based microtomography
(SR-µCT) has become a central tool for investigating the morphology of cultural heritage samples. SR-µCT accesses the 3D
inner structure in a non-invasive way for obtaining images with
a higher resolution (voxel sizes ranging from a few hundreds
of nanometers to a few microns) and far shorter acquisition
times than a conventional tomograph. After the pioneering
work at the ESRF in palaeontology and palaeo-anthropology,
synchrotron facilities such as SLS, Diamond and SOLEIL join
the development of SR-µCT for cultural heritage specimens.
At SOLEIL, the PUMA beamline will be devoted to investigation
of ancient materials with tomography and scanning X-ray
imaging methods in the context of the development of the
European research platform for ancient materials IPANEMA.
PUMA will join two tomography beamlines at SOLEIL: PSICHE
and ANATOMIX.
The three SOLEIL tomography beamlines, fed by insertion
devices, have complementary characteristics, as each one
of them is tailored for different needs of tomography experiments. PSICHE, already available to the users, is a high-pressure
diffraction and tomography beamline working at 15-80 keV,
with a maximum beam size of 15×6 mm2 (H×V). PSICHE is
prepared for hosting large sample environments and heavy
Felisa Berenguer1 - Andrew King2 - Timm Weitkamp2
Sebastian Schöder2 - Pascal Mercere2 - Philippe Janvier3
Thierry Moreno2 - François Polack2 - Loïc Bertrand1
Serge Cohen1 - Pierre Gueriau3 - Didier Merle3
Jean-Sébastien Steyer3 - Florent Goussard3
Stéphanie Gastou3
IPANEMA, CNRS, Ministère de la Culture et de la Communication, USR 3461,
91192, Gif-sur-Yvette, France
2
SOLEIL SYNCHROTRON, Division Experiences, 91192, Gif-sur-Yvette, France
3
CR2P, Muséum National d’Histoire Naturelle, UMR 7207, 75005, Paris, France
1
specimens, and will be optimized for fast tomographic data
acquisition with white beam (0.1 sec per full tomograph)
and in-situ experiments. PUMA will be opening to the users
in the second half of 2015. The beamline tomography setup,
designed for exploiting phase contrast imaging, will deliver
a 20×10 mm2 (H×V) beam in the energy range from 15 to
60 keV. The key development will be automation of data acquisition and analysis in order to measure large sets of specimens
(high throughput corpus studies) combined with high-definition, up to 12k×12k sections. Both PUMA and PSICHE will
give access to spatial resolution of 1 to a few microns, whereas
higher resolution will be available at ANATOMIX (open end
2015): pixel sizes down to 200 nm (for parallel-beam tomography) and 30 nm (for microscopy) will be available. ANATOMIX
will offer various phase-contrast imaging modalities (including
grating interferometry) and will be optimized to perform fast
acquisition experiments in the energy range from 5 to 25 keV.
With these three beamlines, SOLEIL will cover a wide spectrum
of possibilities for tomographic study of ancient materials,
from small to medium size fossil specimens to archaeological
artifacts (tools, ceramic and metallic objects). We will also
present test experiments that have already been performed
at the beamline METROLOGY.
127
P-26
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Mathieu Thoury1 - Sébastien Ancelin1 - Felisa Berenguer1
Serge Cohen1 - Marie-Angélique Languille1
Regina Oprandi1 - Sebastian Schoeder2 - Loïc Bertrand1
The European research
platform on ancient
materials IPANEMA
at Synchrotron SOLEIL
1
The building hosting the IPANEMA European research platform on ancient materials (CNRS, Ministère de la Culture et
de la Communication) was inaugurated in September 2013
at the SOLEIL synchrotron, France. The activities of IPANEMA
are centred on two areas: interdisciplinary research in methodology and medium-term support to synchrotron proposals,
for four fields of application: archaeology, cultural heritage,
palaeontology and palaeo-environmental sciences.
research, among which half were selected for beamtime and
the team has supported users by participating to project
definition and implementation, experiment preparation,
complementary characterisation and data processing.
IPANEMA fosters new methodological concepts and developments, in particular in synchrotron X-ray imaging
(development of the PUMA beamline, microtomography),
UV/visible microimaging, and statistical analysis of data.
Since the initiation of IPANEMA, more than 200 proposals
were submitted to the SOLEIL facility on ancient materials
Bibliography
[1] L. Bertrand, M.-A. Languille, S. X. Cohen, L. Robinet, C. Gervais, S. Leroy,
D. Bernard, E. Le Pennec, W. Josse, J. Doucet, S. Schöder. European research
platform IPANEMA at the SOLEIL synchrotron for ancient and historical
materials. J. Synchrotron Radiat., 18(5):765–772, 2011.
[2] L. Bertrand, M. Cotte, M. Stampanoni, M. Thoury, F. Marone, and S. Schöder.
Development and trends in synchrotron studies of ancient and historical
materials. Phys. Rep., 519(2):51–96, Oct 2012.
[3] L. Bertrand, L. Robinet, M. Thoury, K. Janssens, S. X. Cohen, S. Schöder.
Cultural heritage and archaeology materials studied by synchrotron
spectroscopy and imaging. Appl. Phys. A, 106(2):377–396, 2011.
128
2
IPANEMA, CNRS, MCC, 91192, Gif-sur-Yvette cedex, FRANCE
Synchrotron SOLEIL, PUMA beamline, 91192, Gif-sur-Yvette cedex, FRANCE
The new building hosts facilities for sample preparation,
X-ray, infrared and UV/visible and SEM characterisation and
an instrumentation workshop. Offices and user facilities allow
hosting researchers working on ancient materials at the site.
Specific research partnerships were set up with leading
international institutions, in particular the Smithsonian Institution of the USA and NWO, the Netherlands organisation
for scientific research. At the European level, IPANEMA is part
of the European Research Infrastructure network IPERION-CH
and was supported as part of FP7 CHARISMA (2009–2014).
P-27
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Olga Otero1 - Renaud Boistel2 - Anthony Herrel3
Lukas Helfen4 - Lukas Helfen5
Université de Poitiers - UFR SFA, iPHEP UMR CNRS 7262, 86073, Poitiers, France
CNRS, iPHEP UMR CNRS 7262, 86073, Poitiers, France
3
CNRS, UMR7179 MNHN, 75231, Paris, France
4
European Synchrotron Radiation Facility (ESRF), id19, 38043, Grenoble, France
5
ANKA Light Source / Institute for Photon Science and Synchrotron
Radiation, Karlsruhe Institute of Technology, D-76021, Karlsruhe, Germany
1
3D X-ray imaging
reveals hidden hearing
apparatus of ancient
fishes
2
Synchrotron X-ray imaging of fossilized fishes is helping
one to better understand how sound transmission in the
course of evolution developed. Otophysan fish represent
more than half of the freshwater fish today, and include wellknown members such us piranhas, catfish and minnows.
They show an astonishing wide range of morphologies, in
relation with the variety of habitats that they occupy in all
continents with the exception of Antarctic. This evolutionary
success story is often related to the evolutionary advantage
brought by their Weberian Apparatus (WA), an original
complex structure compound of an ossicular complex and
soft tissue, which allows acute reception and transmission
of sounds and vibrations. If only otophysan fish have a WA,
each of the four extant lineages (Characiformes, Cypriniformes, Gymnotiformes and Siluriformes) shows a particular
organisation. Although the anatomy of the WA in extant fish
has been accurately described [e.g. 1], the modalities of the
apparition of this complex remain rather dull. Notably, the
anatomy of the various WA patterns in early otophysan fish
differs from the extant and is highly debated as the different
experts do not agree in their interpretation. Moreover their
functional efficiency in sound reception and transmission
remains unknown.
Apart from the established technique of synchrotron
tomography, a novel X-ray imaging modality is helping
to study fossils embedded in flat stone. Synchrotron laminography was developed at the ESRF beamline ID19 [2]
and serves for reconstruction of regions of interest on flat
stone specimens, like fossils [3]. The laminography instrument installed at ID19 provides a unique opportunity to use
phase contrast [4] for highly sensitive imaging compared to
its laboratory counterparts. This along with the high spatial
resolution provided is particularly suited for truly non-destructive imaging of the Weberian regions in the fossils embedded in flat stone.
We use X-ray laminography at the ESRF to describe accurately
the WA structures in extant and extinct fish, with the aim to
help and resolve the heated debate about the origin of WA.
In our presentation, we focus on the 3-D images obtained
and the details of the bony anatomical architecture of WA
revealed in fossils.
Bibliography
[1] Chardon, M., (1968), MRAC, Sc. Zool, 169, pp. 277.
[2] Helfen, L. et al., (2005), Appl. Phys. Lett. 86, 071915.
[3] Houssaye, A. et al., (2011), J. Vertebr. Paleontol.
[4] Helfen, L. et al., (2009), Appl. Phys. Lett. 94, 104103.
129
P-28
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Antonio Brunetti1- Anna de Palmas2 - Claudio Bulla2
Nick Schiavon3 - Giampaolo Piga1
University of Sassari, Dipartimento di Scienze Politiche, Scienze della
Comunicazione, Ingegneria dell’Informazione, 07100, Sassari, Italy
2
University of Sassari, Dipartimento di Storia, Scienze dell’Uomo e della
Formazione, 07100, Sassari, Italy
3
University of Evora, Hercules Laboratory and Evora Geophysical Centre,
7000/809, Evora, Portugal
1
An XRF/Monte Carlo
study of Nuragic
samples from Sardinia,
Italy
Sardinia is the second largest island in the Mediterranean
and is well-known for its Nuragic civilisation, which thrived
in the Bronze and Early Iron Ages from XX to VII centuries BC.
Metallurgy developed greatly during this period, and this
provides us with important information on the technology used in the economic activities of the Nuragic people.
A great variety of bronze artefacts have been found: axes,
chisels, awls, wedges, drills, files and saws used for working wood, and scrapers, blades, borers and punches for
working leather. The importance of these unique bronze
productions is so far not supported by in-depth knowledge
about the qualitative and quantitative chemical composition of the alloys. Moreover, many of these bronze
samples show corrosion signs and also the presence of
the so-called patina and a protective layer. Thus, from the
archaeometric point of view, their surface can be considered as a multilayered structure that makes it hard to obtain
reliable quantitative data on the bronze composition. The
Bibliography
[1] U. Bottigli, A. Brunetti, B. Golosio, P. Oliva, S. Stumbo, L. Vincze, P. Randaccio,
P. Bleuet, A. Simionovici, A. Somogyi, Voxel-based Monte Carlo simulation
of X-ray imaging and spectroscopy experiments, Spectrochim. Acta Part B
59 (2004), 1747-1754
[2] B. Golosio, A. Brunetti, G.L. Masala, P. Oliva, T. Schoonjans, Monte Carlo
simulation of X-ray imaging and spectroscopy experiments using quadric
geometry and variance reduction techniques, Comput. Phys. Commun.
185 (2014) 1044-1052
[3] A. Brunetti and B. Golosio, A new Monte Carlo code for simulation
of the effect of irregular surfaces on X-ray spectra, to be published
on Spectrochim. Acta Part B (2014)
[4] N. Schiavon, A. Celauro, M. Manso, A. Brunetti, F. Susanna, Iron-Age bronze
statuettes in Southern Portugal: combining archaeological data with
EDXRF and BSEM + EDS to assess provenance and production technology,
Appl. Phys. A: Mater. Sci. Process. 113 (2013) 865-875
130
latter represents an important factor for the classification
of the production site and technology used. XRF analysis is
a powerful non destructive tool for Cultural heritage sample
analysis. It is based on the interaction of the X-ray with the
matter producing, besides others effects, characteristic
X-ray photons which represents a unique marker of the
presence of a chemical element inside the sample. However, the presence of the two outer layers, patina and protective ones, alters the number of the photons produced
making very difficult to obtain a quantitative estimation
at least with standard approach such as the Fundamental
Parameters one. Here this problem will be addressed by a
new, innovative approach based on a fast Monte Carlo simulation of the experiment performed [1-4]. This approach
allows to consider any kind of multilayer structures as well
as to take in account the presence of rough surfaces that
is typical in Cultural Heritage samples. Some results will be
reported and discussed.
P-29
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Multi-analytical
study of historical
semiconductor
pigments
for the detection
of impurities and trace
metal ions
During the mid 19th century a new class of pigments, based
on semiconductors including ZnO, ZnS, and CdS, substituted
the pigments used by painters in earlier periods. Despite their
improved properties in terms of hiding and handling power with
respect to traditional materials, early formulations of synthetic
pigments have proven to be chemically unstable. Many impurities were introduced unintentionally during manufacturing, as
has been highlighted by recent results obtained in our research
group based on luminescence spectroscopy of Zn-based
pigments [1]. In parallel, spectroscopic investigations on both
pure ZnO and paint models have demonstrated that physical
and chemical interactions affect the UV and visible emissions,
leading to the observation of considerably different emission
profiles [2]. Fluorescent inclusions in paint samples containing
ZnO have been also investigated at DISCO beamline at SOLEIL
synchrotron through the use of raster-scanning microspectroscopy and full-field microimaging [3]. From Fluorescence imaging
and Fluorescence spectroscopy measurements of ZnO and ZnS
samples [4], we suspected the presence of metallic impurities
including traces of Pb, Fe, Mn and Cu. The presence of some of
these impurities has been confirmed by Electron Paramagnetic
(EPR) measurements performed at the University of Lille.
Valentina Capogrosso1 - Anna Cesaratto1 - Sara Bellei2
Francesca Gabrieli3 - Francesca Rosi3 - Laura Cartechini3
Nicolas Trcera4 - Caroline Tokarski5 - Herve Vezin5
Aviva Burnstock6 - Austin Nevin2
Politecnico Di Milano Physics, Departement Piazza Leonardo Da Vinci, 32 20133, Milan, Italy
Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133, Milan, Italy
3
IFN-CNR, Piazza Leonardo da Vinci 32, 20133, Milan, Italy
4
Institute of Molecular Science and Technologies, Via Elce di Sotto, 8, 06123,
Perugia, Italy
5
Synchrotron SOLEIL, Saint Aubin, BP48 F-91192, Gif-sur-Yvette Cedex, France
6
Université de Lille 1 Sciences et Technologies, Villeneuve d’Ascq Cedex, 59655,
Lille, France
7
The Courtauld Institute of Art, Somerset House Strand, WC2R 0RN, London, Great Britain
1
2
In this work, we present the application of synchrotron-based
analysis of the impurities in historical samples of ZnO, ZnS
and CdS-based pigments. The necessity of a micrometric
spatial resolution and sub-ppm sensitivity for investigating
trace and heterogeneous impurities in semiconductor based
pigments required the access to synchrotron radiation
sources. Analysis was performed at the LUCIA beamline at
the SOLEIL synchrotron for the simultaneous detection of
the atomic distribution and the oxidation state of the specific
metal impurities in our samples. We revealed the presence
of trace metal ions in powder samples by means of microX-ray Fluorescence (XRF) mapping [5] and we investigated
the oxidation states and coordination of metallic inclusions
by means of micro-X-ray Absorption (XAS) spectroscopy.
The mapping of metal impurities within pigment particles
provides data which can allow us to discriminate different
manufacturing routes and to better understand the chemical reactivity of pigments in the presence of most common
organic binders. This work is focused to obtain markers for
future in situ analysis of paint-samples with evident implications for the conservation and treatment of early 20th
century paintings.
Bibliography
[1] Comelli D., et al., Appl. Phys. A 106 (1), 25-34 (2011).
[2] Clementi C., et al., Appl. Spectr. 66, 1233-41 (2012).
[3] Thoury M., et al., Anal. Chem. 83 (5), 1737-1745 (2011).
[4] Nevin A., et al., Proc. of SPIE 8790, 87900U-1 (2013).
[5] Casadio F. and Rose V., Appl. Phys. A 111 (1), 1-8 (2013).
131
P-30
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Microchannel array
derived high resolution
confocal X-ray
fluorescence imaging
for art and archaeology
X-ray fluorescence imaging (XFI) is a nondestructive tool
for studying trace element distribution. Confocal XFI, a less
common variant, enables higher spatial resolution imaging
and depth information of fragile or valuable objects for which
sectioning is challenging or undesirable. This presentation
compares results from several art and archaeology samples
studied at scan-probe microscopy station 20-ID-B at the APS
synchrotron using different fluorescence detection modes.
Standard and confocal modes of XFI were used to obtain
elemental distribution images from archaeological bone
samples excavated from the Royal Naval Hospital Cemetery (c.
A.D. 1793-1822) near English Harbor, Antigua. These samples
were investigated to answer key questions about whether lead
poisoning played a role in the demise of the British military
in West Indies, and whether the observed lead is biogenic
Bibliography
[1] Woll, A. R., Agyeman-Budu, D., Choudhury, S., Coulthard, I., Finnefrock,
A. C., Gordon, R., Hallin, E., Mass, Jennifer (2014). Lithographically-fabricated
channel arrays for confocal X-ray fluorescence microscopy and XAFS.
Journal of Physics: Conference Series, 493, 012028. doi:10.1088/17426596/493/1/012028
132
Sanjukta Choudhury1 - Arthur R. Woll2
David Agyeman-Budu2 - Treena Swanston3
Tamara Varney4 - David M. L. Cooper3 - Robert A. Gordon5
Emil Hallin6 - Graham N. George1 - Ian Coulthard7
Ingrid J. Pickering1
University of Saskatchewan, Geological Sciences, SK S7N 5E2, Saskatoon, Canada
Cornell University, Cornell High Energy Synchrotron Source, NY 14853, Ithaca, USA
3
University of Saskatchewan, Anatomy and Cell Biology, SK S7N 5E5, Saskatoon, Canada
4
Lakehead University, Anthropology, ON P7B 5E1, Thunder Bay, Canada
5
Argonne National Laboratory, PNCSRF, Il 60439, Argonne, USA
6
Canadian Light Source, Senior Scientist, SK S7N 2V3, Saskatoon, Canada
7
Canadian Light Source, Bioxas, SK S7N 2V3, Saskatoon, Canada
1
2
or diagenic. Remarkably improved lateral spatial resolution
(3 × 5 microns μm2) for fluorescence emission ranging from 3.6
to 14.1 keV) is achieved when microchannel arrays [1], recently
developed at Cornell High Energy Synchrotron, were employed in confocal detection. Microchannel array derived high
resolution confocal detection was also used to investigate
the nature of the iron containing corrosive layers in ancient
stained glass samples, obtained from Paderborn Cathedral,
Germany (13th Century), in order to aid the study regarding the
efficacy of various cleaning methods used in the restoration
process. Initial imaging and spectroscopy results obtained in
this study will be presented. Due to the energy-independent
nature of the microchannel array derived confocal probe
volume, correlations among different elemental features can
be unambiguously identified.
P-31
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Phil K. Cook1,2 - Marie-Angélique Languille3
Élise Dufour4 - Cristian Mocuta4 - Delphine Vantelon5
Loïc Bertrand1,2
Micro-X-ray
fluorescence
evidences elemental
fluctuation on a short
time scale in fish
otoliths
1
Archaeological fish otoliths, “ ear stones, ” composed of aragonite (CaCO3) and an organic template, are increasingly
employed for palaeoenvironmental reconstructions [1]. An
individual’s life history (salinity and temperature of water inhabited) is encoded within the elemental composition of daily
(~5 µm thick) and seasonal (300–400 µm) growth increments.
Among the minor and trace elements present is Sr at a typical
concentration of 5–50 µmol/g [2]. Measurement of Sr content
can reveal the fish’s environment at the time of deposition
with a temporal resolution proportional to lateral resolution.
Laser ablation (LA) mass spectrometry (MS) and high-current
electron microprobe (EPMA) analyses are often employed
for such elemental measurements. However, both of these
techniques produce significant ablation of the sample.
The multi-element, sensitive, fast, and non-destructive analysis
promised by synchrotron micro-X-ray fluorescence (µXRF)
makes it an attractive technique [3]. Elemental quantification
has been carried out on 6 archaeological otoliths along with
modern counterparts in order to study their small-scale
elemental variation. Experiments were performed using medium-energy and tender X-rays with on-sample spot size as
small as 4×3 µm2 (H×V). Maps have been obtained for full coreto-edge sections of otoliths up to 3.2×0.8 mm2. Using tender
X-rays permits a lateral resolution equivalent to the spot size.
From the high lateral resolution elemental maps, concentration fluctuations in strontium content along the growth
axis can be seen with lengths as short as a few micrometres.
Measurements in the medium-energy X-ray range show
homogeneous increments, but the higher lateral resolution tender X-ray maps reveal heterogenities in elemental
content within isochronous increments on a length scale
of several micrometres. Contamination on the edge of the
otoliths can be identified from handling and preparation.
Surface contamination from sample preparation can be
detected and does not prevent analysis of the otolith overall.
After X-ray analysis, the samples were examined under
visible, UV fluorescence, and electron microscopy for radiation-induced side effects (RISE). Medium-energy X-rays resulted in a barely noticeable impact, but using tender X-rays,
more significant RISE was observed. These RISE appear to
be primarily dose dependent and are hypothesised to be
in the organic fraction. SR-µXRF is often labelled non-destructive, but these observations highlight the need for study
and consideration of potential side effects resulting from
analyses. SR-µXRF provides a powerful tool for laterally resolved elemental quantification of biomineral palaeoproxies,
but requires reflection on its true resolution limits and potential sample side effects.
IPANEMA, 91192, Gif-Sur-Yvette, France
Synchrotron SOLEIL, 91192, Gif-Sur-Yvette, France
3
CNRS, CRCC, 75005, Paris, France
4
Muséum National d’histoire Naturelle / CNRS, Archéozoologie,
Archéobotanique, 75005, Paris, France
2
Bibliography
[1] M.C. Disspain, C.J. Wilson, and B.M. Gillanders, Archaeol. Oceania, 2012, 47, 141.
[2] S.E. Campana, Mr. Ecol. Prog. Ser., 1999, 188, 263.
[3] B.D. Walther and K.E. Limburg, J. Fish Biol., 2012, 81, 796.
133
P-32
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Marine Cotte1 - Paul Tafforeau1 - Émeline Pouyet1
1
ESRF, 38000, Grenoble, France
Study of ancient
materials at the X-ray
imaging beamlines,
at the European
Synchrotron Radiation
Facility
The X-ray imaging group at the European Synchrotron
Radiation Facility, Grenoble, France is composed of 5
beamlines, which offer a very wide range of accessible
lateral resolution and corollary field of view, as well as an
extended set of imaging and analytical tools. The ID17
beamline is primarily dedicated to biomedical applications,
and delivers a very large beam (~150×6 mm²) suitable
for the tomography of large samples. The ID19 beamline
offers versatile capabilities for 3D imaging, with different
contrast modes, acquisition times, sample environment...
The beamsize is slightly lower (~75×15 mm²), but the spatial
resolution is improved (from 100 to ~0.3 µm). The ID16A
beamline, currently in construction, will provide ultimate
capabilities for imaging at the nano-scale (down to 10 nm).
These three beamlines focus mainly on a morphological
characterization, with some chemical information limited
to elemental composition and mapping. Conversely,
the ID21 and ID16B beamlines offer multi-analytical
platforms for a more precise chemical characterization
of samples. X-ray fluorescence, diffraction, absorption
Bibliography
[1] Cotte, M.; Susini, J.; Dik, J.; Janssens, K., Synchrotron-based X-ray absorption
spectroscopy for art conservation: looking back and looking forwards.
Accounts of Chemical Research 2010, 43 (6), 705-714.
[2] Tafforeau, P., Boistel, R., Boller, E., Bravin, A., Brunet, M., Chaimanee, Y.,
Cloetens, P., Feist, M., Hoszowska, J., Jaeger, J.-J., Kay, R.F., Lazzari, V., Marivaux,
L., Nel, A., Nemoz, C., Thibault, X., Vignaud, P. and Zabler, S., Applications
of X-ray synchrotron microtomography for non-destructive 3D studies
of paleontological specimens Applied Physics A, Materials Science
& Processing 2006, 83: 195-202.
134
spectroscopy can be combined to infrared spectroscopy to obtain a full identification of components, with a
beam ranging from a few microns in the infrared domain,
to ~40 nm in the hard X-ray domains.
These beamlines, in particular ID19 and ID21, are regularly
successfully used for the analysis of ancient materials, the
word “ ancient ” covering fragments from design objects
of the 50’s and 60’s, to fossils of about 600 million years.
At ID21, X-ray and IR micro-analyses are applied to a large
range of materials (paintings, glasses, inks, ceramics, metals,
biological remains, polymers...) with the two-fold objectives of rediscovering ancient artistic technologies, and
understanding degradation processes. At ID19, paleontology is a major field of research, where 3D imaging reveals
non-invasively fundamental information hidden in the
micro-structure of bones, teeth, fossils of animals, of plants...
This talk will aim both at giving an overview of these applications as well as at presenting the different imaging
capabilities, in particular the most recent ones developed
in the context of the ESRF upgrade programme.
P-33
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Pisutti Dararutana1
1
The Royal Thai Army Chemical Department, Phaholyothin Road, Chatuchak,
10900, Bangkok, Thailand
Microanalysis study on
lanna-style glass using
X-ray spectroscopy
based on synchrotron
radiation
Differences of archaeological objects found in Thailand, especially glasses. Due to the complex nature of materials, extremely
sensitive, spatially resolved, multi-elemental and versatile analytical instruments were needed. The techniques employed should
be as a noninvasive as possible and able to give complementary
information from macroscopic to nanometer scales. Lanna-style
decorative glass which called ACG/ABG is one of decorative
glasses which are found throughout Thailand in special places,
such as, Buddhist temples, which, for centuries, have served
as community centers for the locals. It is found mostly in the
northern and northeastern Thailand, and some parts of Laos,
Burma and China. As the glasses have kept deteriorating over
time, restorations must be performed routinely to preserve these
cultural crafts for later generations to appreciate.In this work,
micro-beam X-ray fluorescence spectroscopy based on syn-
chrotron radiation was used to analyze elemental distribution
of the Lanna-style glass. Scanning electron microscope coupled
with X-ray fluorescence spectroscopy and Proton-induced
X-ray emission spectroscopy were also carried out to detect
composition and structure. Compositional analysis showed
that the main contents were SiO2 and PbO. K2O and CaO were
as minor contents. The differences in color were affected from
the addition of iron, copper and manganese. Cross-sectional
SEM observations of ACG/ABG showed three different layers
including metal substrate, binder and coated glass. The glasses
were mostly transparency with plenty and bubbles. It is mostly
lead-silica based glasses. Their colors resulted from metal ions.
It can be concluded that these techniques in combination are
powerful for the investigation of heterogeneous glassy materials
and to answer the archaeology’s questions.
Bibliography
[1] I. Nakai, M. Mutsunaga, M. Adachi, J. Phys. France. 2 (1997) 1033.
[2] S. Quartieri, et al., Eur. J. Mineral. 14 (2002) 749.
[3] S. Padovani, et al., Applied Physics A. 79 (2004) 223.
[4] P. Arletti, et al., Applied Physics A. 83 (2006) 239.
[5] D. Barilaro, et al., Vibrational Spectroscopy. 42 (2006) 381.
[6] W. Klysubun, et al., Analytical and Bioanalytical Chemistry. 399 (2011) 3033.
[7] K. Won-in, et al., Spectrochimica Acta A. 83 (2011) 231.
[8] K. Won-in, et al., Journal of Radioanalytical and Nuclear Chemistry, 294
(2012) 247.
[9] K. Chotichutrakul, Thai Art and Culture Vol.6: Ratanakosin Art: Glass Mosaic
(Fine Arts Department, Thailand 1982).
[10] N. Punjabhan and S. Na Nakhonphanom, The Art of Thai Wood Carving:
Sukhothai, Ayutthaya, Ratanakosin (Rerngrom Publishing Co.,Ltd., Thailand
1992).
[11].N. Punjabhan, et al., The Charm of Lanna Wood Carving (Rerngrom
Publishing Co.,Ltd., Thailand 1994).
[12].P. Dararutana, Journal of Electron Microscopy Society of Thailand. 12
(1998) 38.
[13].P. Dararutana, N. Sirikulrat, T. Tunkasiri, in s Book of the 16th International
Conference on X-ray Optics and Microanalysis (Vienna), 2001.
[14].P. Dararutana, N. Sirikulrat, in Microscopy Book Series No. 3 Vol. 2: Modern
Research and Education Topics in Microscopy, (Formatex, Spain 2007).
135
P-34
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Rafaela Debastiani1 - Rolf Simon1 - Andrea Wähning2
Tilo Baumbach1
1
136
Karlsruhe Institute of Technology, IPS-ANKA, D-76344, Eggenstein-Leopoldshafen, Germany
Badisches Landesmuseum Karlsruhe, 76131, Karlsruhe, Germany
Analysis of Roman
mural paintings from
Wössingen (Germany)
using synchrotron
radiation
2
From 1st to 3rd centuries AD, Roman province in Germany lived a
peaceful and prosper epoch. In this epoch, there was a culturally
blossoming, towns were founded and buildings were decorated
with mural paintings. The study of mural paintings helps to
obtain information about the origin of the pigments (by trace
elements), possible changes and restaurations in the mural
paintings and the building function (private, public baths, etc).
Fragments of Roman mural paintings from Wössingen,
Germany, from 1st to 3rd centuries AD, are being analyzed at ANKA
Synchrotron, in Karlsruhe, Germany. These fragments are from
Badisches Landesmuseum Karlsruhe’ collection and provide us
a big color palette.
X-ray fluorescence (XRF), X-ray diffraction (XRD) and infrared
spectroscopy (IR) are providing data about chemical composition, mineral phases and molecular information of the
pigments. Preliminary XRF analysis identify some possible
pigments for each color. S, Ca, K, Mn, Fe, Cu, Zn, As, Rb, Sr, Hg,
Pb are some of the elements present in the pigments. For a
complete identification of the pigments, XRD and IR analysis
are being performed.
P-35
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Neutron resonance
transmission imaging
for 3D elemental
mapping at the ISIS
spallation neutron
source
Neutrons have been widely applied in archaeometric
research since 1960, with a growing number of innovative
methods allowing for non-destructive or non-invasive
analysis [1,2]. A recent application concerns neutron resonances that can be used as fingerprints to identify and
quantify elements within the bulk of different objects.
Indeed, Neutron Resonance Transmission Imaging (NRTI) has
been successfully applied to the 2D elemental mapping of
archaeological samples [3].
Here we report on the first three-dimensional elemental
imaging by NRT. A dedicated set-up at the INES (Italian
Neutron Experimental Station) beamline of the ISIS spal-
Giulia Festa1,2 - Enrico Perelli Cippo3 - Daniela di Martino1
Roberto Senesi2 - Carla Andreani2 - Erik Schooneveld4
Winfried Kockelmann4 - Nigel Rhodes4 - Katalin Biro5
Giuseppe Gorini1,6
University of Milano-Bicocca, Physics Department, I-20126, Milan, ITALY
University of Roma Tor Vergata, Physics Department, I-00133, Rome, ITALY
3
CNR, Istituto di Fisica dei Plasmi, 20125, Milan, ITALY
4
ISIS Facility, STFC Rutherford Aplleton Laboratory, OX11 0QX, Chilton, UK
5
Hungarian National Museum, Department of Archaeology, H-1088,
Budapest, HUNGARY
6
CNISM, Unita’ di Ricerca di Milano Bicocca, I-20126, Milan, ITALY
1
2
lation neutron source was used for the experiments [4,5].
Transmission spectra were obtained by measurement of
the flight time of epithermal neutrons passing through the
sample, an early mediaeval disk fibula [6] from the Hungarian National Museum in Budapest. The same object had
previously been analyzed through 2D NRTI [3] and other 3D
elemental imaging techniques, like PGAI (Prompt Gamma
Activation Imaging) [7].
The methodology and analysis procedures used in the
reconstruction of the 3D NRT elemental image will be described. Our results will be compared with previous results.
Further applications and improvements will be discussed.
Bibliography
[1] G. Artioli “ Scientific Methods and Cultural Heritage ”, Oxford University Press
(2010).
[2] W. Kockelmann et al., “ Neutrons in cultural heritage research ” Journal
of Neutron Research 14, 37 (2006).
[3] E. Perelli Cippo et al., “ Imaging of cultural heritage objects using neutron
resonances ” J. Anal. At. Spectrom. 26, 992 (2011).
[4] G. Gorini et al., « Ancient Charm: A research project for neutron-based
investigation of cultural-heritage objects » Il Nuovo Cimento C 30, 47-58 (2007)
[5] http://ancient-charm.neutron-eu.net/
[6] A. Kiss “ Das awarenzeitlich gepidesche Graeberfeld von Koelked-Feketekapu ”
Studien zur Archaelogie der Awaren 5, Innsbruck (1996).
[7] R. Schulze et al., “ The ANCIENT CHARM project at FRM II: three-dimensional
elemental mapping by prompt gamma activation imaging and neutron
tomography ” J. Anal. At. Spectrom. 28, 1508 (2013).
137
P-36
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Renfei Feng1 - Jason Maley2 - Ruth Hoffemyer2
Tom Ellis1 - Don Brinkman3 - Ramaswami Sammynaiken2
Experimental Facilities Division, Canadian Light Source, S7N 2V3, Saskatoon, Canada
Saskatchewan Structural Sciences Centre, University of Saskatchewan,
S7N 5C9, Saskatoon, Canada
3
Preservation & Research, Royal Tyrrell Museum, T0J 0Y0, Drumheller, Canada
1
Reading about the life
of Dinosaurs recorded
on the enamel of teeth
2
The enamel of teeth is mainly calcium hydroxyl apatite which
itself does not undergo much structural change after millions
of years. Dinosaur teeth have a fossilized core and an almost
intact enamel. Over the period of 60 million years, chemical
changes in the enamel are influenced by the environment in
which the fossil was preserved, e.g., metal ion diffusion into
available structural sites and ion replacement. The fossilized
core would represent a reasonable template of the dentine
structure.
and whether or not the teeth were worn down and shed.
High doses of UV or gamma radiation induce different types
of defects in enamel.
Studies on the teeth of mammals show that the structure
and ordering of the enamel in teeth represent the hardness
or types of food eaten. Hunter-Schreger Bands (HSB) was
observed in human and other mammals but not in insectivores and multituberculates. The rate of growth of teeth
and size of enamel crystallites indicate the age of animal,
138
Our investigation employs several advanced instrumental
methods to read the information present in the microanatomy of enamel on dinosaur teeth. The results from Micro
X-ray Fluorescence Mapping (XRFM), X-ray Absorption Spectroscopy (XAS) and Micro Laue Diffraction Mapping (LDM)
will be presented, which show a very good snap shot of
the environment, ion substitutions projected structure and
ordering for the different types of dinosaurs. Diet, migration
patterns, ecosystem type, radiation exposure and stage of
dental evolution could be revealed and would support to
future studies on the biology, physiology, and ecology of
extinct animals.
P-37
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Marine Gay1 - Matthias Alfeld2 - Michel Menu3
Éric Laval3 - Pablo Arias4 - Ina Reiche1,5
Laboratoire d’Archéologie Moléculaire et Structurale, CNRS-UMR8220,
UPMC, 75005, Paris, France
2
Deutsches Elektronen-Synchrotron DESY, PETRA III, 22607, Hambourg, Allemagne
3
Centre de Recherche et de Restauration des Musées de France, MCC,
CNRS-UMR8247, 75001, Paris, France
4
Universidad de Cantabria, Instituto Internacional de Investigaciones
Prehistóricas de Cantabria, 39005, Santander, Spain
5
1
Palaeolithic paint
palette used at
La Garma cave
(Cantabria, Spain)
investigated by means
of complementary
in situ and synchrotron
analytical methods
Understanding the meaning of Palaeolithic graphical
expression is one of the key issues of Prehistoric research.
It includes the study of the painting matter which provides
significant sources of information in the quest of the comprehension of the technical skills of prehistoric artists and
the “ chaîne opératoire ” of the painting activities. La Garma
cave, listed as World Heritage by UNESCO in 2008, is part of
the most exceptional sites discovered at the end of the 20th
century in the North of the Spain. It offers over 500 graphical
units covering a wide chronological range, dating from the
Aurignacian to the Magdalenian period, and spread on the
wall of numerous rooms. This rock art is connected with large
surfaces rich in occupational remains, conferring to this cave
an important position in the study of the Upper Palaeolithic
in this region.
This cave gathers a large assortment of colours (red, yellow,
purple and black), associated to different mineral phases
(iron and/or manganese oxides, charcoal and mixtures).
A detailed characterisation of the mineral pictorial matter
used for a same colour is crucial to understand the organi-
Bibliography
[1] P. Arias, C. González Sainz, A. Moure Romanillo and R. Ontañón, T.P. 57, 41-56
(2000)
[2] P. Arias, E. Laval, M. Menu, C. González Sainz and R. Ontañón, Anthropologie
115, 425-445 (2011).
[3] M. Wilke, F. Farges, P. E. Petit, G. E. Brown Jr. and Fr. Martin, Am. Min. 86,
714-730 (2001).
sation of the rock art in this cave, to explain its singularities,
looking for various hands that potentially performed the
decorations of distinct figures in the different rooms.
A preliminary analysis by energy dispersive X-ray spectrometry coupled to a scanning electron microscope (SEM-EDS)
has been carried out on twenty-five samples taken from the
medium and lower gallery of the cave. Different types of
hematite (Fe203) and goethite (FeOOH) have been distinguished, revealing the use of different paint “ pots ” by prehistoric
artists [2]. In order to improve this issue, a speciation analysis
of Fe was performed at the P06 beamline of PETRA at DESY
(Hamburg’s synchrotron) by high-resolution micro X-ray absorption near edge structure (XANES) measurements at the
Fe K-edge. It will allow giving more detailed insights into the
oxidation state and the coordination environments for Fe [3].
Complementary, to have a global comprehension of the
rock art repartition inside the cave, an on-site systematically
study of the prehistoric representations have been initiated
by the implementation of a self-built X-ray fluorescence
(XRF) portable and non-invasive spectrometer. This spectroscopic study allows illustrating the strong potential of
such in situ analyses to acquire statistically relevant data in
a cave environment while preserving the integrity of these
representations. In a wider perspective, the combination of
such complementary analytical methods will bring a better
understanding of the symbolic practices of past societies
and the cultural relationships within the Cantabrian region
at the Upper Palaeolithic.
139
P-38
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Claire Gervais1 - Marie-Angélique Languille2
Solenn Réguer3 - Valerie Briois3 - François Baudelet3
Bern University of Applied Sciences, 3011, Bern, Switzerland
IPANEMA, CNRS, 91191, Gif sur Yvette, France
3
Synchrotron SOLEIL, 91191, Gif sur Yvette, France
1
X-ray absorption
spectroscopy
of the photosensitive
pigment Prussian Blue:
a multi-beamline
approach to study
its fading process
X-ray absorption spectroscopy (XAS) has been widely used to
study the local structure of pigments. The high brilliance now
available at third-generation synchrotrons coupled with the use
of efficient focusing optics and detectors gives access to high
photon density, micro-spatially resolved XAS measurements and
sub-seconds to min time-resolved XAS experiments.
In the case of the photosensitive Prussian blue, an iron-based
pigment known to fade under daylight or under anoxia, state
of the art XAS beamlines have been successfully used to characterize the pigment when embedded in different substrates
[1], study the reduction of Fe(III) at the origin of the fading, and
follow the fading kinetics in different environments (such as
low-oxygen atmosphere or high relative humidity) and for
different substrates [2]. However, “ every rose has its thorn
” and the high density of photons at the sample position for
micro scale characterizations may lead to radiation damages
Bibliography
[1] C. Gervais, M.-A. Languille, S. Réguer, M. Gillet, S. Pelletier, C. Garnier,
E. P. Vicenzi, and L. Bertrand, “ Why does Prussian blue fade? Understanding
the role(s) of the substrate, ” J. Anal. At. Spectrom., vol. 28, no. 10, p. 1600,
Sep. 2013.
[2] C. Gervais, M.-A. Languille, S. Reguer, M. Gillet, E. P. Vicenzi, S. Chagnot,
F. Baudelet, and L. Bertrand, “ Live ”Prussian blue fading by time-resolved
X-ray absorption spectroscopy, ” Appl. Phys. A, vol. 111, no. 1, pp.
15–22, Jan. 2013.
[3] F. Baudelet, Q. Kong, L. Nataf, J. D. Cafun, A. Congeduti, A. Monza,
S. Chagnot, J. P. Itie, “ ODE: a new beam line for high-pressure XAS and
XMCD studies at SOLEIL ”, High Pressure Research, 31(1):136-139, 2011.
[4] E. Fonda, A. Rochet, M. Ribbens, L. Barthe, S. Belin, and V. Briois, “ The SAMBA
quick-EXAFS monochromator: XAS with edge jumping., ” J. Synchrotron
Radiat., vol. 19, no. Pt 3, pp. 417–24, May 2012.
140
2
that must be considered for sensitive artefacts. This was the
case for Prussian blue, which in some cases underwent a
reduction induced by the synchrotron light.
We will report here on our experience concerning the analysis of Prussian blue model samples during X-ray absorption
spectroscopy performed at three bending magnet beamlines
of the synchrotron SOLEIL, that differ by their optics scheme,
beam size, photon density and acquisition time: Step by
step XAS at the DiffAbs beamline [1] with meso-beam
(200 µm×300 µm), Energy-dispersive XAS at ODE beamline
[3] with micro-beam (30 µm×30 µm) and quick-XAS at SAMBA
beamline [4] with macro-beam (5 mm × 0.8 mm). For the former the typical time resolution for one high-quality spectrum
is 20 min whereas for the two latter ones, sub-seconds time
resolution is available and requires averaging over several
spectra to get sufficient statistics for our diluted PB samples.
Through various examples of Prussian blue samples (cyanotypes, Prussian blue on paper, in gelatin and dyed textiles),
we will discuss the choice of the XAS experimental conditions, that is often a subtle balance between the goal of the
analysis (characterization or fading kinetics), the sensitivity of
the sample towards beam damage (observed to vary with
the substrate), and its heterogeneity. We will show that the
three beamlines are complementary in their approach and
allow to tackle the mechanisms behind Prussian blue fading
in a most profitable way.
We will also show that radiation damage can have different
consequences, such as pigment excitation leading to photoreduction and fading, or irremediable deteriorations of the
substrate. We will finally discuss the strategies we have developed to estimate radiation damage by calculating the dose
absorbed by the sample, and... use it to study the mechanisms
behind Prussian blue photoreduction [2].
P-39
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Victor Gonzalez1 - Gilles Bastian1 - Thomas Calligaro1
Myriam Eveno1 - Bruno Mottin1 - Élisabeth Ravaud1
Gilles Wallez2 - Michel Menu1
Sr-XRD characterization
of lead white in Goya’s
paintings
1
This work focuses on the composition and microstructure
of the lead white pigment employed in historical paintings
by means of SR-XRD combined with Rietveld refinement.
The objective is to relate the samples precise compositions
with historical texts, and ancient fabrication processes. The
studied materials are a set of 15-20 micro-samples collected
on masterpieces painted by Goya (1746-1828). The very small
size of the samples (<100 µm) and the complexity of the
chemical system motivates the use of synchrotron beam in
order to quantify the crystalline phases by SR-XRD.
Historical sources indicate that the lead white used by Goya
was not produced in Spain but rather imported, mainly from
Holland. Ancient inventory records mention various qualities of this pigment (albayalde fino, entrefino, ordinario, de
tabletas, de Holanda, de Venecia) sold at different prices that
the painter could select according to the expected pictorial
result. The advanced characterization of the constitutive
materials of the lead white based paint layers should constitute a precious tool for a better understanding of the artist
technique, and the pigment fabrication process.
Easel paintings contain various pigments dispersed in an
organic matrix. Lead white was the most common pigment,
present in the preparation layers as well as in the paint layers,
sometimes mixed with other colors. Lead white is composed
of two main lead carbonates phases, i.e. cerussite PbCO3 and
hydrocerussite 2PbCO3.Pb(OH)2, sometimes associated with
plumbonacrite Pb5O(OH)2(CO3)3. In addition, the pigment
is often combined with several crystalline extenders such
as calcite CaCO3. The phase proportions are related to the
manufacture processes and the post-synthesis treatments
applied by the manufacturers.
Samples were first analyzed by SEM-EDX. All preparation
layers appear to be lead white based, most of the time mixed
with earth-based pigments. Most pictorial layers also contain
lead white. SR-XRD will permit the precise identification and
quantification of the various mineral phases: it will then be
possible to connect those results to the use Goya made of
this pigment in his work.
Bibliography
2
C2RMF, Recherche, 75001, Paris, France
IRCP, PCMTH, 75005, Paris, France
This research is part of a Ph.D. work started at the C2RMF
in 2013 bearing on the fine characterization of lead white
in paintings and its evolution over time. The project was
submitted to the ESRF call for beam time for the end of
2014. The present communication will present the scientific
context of this work and the expected results of the SR-XRD
measurement campaign.
[1] R. J. Gettens, H. Kühn and W. T. Chase, Lead white, in Artists’ pigments:
a Handbook of their history and Characteristics (A. Roy, ed.), 1993, vol. 2,
p. 67–81
[2] M. Stols-Witlox, ‘The heaviest and the whitest’: lead white quality in north
western European documentary sources, 1400-1900 in Studying Old
Master Paintings – The National Gallery Technical Bulletin 30th Anniversary
Conference Postprints, (Archetype ed. London), 2011, p. 284-294.
[3] E. Welcomme, P. Walter, P. Bleuet, J.-L. Hodeau, E. Dooryhée, P. Martinetto
and M. Menu, Classification of lead white pigments using synchrotron
radiation micro X-ray diffraction, App. Phys. A, 2007, vol. 89, p. 825–832.
[4] R. Bruquetas, Sources for the study of pigments used by Goya and other
18th-century Spanish painters, in The artist process - Tech. & Interpretation
(Archetype ed. London), 2012, p. 138-146.
141
P-40
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Synchrotron radiation
µXRF and µXANES:
in search of oxygenic
photosynthesis
in archean and
proterozoic samples
One approach to understanding the appearance and evolution of life on Earth is to travel as far back in time as possible,
to study the most primitive forms of life. This can be achieved
by the study of the geological record, only witness of Earth
ancient history. Sedimentary rocks of the Archean geological
eon (from 4.0 to 2.5 billion years (Ga) in the past), hold the
most ancient fossils known today.
We focus our work on the evolution and the spread of oxygenic
photosynthesis (OxPh), sometime between 3.5 and 2.4 Ga ago.
OxPh, whereby oxygen is released to the environment as
a metabolic by-product, developed from anoxygenic photosynthesis which, although primitive, was already itself a
complex form of metabolism. A widely accepted theory
puts the evolution of oxygenic photosynthetic bacteria in
the front row to explain the Great Oxidation Event (GOE) [1],
which records an appreciable rise in the concentration of
oxygen in Earth’s oceans and atmosphere around 2.4 billion
years (Ga) ago [2], prior to which the oceans were most likely
anoxic [3]. The GOE marked a key point in the history of the
biosphere, as the increase of oxygen concentration in oceans
and atmosphere allowed the development of more complex
Bibliography
[1] Buick R. (2008). When did oxygenic photosynthesis evolve?, Philosophical
Transactions of the Royal Society B, 363, 2731-2743.
[2] Bekker A., et al. (2004). Dating the rise of atmospheric oxygen, Nature, 427,
117-120.
[3] Holland H. D. (2006). The Oxygenation of the atmosphere and oceans,
Philosophical Transactions of the Royal Society B, 361, 903-915.
142
Axelle Hubert1,2 - Alexandre Simionovici2
Laurence Lemelle3 - Ivo Zizak4 - Alexei Erko4
Frances Westall1
Centre de Biophysique Moléculaire, CNRS, 45071, Orléans, France
Institut des Sciences de la Terre, Université Jospeh Fourier, 38041, Grenoble, France
3
Laboratoire de Géologie de Lyon, CNRS-ENS, 69622, Villeurbanne, France
4
Institute of Nanometre Optics & Technology, HZB, 12489, Berlin, Germany
1
2
forms of life and the blossoming of biodiversity. However,
the evolution of oxygenic photosynthetic bacteria has still
to be constrained in time.
One approach to this problem is the study of the chemical
and mineralogical signatures of OxPh at various scales to
determine the local to global impact of oxygen on the
chemistry of the oceans and atmosphere in the Archean
and Paleoproterozoic geological record (from 4.0 to 1.8 Ga).
Within this context, we are investigating the signatures of
OxPh at the local scale within the immediate (mm-μm)
vicinity of fossilized photosynthetic microbial mats and cells.
In order to cover the period of time assigned to the evolution of OxPh, we prepared samples of cherts of Archean
(Josefsdal) and Paleoproterozoic (Gunflint) sedimentary
rocks, ranging from 3.47 to 1.9 Ga, containing fossilized relics
of putative photosynthetic activity, sectioned using Fast Ion
Beam techniques to optimized dimensions of 15×10×2 μm.
We conducted Synchrotron radiation X-ray Fluorescence
spectrometry (XRF) and X-ray Absorption Near-Edge
Structure spectroscopy (XANES) analyses at the MySpot
beamline of the Bessy synchrotron in Berlin, Germany using
a monochromatic beam of 7-12 keV energy, focused by
monocapillaries to 1.5 μm on these samples. We studied
the spatial distributions and oxidation states of life/bacterial
activity-related elements (e.g. Mg, P, S, Ca), transition metals
(e.g. V, Mn, Fe, Co, Ni, Cu, Mo), and trace elements (e.g. Se, Sr,
Ba, La, Ce, Nd, Sm, Eu), which bring crucial information on
the micro-organisms and their environment. To do so, we
have developed a new absolute quantification method for
SR-XRF analyses by indirectly quantifying the light elements,
undetected by XRF, but nonetheless present in the samples
(e.g. H, C, N, O, Na).
P-41
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Frederic Jamme1 - Mathieu Thoury1,2
Bertrand Cinquin1 - Matthieu Réfrégiers1
1
Synchrotron SOLEIL, DISCO, 91192, Gif sur Yvette, France
IPANEMA, 91192, Gif sur Yvette, France
DISCO beamline:
new developments
and applications in art
and archaeology
2
UV luminescence techniques have been used by conservators
and museum scientists for decades, providing a analysis of
art and heritage materials.
DISCO beamline, which monochromatic beam supplies two
DUV-visible microscopes, provides a new and unique approach to characterize the luminescence of ancient materials.
Indeed, the luminescence spectra obtained at high spectral
and spatial resolutions have made it possible to identify previously hard-to-identify constituents of musical instruments
and pictorial works.
We will present recent and future developments at the DISCO
beamline and research applications in art and archaeology.
Bibliography
[1] Giuliani, F. Jamme, V.Rouam, F. Wien, J.L. Giorgetta, B. Lagarde,
O. Chubar,S. Bac, I. Yao,S. Rey, C. Herbeaux, J.L Marlats, D. Zerbib,F. Polack
and M. Réfrégiers, J. Synchrotron Rad. 2009, 16: 835- 841.
[2] Jamme, F., Villette, S., Giuliani, A., Rouam, V., Wien, F., Lagarde, B., & Refregiers,
M. Microscopy and Microanalysis, 2010, 16(5): 507-514.
[3] Tawil, G., Jamme, F., Réfrégiers,, M., Viksø-Nielsen, A., Colonna, P.,
& Buléon, A. Analytical Chemistry, 2011, 83(3): 989–993.
[4] Jamme, F., Kascakova, S., Villette, S., Allouche, F., Pallu, S., Rouam, V.,
& Refregiers, M. Biology of the Cell, 2013, 105(4): 277–288.
[5] Zubkovs, V., Jamme, F., Kascakova, S., Chiappini, F., Le Naour, A., & Refregiers,
M. Analyst, on line first
[6] Thoury, M., Echard, J. P., Réfregiers, M., Berrie, B., Nevin, A., Jamme, F.,
& Bertrand, L. Analytical Chemistry, 2011, 83(5): 1737–1745.
143
P-42
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Zsolt Kasztovszky1 - Katalin T. Biro2 - Veronika Szilagyi3
Andor Hajnal4 - Karoly Özvegy5 - Ágnes Szekeres5
Centre for Energy Research, Hungarian Academy of Sciences,
Nuclear Analysis and Radiography Department, 1121, Budapest, Hungary
2
Hungarian National Museum, 1088, Budapest, Hungary
3
Isotoptech Ltd, 4026, Debrecen, Hungary
4
Grafoproduct Ltd, 24000, Subotica, Serbia
5
Municipal Museum of Subotica, Department of Archaeology
and Numismatics, 24000, Subotica, Serbia
1
Provenance study
of archaeological
obsidian using
non-destructive
Prompt Gamma
Activation Analysis
Obsidian was one of the most popular raw materials to
produce prehistoric stone tools. Thanks to the very specific
geological pre-conditions of its formation, the main geological
sources are well localized worldwide. The classical geological
sources of obsidian in Central Europe can be found in the
Tokaj-Eperjes Mountains and in the SE foreland of the Carpathians in Ukraine, while other sources used in prehistory
are known in the Mediterranean region (e.g. Sardinia, Lipari,
Melos). Sources in Anatolia and in Armenia are also well known
and well characterized. According to the literature [1], three
main types of Carpathian obsidians exist, denoted as C1 for the
North-Tokaj (Slovakian) origin, C2 for the South-Tokaj (Hungarian) origin, and C3 for the Sub-Carpathian (Ukrainian) origin.
Moreover, C2 group can be subdivided to C2T (Tolcsva), C2E
(Mád- Erdőbénye) and C2Tr (Tolcsva “ red ”) types.
Since 2003, prompt-gamma activation analysis (PGAA) at the
Budapest Neutron Centre has been successfully used for characterisation and for provenance research of obsidian artefacts [2].
PGAA that utilizes a guided external cold or thermal neutron
Bibliography
[1] Williams-Thorpe, O., Warren, S. E., Nandris, J., 1984. The distribution
and provenance of archaeological obsidian in Central and Eastern Europe.
Journal of Archaeological Science 11, 183-212.
[2] Kasztovszky, Z., Biró, K. T., Markó, A., and Dobosi, V., 2008. Cold neutron
prompt gamma activation analysis—a non-destructive method
for characterization of high silica content chipped stone tools and raw
materials, Archaeometry, 50(1), 12-29.
[3] Révay, Z., 2009, Determining Elemental Composition Using Prompt
Gamma Activation Analysis, Analytical Chemistry, 81, 6851-6859.
[4] Szentmiklósi, L., Belgya, T., Révay, Z., and Kis, Z., 2010, Upgrade
of the prompt gamma activation analysis and the neutron-induced
prompt gamma spectroscopy facilities at the Budapest Research Reactor,
Journal of Radioanalytical and Nuclear Chemistry, 286, 501-505.
144
beam is a non-destructive analytical method enables us to
quantify most major components and some characteristic
trace elements in a few cm3 volume [3, 4]. The method does
not require any sampling or preparation; almost any size of
objects can be placed into the neutron beam. Furthermore,
any impairment of the object is caused by the investigations.
In this paper, we discuss the provenance of archaeological
obsidians found in Subotica (Szabadka, North Serbia) region,
applying PGAA.
The stone implements found at the coast of the Ludas lake
constitute the substance of the examination.The lake is situated nearby Subotica (Szabadka) in northern Serbia, in the
Autonomous Province of Vojvodina, about 20 km from the
Hungarian-Serbian border in the Southern part of the Great
Hungarian Plain, situated in the heart of a terrestrial sedimentary area. No exploitable lithic raw material can be found in
the neighbouring areas (cca. 100 km radius), thus imported
lithic raw materials had to be obtained for everyday use. The
mentioned area is situated at the crossroads of trade networks
and borderlines of different cultures since the prehistoric age.
The stone implements found here certainly do not come from
the neighbourhood. The primary aim of this study is to find
out the commercial contacts of the area in the prehistoric age,
i.e., where was the raw material of their tools obtained from?
Would it support or refute the trade routes and contacts set up
by the archaeologists and based on the previous excavations?
Obsidian is only one element of this system here which is not
numerous but very important as trade and contact marker. For
these purposes, the composition of the Serbian archaeological obsidian pieces have been compared with our database
of PGAA results about more than 300 archaeological and
geological samples.
P-43
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Ziga Smit1 - Mateja Kos3 - Sasa Rudolf3 - Zora Zbontar3
Tina Lah3
Faculty of mathematics anf physics, University of Ljubljana, Jadranska 19,
1000, Ljubljana, Slovenia
2
Jožef Stefan Institut, Jamova 39, 1000, Ljubljana, Slovenia
3
National Museum of Slovenia, Prešernova 20, 1000, Ljubljana, Slovenia
4
Faculty of Arts, University of Maribor, Koroška 160, 2000, Maribor, Slovenia
1
Datatreasure - a new
tool for dissemination
of scientific analytical
results
From 2001- 2006 an action, dealing with non-destructive
analysis of museum objects (COST G8) was taking place in
the scope of European COST actions.
It is COST G8 legacy that gave us the idea of preparing an
European project which should connect natural scientists
and museum professionals. After the action ended, we discovered that only a small amount of the results of expensive
scientific analyses of artifacts were published and disseminated. Vast majority of the results never saw the daylight and
were lost to other researchers. We also noted that there is a
strong tendency to limit the usage of the data to only one
field of expertise, for instance conservation – restoration.
Our idea is to gather as many as possible of various types of
scientific analytical results (elemental and oxide quantities,
published and unpublished) and make them available to the
scientific and professional audience.
In the last 20 years, a whole range of new methods, mainly
from the field of natural sciences, were introduced in museum
work. Those methods were first tested in various fields of work
and later became a routine procedure. Besides conservation –
restoration, they can be used in curatorial work, at establishing
of date of making, authorship or provenance, authentication,
etc. Large quantity of samples of different museums was
analyzed. The results were stored at institutions involved in the
research. Afterwards, only a small part of the results were interpreted and even less published in various publications. Thus,
the most part of valuable information is lost to the researchers.
Our main idea derives from the concept of sharing knowledge
for gaining knowledge. We think that it is necessary to make
all the results of expensive scientific procedures available
to users. We plan to create an online database of results of
analytical methods, equipped with a search engine that will
allow quick and efficient gathering of data. The data will also
be useful for comparison.
Because of this, it will be possible to get maximum effect
from EDS, ICP AES, LA ICP MS, PIGE, PIXE, RAMAN, XRF and
many other analytical methods and enrich our knowledge
in the fields of basic and advanced art research.
We expect the project DataTreasure to have following
impacts:
tEJSFDUVTFPGEBUBJOSFTFBSDIoUIFEBUBCBTFXJMMTFSWFBTB
large source of data to be used for comparisons, which are
a key part of this kind of research
tFEVDBUJPOBMQVSQPTFTUIFQPTTJCJMJUZPGDPOUSPMMJOHUIFJS
own results on the basis of a strong reference base
tEJTTFNJOBUJPOPGLOPXMFEHFoSFMBUFESBUJPOBMJ[BUJPOPG
costs (avoiding duplication of analysis), access to data
for scientific work and for raising public awareness of the
eligible use of public funds,
tTVTUBJOBCMFEFWFMPQNFOUoBQQMJDBCJMJUZPGEBUBJOPUIFS
sectors, strengthening of interdisciplinary cooperation and
institutional integration
tPOMJOFQVCMJTIJOHoGBTUBOEGSFFXJUIBTUBUVTPGTDJFOUJmD
publication
145
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L.K. Herrera1 - A. Justo2 - M. Salome3 - G. Martinez-Criado3
A. Muñoz-Paez1
Universidad de Colombia, Education, 11001, Bogota, Colombia
Instituto de Ciencia de Materiales de Sevilla, Consejo Superior
de Investigaciones Científicas-Universidad de Sevilla, Research, 41092, Sevilla, Spain
3
European Synchrotron Radiation Facility, Research, BP 220, 38043, Grenoble, France
1
Metal pipes of Spanish
Baroque organ:
an elemental analysis
2
This paper describes the distributions and correlations of
elemental distributions present in the tin and lead phases
of a pipe from a Spanish baroque organ. The composition and microstructure of the pipe were studied using a
combination of laboratory techniques and microanalytical
methods at a synchrotron radiation source. The soft and
hard X-ray microprobes allowed for elemental imaging of
the main phases and low concentrated elements at (sub-)
micrometer scales. X-ray microscopy beamline ID21 was
used to record µXRF and µXANES data at low excitation
energies, 4.05 and 7.3 keV. As expected, it was found that
the main components of the metal pipe, tin (80 %) and lead
(20 %), formed segregated phases. The presence of Hg, Ni,
Fe and Cu was detected into the lead phase, being their
concentration within the range of 0.05-0.01 %.
This study reveals the different minor and major elements and
their localization in the two microsized segregated areas using
micro-XRF, knowledge of relevance in the construction of new
organs. Ancient organ builders used the lead available in the
17th century, and they produced a unique sound that now
might be reproduced by adding the impurities that came naturally in old “ pure ” lead and have been discovered now. These
results are important for the new organ builders because the
lead casted today is totally pure. So, that new builders may
reproduce antique technology to make better organ pipes
by adding low concentrated elements. Our findings indicate
that the main corrosion product formed in the upper layer was
laurionite, PbCl(OH), unexpected compound since chlorine
was not present in the initial alloy. This result corroborated
the preferential attack of Cl on the lead phase and not the
tin phase, thus suggesting an incorrect cleaning procedure.
Bibliography
[1] L.K. Herrera, A. Duran, M.C. Jiménez de Haro, J.L. Perez-Rodriguez,
Á. Justo Coalition. CSIC Thematic Network on Cultural Heritage (Electronic
Newsletter) 14 (2007) 10-14.
[2] A. Justo, M.C. Jiménez, M.B. Sigüenza, A. Durán, J.L. Pérez-Rodríguez:
Internal report “ Estudio científico de muestras procedentes del Órgano
de la Catedral de Zaragoza ”. CSIC (2004). 1- 40.
[3] W.R. Lewis: The metallurgy of tin lead alloys for organ pipes. ISO information.
(1974). 767-774.
[4] G. Grenzing, E. Zindel: Organ Journal. 1 (2007) 4-8
[5] A. Justo-Estebaranz, L.K Herrera, A.Duran, B. Sigüenza, M.C Jimenez de Haro,
O. Laguna, A. Justo. Stud Conserv 57, (2012) 21-28
[6] L.K. Herrera. Physico-Chemical Research of Cultural HeritageMaterials
using Microanalytical Methods. PhD Dissertation, University of Seville 2009.
[7] L.K Herrera, A. Justo, A. Muñoz-Paez, J.A. Sans, G. Martinez-Criado.
Analytical and Bioanalytical Chemistry, 395 (2009) 1969–75.
146
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Sara Sa1 - Manuel Pereira2 - Sonia Domingos3
Antonio Candeias3 - Agnes Le Gac1
Universidade nova de Lisboa, Departamento de Conservação e Restauro,
Faculdade de Ciências e Tecnologia, 2829-516, Caparica, Portugal
2
Universidade Técnica de Lisboa, Centro de Estudos em Recursos Naturais e
Ambiente / Centro de Petrologia e Geoquímica, Instituto Superior Técnico,
3
Universidade de Évora, Laboratório Hércules, Centro de Química de Évora,
7000-809, Évora, Portugal
1
Thai mask under
scrutiny: combined use
of X-ray spectroscopic
techniques
and mid-infrared
spectroscopy
This study focuses on a mask used in modern Khon performance,
a classical dance drama from Thailand originally performed as
a court entertainment but evidencing nowadays a popular
style for common folk. The mask under study is an elaborate
polychrome headdress, 42 cm high, depicting a peacock in the
round, called ‘Nokyoonh’ and used in specific episodes from the
Ramakien, the Thailand’s national epic. Dated from the 1960s,
this headdress was brought from Bangkok by Francisco Capelo
in 2013, and joined the Museu da Marioneta (Puppet Museum)
collection, in Lisbon, this very year.
According to the available information on the current manufacturing process, Khon masks are made of fibers from the sa rice
paper applied on a top clay model, and after being removed
from the mold, painted with acrylic paints [1]. Depending on
the character that is being represented, gold leaf can be applied,
as it seems to be the case regarding the golden tiara which
completes the headdress.
Bibliography
[1] N. Chandavij, P. Pramualratana. Thai Puppets & Khon Masks. River Books,
Michigan, 1998.
[2] A. Le Gac, R. Estrompa, J.C. Frade, S. Pessanha, T.I. Madeira, A. Cardoso,
J. Mirão, A. Candeias, M.L. Carvalho. Multianalytical approach for
the authenticity of an eighteenth-century Pascal Taskin harpsichord,
Journal of Analytical Atomic Spectrometry, 27, 2012, 626-643
[3] J. Lang and A. Middleton, Radiography of cultural material, Elsevier, Oxford,
2005, 20-48
[4] S.R. Stock. MicroComputed Tomography: Methodology and Applications,
CRC Press, 2008
[5] N.C. Debnath, S.A. Vaydia. Application of X-ray diffraction technique
for characterisation of pigments and control of paints quality,
Progress in Organic Coatings, 56 (2-3), 2006, 159–168
[6] O. Chiantore, D. Scalarone, T. Learner. Characterisation of artists’ acrylic
emulsion paints, Journal of Polymer Analysis and Characterisation, 8,
2003, 67-82
Because very little is known on this specific mask from a material
and technological viewpoint, this study aimed at getting a first
insight into the support and polychrome coating implementation by combining several X-ray spectroscopic techniques and
mid-infrared (IR) spectroscopy.
Besides fundamental visual records first obtained by digital
photography, digital microscopy under visible and ultraviolet
illumination, and optical microscopy [2], non-invasive portable
digital X-ray Radiography (XRR) was carried out in situ in an
attempt to put in evidence specific aspects of the headdress
inner structure and assembly [3].
Scanning Electron Microscopy coupled with Energy Dispersive
X-ray Spectroscopy (SEM-EDS) was used on a well selected
set of samples, on planar and cross sections for providing SEM
imaging at high magnifications, elemental composition and
mapping, and allowing the assessment of the type of gold alloy
used and its fineness.
As a non-destructive imaging technique, X-ray Micro-Computed
Tomography (µCT) was also implemented on the aforesaid
samples for yielding 3D static and dynamic visualization of their
morphology and microstructure [4]. It was useful to compare
the density, porosity and texture of the fibrous substrates joined
together and of all the pictorial layers too.
X-ray Diffraction (XRD) was particularly well adapted to assess
which ground and pigments were used, and whether they were
employed as single matter or in admixtures [5].
For its ability to improve reproducibility, provide molecular information and obtain spectra from a very wide range of ancient
and modern substances, Attenuated Total Reflectance (FTIR-ATR)
as an IR technique complemented the other ones with further
information on the binder used in the paint films [6].
The overall data allowed not only to have a better understanding
of the construction techniques and final touches applied to this
contemporary Thai mask, but also to compare the gathered
results with the literature content [1].
Acknowledgements:
To Maria José M. Santos & Maria Carrelhas, Directors of Museu
da Marioneta.
147
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Technological aspects
of a pair of wax-cast
figurines unveiled by
multi-analytical
techniques
Seven complementary techniques were successfully applied to
study a pair of very alike colored wax figurines belonging to Museu Nacional Machado de Castro, Coimbra (Portugal): Examination under visible and ultraviolet light, Neutron Tomography (NT),
X-ray Radiography (XRR), Energy Dispersive X-ray Fluorescence
(EDXRF), Scanning Electron Microscopy coupled with Energy
Dispersive X-ray Spectroscopy (SEM-EDS), Gas Chromatography
with Mass spectrometry (GC-MS) and Raman spectroscopy (RS).
These eighteenth-century figurines in the round, 30 cm high,
depict Francis of Assisi in a very naturalistic way, as an emaciated
“ Lesser Brother ”living in poverty, clad in a rough homespun and
barefoot. Each statuette stands on a marble-like cylindrical base
decorated with rococo motifs.
While very little is known about the circumstances under which
these artworks were brought together, what makes the connection
between them so singular is that they were cast from the same
model. Their study offers the unique opportunity to verify aspects
inherent to the production of multiples copies in wax casting.
The figurines were examined in situ with normal and racking
Bibliography
[1] J. Lang and A. Middleton, Radiography of cultural material, Elsevier,
Oxford, 2005, p. 20-48.
[2] B. H. Stuart, Analytical Techniques in Materials Conservation, John Wiley &
Sons Ltd, Chichester, 2007, Chapter 6.3 “ X-ray fluorescence spectroscopy ”,
p. 234-240.
[3] M.I. Prudêncio, M.A. Stanojev Pereira, J.G. Marques, M.I. Dias, L. Esteves,
C.I. Burbidge, M.J. Trindade and M.B. Albuquerque, Neutron Tomography
for the assessment of consolidant impregnation efficiency in Portuguese
glazed tiles (XVII century), Journal of Archaeological Science 39 (4) 2012,
964-969.
[4] A. Le Gac, A.I. Seruya, J. Bleton, S. Voduy and J.C. Frade, Raised
decorations applied to baroque polychrome sculpture in Coimbra, Portugal:
a production of painter-gilders or sculptors?, in S. Eyb-Green (Ed.),
Technology and Interpretation Reflecting the artist’s Process,
4th International Symposium of the ICOM-CC ATSR Working group,
Archetype Publications, London, 2012, p. 90-111.
148
Agnes Le Gac1 - Teresa Madeira2 - Marco Pereira3
Joana Santos3 - Isabel Nogueira4 - Marta Manso5
Jean Bleton6 - Stéphane Longelin5 - Antonio Candeias7
Maria Luisa Carvalho5
Universidade Nova de Lisboa, Departamento de Conservação e Restauro,
Faculdade de Ciências e Tecnologia, 2829-516, Caparica, Portugal
2
Universidade de Lisboa, Departamento de Física, Faculdade de Ciências,
3
Universidade Técnica de Lisboa, Centro de Ciências e Tecnologias
Nucleares, Instituto Superior Técnico, 2695-066, Bobadela, Portugal
4
Universidade Técnica de Lisboa, Instituto de Ciência e Engenharia de Materiais e Superfícies, Instituto Superior Técnico, 1049-001, Lisboa, Portugal
5
Universidade de Lisboa, Centro de Física Atómica, Faculdade de Ciências,
6
Université Paris-Sud, Laboratoire d’Études des Techniques et Instruments
d’Analyse Moléculaire, Institut Universitaire de Technologie d’Orsay, 91400,
Orsay, France
7
Universidade de Évora, Laboratório Hércules, Centro de Química de Évora,
7000-809, Évora, Portugal
1
light, under visible and ultraviolet light, to document their specific
shape, textures and state of preservation.
As non-destructive technique particularly suitable to visualize
hydrogen rich substances and organic artifacts, NT was used for
assessing different densities within wax and material thickness
and the joint techniques.
Non-invasive portable digital XRR offered the possibility of looking
through the inner structure of both objects. Front and side views
were taken aiming at looking for eventual metallic elements that
ensure the figurine and pedestal adequate holding [1].
In a preliminary approach, portable EDXRF was also used in situ to
search for elemental composition of all the constitutive parts [2].
SEM imaging (Backscattering Electron and Secondary Electron
modes) was undertaken on well representative samples, for
high magnification records (×25-5,000), chemical contrast and
topographical aspects. Area and point analyses were carried out
by SEM-EDS, equipped with mapping facilities, to provide data
on all materials employed to achieve the plastic and chromatic
effects: pigments, gilding and fibers. Furthermore semi-quantitative analysis was performed on the gold leaf for thickness and
fineness assessment [3].
GC-MS was used to identify the wax-rich mixture chosen as
foundation material.
RS was useful as complementary molecular technique to accurately determine the inert and coloring agents employed to give
the statuettes their final appearance.
The gathered data allowed for a systematic comparison to be
drawn between the two figurines and verify how far their manufacturing process was the same. It also gave an opportunity
to establish a parallel between the concrete reality of this case
study and the theoretical content of historical art technological
sources on wax-casting [4].
P-47
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Thai mask
under scrutiny:
Combined use
of X-ray spectroscopic
techniques
and infrared
spectroscopy
This study focuses on a Thai mask which is strictly speaking
an elaborate polychrome headdress (42 cm high) depicting a
peacock in the round, called ‘Nokyoong’ in Thai. This mask may
have been worn in two traditional Thai costumed dance-dramas
based on the ‘I-Knao’ narrative. The first dance, called ‘Yarun in
pursue of the peacock’, is based on an I-Knao poem by King
Rama II and practiced since 1817. It consists of two dancer-actors
only, one enacting the hunter role of ‘Yarun’ and the other one, a
peacock role [1]. It is also classified as ‘Lakorn Nai’, a performance
excusively displayed in the Royal precincts. The second dance
‘Rabum Mayurapirom’, consists of multiple performers dressed as
peacock characters. While the choreography of this play was invented by Peaw Sanitwongsenee and its melody was composed
by Montree Tramoch, the premiere of Rabum Mayurapirom took
place in 1961 [2].
Bibliography
[1] S. Pothiwhetchakul. Master of Arts Thesis. Chulalongkorn University,
Bangkok, 1996.
[2] I. Boonprakob, an online article (accessed 2014):
http://taopuyimbunhotmail.blogspot.com/2009/01/blog-post_15.html.
[3] A. Le Gac, R. Estrompa, J.C. Frade, S. Pessanha, T.I. Madeira, A. Cardoso,
L. Piorro, J. Mirão, A. Candeias, M.L. Carvalho. Multianalytical approach
for the authenticity of an eighteenth-century Pascal Taskin harpsichord,
Journal of Analytical Atomic Spectrometry, 27, 2012, 626-643
[4] J. Lang and A. Middleton, Radiography of cultural material, Elsevier, Oxford,
2005, 20-48
[5] S.R. Stock. MicroComputed Tomography: Methodology and Applications,
CRC Press, 2008
[6] N.C. Debnath, S.A. Vaydia. Application of X-ray diffraction technique
for characterisation of pigments and control of paints quality, Progress
in Organic Coatings, 56 (2-3), 2006, 159–168
[7] C. Selwitz. Cellulose Nitrate in Conservation. The Getty Conservation
Institute, Los Angeles, 1988.
Agnes Le Gac1 - Sara Sa1 - Wantana Klysubun2
Manuel Pereira3 - Sonia Costa4 - Antonio Candeias4
1 Universidade Nova de Lisboa, Departamento De Conservação E Restauro,
Faculdade De Ciencias E Tecnologia, 2829-516 Caparica, Portugal
2 Synchrotron Light Research Institute, Research Facility Division, 111 University
Avenue, Muang District, 30000 Nakhon Ratchasima, Thailand
3 Universidade Tecnica de Lisboa, Centro de Estudos Em Recursos Naturais
e Ambiente / Centro de Petrologia e Geoquimica, Instituto Superior Tecnico,
1049-001 Lisboa, Portugal
4 Universidade de Evora, Laboratorio Hercules, Centro de Quimica De Evora,
7000-809 Evora, Portugal
Dated from the 1960s, the headdress under study was brought
from Bangkok by Francisco Capelo in 2013, and joined the
Museu da Marioneta (Puppet Museum) collection, in Lisbon,
that very year.
Because very little is known on this specific mask from a material
and technological viewpoint, this study aimed at getting a first
insight into the support and polychrome coating implementation by combining several X-ray spectroscopic techniques and
infrared (IR) spectroscopy.
Besides fundamental visual records first obtained by digital
photography, digital microscopy under visible and ultraviolet
illumination, and optical microscopy [3], non-invasive portable
digital X-ray Radiography (XRR) was carried out in situ in an
attempt to put in evidence specific aspects of the headdress
inner structure and assembly [4].
Scanning Electron Microscopy coupled with Energy Dispersive
X-ray Spectroscopy (SEM-EDS) was used on a well selected
set of samples, on planar and cross sections for providing SEM
imaging at high magnifications, elemental composition and
mapping, and allowing the assessment of the type of gold alloy
used and its fineness.
As a non-destructive imaging technique, X-ray Micro-Computed
Tomography (µCT) was also implemented on the aforesaid
samples for yielding 3D static and dynamic visualization of their
morphology and microstructure [5]. It was useful to compare
the density, porosity and texture of the fibrous substrates joined
together and of some of the pictorial layers.
X-ray Diffraction (XRD) analysis was carried out to assess which
ground and pigments were used, and whether they were employed as single matter or in admixtures [6].
For its ability to improve reproducibility, provide molecular information and obtain spectra from a very wide range of ancient
and modern substances, micro Fourier Infra Red spectroscopy
(µ-FTIR) analysis complemented the other ones with further
information on the binder used in the paint films [6].
The overall data allowed to have a better understanding of
the construction techniques and final touches applied to this
contemporary Thai mask.
Acknowledgements: To Maria José Santos, Director of the Puppet
Museum, and Maria Carrelhas.
149
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Heinz-Eberhard Mahnke1,2 - Verena Lepper3,4
Freie Universität Berlin, FB Physik and TOPOI, 14195, Berlin, Germany
Helmholtz-Zentrum Berlin, 14109, Berlin, Germany
3
Staatliche Museen zu Berlin, Ägyptisches Museum und Papyrussammlung,
10117, Berlin, Germany
4
Humboldt-Universität zu Berlin, 10178, Berlin, Germany
1
2
Virtual unfolding
and unrolling of papyri
– identification
of hidden texts
In collections in various museums around the world,
there are numerous objects of folded and rolled ancient
papyri and other manuscripts often inscribed with texts of
historic and archeological value. To make such texts readable,
tedious procedures (and sometimes totally unsuccessful)
are necessary for unfolding and unrolling these delicate and
brittle objects. With recent progress in X-ray tomography
CT with respect to resolution (i) and sensitivity (ii) it is now
possible to develop procedures for a virtual solution:
(i) The recent reading by X-ray CT of a Mandaic text impressed onto a thin pure lead foil and rolled [1] nicely
illustrated the achievements in resolution.
(ii) A demonstration on a parchment role from the Norfolk
archive dating from the year 1778 as an example for organic material showed that if metal containing inks such
as iron gall ink were used the inscription is disclosed by a
tomographic virtual unrolling [2].
Bibliography
[1] D. Neuber, Chr. Reinhart, Giesserei-Rundschau 59 (2012) 133-135
[2] D.Mills, O.Samko,P. Rosin, K.Thomas, T.Wess T, G.Davis: Apocalypto: revealing
the unreadable, Proc. SPIE 8506, Developments in X-ray Tomography 2012,
VIII:85060A. OpenURL
150
We report the development of a procedure for sorting
out proper objects for tomographic inspection. With X-ray
fluorescence possible objects are first screened for metal
containing ink like iron or copper from iron gall or copper
vitriol. Only objects with positive metal signals are then
chosen for tomographic scans.
Samples prepared for demonstration from modern material
(papyrus and ink) with written symbols and without have
been tested and nicely support the chosen procedure. In
the case of iron, however, one has to expect surprises since
the sensitivity for revealing writings is blurred by Fe inherent
already in the papyrus material itself.
P-49
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Micro X-ray
fluorescence with
synchrotron radiation
(SR µ-XRF) and energy
dispersive X-ray
microanalysis coupled
to field-emission
scanning electron
microscopy (EDX-FESEM)
for studying
the degradation of wool
historical textiles dyed
with iron-tannin dyes
Historical textiles are an important part of our cultural
heritage, but such fragile textiles are subjected to several
types of degradation that damage their integrity and readability. The knowledge of their degradation mechanisms
is a matter of importance to improve the conservation of
these materials. Textile dyeing is one of the main sources of
fibre damage and, among the different dyeing techniques,
iron-tannin dyestuffs are known to cause specific and intense
damage to textiles. In particular our study was focused on
the deteriorating effects of tannins on wool threads, and
specifically on the chemical characterization of the dyed
wool cross-sections.
Two different analytical methods were applied to fully
characterise the chemical composition and the elemental
distribution in the dyed cross-sections of reference wool
samples and historical textiles: micro X-ray Fluorescence with
Synchrotron Radiation (SR µ-XRF) and Energy Dispersive X-ray
microanalysis coupled to Field-Emission Scanning Electron
Annalaura Restivo1 - Sandro Jurinovich1 - Ilaria Degano1
Erika Ribechini1 - Simone Bugani2
Josefina Perez-Arantegui3
Università di Pisa, Dipartimento di Chimica e Chimica Industriale, 56126,
Pisa, Italy
2
Università di Bologna, Dipartimento di Chimica Industriale e dei materiali,
40136, Bologna, Italy
3
Universidad de Zaragoza, Instituto Universitario de investigación
en Ciencias Ambientales, 50009, Zaragoza, Spain
1
Microscopy (EDX-FESEM). Elements present in the wool
matrix (like S) and others added in the mordanting process
(Fe) were investigated. The employment of SR µ-XRF allowed
us to obtain elemental mapping in the threads with high
spatial resolution, whereas EDX-FESEM was used to study
the spatial variation of the light elements.
The results highlighted the advantages of working with
complementary analytical techniques. Iron, one of the
elements more actively involved in the redox degradation
processes, was spatially confined to the external part of the
fibres, while no traces of this element were detected in the
cortex of the threads. On the contrary, sulphur mapping
showed that high amounts of this element were present in
the core of the fibre, but its concentration decreased from
the core to the cuticle. EDX-FESEM quantitative data disclosed three different degrees of degradation on the basis
of C/S ratios along the fibre section; the low C/S ratio in the
cuticle (high S content) corresponded to non-degraded
fibres. The presence of sulphur-rich proteins is extremely
important due to their influence on the mechanical and
thermal properties of wool, and the disulphide bonds are
fundamental in maintaining the three-dimensional structure
of wool. Also two different trends were identified for C/O
ratio by EDX-FESEM, and the high C/O ratio in the cuticle was
assigned to non-oxidized fibres. The oxidative mechanisms
may have affected the external lipid layer of the wool, and
the surface C/O ratio was identified as a good indicator of
fibre degradation, highlighting the occurrence of oxidation
reactions. In general, both morphological and elemental
analysis of wool specimens showed that the dyeing process
(addition of mordants and tannins) increased the rate of wool
damage, irrespectively of the type of raw materials exploited.
151
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Sofia Pessanha1 - Mario Costa1 - Maria Ines Oliveira1
Maria Estrela Jorge2 - Maria Luisa Carvalho1
Centro de Fisica Atomica da Universidade de Lisboa, Av. Prof Gama Pinto, 2,
2
Centro de Quimica e Bioquimica da Faculdade de Ciencias
da Universidade de Lisboa, Campo Grande, 1649-010, Lisboa, Portugal
1
Analysis of the silver
content in “ dinheiros ”
minted during
the reign of D. Fernando
of Portugal (13671383) – debasement
or mineral impurity?
“ Dinheiros ” are the first Portuguese coins, minted with a billon alloy (copper and silver). In this work, a set of “ dinheiros ”
from D. Fernando of Portugal (reign 1367-1383) was analyzed
and the composition of the alloy was compared with other
“ dinheiros ” from previous reigns (from 1223 to 1367). By
using the X-ray Fluorescence (XRF) analysis, a problem for
an accurate quantification may arise from their preservation
state: usually a corrosion layer appears on the original surface
of the object, which is composed by a variety of copper or
silver based compounds. Although the coins were in good
state of conservation and no active corrosion was macroscopically observable, the surface of the coins was further
evaluated by means of X-ray Diffraction (XRD). In order to
overcome this hindrance, the silver K/L intensity ratios were
determined and compared for the analyzed samples - K/L
intensity ratios are constant for different Cu-Ag alloys but are
Bibliography
[1] M.F. Guerra, J.N. Barrandon, F. Magro, F.B. Gil, analyse de dinheiros de la
1re dynastie du Portugal: nouvelles approches, Revue d’archéométrie, 13,
(1989) 31-41
very sensitive to changes introduced by a corrosion layer. This
way, “ clean ” spots were identified and quantitative analysis
carried out. The obtained results are similar to the ones
obtained in a previous study [1] where a clear decrease of
the Ag content was determined: from 8-9 % in the previous
reigns to 0.2-0.3 % in the coins attributed to D. Fernando. The
silver contents determined is very well comparable to the
silver content determined in other copper or bronze artifacts
analyzed, even in a copper counting bead, leading us to
believe that this low amount of silver was not intentionally
introduced to create a billon alloy but relates to impurities
present in the original mineral specimen.
Acknowledgments:
M. E. M. Jorge would like to thank the project PEst-OE/QUI/
UI0612/2013 for the funding.
P-51
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Giampaolo Piga1 - Antonio Brunetti1
Assumpcio Malgosa2
University of Sassari, Scienze Politiche, Scienze della Comunicazione e Ingegneria dell’Informazione., 07100, Sassari, Italy
2
Universitat Autonoma de Barcelona, Unitat de Antropologia Biologica,
Departament de Biologia Animal, Biologia Vegetal i Ecologia, 08193, Bellaterra
(Barcelona), Spain
1
Interdisciplinary
study of cremation
urns from the iron age
necropolis of Sebes
(Flix, Tarragona, Spain).
In recent decades, research and experience of cases have
greatly increased the ability to recognize and interpret the
burnt bones. The ability to preserve the bones during the
micro-excavation, to distinguish between burned human
remains and other materials, and the determination of the
combustion temperature, time duration and intensity distribution throughout the body after focusing on microscopic
changes in the bone may be important for understanding funeray practices and customs within archaeological contexts.
Thus, new experimental methods are needed to better clarify the variety of factors that involves the study of funerary
urns. In this work we present a interdisciplinary study of
cremation urns belonging to the necropolis of Sebes (Flix,
Tarragona, Spain) through various processes [CT-computed
tomography, micro-excavation, skeletal anthropology study;
X-ray Diffraction (XRD), X-ray Fluorescence (XRF) and Fourier
transform infrared spectroscopy (FT-IR) analysis to determine
the cristallinity and the fire temperature] with the aim to improve the methodology used by different authors [1,2] for
better understand funerary practices and customs within
archaeological contexts. In addition to traditional research
methods, the application of chemical and physical techniques such as XRF, XRD and FT-IR is increasingly accepted
in archaeological and forensic studies [3]. X-ray diffraction
and FT-IR analysis have several significant advantages
which are complementary for our full understanding of
the firing process whether in anthropological and forensic
contexts [3,4].
Computed tomography (CT ) has been recognized by
scientists as a very efficient tool for non-destructive study
of archaeological artefacts, fossil/no fossil skeletal materials
and especially for mummies studies. Comprehensive studies
of the contents of archaeological cremation urns with CT are
quite rare in the literature.
Bibliography
[1] Harvig, L., Lynnerupp, N. 2012. Computed tomography and computed
radiography of Late Bronze Age cremation urns from Denmark:
an interdisciplinary attempt to develop methods applied in Bioarchaeological
cremation research. Archaeometry 54, 369–387.
[2] Minozzi, S., Giuffra, V., Bagnoli, J., Paribeni, E., Giustini, D., Caramella, D.,
Fornaciari, G. 2010. An investigation of Etruscan cremations by computed
tomography (CT). Antiquity, 84, 195–201.
[3] Piga, G., Malgosa, A., Thompson, T.J.U, Guirguis, M., Enzo, S., 2012. A unique
case of prone position in the primary cremation Tomb 252 of Monte Sirai
necropolis (Carbonia, Sardinia, Italy). International Journal of
Osteoarchaeology (DOI: 10.1002/oa.2270).
[4] Piga, G., Solinas, G., Thompson, T.J.U., Brunetti, A., Malgosa, A., Enzo, S. 2013.
Is X-ray Diffraction able to distinguish between animal and human bones?
Journal of Archaeological Science 40, 778–785.
153
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Alicja Rafalska-Lasocha1 - Marta Grzesiak-Nowak2
Justyna Olszewska-Swietlik3 - Bozena Szmelter-Fausek3
Wieslaw Lasocha1
µ-XRPD investigations
of the pigments
in 17th century panel
paintings from Gdansk
and the northern
region of Poland
1
Proper recognition of artists’ technology and techniques
often requires applying a broad range of interdisciplinary
research methods based on the study of written sources
(treatises and manuscripts), old painting workshops, practical
reconstruction of formulas, artistic experience and physical
and chemical investigations [1]. The panel paintings by
Anton Möller (1563/65-1611), Isaak van den Blocke (15891628) and Hermann Han (1580-1627/28) who lived in Gdańsk
(Poland) were investigated in this study.
Chemical composition of grounds and pigments used by 17th
century masters in several panel paintings were identified by
means of µ-XRPD technique. Calcite and lead white were detected in ground and white layers. Due to the fact that XRPD
is one of the best methods to identify chemical compounds
with similar elemental composition we were able to identify
two kinds of lead white: cerrusite and hydrocerrusite in the
investigated samples.
In blue paint layers we have identified azurite and ultramarine. What is interesting, thanks to µ-XRPD technique we were
able to identify two different blue pigments used by the
master in the same blue paint layer. The results obtained for
one of the paintings suggest that smalt or other amorphous
blue pigment was used.
In the case of yellow paint we have identified lead tin yellow
type I. Old masters used two types of lead tin yellow: lead tin
yellow type I (Pb2SnO4) and lead tin yellow type II (PbSnO3).
Their powder diffraction patterns are different and each of
them can be easily detected by XRPD.
The investigations of red paint layers with the use of µ-XRPD
excluded existing in the paintings crystalline red pigments,
which suggests that red lakes were used by the masters. In
one sample µ-XRD revealed aluminum oxide Al2O3, whereas
from the reaction between alkali and alum hydrated alumina
Al(OH)3 should be obtained. In practice, it is difficult to characterize this substrate, partly because it is amorphous and
highly variable [2]. The presence of Al2O3 in the sample will
be the subject of further studies on production and chemical
characterization of dyestuff used by 17th century masters.
Described above results clearly show that contrarily to the
microdiffraction on not easily accessible synchrotron beams,
microdifraction technique with the use of laboratory X-ray
source is suitable for analysis of typical for panel paintings
thin paint layers and this technique can be widely used to
enrich the knowledge about cultural heritage objects.
All measurements were carried out on X’PERT PRO MPD
diffractometer, Cu Kα radiation, 40 kV and 30 mA, a graphite
monochromator and PIXCEL PSD detector. The apparatus
was equipped with a collimator (output beam diameter
0.1 mm). Phase analysis and pigment identification were
performed with the use of PDF4+ database.
Bibliography
[1] Artioli, G., Scientific methods and cultural heritage, Oxford University
Press, 2010
[2] Kirby, J., Spring, M., Higgitt, C. 2005. The Technology of Red Lake Pigment
Manufacture: Study of the Dyestuff Substrate, National Gallery Technical
Bulletin, Vol. 26, 2005, pp. 77-78, 80.
154
Jagiellonian University, Faculty of Chemistry, 30-060, Krakow, Poland
Jerzy Haber Institute of Catalysis And Surface Chemistry, PAS,
30-239, Krakow, Poland
3
Nicolaus Copernicus University, Institute for the Study, Conservation
And Restoration of Cultural Heritage, 87-100, Torun, Poland
2
P-53
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Paula R. P. Allegro1 - Marcia A. Rizzutto1 - Tiago F. Silva1
Nemitala Added1 - Jessica F. Curado1 - Ana G. Guimarães2
Marcia Barbosa2
ED-XRF and PIXE
analysis of a modern
Italian painting
1
Energy Dispersive X-ray Fluorescence (ED-XRF) [1] and in-air Particle induced X-ray emission (PIXE) [2,3] are physical techniques
used to determine the elemental constituents of a material. To
perform PIXE and ED-XRF it is not necessary to take a sample of
the material, so they suit very well to determine the elemental
constituents of Cultural Heritage objects, like paintings, with very
good results, as seen in [4,5]. The main advantage of ED-XRF analysis is that this technique can be done in situ, while PIXE allows
measurements of different layers of the material.
Those paintings in the back part are not recognized as painted
by the same artist who painted the front part. Our group have
already studied two of these five paintings recently and determined the authorship of the compositions on their verso [7,8].
The Museum of Contemporary Art of the University of São Paulo
(MAC-USP), Brazil, has a collection of Italian paintings, which
constituted a panorama of the main trends of Modern painting
in Italy from the 1920s to the 1940s [6]. Inside this collection, five
paintings are subject of interesting research in the museum,
because they have another composition on their verso, exceptional phenomenon of the artistic practices of the interwar period.
Bibliography
[1] E. P. Bertin, “ Principles and practice of X-ray spectrometric Analysis ”,
Plenum Press, Londres, (1975) 1079.
[2] S. A. E. Johansson, J. L. Campbell, « PIXE, A Novel Technique for Elemental
Analysis », John Wiley and Sons (1988).
[3] F. Folkmann et al., Nuclear Instruments and Methods 116 (1974) 487.
[4] P. A. Mandò et al., Nuclear Instruments and Methods B 239 (2005) 71.
[5] Z. Szökefalvi-Nagy et al., Nuclear Instruments and Methods B, 226 (2004) 53.
[6] A. G. Magalhães et al., VI Encontro de História da Arte, 2010, Campinas.
A História da Arte e suas Fronteiras. Campinas: UNICAMP/IFCH 1 (2010 ) 45.
[7] M.A. Rizzutto et al., External-PIXE analysis for the study of pigments from
a painting from the Museum of Contemporary Art, Nucl. Instr. Meth. B
(2014), http://dx.doi.org/10.1016/j.nimb.2014.02.108
[8] A. G. Magalhães et al., Revista de História da Arte e Arqueologia – Unicamp,
19 (2013) 141.
2
Institute of Physics, University of São Paulo, 05508-090, São Paulo, Brazil
Museum of Contemporary Art, University of São Paulo, 05508-900, São Paulo, Brazil
In this work, ED-XRF and PIXE analysis have been carried out to
determine the elemental constituents of the painting entitled “ Il
pittore all’aria aperta ” (62.5 × 50.3 cm), oil on canvas, produced
in 1919 by Virgilio Guidi. This painting is of particular interest due
to an incomplete composition of an unknown artist on its verso.
ED-XRF measurements in both sides of the painting were done
at MAC-USP using a miniature Ag X-ray tube system and a SSD
detector. PIXE measurements in the front composition were
performed at Laboratório de Análises de Materiais por feixes
iônicos (LAMFI), belonging to the University of São Paulo, Brazil,
using a proton external beam with an incident energy about
2.4 MeV and two Si-PIN detectors.
Preliminary data analysis of PIXE and XRF measurements have
shown the mayor elemental constituents of the painting are
Zn, Ca, Fe and Co, suggesting the use of white zinc, gypsum,
iron oxides and cobalt blue pigments by the artist. Some traces
elements detected, like S, Cr, Pb, Se and Sr, are still under analysis and can help in the determination of the authorship of the
verso composition.
155
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Neutron diffraction
on lapis lazuli:
characterisation
of rocks and artworks
for a provenance study
Lapis lazuli is a semi-precious blue stone, being used for glyptic as early as 7000 years ago: jewels, amulets, seals and inlays
are examples of objects produced using this material. Only
few sources of lapis lazuli exist in the world due to the low
probability of geological conditions in which it can be formed [1], so that the possibility to associate the raw material
to man-made objects is helpful to reconstruct trade routes.
This is especially true for ancient contexts where there is an
absence or scarceness of written evidences [2]. Although
the Badakhshan mines in Afghanistan are widely considered
as the only sources of the lapis lazuli in ancient times [2-4]
other sources have been taken in consideration: Tajikistan
(Pamir Mountains) [3,5], Pakistan (Chagai Hills) [5,6], Siberia
(near Lake Baikal) [3], Iran [3] and Sinai [7] (these last two not
geologically confirmed and their interpretations still debated
[4]). Results obtained using physico-chemical analysis (AAS)
on limited quantities of cut wastes from Shahr-i-Sokhta [5]
Bibliography
[1] Wyart J. et al, Gems & Gemmology 17 (1981) 184-190
[2] Tosi M., Gururajamanjarika, Studi in onore di G. Tucci, Ist. Univ. Orientale,
Napoli (1974) 3-22
[3] Herrmann G., Iraq 30(1) (1968) 21-57
[4] Herrmann G. et al, Reallexikon der Assyriologie und Vorderasiatischen
Archäologisch, ed. W. de Gruyter, Berlin (1983), 6: 489-492
[5] Casanova M., South Asian Archaeology, World Archaeology,
Prehistory Press, 14 (1992) 49-56
[6] Ballirano P. et al, American Mineralogist, 91 (2006) 997-1005
[7] Nibbi A. “ Ancient Egypt and some Eastern Neighbours ”. Park Ridge,
Noyes Publication (1981) 2: 33-55
[8] Zöldföldi J. et al, Proceeding of 34th Int. Symp. on Archaeometry
(Zaragoza, Spain, 2004), (2006) 353-360
[9] Lo Giudice A. et al, Analytical and Bioanalytical Chemistry 395(7)
(2009) 2211-2217
[10] Re A. et al, Nuclear Instruments and Methods in Physics Research
B 269(20) (2011) 2373-2377
[11] Re A. et al, Applied Physics A 111(1) (2013) 69-74
[12] Gallo L.M., Cataloghi, XVI, Torino, (2004) 287pp
156
Alessandro Re1 - Jacopo Corsi1 - Debora Angelici1
Alessandro Lo Giudice1 - Alessandro Borghi2
Emanuele Costa2 - Antonella Scherillo3 - Francesco
Grazzi4 - Lorenzo Mariano Gallo5 - Giovanni Pratesi6
Università di Torino and INFN, Dipartimento di Fisica, 10125, Torino, Italy
Università di Torino, Dipartimento di Scienze della Terra, 10125, Torino, Italy
3
STFC, Rutherford Appleton Laboratory, ISIS facility, OX11 0QX, Didcot, United Kingdom
4
CNR, ISC, 50019, Sesto Fiorentino (FI), Italy
5
Museo Regionale di Scienze Naturali, 10123, Torino, Italy
6
Università di Firenze, Dipartimento di Scienze della Terra and Museo
di Storia Naturale, 50121, Firenze, Italy
1
2
are in agreement with a Pamir Mountains and Chagai Hills
provenance, other than Badakhshan. Moreover, there is some
evidences that also in Renaissance the Chagai Hills deposits
was used as source of lapis lazuli to produce ultramarine
blue pigment [6]. Nevertheless a systematic and exhaustive
provenance study of the raw material used for artworks is
still lacking and lapis lazuli provenance is then a still open
question. Since art and archaeological objects produced
using lapis lazuli are valuable, only non-invasive techniques
can be used to identify the provenance of the raw materials.
For this kind of investigation Prompt Gamma Activation
Analysis (PGAA) was proposed and preliminary studies on
rock samples were promising [8].
Our group started a provenance study of this material in
2007, using a protocol based on a multitechnique approach
[9-11]. Due to the heterogeneity of lapis lazuli it is very difficult to identify provenance markers analysing the mean
elemental composition of the whole rocks or artworks, but
the different phases composing lapis lazuli rocks have to be
identified to give some clues about provenances. Thanks
to the high penetration of neutrons, it has been possible
to recognize the different phases composing several rocks,
through the analysis of the diffraction patterns obtained at
the time of flight (TOF) diffractometer INES (Italian Neutron
Experimental Station) operating at ISIS facility (RAL, UK).
In this contribution the results obtained on 13 rocks from 4
different provenances and on 3 artworks from the XIX century Savoy Collection (Museo Regionale di Scienze Naturali)
[12] will be presented. The differences among the sources
can be used to have some indications about the provenance
of artworks and objects made in lapis lazuli whose origin is
not known. These results can be extended to archaeological
samples and can be a good starting point to answer still
debated archaeological questions.
P-55
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DiffAbs and LUCIA
beamlines
complementarity
to study ancient
materials.
The diagnosis of the degradation state and the development
or improvement of conservation strategies for different materials as metals [1-3] and paintings [4,5], are of great interest
for the preservation of the historical or artistic artefacts.
Thus, it is crucial to characterize (structure, elementary composition) and locate (at micrometric scale) the constitutive
phases of the studied materials, according to their key role
in the alteration processes.
These studies make the most of the available complementarities of the DiffAbs and LUCIA beamlines at SOLEIL
synchrotron. These beamlines are actually complementary
in the energy range, the beam size and the techniques they
offer. In addition, these two beamlines are part of the most
requested by users studying ancient materials running X-rays
based synchrotron techniques.
The DiffAbs beamline provides a monochromatic X-ray
beam, tunable in the 3-23 keV energy range. The multi-scale
beam size, standard (300 µm) and microbeam (10 µm), can
be used in conjunction with all the analysis techniques available at the beamline: XRD, XAS and XRF. The simultaneous
Solenn Réguer1 - Cristian Mocuta1 - Filipe Alves1
Dominique Thiaudière1 - Delphine Vantelon2
Nicolas Trcera2 - Benedikt Lassalle2 - Damien Roy2
Pierre Lagarde2
1
2
Synchrotron SOLEIL, DiffAbs beamline, 91192, Gif sur Yvette, France
Synchrotron SOLEIL, LUCIA beamline, 91192, Gif sur Yvette, France
combination of such techniques offers the possibility of complementing the local structure information by data on the
long range order, which is essential for a full characterization
of the studied material. All the measurements are performed on the 6/8 circle kappa diffractometer using different
well-adapted detectors, ensuring that all experiments are
carried out on the same zone of the sample, in absolutely
identical physico-chemical conditions (temperature, reactive
solution, etc.).
The LUCIA beamline is a tender (0.8-8 keV) X-ray microprobe
with capabilities for chemical speciation by µ-XAS and for
elemental mapping by µ-XRF with a spot size of 2.5×2.5 µm²
obtained by two mirrors dynamically bendable in the Kirkpatrick-Baez configuration [6]. It allows the possibility to
measure heterogeneous samples at the micrometric size and
to combine these two element-specific and non-destructive
techniques for phase’s local structure characterization.
Since they opened, DiffAbs and LUCIA beamlines proved
their competitiveness to study materials for various topics
including cultural heritage.
Bibliography
[1] Monnier J., Reguer S., Foy E., Testemale D., Mirambet F., Saheb M.,
Dillmann P. and Guillot I. Corrosion Science, 78, 293-303, 2014.
[2] Monnier J., Vantelon D., Reguer S. and Dillmann P. Journal of Analytical
Atomic Spectrometry, 26, 885-891, 2011.
[3] Reguer S., Mirambet F., Dooryhee E., Hodeau J.L., Dillmann P. and Lagarde,
P. Corrosion Science, 51, 2795-2802, 2009
[4] Santoro C., Zarkout K., Le Hô A. S., Mirambet F., Gourier D., Binet L.,
Pagès-Camagna S., Reguer S., Mirabaud S., Le Du [Y] Griesmar P.,
Lubin-Germain N., and Menu M. Applied Physics A: Materials Science
& Processing, 114, 637-645, 2014
[5] Robinet L., Spring M., Pages-Camagna S., Vantelon D., Trcera N. Analytical
Chemistry, 83, 5145-5152, 2011
[6] A.-M Flank, G. Cauchon, P. Lagarde, S. Bac, M. Janousch, R. Wetter,
and J.-M. Dubuisson., F. Langlois, M. Idir, T. Moreno, D. Vantelon. NIM
in Physics Research B, 246, 269-274, 2006
157
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Marcia A. Rizzutto1 - Elizabeth A.M. Kajiya1
Pedro H.O.V. Campos1 - Martha Aldred1 - Jessica F. Curado1
Suene Bernardes1 - Ana G. Magalhães2 - Marcia Barbosa2
The Italian painting
‘‘A Adivinha’’ by Achille
Funi analyzed using
non destructive
techniques
1
The painting A Advinha (The fortune-teller) by Achille Funi
was analyzed with non destructive techniques as energy
dispersive X-ray fluorescence, images and computed radiography (CR). This painting, oil on wood of 46 × 46 cm,
belongs to the collection of the Museum of Contemporary
Art of the University of São Paulo (MAC USP). The museum
has a collection of Italian paintings [1], which constituted
a panorama of the main trends of Modern painting in Italy
from the 1920s to the 1940s [2]. This painting was analyzed
aiming at the better characterization of the artist’s procedures and his work, and also a construction of a data base
of the pigments of this artist. A portable X-ray Fluorescence
(PXRF) system was employed to identify the pigments used
by the artist and is composed of a Si-drift detector with an
active area of 7 mm2 and a Be-window with 12.5 microns
thickness. The system uses an Ag-anode X-ray tube working at 30 kV and 5 µA of voltage and current respectively.
The PXRF analysis allow the identification of the different
pigments that have the elemental composition of lead,
zinc, chromium, iron, mercury, calcium, etc. The analysis of
the pigments used in a painting is extremely important for
restoration and conservation process and can also allow
the identifying the pigments that may suffer degradation.
This knowledge allows one to adopt specific practices for
storage and/or exhibition of paintings, and, also the choice
of the most suitable treatments to reverse or to stop deterioration processes.
The image (visible light, infrared reflectography, ultraviolet
photography, tangential light) and radiography techniques
used were useful to reveal internal details that are invisible
the naked eye. In this painting, these analyses revealed
that the painting was in a good state of conservation and
also allowed to identify the successive phases of the artist’s
creation process. The analysis revealed hidden drawings performed by the artist under the painting and the preparatory
drawings and finally the changes made.
Bibliography
[1] A. G. Magalhães, M. A. Rizzutto, E. A.M. Kajiya, P. O. V. Campos, Revista
de História da Arte e Arqueologia – Unicamp, 19 (2013) 141.
[2] A. G. Magalhães, B. Faria, F. Lopes, VI Encontro de História da Arte, 2010,
Campinas. A História da Arte e suas Fronteiras. Campinas: UNICAMP/
IFCH 1 (2010) 45.
158
2
Instituto de Física, Universidade de São Paulo, 05508-090, São Paulo, Brazil
Museu de Arte Contemporânea, Universidade de São Paulo, 05508-050,
São Paulo, Brazil
P-57
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Neutrons
and complementary
methods for
archaeometallurgy
investigations
The application of analytical tools in the investigations of
the objects of Cultural Heritage usually concern dating,
provenance, manufacturing techniques, workshop affinities,
as well as fake identification, conservation or preservation
of objects. Neutrons are perfect tools of archaeometrical
studies due to their non-destructive and non-invasive
nature. Various kinds of neutron techniques can be used
to explore the compositional or structural features of the
samples. Based on the detection of characteristic γ-photons
produced in (n, γ) reaction, one can determine the ‘bulk’
elemental composition of the objects. Or, investigation of
neutron scattering patterns gives information on the atomic,
molecular or nano-scale structural properties: crystalline/
amorphous morphology, phase composition, mechanical strains, impurities, etc. Furthermore, neutron imaging
techniques (tomography/radiography) play an important
role in the exploration of the deep bulk topology or in-side
content of artefacts.
Bibliography
[1] Kasztovszky Zs, Rosta L; How can neutron contribute to Cultural Heritage
Research; Neutron News, 23, 25-28, 2012
[2] Káli Gy, Rosta L, Sánta S, Eszenyi G., Characterization of archaeological
and museological metal-related artefacts by TOF-ND at Budapest Neutron
Centre, ICNS 2013, Edinburgh
[3] Rosta L, Belgya T, Káli Gy, Kasztovszky Zs, Kis Z, Kovács I, Maróti B,
Szentmiklósi L, Szőkefalvi-Nagy Z, Jambon A, Rehren Th; Proof of
the Meteoritic Origin of Mankind’s Earliest Iron Artefacts through Neutron
BOE9SBZ"OBMZTJT)6/("3*"/"3$)"&0-0(:&+063/"-t8*/5&3
http://www.hungarianarchaeology.hu
[4] Káli Gy, Horváth E, Kasztovszky Zs, Kovács I, Maróti B, Mráv Zs, Rosta L,
Szőkefalvi-Nagy Z, Archaeometry Investigation of Late Roman Silversmith
Objects, Research report 2014 (to be published)
Laszlo Rosta1
1
Wigner Research Centre for Physics, Budapest Neutron Centre, H-1525,
Budapest, Hungary
The Budapest Neutron Centre (BNC) has long traditions in
application of neutrons for archaeology research. In particular,
the Prompt Gamma Activation Analysis (PGAA) group has
made a pioneering work to apply this technique to archaeometry. Small Angle Neutron Scattering (SANS) and Neutron
Diffraction (ND), Neutron and Gamma Radiography (NGR)
facilities have been involved in various archaeological research
project, both at national and European level. Since 2009 BNC
contributes to the EU FP7 Cultural Heritage Research project
called CHARISMA. The project gathers large European museums as well as provides access to a network of large scale
facilities; BNC is one of the transnational access providers by
the services offered at its neutron facilities: diffractometers
(ND), SANS, PGAA stations and imaging facilities. Complementary measurements are offered by the use of External Beam
PIXE and compact XRF Spectrometers, microscopes, mass
spectrometers etc. also at BNC site.
Neutron methods and complementary techniques available at
BNC and their relevance to investigation of objects of Cultural
Heritage, in particular applications to archaeometallurgy will
be presented. A review of case studies as comprehensive
analysis of artefacts by combined neutron techniques will
be demonstrated. For example, manufacturing processes of
the earliest Hungarian Bronze Age defensive armour such
as helmets, greaves and cuirass were studied by PGAA, PIXE
and ToF-ND [1]. Medieval steel objects e.g. swords of Vikings,
knifes from India and Syria were investigated to reveal their
iron phase structure and composition relevant for the ancient
manufacturing technologies [2]. Another highlight resulting
from a sequence of neutron studies is the prove of meteoritic
origin of the mankind’s earliest known iron objects, a set of
elongated iron beads, excavated 100 years ago at Gerzeh,
Egypt in a tomb dated to circa 3300 BC. Predating the invention of bloomery smelting by nearly two millennia, they are
commonly assumed to be made from meteoritic iron. Our set
of neutron measurements has provided unambiguous results
to offer a comprehensive interpretation of the origin and
fabrication of these beads and their significance for the history of iron working development [3]. Objects of late Roman
silversmith activity attracts nowadays considerable interest
– the comparative analysis of various silver objects marked
with stamp of known imperial workshops and pieces of similar
silversmith appearance without “ certificate ” can reveal the
same origin of these objects due to the identification of archaeometallurgical parameters by neutron measurements [4].
159
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The PUMA beamline
Researchers in the cultural heritage field have become an
important group of the synchrotron community. However,
the limited amount of beamtime available at 3rd generation
synchrotron sources often restricts the research done to
“ exceptional ” or “ highlight ” samples and makes it difficult
to investigate statistically meaningful numbers of typical
objects (corpus analysis). To overcome these problems, and
to provide tools specially adapted to the synchrotron communities of archaeology, conservation, paleo-environments
and palaeontology, the project to construct PUMA (“ Photons
used for Ancient Materials ”), a specially adapted beamline
at the synchrotron SOLEIL, was created.
The construction of PUMA has been financed by the region
Île de France and the French ministry of research and higher
education and will be operated by SOLEIL and the IPANEMA
CNRS unit. While it will be open to users from all scientific
fields, the beamline will be optimized for cultural heritage
science and a large part of the beamtime will be reserved
for these communities.
Bibliography
[1] L. Bertrand, M.-A. Languille, S.X. Cohen, L. Robinet, C. Gervais, S. Leroy,
et al., European research platform IPANEMA at the SOLEIL synchrotron
for ancient and historical materials, Journal of Synchrotron Radiation.
18 (2011) 765–772.
[2] L. Bertrand, M. Cotte, M. Stampanoni, M. Thoury, F. Marone, S. Schöder,
materials, Physics Reports. 519 (2012) 51–96.
160
Sebastian Schöder1 - Felisa Berenguer2 - Serge X. Cohen2
Aurélien Delmotte1 - Thierry Moreno1 - François Polack1
Sébastien Ancelin2 - Françoise Deschamps1 - Didier Dallé1
Loïc Bertrand2
1
2
Synchrotron SOLEIL, PUMA beamline, 91192, Gif-Sur-Yvette, France
IPANEMA, 91192, Gif-Sur-Yvette, France
PUMA will be a high energy (4 to 60 keV) X-ray beamline that
will provide to its users both full field phase contrast tomography and scanning microbeam techniques with micrometric resolution. The robust optical setup will allow a simple
transition between the full field and microbeam modes of
the beamline. A double crystal monochromator with a Si 111
and a Si 220 set of crystals will be used for energy selection.
In addition, experiments will be able to use the white beam.
Focusing for microbeam operation will be done by a SOLEIL
designed Kirckpatrick-Baez mirror system. A set of two high-intensity pinholes will allow imaging users to isolate the coherent part of radiation for phase contrast experiments. A field
of view of 20 mm (horizontal) and 10 mm (vertical) will be
available for full-field experiments. The setup will be optimized
for X-ray imaging, absorption and fluorescence spectroscopy
as well as diffraction and small angle scattering experiments.
The beamline is currently under construction, commissioning
will begin at the beginning of 2015. The beginning of user
operation is foreseen for the second half of 2015.
P-59
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Tatiana Severin-Fabiani1,2 - Mathieu Thoury1,2
Luc Robbiola3 - Benoit Mille4 - Matthieu Réfrégiers2
Loïc Bertrand1
Imaging
photoluminescence
heterogeneity
of corrosion products
at sub-microscale
in cultural heritage
metallic artefacts
1
Novel imaging approaches based on synchrotron UV/visible
photoluminescence (PL) allow studying a variety of ancient
materials at a sub-microscale [1,2]: (a) deep UV excitation allows probing luminophores not attainable with conventional
systems, while (b) decreasing the complex scattering effects
encountered in the visible and IR. (c) High resolution spectral
imaging enables accessing the complex heterogeneity of the
various phases which contributions are otherwise averaged
when studied at a macroscopic scale [3]. Corroded layers in
copper-based archaeological artefacts are notoriously challenging to characterize because of their heterogeneous structure
at the microscale due in particular to the presence of multiple
phases and partial amorphous character during the long-term
alteration processes [4].
We optimized synchrotron PL micro-imaging in order to
collect the relevant information on the nanoscale structure
and PL properties of corroded bronze objects. We studied a
corpus of 10 bronze artefacts from distinct burying environments (air, soils from various periods or regions) composed of
binary Cu–Sn, ternary Cu–Sn–Pb or tin-free alloys in several
advanced degradation states. The excitation tunability at the
DISCO synchrotron beamline (200–600 nm) and the emission
spectral selectivity allowed to detect PL from Sn- and Cubased alteration products between 320 and 1100 nm. Copper
and tin oxides, often encountered in natural patinas, exhibit
semiconducting properties that were exploited for characterisation in the 3.6 and 2.1 eV energy ranges, respectively.
In order to tackle both the great variability of corrosion layers
dimensions, ranging from tens of micrometers to few millimeters, and their crystalline heterogeneity, we optimised the
spatial dynamics available in micro-imaging, determined by
the lateral resolution of 150 nm over mm-sized fields of view.
Bibliography
[1] L. Bertrand, M. Cotte, M. Stampanoni, M. Thoury, F. Marone, and S. Schöder.
materials. Phys. Rep., 519(2):51–96, Oct 2012.
[2] M. Thoury, J.-P. Echard, M. Refregiers, B. Berrie, A. Nevin, F. Jamme
and L. Bertrand. « Synchrotron UV-visible multispectral luminescence
micro-imaging of historical samples ». Anal. Chem., 83(5), pp.1737-1745 (2011).
[3] L. Bertrand, M. Refregiers, B. Berrie, J.-P. Echard and M. Thoury. « A multiscalar
photoluminescence approach to discriminate among semiconducting
historical zinc white pigments. », Analyst, 138(16), pp. 4463-4469 (2013).
[4] P. Piccardo, B. Mille, L. Robbiola, « Tin and copper oxides in corroded
archaeological bronzes », Corrosion of Metallic Heritage Artefacts,
Eds. P. Dillmann, G. Beranger, P. Piccardo and H. Matthiessen, Woodhead
Pub., UK, Chap. 14, 2007.
IPANEMA, F-91192, Gif-sur-Yvette cedex, France
SOLEIL synchrotron, F-91192, Gif-sur-Yvette cedex, France
3
Laboratoire TRACES, UMR 5608, 31058, Toulouse Cedex 9, France
4
C2RMF, UMR171, 75001, Paris, France
2
Both morphology and PL properties of corrosion phases at
high resolution could inform on the original alloy nanoscale
composition, the environment of the object that governed
long-term corrosion processes as well as preservation. Future
developments of the technique will aim at a better correlation
between spatial and spectral information.
161
P-60
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Salvatore Siano1 - Iacopo Osticioli1 - Maria Cristina Guidotti2
G. Capriotti3 - N. Kardjilov4 - A. Scherillo5 - Juri Agresti1
Istituto di Fisica Applicata “ N. Carrara ”, CNR, 50019, Firenze, Italy
Soprintendenza Per I Beni Archeologici Della Toscana, 50121, Firenze, Italy
3
Istituto di Studi Sul Mediterraneo Antico, CNR, I-00015, Roma, Italy
4
Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh, D-14109,
Berlin, Germany
5
Isis Facility, Ral, OX11 0QX, Chilton-Didcot, United Kingdom
1
Combined neutron,
X-ray, and laser
techniques for
technological
and compositional
investigations of hollow
bronze figurines
2
Here, a multi-analytical non-invasive investigation aimed at
describing the execution processes and characterising the
alloy compositions and deterioration phenomenologies of
small bronze artefacts has been carried out, which included
neutron, X-ray, and laser techniques. These have been successfully applied in order to address archaeometallurgical
problems, which were encountered while investigating a set
of three similar figurines of different sizes representing Osiride
(maximum height of about 37 cm) from the antiquarian collection of Florence’s Egyptian Museum. The artefacts were hollow castings with almost intact casting cores and presented
interpretation problems concerning their manufacturing
procedures and state of conservation, which were not decipherable in a non-invasive way using traditional techniques.
Thus, in particular, X-ray radiography did not allow a sufficient
image contrast at the inner metal wall contours because of
the high degree of corrosion and mineralisation of the latter,
along with their small thicknesses and relatively strong curvatures. On the other hand, the comparison between the inner
and outer surfaces, along with the discrimination of the core
nails and repairs, have a crucial importance in order to distinguish between direct and indirect casting methods, as well as
for interpreting the execution procedure of the wax model for
casting and the joining techniques used. In general, in many
cases the level of contrast provided by traditional X-ray imaging is insufficient for such thorough descriptions of the technological features of ancient copper alloy statuettes, which can
often be much more effectively derived by means of neutron
tomography. Although application case studies of the latter
were previously reported [1], here, we exploit for the first time
high-resolution neutron tomography, which was carried on
CONRAD2 at Helmholtz-Zentrum Berlin (HZB), for thorough
interpretation of the crafting processes of ancient bronze
figurines. At the same time, the present work also include
compositional characterisations using portable XRF-XRD, laser
induced plasma spectroscopy (LIPS), and TOF-ND carried out
on INES at ISIS-RAL (UK). All these techniques are non-invasive and provide a powerful complementary analytical set
for achieving reliable surface [2], depth profile [3], and bulk
analyses [4], thus allowing exhaustive characterisation of the
raw materials and corrosion phenomenologies. Their application in combination with high-resolution neutron tomography in order to solve the specific interpretation problems of
mentioned Egyptian figurines, allowed us to achieve methodological results of general valence, which can be exploited
in similar archaeometallurgical investigation.
Bibliography
[1] R. Van Langh, E. Lehmann, S. Hartmann, A. Kaestner, F. Scholten,
The study of bronze statuettes with the help of neutron-imaging
techniques, Anal Bioanal Chem 395 (2009) 1949–1959.
[2] M. Ferretti, S. Siano, The gilded bronze panels of the Porta del Paradiso
by Lorenzo Ghiberti: Non-destructive analyses using X-ray fluorescence,
Applied Physics A 90 (2008) 97-100.
[3] S. Siano, L. Bartoli, A. Mencaglia, M. Miccio, J. Agresti, J., Use of neutron
diffraction and laser-induced plasma spectroscopy in integrated
authentication methodologies of copper alloy artefacts, Nuovo Cimento
B 124 (2009) 671-686.
[4] S. Siano, L. Bartoli, W. Kockelmann, M. Zoppi, M. Miccio “Neutron
metallography’’ of archaeological bronzes, Physica B 350 (2004) 123–126.
162
P-61
Bleu/Blue
10 sept. 2014 17:00 > 20:00
A new approach
to X-ray microanalysis
of museum specimens
One of the most fundamental methods for characterizing
many museum specimens involves performing an analysis
that yields their elemental composition. Particularly when
combined with two dimensional chemical mapping, this information may yield clues to a specimen’s origin and history.
We have developed an instrument that provides this data
with unprecedented sensitivity and accuracy. It combines
a Smithsonian Astrophysical Observatory (SAO) microcalorimeter spectrometer, that was originally developed for
X-ray astronomy missions under NASA auspices, with a
commercially available variable pressure-scanning electron
microscope (VPSEM). Although the microcalorimeter’s appli-
Eric Silver1 - Ed Vicenzi2 - Ting Lin1
Harvard-Smithsonian Center For Astrophysics, 60 Garden St., 02138, Cambridge,
MA, USA
2
Smithsonian Institution Museum Conservation Institute, 4210 Silver Hill Road,
20746, Suitland, MD, USA
1
cation to microanalysis may seem far afield from astrophysics,
its broad band, high resolution spectral performance enables
the spin-off application discussed here. The 2-D images generated by the microcalorimeter/VPSEM combination yield high
resolution maps of the elemental constituents of the sample.
Examples of diverse specimens that require such spatial
fidelity to fully understand their origin and history include:
early photographs (nineteenth century metal-based daguerreotype plates), geological materials (asteroidal/Martian
meteorites), archeological artifacts, objects of fine art, and
novel nano-technological coatings for the conservation of
high value objects.
Bibliography
[1] M.S. Barger and W.B. White, 2000. The Daguerreotype: Nineteenth-Century
Technology and Modern Science, The Johns Hopkins University Press,
(2000).
[2] E.P. Vicenzi, A TOF-SIMS and FIB Examination of Nano- and Micro-structures
in 19th Century Daguerreotype Photographs, 24th Annual Workshop
on Secondary Ion Mass Spectrometry, May 14-18 (2012).
[3] A.Elena Charola and Robert J. Koestler. Smithsonian Contributions
to Museum Conservation No. 3. Smithsonian Institution Scholarly Press,
Washington, DC. (2013).
[4] E. H. Silver, N.S. Brickhouse, Ting Lin, G.X. Chen, K. Kirby, J.D. Gillaspy,
J. N. Tan, and J. M. Laming, X-ray Spectroscopy of Highly Charged Ions
in Laboratory and Astrophysical Plasmas, in Recent Advances in Spectroscopy:
Astrophysical, Theoretical and Laboratory Perspectives , Springer Astrophysics
and Space Science Series, 2009.
[5] E. Silver, G. Austin, J. Beeman, F. Goulding, E.E. Haller, D. Landis
and N. Madden, An NTD germanium-based microcalorimeter with 3.1eV
energy resolution at 6keV, Nuclear Instruments & Methods in Physics
Research Section , 545(3): 683-689 (2005).
163
P-62
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Hanna M. Szczepanowska1 - Sabine Rolland du Roscoat2
Jean-Francis Bloch4 - Thomas Mathia3
Smithsonian Institution, Research, Non-Profit, Government, 20746, Suitland, USA
ESRF, Research, Grenoble, France
3
LTDS, CRNS, Research, Ecully, France
4
Grenoble University, Research, Grenoble, France
1
Synchrotron X-ray
micro-tomography,
SEM and CLSM applied
to characterization
of fungi induced stains
on artworks on paper
2
Fungal biodeterioration of artworks on paper is manifested by staining and structural polymer degradation
of paper by fungal enzymatic activities. Fungal staining
of paper results from complex interactions of heterogenous cellular materials (paper) with living systems (fungi).
The pigments are bi-products of bio-chemical processes within fungal cell structures defined as secondary metabolites.
Although fungal biodeterioration of cultural heritage has
been studied for number of years the focus was on visual
effects of biodeterioration or identification of fungal species;
no studies of interfaces of fungi and paper matrix have been
undertaken. The black stains on paper caused by pigmented
mycelium and spores only recently received some attention
[1,2,3]. This investigation explores black stains on paper
attributed to Dematiaceous, meristematic fungi and their
interactions with the paper matrix. X-ray tomography using
synchrotron radiation employed in this study visualized in
3D mode interaction of fungal mycelium with the paper
matrix complementing surface morphology captured on
SEM micrographs and scanning laser microscopy of paper
with fungal deposits.
Materials and methods. The samples of fungal stains were
obtained from a 1920 Engraving on paper and a 17th century study sheet from the collection of Maltese Archives,
Malta. The fiber of both papers was cotton. Low-vacuum
environmental SEM Hitachi S3700N and S4700 were used for
back scattered electron imaging, in a range of 12-15kV and
1 kV-0.5 kV respectively. Confocal scanning laser microscopy
(CLSM), Keyence VX9700, captured spatial distribution of fungal spores on the surface of paper. X-ray tomography carried
out on a designated beam line at the European Synchrotron
Radiation Facility (ESRF), Grenoble, France, aimed to model
3D visualization of fungal mycelium in the paper matrix. The
voxel size of 0.7 µm3 was used to characterize paper fibers
and fungal filaments. The 2 mm × 2 mm samples were exposed to a homogenous and coherent beam at 17.6 keV at
different viewing angles. The X-ray absorption radiographs
were captured by CCD FReLon camera.
Bibliography
[1] H. M. Szczepanowska, Th. Mathia and P. Belin. Morphology of fungal stains
on paper characterized with multi-scale and multi-sensory surface
metrology”. Scanning 36 (2013), p.76-85.
[2] H. M. Szczepanowska, Living systems on heterogeneous cellular substrate:
contribution to a better understanding of dynamic interfaces of fungal
pigmentation and paper in biodeterioration of cultural heritage.
(Unpublished Doctoral Theses, LTDS, University of Lyon, France, 2012).
[3] K Sterflinger and W E Krumbein. Dematiaceous fungi as a major agent
for biopitting on Mediterranean marbles and limestones.
Geomicrobiological Journal 14 (1997), p.219-230.
164
Results and discussion. Scanning laser microscope image
(Figure 2A) shows morphology of fungal thick-walled spores
in aggregates and chain formations along paper fibers.
The spores appear to be attached to the surface of paper
fibers. The X-ray radiographs (Figure 2C and D) provide
information about fungal growth pattern inside the paper
matrix. Our preliminary data shows that X-ray microtomography might become a valuable technique in defining the
relationship between fungal growth and paper substrate,
complement data of bio-deposits morphology obtained by
SEM and CLSM imaging. The findings contribute to a better
understanding of fungi and paper interactions and patterns
of fungal growth guiding modeling of fungal remediation
and preservation strategy.
P-63
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Manako Tanaka1 - Kazuhiro Nagata2 - Masayoshi Ito3
Maki Tokugawa4
Tokyo University of the Arts, Art Innovation Center, 110-8714, Tokyo, Japan
Tokyo University of the Arts, Conservation Science Laboratory, 110-8714, Tokyo,
Japan
3
Japan Synchrotron Radiation Research Institute, Research and Utilization
division, 679-5198, Hyogo, Japan
4
Tokugawa Museum, Director, 310-0912, Ibaraki, Japan
1
Investigation
of raw material
and manufacturing
technique of traditional
Japanese matchlock
guns using SR-XRF
and synchrotron
radiography
It is said that traditional Japanese iron has good workability
and does not rust easily. The reasons of these characteristics
are derived from the raw materials, iron making technique
and iron manufacturing technique in ancient Japan. In
traditional Japanese iron making, Tatara smelting, iron
sand was used as a raw material. The temperature and the
frequency of forging decide the aesthetic value and the
mechanical value of Japanese iron artifacts. Matchlock
gun is one of the typical iron artifacts in Japan. Matchlock
guns were introduced into Japan in the 16th century by
Europeans. It is said that steel made from domestic iron
sand and/or imported steel was used as the raw material
of the barrel. However, the details have not been clarified yet because of the limited number of investigations.
Bibliography
[1] M. Tanaka and M. Kitada:Microstructure of Japanese Matchlock Gun
Fabricated by a Kunitomo Gunsmith in the Edo Genroku Period,
Journal of the Japan Institute of Metals Vol.76, pp. 489-495, (2012).
[2] M. Tanaka and M. Kitada: Material Analysis of Ornamental Metal
and Gunstock of Japanese Matchlock Guns and Percussion Lock Guns
Fabricated in the Edo Period, Journal of the faculty of fine arts,
Tokyo University of the Arts Vol.8, 17-29, (2012).
[3] M. Tanaka, M. Kitada and M. Nishijima: Microstructure and Nonmetallic
Inclusions in Japanese Percussion Lock Gun Fabricated in the Late Edo
Period, Journal of the Japan Institute of Metals vol. 74, pp.779-787, (2010).
[4] M. Tanaka and M. Kitada:Composition and Microstructure of Nonmetallic
Inclusions of Japanese Matchlock Gun (Hinawaju) Fabricated in the Edo
Period, Journal of the Japan Institute of Metalsvol.74, pp. 250-257, (2010).
2
It is considered that the barrel of a Japanese matchlock gun
was made mainly by hot forging, although the detailed fabrication technique of the barrel is not clear as it was carried
out in secret. In my doctoral study, I studied the metallurgical
microstructure of Japanese matchlock guns using destructive methods. Through the studies, I got new informations
on raw materials and the fabrication techniques on Japanese
matchlock guns [1-4]. However, essentially, the study of the
artifacts, cultural property, should be done using nondestructive methods. Those are the reasons why we started the nondestructive study of iron artifacts using the advanced analytical instruments such as synchrotron radiation. Steel barrels
of traditional Japanese matchlock guns fabricated in the
middle Edo period (17-18th century) have been investigated.
The purpose of this work is to analyze Japanese iron
matchlock guns by synchrotron radiation and to investigate
the raw material and fabrication technique of the steel barrel.
Another purpose is to contribute to the development of
the nondestructive study of iron artifacts. The compositions
of trace heavy elements are determined by synchrotron
X-ray fluorescence analysis (SR-XRF). The internal structure
is investigated with synchrotron X-ray radiography. It was
concluded that most of the heavy elements in iron sands
are eliminated to the slag as a result of smelting, refining,
and forging processes. Among the heavy elements, only
Ba and Ce remain in the final products. There is a possibility
that such trace heavy elements can be used as an indicator
for estimating the raw materials. It also became clear that
by using synchrotron X-ray radiography, we can identify the
joint area of the steel and the distribution of nonmetallic
inclusions. It was confirmed that by using nondestructive
methods such as synchrotron radiation, we can get some
important information on the raw material and fabrication
technique of iron artifacts. We will continue our study on
iron artifacts using not only synchrotron radiation but also
neutron imaging to develop the nondestructive study of
iron artifacts.
165
P-64
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Manako Tanaka1 - Yoshinori Shiota2 - Hiroyuki Hasemi3
Takenao Shinohara4 - Anton Tremsin5 - Yoshiaki Kiyanagi2
Tokyo University of The Arts, Art Innovation Center, 110-8714, Tokyo, Japan
Nagoya University, Graduate School of Engineering, 464-8603, Nagoya, Japan
3
Hokkaido University, Graduate School of Engineering, 679-5198, Hokkaido, Japan
4
Japan Atomic Energy Agency, J-Parc Center, 319-1195, Ibaraki, Japan
5
University of California at Berkeley, Space Sciences Laboratory, CA 94720,
Berkeley, USA
1
Investigation
of traditional Japanese
matchlock guns using
pulsed neutron
imaging
2
One of the characteristics of traditional Japanese iron is good
workability and rust resistance. The reasons of these characteristics are derived from the raw materials, iron making technique
and iron manufacturing technique in ancient Japan. Japanese
match lock gun is representative of Japanese iron artifacts.
It is said that the barrel of a Japanese matchlock gun was made
mainly by hot forging. But the detailed fabrication technique
of the barrel is not clear as it was carried out in secret. We have
been studying the metallurgical microstructure of Japanese
matchlock guns using destructive methods [1,4] and nondestructive methods such as synchrotron radiation. Furthermore,
recently we have started the nondestructive study of Japanese
matchlock guns using neutron. In this poster, we will present the
nondestructive study of Japanese matchlock guns using pulsed
neutron source at J-PARC in Japan.
We analyzed Japanese matchlock guns by using the pulsed
neutron time-of-flight (TOF) method which our collaborator, Prof.
Kiyanagi developed5. It’s getting clear that an image indicating
the number density, the crystal structure, the preferred orientation, and the strain of the material can be obtained by using the
energy analysis at a pulsed neutron source. Concerning the nondestructive methods, physical quantity like this can be obtained
only by neutron. The purpose of this study is to analyze precious
Japanese matchlock guns using pulsed neutron imaging and
to evaluate those crystallographic texture and microstructure.
The final goal of our study is to contribute to the development
of the nondestructive study of iron artifacts.
Experiment is carried out by pulsed neutron imaging using
the TOF method. Before analyzing, we checked the radioactive
activation of impurities in Japanese matchlock guns by using
handheld XRF. A 2D-PSD is used to get the spatial dependent
of TOF data. Distribution of nonmetallic inclusions and inlaid
piece of the barrel are observed from spectrum transmission
images. Information of the crystal structure, crystallite size,
and crystal strain of the barrels are obtained from the Bragg
edge. The crystal structures and crystallite sizes show differences
between the center of the barrel and the muzzle of the barrel.
According to our previous destructive study, this result shows a
possibility that the muzzle is reinforced with higher carbon steel
to resist a strong impact by the explosion of the gunpowder.
From the strain calculated from 110 edge, the welding region
of the barrel is considered. It is concluded that by analyzing the
crystallographic texture and microstructure by pulsed neutron
imaging, we can clarify the metallurgical characteristics of iron
artifacts and reveal the traditional Japanese iron making and
forging techniques. Our study shows the usefulness of the pulsed
neutron imaging and there is a possibility that this method can
contribute to the development of the nondestructive study of
metal artifacts.
Bibliography
[1] M. Tanaka and M. Kitada:Microstructure of Japanese Matchlock Gun
Fabricated by a Kunitomo Gunsmith in the Edo Genroku Period, Journal
of the Japan Institute of Metals(J. Jpn. Inst. Met.) Vol.76, pp. 489-495, (2012).
[2] M. Tanaka, M. Kitada and M. Nishijima: Microstructure and Nonmetallic
Inclusions in Japanese Percussion Lock Gun Fabricated in the Late Edo
Period, J. Jpn. Inst. Met. vol. 74, pp.779-787, (2010).
[3] M. Tanaka and M. Kitada:Composition and Microstructure of Nonmetallic
Inclusions of Japanese Matchlock Gun (Hinawaju) Fabricated in the Edo
Period, J. Jpn. Inst. Met. vol.74, pp. 250-257, (2010).
[4] M. Tanaka and M. Kitada: Microstructure of Japanese Matchlock Gun
Fabricated in the Edo Period, J. Jpn. Inst. Met. vol. 73, pp. 778-785, (2009).
[5] Y. Kiyanagi, H Sato, T Kamiyama and T Shinohara: A new imaging method
using pulsed neutron sources for visualizing structural and dynamical
information, Journal of Physics, Conference Series 340, 012010 (2012).
166
P-65
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Wantana Klysubun1 - Prapong Klysubun1 - Yuying Huang2
Nirawat Thammajak1 - Panidtha Sombunchoo1
Somdech Leelamanotham3
Investigating bronze
ring fragments from
Non Pa Cha Gao
archaeological site
with synchrotron X-ray
techniques
Synchrotron Light Research Institute, 111 University Ave., Muang, 30000, Nakhon
Ratchasima, Thailand
2
Shanghai Synchrotron Radiation Facility, 239 Zhangheng Rd., Pudong, 201204,
Shanghai, China
3
The 12th Regional Office of Fine Arts, Pimai-Chumpuang Rd., Pimai, 30110,
Nakhon Ratchasima, Thailand
Non Pa Cha Gao is located in Nakhon Rachasima, Thailand
provides an important evidence of secondary burial culture
in South East Asia, dating back 2400-1100 years in the past.
The site, excavated in 2003, holds a large number of massive
ceramic vessels containing human bones, along with bronze
rings and ceramic pieces buried as tribute for the deceased,
were found 0.5-1 meter below the datum. In this work, we
have investigated small bronze ring fragments with thickness
varying from 3-6 mm and projected diameters varying
from 7-8 cm using synchrotron radiation X-ray fluorescence
(SRXRF) mapping, quantitative SRXRF analysis, and X-ray
absorption near edge spectroscopy (XANES). To the extent
of our knowledge, this is the first analytical study on bronze
artifacts found in Thailand that utilizes synchrotron radiation techniques. Elemental mapping at 40 µm resolution
on cross-sectional areas of 4-9 mm2 shows non-uniformity
of constituent composition, i.e. copper, tin, lead, arsenic,
and nickel. In addition, variation of copper concentration is
clearly in contrast to those of tin, lead, and arsenic. Microscopic visual inspection indicates that corrosion had penetrated
deep into the bronze bodies. Alloy compositions determined
by SRXRF analysis from five fragments are 69-87 % Cu, 2133 % Sn, 0.1-0.7 % Pb and 0.1-0.6 % As. Aluminum, silicon,
phosphorous, sulfur, chlorine, calcium, and iron are also
detected in the bronze bodies suggesting that segregation
and mineralization from the surrounding environment had
taken placed. Corrosion products were investigated by Cu
K-edge, Sn L3-edge, and P K-dege XANES measurements,
and it was found that the predominant species are copper
chlorine, cuprite, stannic oxide, and phosphate.
1
167
P-66
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Lien van de Voorde1 - Eddy Verhaeven2 - Bart Vekemans1
Robin de Wolf1 - Peter Vandenabeele3 - Laszlo Vincze1
Ghent University, Department of Analytical Chemistry, 9000, Ghent, Belgium
Antwerp University, Faculty of Design Sciences, 2000, Antwerpen, Belgium
3
Ghent University, Archaeometry Research Group, 9000, Ghent, Belgium
1
168
Use of a novel portable
XRF/XRD instrument
for studying pigments
and model paintings
2
The use of X-ray based spectroscopic techniques for the
investigation of cultural heritage objects provides valuable
compositional/structural information on the examined
materials in a non-destructive way. Due to the rapid evolution of compact, portable X-ray instrumentation in the last
25 years it is now unnecessary to remove exhibited artefacts
from their original location, enabling the more preferable
relocation of the instrument/researcher to the museums
instead. While analytical methods using X-ray fluorescence
is a preferred method of choice to obtain information on
the elemental composition, very often the elemental information only is insufficient and should be coupled with
crystallographic data on the art or archaeological object
under investigation. This additional information can be obtained by e.g. using the X-ray powder diffraction method.
The Surface Monitor presented in this contribution is a
portable instrument which provides a simultaneous measurement of X-ray Fluorescence (XRF) and X-ray diffraction
(XRD) on cultural heritage materials. The instrument is
commercially available, manufactured by Assing S.p.A. (Italy).
This study reports analyses based on simultaneously collected XRF spectra and XRD patterns using the Surface Monitor
for retrieving elemental and crystallographic information on
pigments and model paintings. The primary goal of these
investigations was to obtain information about the performance of this commercially available portable instrumentation. Next to evaluating the instrumental figures of merit,
future perspectives of using the instrument in the research
of paintings and other objects of art exhibited in museums
will be discussed.
P-67
Bleu/Blue
10 sept. 2014 17:00 > 20:00
Angela Vasilescu1 - Bogdan Constantinescu1
Daniela Stan1 - Martin Radtke2 - Uwe Reinholz2
Günter Buzanich2 - Daniele Ceccato3
Studies on ancient
silver metallurgy using
micro-SR-XRF
and micro-PIXE
1
The metallurgical aspects of silver adornments offer to the
archaeologist important information about the provenance of
these items – mines, metal production workshops, jewelry makers, commercial relations. In the case of silver, gold, bismuth,
zinc and antimony can be used as fingerprint elements for
East European geological deposits (e.g. Bi for South Thracian
and Greek silver). The presence of copper and lead is directly
related to the metallurgy of silver, copper being used to increase the mechanical properties of the metal.
Some Thracian-Dacian adornments found on Romanian
territory from the Agighiol treasure (4th Century B.C.) and
Poiana Galati (1st Century A.D.) were investigated in this work.
To determine the composition of major (Ag) and minor (Cu, Au,
Pb) elements, in-museum XRF analysis was performed initially.
With special permit, two series of sub-millimetre-sized samples
from some artifacts belonging to above mentioned treasures
(appliqués, beads and small bracelets) could be analyzed using
the micro-SR XRF beam at BESSY at the BAM-line, at 20 keV
excitation energy, as well as in the 2 MeV proton micro-PIXE
beam at INFN Legnaro, obtaining maps and point spectra.
As main results, we mention the identification of bismuth in
the Agighiol samples - suggesting their provenance from Southern Thrace or Northern Greece, a homogeneous distribution
of silver, copper and lead - indicating an advanced metallurgy
(for Antiquity) and the presence of bromine and chlorine
(well-known silver corrosion agents) - giving information on
soil characteristics for the place of recovery of the artifacts.
For some Dacian bracelets from the Poiana Galati hoard we
identified the use of copper, zinc and tin (most probably from
bronze and brass) in the metallurgical process, as components
of the silver alloy. This procedure increased the mechanical
resistance of adornments, silver being a “ soft ” metal. In the
case of one bracelet, the elemental maps for the analysed
area revealed strong inhomogeneity in the copper map and
superposition of silver, gold and lead. Copper inhomogeneity
reflects a quite primitive alloying procedure while gold and
lead, accompanying silver, reflect the composition of the
initial mineral.
Horia Hulubei National Institute for Nuclear Physics and Engineering,
Applied Nuclear Physics department, RO-077125, Magurele (Ilfov), Romania
2
Federal Institute for Materials Research and Testing, BAM, D-12489,
Berlin, Germany
3
INFN Laboratori Nazionali di Legnaro, Dipartamento di Fisica
dell’Universita di Padova, I-35020, Legnaro (Padova), Italy
Bibliography
[1] National History Museum of Romania, The Treasure (in Romanian), Age-Art
Bucharest (2009), ISBN 978-973-88353-5-1
[2] B. Constantinescu, A. Vasilescu, M. Radtke, U. Reinholz, C. Pacheco, L. Pichon,
E. Oberlander-Tarnoveanu, SR XRF and micro-PIXE studies on ancient metallurgy of thirteen Dacian gold bracelets, Appl.Phys.A (2012) 109, 395-402
[3] A. Vasilescu, B. Constantinescu, R. Bugoi, D. Ceccato, D. Grambole,
F. Herrmann, Micro-elemental analysis of some Transylvanian meteorites
and lunar samples, Nuclear Instruments and Methods in Physics Research
B 267 (2009) 2233–2235
169
P-68
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10 sept. 2014 17:00 > 20:00
Louisiane Verger1,2 - Laurent Cormier2 - Olivier Dargaud1
Nicolas Trcera3
Cité de la Céramique, Sèvres et Limoges, Laboratoire, 92310, Sèvres, France
Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie
(IMPMC), Université Pierre et Marie Curie (UPMC), Physique des Amorphes,
Liquides et Minéraux, 75005, Paris, France
3
Synchrotron SOLEIL, LUCIA beamline, 91190, Saint-Aubin, France
1
170
Chromium in pigments
and enamels produced
at the “ Sèvres Cité
de la Céramique ”:
a Cr K-edge X-ray
absorption study
2
Chromium is at the origin of a wide variety of coloration
(green, pink and brown) on Sèvres porcelains. This element
was introduced for the first time at the “ Manufacture of
Sèvres ” in 1804, a few years after its discovery by Vauquelin.
Since this period, Cr is the basis of most pigments synthesized at the “ Manufacture of Sèvres ”. The mixture of these
pigments with a colourless frit is applied on the porcelain
and fired at high temperature to form an enamel, i.e. a mix
of crystalline and glassy parts. However the origin of colours
due to Cr in enamels and how it can be controlled by heating
treatments is still not well understood.
Observations under a scanning electron microscope (SEM),
UV-visible spectroscopy and X-ray diffraction analyses were
combined to X-ray absorption spectroscopy (XAS) in order
to characterize the enamel layer, the structural environment
of Cr and its relation to coloration properties.
We have observed that the enamels are composed of small
grains of pigment (5–30 µm) embedded in a glassy matrix.
In order to selectively probe the Cr environment and its oxidation state in pigments and enamels, we have used X-ray
absorption near edge structure (XANES) spectroscopy at the
Cr K edge (LUCIA beamline, SOLEIL). This study is focussed on
the investigation of the pre-edge feature which is sensitive
to both redox and coordination. The spatial resolution of the
X-ray beam on LUCIA beam line (4×4 µm2) was mandatory
to characterize pigments embedded in the glassy matrix.
Firstly, the analyses on a pigment rich in eskolaite Cr2O3
will be discussed. It is used to produce green empire
decoration on porcelain. Observations under a scanning
electron microscope (SEM) with EDX analyses highlight
heterogeneity of composition along the grains of pigment:
Cr is more concentrated near the surface of the particle.
The micro-focused synchrotron beam enables us to
characterize two different chemical environments of Cr,
eskolaite being at the periphery. This was not predicted by
XRD measurements, as eskolaite was the only crystalline
phase detected.
Chromium is also used to obtain pink decoration, with a
pigment mainly composed of malayaite CaSnSiO5 doped
with Cr. A variability of Cr speciation and environment will
be demonstrated using XAS.
Finally, the interactions of the grains of pigment and
the uncoloured frit play a key role in colour changes.
For instance the enamel composed of the spinel ZnAl2O4:Cr
evolves from pink to brown during the heating treatment.
Micro-XANES measurements reveal the formation of a
reactive layer between the grain of pigment and the glassy
matrix, which explain the variation of colour.
This study is then a new approach of chromium oxides:
through a patrimonial point of view, it also brings fundamental information about chromium environment in
spinels, solid solutions and glass matrices.
P-69
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10 sept. 2014 17:00 > 20:00
Elizabeth A. Willneff1 - Bronwyn A. Ormsby2
Cherno Jaye3 - Daniel A. Fischer3 - Sven L.M. Schroeder4
University of Manchester, SCEAS, M13 9PL, Manchester, UK
Tate, Tate, SW1P 4RG, London, UK
3
NIST, NIST, 20899, Gaithersburg, USA
4
University of Manchester, Chemistry, M13 9PL, Manchester, UK
1
Conservation
of artists’ acrylic paints:
application of near
edge X-ray absorption
fine structure (NEXAFS)
spectroscopy
to understanding
the impact of wet
cleaning treatments
on paint film surfaces
2
Artists’ acrylic paints make up a significant fraction of modern
and contemporary works-of-art. From a conservation perspective these paints, because of their relative youth, are less
well understood than oil-based counterparts. As conservation
treatments of acrylic paints become more commonplace understanding the impact of wet cleaning treatments becomes
more important, which has resulted in investigations with a
variety of analytical techniques including, for example, FTIR,
mass spectrometry and AFM [1]. Progress has been made
in identifying the causes of variations in pigment, gloss and
surfactant levels as a function of paint brand and cleaning
treatment [2]. Novel cleaning treatments have been assessed
for cleaning efficacy [3]. However, detailed examination of
the fundamental surface processes resulting from cleaning
treatments has proved to be challenging. The primarily organic layers (e.g. cleaning residues, pigment) present at low
concentrations at the uppermost paint surface following
cleaning treatments are difficult to distinguish from a substrate with similar elemental composition. We have therefore
applied near-edge X-ray absorption fine structure (NEXAFS)
spectroscopy to overcome these challenges by studying
model artists’ acrylic paint films as a function of paint brand,
pigment, cleaning treatment and age [4,5].
Bibliography
[1] Ormsby, B., Learner, T. Rev. Conserv. 2009, 29 - 41.
[2]. Kampasakali, E. et al. Stud. Conserv. 2011, 56, 14.
[3] Keefe, M. et al. Coatings Tech. 2011, 8 (9), 30-43.
[4] Willneff, E.A., Ormsby, B.A., Stevens, J.S., Jaye, C, Fischer, D.A., Schroeder,
S.L.M. Surf. Interface Anal. DOI: 10.1002/sia.5376 (2014).
[5] Willneff, E.A., Ormsby, B.A., Schroeder, S.L.M., Spectroscopic Techniques
and the Conservation of Modern Paints. In preparation for Heritage Science
(4/2014)
NEXAFS measurements performed at beamline U7A of the
NSLS (Brookhaven, USA) in partial electron yield mode provided surface sensitive molecular level chemical state information which could be used to identify changes in paint films
before/after cleaning treatments. The benefit of clearance
steps at removing cleaning system residues was assessed
and changes in pigment levels at the surface were probed.
In addition to single point measurements the complementary
benefit of NEXAFS imaging was investigated. These results
were used in conjunction with other spectroscopies (XPS,
ATR-FTIR), microscopy (SEM) and visual inspection to build up
a broader picture of how the surface chemistry of these paint
films responds to, and changes with wet cleaning treatments.
171
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Characterisation
of excavated
Napoleonic artefacts
from the Berezina
battlefield in Belarus
using neutron
techniques
An important collection of artefacts have been unearthed
during preventative archaeological surveys in 2012 and 2013
around the village of Stoudienka in Belarus – the site of the
Napoleonic army’s passage during the retreat from their
Russian campaign in November 1812. Recovered objects
such as fragments of bronze eagles, brass plates and buttons
with faint outlines of inscriptions and several lead bullets
have resulted in historian’s needs for further characterization
to reveal otherwise uncertain information, for example their
mode of destruction. The Belarus Academy of Science and
172
V. Danilovitcha1 - S. Dernovitcha1 - Z. Kharytanovitch1
V. Kochman1 - V. Lakiza1 - I. Groutso2 - C. Cardon3
Jerome Beaucour3 - B. Cubitt4 - C. Dewhurst4 - T. Pirling4
D. Atkins4
National Academy of Sciences Academy of Sciences of Belarus, Institute
of History, BY-220072, Minsk, Republic of Belarus
2
Maxim Tank Belarusian State Pedagogical University, BY-220050, Minsk, Republic
of Belarus
3
Centre d’Études Napoleoniennes, F-92300, Levallois, France
4
Institut Max von Laue – Paul Langevin, F-38042, Grenoble Cedex 9, France
1
the Centre d’Etudes Napoleoniennes collaborated with
the Institute Max Von Laue Paul Langevin (ILL) in a series
of experiments using non-destructive neutron diffraction
techniques available at the ILL on selected artefacts: Small
Angle Neutron Scattering on instrument D33 for material
characterization and surface examination and mechanical
deformation analysis on the strain imager SALSA, in order
to better understand their importance and obtain clearer
knowledge of events which took place on the battlefield
more than 200 years ago.
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Audrey Cochard1 - Solenn Réguer2 - Joël Douin1
Marie-Hélène Mathon3 - Sébastien Joulie1 - Nicolas
Ratel-Ramond1 - Jean-Marc Olivier4 - Philippe Sciau1
Study of “old ”
Duralumin used
in airplanes by crossing
laboratory analyses
and archives
researches
1
Aluminum-copper alloys were used a lot for aircraft from the
World War I until now for structural applications. A precise
knowledge of the nature of these alloys begins to interest
the industrial heritage field. However, although these materials were processed less than a century ago and used in an
industrial context, structural data are very limited. In many
cases their structure was not investigated on the nanometer
scale, which is fundamental to understand the mechanical
properties [1] and the corrosion behavior of age-hardenable
aluminum alloys. The link with archival documents from
aircraft manufacturers is complex for the alloys made before
1960-70, because the existing archival data of manufacturers
are fragmentary [2]. The best way to highlight these “ historical ” alloys is obtained by crossing the available archive data
and precise laboratory analyzes.
The present study focuses on the Breguet 765 Saraha built in
1958. This double-deck military aircraft was built during the
post-Wold War II boost of the French aeronautical industry. It
is currently in renovation by the association Ailes Anciennes
Toulouse [3]. Up to now, no direct information concerning
the nature of alloys used in the manufacturing Breguet 765
Sahara was available as most of Breguet company archives
has been lost. However, first laboratory analyses revealed
that at least two different compositions were used for the
rivets, respectively the A-U3G and A-U4G alloys, as described
in scientific literature by Tournaire and Renouard in 1955 [4].
The A-U3G alloy, easier to use, was developed to substitute
the A-U4G alloy at the same time that the conception of the
Breguet 765. These two types of rivets have been analyzed
using a combination of techniques: electron microprobe,
transmission electron microscopy, X-ray synchrotron diffraction and neutron diffraction. TEM investigations confirmed
that these “ old ” alloys contain much more various precipitates in nature and in size that the actual equivalent alloys.
The nano-structure of these two alloys are also very different:
the main precipitates of A-U4G rivets are CuAl2, Mg17Al12,
Al4MnSi0.7 and Al17(Fe3.2Mn0.8)Si2, while for A-U3G precipitates,
the main phase is Al7Cu2Fe. It should be noted that A-U3G
composition, developed later, contains much less sub-micrometric (10-1000 nm) and micrometric (1-10 µm) precipitates.
Interesting structures linked to weak variations of Al/Cu ratio
were observed in each composition. These wavy variations
are rather regular with a periodicity of around 100 nm.
Whether these structures are a consequence of aging over
several decades or not is under investigation.
Bibliography
[1] Dubost, B., Saintfort, P., Durcissement par précipitation des alliages
d’aluminium, Dossier Techniques de l’ingénieur M240 (1991).
[2] Le Roux, M., L’entreprise et la recherche: un siècle de recherche industrielle
à Pechiney, ed. Rive Droite, Histoire industrielle, Paris, 1998.
[3] Hartmann, D., Sauver Brigitte ou le sauvetage et la récupération
du Breguet 765 « SAHARA » d’Evreux à Toulouse, (http://www.calameo.com/
subscriptions/57493).
[4] Tournaire, M., Renouard, M., Alliages pour rivets de la famille du Duralumin,
Revue de l’Aluminium 217 (1955).
Université de Toulouse Paul Sabatier, Cemes, 31055, Toulouse, France
Synchrotron SOLEIL, DiffAbs beamline, 91192, Gif-sur-Yvette, France
3
CEA Saclay, Laboratoire Léon Brillouin, 91191, Gif-sur-Yvette, France
4
Université de Toulouse Le Mirail, Framespa, 31058, Toulouse, France
2
173
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Anna Fedrigo1 - Francesco Grazzi1 - Alan Williams2
Francesco Civita3 - Antonella Scherillo4 - Joe Kelleher4
Floriana Salvemini1 - Marco Zoppi1
Phase composition
and residual strain
mapping of two
Japanese helmets
1
Historical metallurgy is one of the most interesting fields of
archaeometry, especially with regards to the production and
use of steel for arms and armour components. Scientific and
technological research into these kinds of artefacts has scarcely
developed; in particular, a very limited amount of Japanese
armour has been investigated through metallography [1]. In
addition, because of their generally excellent state of preservation, the traditional methods of analysis do not suit these kinds
of objects because of their invasiveness. For these reasons, a joint
research project among CNR-ISC (Florence, Italy), the Stibbert
Museum (Florence, Italy), and The Wallace Collection (London,
U.K.) is carried out using a non-invasive approach, namely thermal neutron diffraction [2-5].
The production of Japanese armours involves several complex
steps that generally differ from one school (or tradition) to
the other [6,7]. The forging processes were orally transmitted
from one armourer to his pupil, thus the knowledge of most
techniques was lost through time, leaving very few written
mentions, reported in a descriptive and non-scientific way [7].
Documentary sources [7] suggest that, particularly with the
introduction of firearms in 1542, the construction technique and
style of Japanese armourers changed to increase the protection
offered by their armour [8].
Here we present novel results from diffraction measurements of
two Japanese helmets attributed to the 17th century (Saotome
and Haruta school), performed by using the instrument Engin-x
(ISIS-UK). The experiment allowed us to map the residual strain
distribution inside a few single platelets along their section.
This study completes the cycle of neutron measurements on
the samples and shed light on the last unresolved questions
raised by previous investigations. Both samples have been
already measured, using neutron diffraction on the INES
beamline (ISIS-UK), to obtain the quantitative phase composition of selected parts. The shape of the ferrite diffraction
peaks has been also thoroughly analysed and semi-quantitative information was obtained about: (i) domain size of the
crystallographic grains; (ii) texture intensity and distribution;
(iii) anisotropic residual strain distribution [3,4]. Considering
the results obtained, the presence of a composite structure
of steel and iron superimposed was suggested for the Haruta
helmet [9]. The morphology and construction method of the
Saotome helmet, identified by means of neutron tomography
performed at the NEUTRA beam-line (PSI, Switzerland), revealed
the presence a novel arrangement of the lamellar plates,
that needed a more thorough understanding of the ancient art
of Japanese armour making [10].
Bibliography
[1] A. Williams, The Knight and the Blast Furnace, Brill, Leiden (2003).
[2] F. Grazzi, et al., J. Anal. At. Spectrom. 26, 1030 (2011)
[3] F. Grazzi, et al., Anal. Bioanal. Chem. 400,1493 (2011).
[4] F. Grazzi, et al., Mater. Sci. Forum 65, 167 (2010).
[5] F. Grazzi, et al., La Metall. Italiana, 5/2011, 13 (2011).
[6] T. Absolon, The Watanabe Art Museum Samurai Armour Collection
(Kabuto & Mengu, Volume I), Toraba (2011)
[7] K. Sakakibara, The manufacture of armour and helmets in 16th century
Japan, Edo (1800), revised and edited by H. R. Robinson, The Holland Press,
London (1963).
[8] http://www.royalarmouries.org/what-we-do/research/analytical-projects/
metallurgy-of-japanese-plate-armour
[9] A. Fedrigo, et al., J. Anal. At. Spectrom., 28, 908-915 (2013)
[10] F. Salvemini, et al., The European Physical Journal Plus 128:87 (2013)
174
Consiglio Nazionale Delle Ricerche - Istituto Dei Sistemi Complessi,
Research, 50019, Sesto Fiorentino, IT
2
The Wallace Collection, Museum, W1u 3Bn, London, UK
3
Museo Stibbert, Museum, 50134, Firenze, IT
4
STFC-ISIS, Research, OX11 0QX, Didcot, UK
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Christine Bläuer1 - Anja Diekamp2 - Jürg Gol3
Yongfeng Hu4 - Josef Hormes5
CSC Conservation Science Consulting Sarl, Fribourg, Switzerland
Institute for Structural Engineering and Material Sciences, Department
of Engineering Science, University of Innsbruck, Innsbruck, Austria
3
Bauhütte, Archäologie, Kloster St. Johann, Müstair, Switzerland
4
Canadian Light Source Inc., Saskatoon, Saskatchewan, Canada
5
Center for Advanced Microstructures and Devices (CAMD), Louisiana State
University, Baton Rouge, USA
1
Mortar samples
from the Abbey of
Saint John at Müstair:
a combined spatially
resolved X-ray
fluorescence and X-ray
absorption (XANES)
study
2
Mortar is a very challenging system for any type of “chemical/
mineralogical” analysis because of its composition from a
broad range of crystalline - and sometimes non-crystallinecompounds with a broad size distribution. Thus, hardly
any synchrotron radiation based experiments have been
reported on the analysis of mortar. For this preliminary study three mortar samples have been investigated from the
Abbey of Saint John, in the Swiss village of Müstair (UNESCO
World Heritage Site since 1983). This abbey was established
ca. 780 and there was basically just one major alteration
when about 1500 the abbey church was modified from a
single-nave Carolingian construction into a three-nave late
Gothic church. Two samples were taken from Carolingian
plaster and the third one from a late Gothic plaster. All three
samples were prepared as microsections and embedded into
a synthetic resin (Araldite 2020). The samples were pre-characterized by one of the authors (Ch.B.) using polarization
microscopy and some standard wet chemical procedures
for determining in an indirect way the various chemical
compounds in the samples. These experiments indicated,
for example, differences between the samples from the
different periods in the composition of the binder materials
(hydraulic components in the Carolingian samples, pure
Dolomite for the Gothic sample) as well as in the composition of the aggregates.
Synchrotron radiation based spatially resolved X-ray fluorescence (XRF) and X-ray absorption near edge structure (XANES)
experiments were carried out at the SXRMB beamline of the
Canadian Light Source covering the energy range between 1.7
and ~10 KeV with a spatial resolution of about 300 × 300 μm2.
Fluorescence was excited with a monochromatic X-ray beam
of 9 keV. For each sample fluorescence spectra for at least
26 different positions were recorded. As expected the main
elements that are detected at all positions with strongly
varying intensity ratios are Si, Ca, and Fe. Additional “ trace ”elements are, for example, P, S, K, and Ti. For the determination
of the speciation of the elements K-XANES spectra of Ca and
Fe were recorded at a few selected points of the samples:
at some “ dark ” spots and at some “ white ” spots – most likely
limepops. The analysis of the Ca-K-XANES spectra shows that
Ca exists in all samples mainly in the form of Calcite; however with significant contributions of other chemical forms.
The Fe-K-XANES spectra are different in the white and the
dark spots indicating a lower valency of Fe in the limepops.
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Alexandria Hunt1 - Barbara Stuart1 - Paul Thomas1
Daniel James2 - Bruno David2 - Jean-Michel Geneste3
Jean-Jacques Delannoy4
The characterisation
of Jawoyn rock art
paintings in Arnhem
Land, Australia using
synchrotron infrared
microspectroscopy
1
In 2006 remote rock art sites of the Jawoyn people in the Northern Territory of Australia were rediscovered during an aerial survey of the Arnhem Land plateau. Subsequently, more than 4000
rock art sites have been rediscovered, including the spectacular
Nawarla Gabarnmang site, which dates back 45000 years making
it one of the earliest human occupation sites in Australia [1,2].
The art at the sites depicts a history of the culture of the Jawoyn
people, contain paintings of different generations and illustrate
an array of pigment types. In 2010 an international team of archaeologists were invited to document these extraordinary sites.
The current project is a study of rock art at one of the Jawoyn
sites being documented known as ‘Little Barra’. The site
contains a range of pigment types, with ochre colours ranging
from reds to yellows, and with white and black pigments also
being observed. Ochre is an important component of paint
used in traditional, as well as modern, Australian indigenous art.
This mineral-based material is mined from particular sites and
is coloured by iron oxides. The source material was extensively
traded across Australia in the past and it has been established
that the chemical composition of ochres is dependent on the
source [3,4]. A series of small paint specimens were collected
from the Little Barra site representing different colour types
and ages.
An investigation of the specimens using synchrotron infrared
microscopy was carried out at the Australian Synchrotron in
Melbourne, Australia. The study provides an understanding
of the composition of the paints used at the Little Barra site.
Synchrotron FTIR microspectroscopy has enabled the minute
samples to be examined in compression transmission mode,
thus avoiding the need to embed the specimens. Mapping
of the samples has been carried out to provide information
about the nature of both inorganic and organic components
in the paint specimens. An in-depth understanding of the
chemistry of the pigments is combined with archaeological
information to build a clearer picture of the social practices
of the Jawoyn people.
Bibliography
[1] B. David, B. Barker, F. Petchey, J.J. Delannoy, J.M. Geneste, C. Rowe,
M. Ecceleston and L. Lamb, ‘A 28,000 year old excavated painted rock
from Nawarla Gabarnmang, northern Australia’, Journal of Archaeological
Science 40, 2493-2501 (2013).
[2] R.G. Gunn, R.L. Whear and L.C. Douglas, ‘Dating the present at Nawarla
Garbarnmang: Time and function in the art of a major Jawoyn rock art
and occupation site in western Arnhem Land’, Australian Archaeology 75,
55-65 (2012).
[3] D.C. Creagh and V. Otieno-Alego, ‘The use of radiation for the study
of material of cultural heritage significance’, Nuclear Instruments and
Methods in Physics Research Section B: Beam Interactions with Materials
and Atoms 213, 670-676 (2004).
[4] P.M. O’Neill, D.C. Creagh and M. Sterns, ‘Studies of the composition
of pigments used traditionally in Australian Aboriginal bark paintings’,
Radiation Physics and Chemistry 71, 841-842 (2004).
176
University of Technology, Sydney, School of Chemistry and Forensic
Science, 2007, Sydney, Australia
2
Monash University, School of Geography and Environmental Science, 3800,
Clayton, Australia
3
Université de Bordeaux 1, Centre National de Préhistoire, 24000, Périgueux, France
4
Université de Savoie/CNRS, Laboratoire EDYTEM, 73376, Le Burget du Lac, France
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Mark Jones1 - Andy Smith2 - Kevin Clancy3
Winfried Kockelmann4
Mary Rose Trust, College Road, PO1 3LX, Portsmouth, UK
STFC Daresbury Laboratory, Keckwick Lane, WA4 4AD, Warrington, UK
3
The Royal Mint, Llantrisant, CF72 8YT, Pontyclun, UK
4
STFC Rutherford Appleton Laboratory, Harwell, OX11 0QX, Didcot, UK
1
The minting of gold
coins in Tudor England
explored by neutron
diffraction
2
Henry VIII of England’s flagship, the Mary Rose, was lost in
action in 1545. Amongst the 19,000 historical artefacts recovered from the wreck of the ship when she was raised in
1982 were 29 gold coins. These coins came from the personal
effects of the officers of the ship and were minted under four
different monarchs of Tudor England. The minting process is
known to have changed during the reign of Henry VIII and
the coins of the Mary Rose reflect this development.
This technique has been applied previously to show variations employed in historical minting processes by providing
information on the orientation of the metal crystallites in
the bulk of a coin and we report here its application to the
minting of gold coins in Tudor England as evidenced in the
collection from the Mary Rose. To confirm the details of the
Tudor minting processes we also had a selection of replicas
made using techniques based on written contemporary
accounts and compare neutron diffraction patterns from
these with those obtained from the historical coins. Finally,
our study was expanded to include an analysis of other historical coinage minted using later technologies.
Texture analysis by neutron diffraction data is non-destructive and reveals changes in the microcrystalline structure of
metals related to the mechanical processes used in forging.
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György Kali1 - Eszter Horvath1 - Zsuzsanna Siklosi2
Maria Bondar3 - Viktoria Kiss3
Wigner Research Centre for Physics, Hungarian Academy of Sciences, Konkoly
Thege Miklós út 29-33., 1121, Budapest, Hungary
2
Institute of Archaeological Sciences, Faculty of Humanities, Eötvös Loránd
University Budapest, Múzeum körút 4/B, 1088, Budapest, Hungary
3
Institute of Archaeology, Center for the Humanities, Hungarian Academy
of Sciences, Úri utca 49., 1014, Budapest, Hungary
1
Non-destructive
and non-invasive
archaeometallurgical
investigation
on Copper age
artefacts from
the Carpathian Basin
Humankind’s earliest metalworking activities can be traced
from the Neolithic. In this period the first wrought metal was
still used to make ornaments only. Metal articles for further use
(personal/utilitarian) appeared in large quantities in the Early
Copper Age also in the territory of present-day Hungary [1].
Copper artefacts of the Carpathian Basin were probably
made of South-Eastern European raw materials. Due to their
geographical location Copper Age communities in the Carpathian Basin played a principal role in the social network of
the South-Eastern and Central European cultural complexes.
The meeting point of these two “ worlds ” is located in the
present-day Hungary. As a consequence, in order to be
able to reconstruct European prehistory understanding the
Hungarian Copper Age is essential.
Bibliography
[1] N. Kalicz: Die terminologischen und chronologischen Probleme der
Kupfer- und Bronzezeit in Ungarn. In: A. Aspes (ed.), Il passaggio dal
Neolitico all’età del Bronzo nell’Europa Centrale e nella regione Alpina,
Problemi cronologici e terminologici, Atti del X Simposio Internazionale
sulla fine del Neolitico e gli inizi dell’età del Bronzo in Europa. Verona 1980,
117-137.
[2] P. Raczky, Zs. Siklósi: Reconsideration of the Copper Age Chronology
of the Eastern Carpathian Basin: a Bayesian Approach. Antiquity 87/336
(2013) 555-573.
[3] J. Banner: Die Péceler Kultur. Archaeologia Hungarica 35. Budapest 1956.
[4] G. Artoli: Chrystallographic Texture Analysis of Archaeological Metals:
Interpretation of Manufacturing Techniques. Applied Physics A 98 (2007)
899-908.
[5] M. Mödlinger, P. Piccardo, Zs. Kasztovszky, I. Kovács, Z. Szőkefalvi-Nagy,
Gy. Káli, V. Szilágyi: Archaeometallurgical Characterization of the Earliest
European Metal Helmets. Materials Characterization 79. (2013) 22-36.
178
In this study we present the non-destructive and non-invasive
archaeometallurgical investigation of three copper objects from
the Copper Age Carpathian Basin. Two of them, a massive bracelet and an axe-adze were unearthed in Rákóczifalva-Bagi-föld.
This Middle Copper Age archaeological site (4300-4000 cal BC)
is of great importance, since its AMS dating pointed out that the
appearance of heavy copper tools can be dated far earlier than it
had been supposed [2]. The third artefact, the absolutely unique
diadem from Vörs is among the most important metal finds from
the Late Copper Age (3500-3000 cal BC) [3]. The non-destructive
and non-invasive character of our investigation was especially
indispensable in this case.
Our research had two main objectives: 1) to deepen our
knowledge about the Copper Age metalworking activity by
identifying the manufacturing technique of the artefacts;
2) to determine the use value of the objects studying their
function and supposed utility.
In case of metals, the traces of the past mechanical (hammering, drawing) or thermal (casting, annealing) treatment or
even the combination of these two processes are reserved in
the crystallographic texture and microstructure. These features
can be observed and analysed on the diffraction pattern [4, 5].
In order to reconstruct the metallurgical processes and to provide evidences for or against the utility of the copper objects,
it was necessary to analyse the microstructure of their metal
phases. Time-of-flight neutron diffraction analysis (TOF-ND)
applied in our study proved to be an appropriate and successful
method to characterise the phase composition, texture, stress
and microstructure of the artefacts without any sampling and
special treatment of the objects.
As a result of the TOF-ND measurements manufacturing process of the investigated artefacts could be reconstructed as a
workflow. In case of the axe-adze, also traces of the intentional
and conscious increase of the use value could be identified.
It could be revealed that the base material of this tool has been
hardened and annealed after the casting process, thus the axe
has gained a special edge on its surface.
P-77
Vert/Green
10 sept. 2014 17:00 > 20:00
Gloria Molia1 - Roberta Difebo2 - Judit Molera3
Trinitat Pradell1
Universitat Politècnica de Catalunya, Departament de Física i Enginyeria
Nuclear, 08860, Castelldefels, Spain
2
Universitat de Barcelona, Dept. de Prehistòria, Història Antiga i Arqueologia,
08001, Barcelona, Spain
3
Universitat de Vic-Universitat Central de Catalunya, Escola Politècnica
Superior, 08500, Vic, Spain
1
Manganese
compounds in historical
glazes
Manganese oxides were to produce black decorations on
glazes since ancient times. For a long time manganese was
thought being dissolved in the glaze, and not much effort was
dedicated to the study of manganese decorations. However,
recent studies1 have demonstrated the presence of several
manganese compounds in historical black decorations such as,
kentrolite (Pb2Mn3+2Si2O9), bustamite ((Ca2+,Mn2+)Si2O6), braunite (Mn2+Mn3+6(O8)SiO4), haussmanite (Mn2+Mn3+2O4), among
other. Their nature and presence/absence seems related to the
materials and processes followed in their production (firing
conditions, raw materials, method of application, etc.). For this
reason, a set of replication experiments was designed to learn
about how the compounds found are related to the technology (methods of application, firing temperature, pigment
and glaze composition, etc.), and also to their appearance
and conservation state of the manganese based decorations
in the historical samples.
Overglaze and underglaze applications of different manganese compounds over a lead glaze and fired at temperatures between 875ºC and 1000ºC are analysed by means
of optical microscopy, Scanning Electron Microscopy (SEM),
Synchrotron radiation micro-XRD and Raman spectroscopy.
SEM-EDX of polished cross sections of the samples gives information about the chemical composition and microstructure
of the crystallites; in particular the morphology, size and distribution of the crystallites. Synchrotron radiation micro-XRD on
thin cross sections of the glazes gives also information about
the nature and crystalline structure of the compounds; this
is particularly important to distinguish between the various
manganese oxides (bixbite, haussmanite). Moreover, the small
size and low contrast typical of those compounds formed
by elements of low atomic weight also strongly limits their
identification by SEM. The advantage of synchrotron light
is the high brilliancy, micrometric spot size, high resolution.
Bibliography
[1] J. Molera, J. Coll, A. Labrador, T. Pradell, Manganese brown decorations in
10th to 18th century Spanish tin glazed ceramics, Applied Clay Science 82
(2013) 86–90
179
P-78
Vert/Green
10 sept. 2014 17:00 > 20:00
Lothar Lambacher1 - Martin Radtke2 - Jessica F. Curado2
Heinrich Riesemeier2 - Jochem Wolters3 - Ina Reiche4,5
Staatliche Museen zu Berlin, Kunstgewerbemuseum, 10785, Berlin, Germany
Bundesanstalt Für Materialforschung und -prüfung, Bamline, 12205,
Berlin, Germany
3
Former Director, Gold Smith School, 75175, Pforzheim, Germany
4
Staatliche Museen Zu Berlin, Rathgen-Forschungslabor, 14059, Berlin, Germany
5
Laboratoire d’Archéologie Moléculaire et Structurale, UPMC - UMR 8220
CNRS, 75005, Paris, France
1
Non-destructive
Synchrotron XRF
analyses of the so-called
“ Gisela gold jewellery ”
(end of the 10th c. AD)
2
The Gisela jewellery is the most important complex of profane jewellery from the Ottonian period originated from
Western Germany (Mainz?), and is dating from the end of
the 10th century AD, that’s common research view [1,3]. But
a lot of questions are not yet answered, for example: How
and why these different objects have been assembled in the
19th c.? To answer these questions it is necessary to know,
whether the jewellery was worked as a real ensemble from
the beginning or not. The determination of the metal alloys
and the significant contents of major and minor elements
permit to establish an objective criterion to group or distinguish several objects of the treasury. This analytical criterion
gives very valuable information for the interpretation of the
origin of this exceptional find that cannot be gained from
archaeological and technological observations alone.
The main aim of the experiment was the determination
of the major, selected minor and trace elements (Ag, Cu,
Sn, Pb) of the twenty golden objects and, by the precise
description of the metal alloys, to argue for or against an
either simultaneous or different processing of the jewellery.
The objects are an outstanding example for the use of me-
dieval techniques. To evaluate the old joining techniques
properly, the composition of the solder were another important point of interest.
Concerning the Gisela pieces, an extensive microscopic
investigation was already carried out [4,5]. The Synchrotron-induced X-ray fluorescence analyses (Sy-XRF) were
thus undertaken on determined, most interesting areas on
the objects. We used the hard X-ray synchrotron beamline
(BAMline) operated by the BAM to determine major, minor
and trace element contents in the different treasury objects
by Sy-XRF. The special performances of the radiation obtained at the BAMline (hard X-rays) allow optimal analysis
of gold objects. At the BAMline, X-rays are produced by a
super conducting wavelength shifter (WLS) with a maximum field of 7 Tesla. For XRF measurements of the major
and minor gold elements, a W/Si Double-Multilayer-Monochromator (DMM) was used to produce an X-ray beam with
an energy of 35 or 40 keV. The gold objects were mounted
in air in a sample frame on a motorized xyz-stage with an
angle of 45° to the X-ray beam. Fluorescence signals were
collected at 90° with respect to the incident beam by a
semiconductor detector covered with selective filters.
A focussed beam with maximum spot sizes of about 100
micrometer is necessary for discrimination between different
parts of the gold jewels. The analysed points on the objects
were selected with the help of a long distance microscope.
The analytical results obtained on the different gold pieces
of the treasury will be compared in this presentation in order
to clarify their origin.
Bibliography
[1] Otto von Falke: Der Mainzer Goldschmuck der Kaiserin Gisela, Berlin 1913.
[2] Mechthild Schulze-Dörrlamm: Der Mainzer Schatz der Keiserin Agnes.
Neue Untersuchungen zum sogenannten «Gisela-Schmuck»
(Römisch-Germanisches Zentralmuseum, Monographien, 24),
Sigmaringen 1991.
[3] Amtje Krug: Der sogenannte «Mainzer Goldschmuck der Kaiserin Gisela».
1. Fundgeschichte und Erwerb, in: Jahrbuch der Berliner Museen 41,
1999, 7-24.
[4] Sybille E. Eckenfels-Kunst, Goldemails, Untersuchungen zu ottonischen
und frühsalischen, Goldzellenschmelzen, Berlin 2008.
[5] Jochem Wolters, Goldschmiedetechnische Beobachtungen am sogen.
«Giselaschmuck», Ms. 2009.
180
P-79
Violet/Purple
10 sept. 2014 17:00 > 20:00
Jessica Curado1 - Marcia Rizzutto1 - Martin Radtke2
Günter Buzanich2 - Uwe Reinholz2 - Heinrich Riesemeier2
1
University of São Paulo, 05508-090, São Paulo, Brazil
BAM Federal Institute for Materials Research and Testing, 12489, Berlin, Germany
Characterization
of emeralds from
Brazil and Colombia
using µ-SRXRF technique
2
Emerald is one of the most important precious stone and
one of the most imitated gems. Their purity, in terms of
mineral inclusions, is one of the factors that determine its
commercial value and also serve as proof of its veracity.
The green color is associated with the presence of minority
elements like chromium, iron, and in some cases vanadium.
The identification and quantification of these elements allows the determination of their region of provenance.
Nowadays, Brazil is the largest producer of Emeralds but the most
valuable and beautiful gems are found in Colombia. The aim of
the present study is therefore to characterize emeralds from different mines of Brazil and Colombia by using Synchrotron Radiation
X-ray Fluorescence Microanalysis (µ-SRXRF). The advantage of this
technique is that the micro beam allows us to select a homogeneous, inclusion free area of the stone to distinguish the elemental
fingerprint according to the provenance of the emerald.
181
P-80
Violet/Purple
10 sept. 2014 17:00 > 20:00
Messaoud Harfouche1
1
SESAME, Synchrotron, 19252, Allan, Jordan
SESAME: a synchrotron
facility offering
advanced tools for
cultural heritage studies
in the Middle East
Synchrotron radiation has become a powerful tool for
studying unique ancient artefacts in cultural heritage such
as works of art and fossils. It has been shown, so far, that
it is possible to obtain information about the chemical
state and local composition of analyzed objects, and to
identify chemical elements that are harmful to them using
synchrotron-based techniques such as X-ray absorption
spectroscopy (XAS).
BASEMA is a hard X-rays beamline, which will be constructed
at Synchrotron-light for Experimental Science and Applications in the Middle East (SESAME) [1]. This beamline is opti-
Bibliography
[1] http://www.sesame.org.jo
182
mized for X-ray spectroscopic studies in all fields of science
and we expect a large demand from the cultural heritage
users’ community due to the wide research topics in the
Middle-East region on different cultural heritage branches.
The XRF/XAFS beamline at SESAME is designed as an analytical facility dedicated to synchrotron-based X-ray absorption
spectroscopy (XAS) and X-ray fluorescence (XRF). Further,
a rudimentary diffraction setup can be implemented.
All three X-ray techniques represent key analytical methods
in environmental sciences, life sciences, cultural heritage,
as well as in a broad range of industrial applications.
P-81
Violet/Purple
10 sept. 2014 17:00 > 20:00
Giuseppina Padeletti1 - Maria Pia Casaletto2
Alessandro Longo3 - Luca Olivi4
CNR, ISMN, 00016, Monterotondo, Italy
CNR, ISMN, 90146, Palermo, Italy
3
ESRF, EXAFS station, 38000, Grenoble, France
4
Elettra Sincrotrone Trieste, Beamline stectroscopy//scattering, 34149,
Basovizza, Italy
1
Further investigation
of lustre-decorated
majolicas by using
X-ray absorption
spectroscopy
2
Lustre is characterised by a heterogeneous metal–glass nanocomposite film, some hundreds nanometers thick. Silver and
copper nanoparticles are dispersed within the outer layers of
the glaze, conferring to the whole materials peculiar optical
properties. In spite of recent studies [1-4], many questions
regarding the chemical composition, the mechanism of metal
reduction and the optical properties of lustre remain still open.
Synchrotron radiation techniques are suitable for detailed studies
on metal-glass nanocomposites [5-6]. For example, X-ray absorption fine structure spectroscopy (EXAFS) can provide useful
information on oxidized phases or atomic clusters dispersed in an
amorphous medium, otherwise not achievable with diffraction
techniques. As reported in previous studies [1-3], the Italian production of lustre-decorated majolicas can be discriminate from
the Hispano-Moresque or Islamic ones by using the different
chemical composition and, in particular, the presence of bismuth
in the form of cosalite (Pb2Bi2S5) in lustred majolicas produced
during the Renaissance period in Central Italy. The presence of
this phase was investigatedd by XRD and successively confirmed
by elemental analysis with ETAAS.
By using X-ray Absorption Spectroscopy we intend to investigate the Bi L3-edge to shed light into the bismuth chemical
speciation and how this is influences by the presence of
other metals such as lead and sulphur. In Furthermore we try
to get information on the chemical state and local environment of metal atoms in the glaze in order to achieve a better
understanding of the mechanism of reduction of different
metals and the manufacturing techniques corresponding
to different productions (Islamic, Hispano–Moorish or Italian
Renaissance lustred majolicas).
Bibliography
[1] G. Padeletti, P. Fermo, Appl. Phys. A 77, 125 (2003)
[2] G. Padeletti, P. Fermo, Appl. Phys. A 79, 277 (2004)
[3] G. Padeletti, P. Fermo. Appl. Phys. A 113, 825 (2013)
[4] S. Padovan, D. Puzzovio, C. Sada, P. Mazzoldi, I. Borgia, A. Sgamellotti,
B.G. Brunetti, L. Cartechini, F. D’Acapito, C. Maurizio, F. Shokoui, P. Oliaiy,
J. Rahighi, M. Lamehi-Rachti, E. Pantos, Appl. Phys. A 83, 521 (2006)
[5] F. Gonella, P. Mazzoldi, Handbook of Nanostructured Materials
and Nanotechnology, Vol. 4, ed. by H.S. Nalwa (Academic, San Diego, 2000)
[6] U. Kreibig, M. Vollmer, Optical properties of Metal Clusters
(Springer, Berlin, 1995)
183
P-82
Violet/Purple
10 sept. 2014 17:00 > 20:00
Thiago S. Puglieri1 - Dalva L.A. de Faria1
1
University of São Paulo, Department of Chemistry, 05.508-000, São Paulo, Brazil
Strategies
and challenges
on metal corrosion
products
characterization
Cultural heritage objects can degrade as any other material,
however, they cannot be replaced because of its cultural
relevance. Preventive conservation strategies are essential
for its preservation and, for the proposition of new or for
the reassessment of the existent ones, a comprehensive
characterization of artworks and their degradation products
is necessary, as well as investigations to understand the
mechanisms of the materials degradation, including synergic
effects. Since 2006, when participating in the SENSORGAN
project, [1] our group is interested in the investigation of Pb
corrosion [2-3] aiming the enlargement of the understanding
on their mechanisms and also the development of new
technologies [4-5] for preventive conservation.
We are mainly focused on the effect of indoor pollutants,
particularly formaldehyde, an insidious organic compound.
[2-3,6-9] Studies of formaldehyde action on Pb reports different controlled ageing conditions, with controversial results,
including the chemical composition of the corrosion layer.
Bibliography
[1] http://goart.gu.se/cgi-bin/senslev1/sensorgan.taf, last accessed
in April 15 2014.
[2] de Faria, D. L. A.; Cavicchioli, A.; Puglieri, T. S. Vib. Spectrosc., 54: 159-163,
2010.
[3] Puglieri, T. S.; de Faria, D. L. A.; Cavicchioli, A. Vib. Spectrosc., 71:24-29, 2014.
[4] Neves, C. A. et al. Sens. Actuators, B, 131:462-469, 2008.
[5] Cavicchioli, A.; de Faria, D. L. A. Sens. Actuators, B, 115:656-665, 2006.
[6] Raychaudhuri, M. R. and Brimblecombe, P. Stud. Conserv., 45:226-232, 2000.
[7] Tetreault, J. et al. Stud. Conserv., 48:237-250, 2003.
[8] Eremin, K. Carbonyl Pollutants: A Museum Perspective, 1998.
http://iaq.dk/iap/iap1998/1998_13.htm, last accessed in April 15 2014.
[9] Bradley, S.; Thickett, D. The Pollutant Problem in Perspective, 1998.
http://iaq.dk/iap/iap1998/1998_05.htm, last accessed in April 15 2014.
[10] de Faria, D. L. A.; Puglieri, T. S.; Souza, L. A. C. J. Braz. Chem. Soc.,
28:1345-1350, 2013.
[11] Grayburn, R. et al. Corros. Sci., 82:280–289, 2014.
184
The reasons for such behavior may lay in the fact that different experimental setups were used, as well as different
characterization techniques, which may not be sensitive to
the same compounds. For example, ordinary XRD probes
large areas on the samples and is sensitive to long range
arrangements, while Raman microscopy is a short range
technique probing areas as small as 1 µm 2. In such a
context, a comprehensive characterization of the corrosion
compounds necessarily demands a significant number of
complimentary techniques.
We have also analyzed corroded artworks from museums [10]
and exposed metal coupons at churches and museums to
explore how hazardous the environment was and although
the experience was successful when the corrosion products
were present in large amounts, it was difficult to characterize
thin layers. Ag, Cu and Pb coupons exposed during 3 months
were analyzed by µ-Raman (532, 632.8, 785 and 1064 nm), XRD
with grazing angle and µ-FTIR but only oxides were identified,
although characteristic bands of sulfates and carbonates were
detected. Electrochemical reduction could be employed but
it does not allow a specific molecular identification and it is
an invasive and destructive technique.
In situations like ours, the use of synchrotron-based techniques
appear as an appealing option due to the much higher radiation throughput that, consequently, enhances the chance of a
successful use of the µ-FTIR and µ-XRD techniques, as well as
other X-ray based techniques (XANES and EXAFS, e.g.).
Considering the above presented comments, although we
are not a current user of synchrotron-based techniques,
we can envisage the importance of such multi-technique
facility in the chemical characterization of systems like ours.
In fact, synchrotron radiation is being successfully applied to
similar problems [11] justifying our interest in enlarging our
knowledge on its potentiality in cultural heritage investigation.
P-83
Violet/Purple
10 sept. 2014 17:00 > 20:00
Herman Winick1
1
Light Source, 94025 Menlo Park, USA
SESAME - a synchrotron
light source
in the Middle East
Developed under the auspices of UNESCO & closely modeled on CERN, SESAME (Synchrotron-light for Experimental
Science & Applications in the Middle East) is an intergovernmental research center now completing a synchrotron
light source in Jordan, scheduled for first operation at the
end of 2015. It will enable world-class research by scientists
from the Middle East/neighboring countries, preventing or
reversing the brain drain. It will also build bridges between
diverse societies, contributing to a culture of peace through
international cooperation in science. It is anticipated that a
major activity at SESAME will be studies relating to human
heritage, including art & archaeology. SESAME is already
being viewed as a model project for Africa & other regions.
The centerpiece of SESAME is a new 2.5 GeV 3rd Generation Electron Storage Ring/Light Source (133.2 m circumference, 26 nm-rad emittance, 12 places for insertion
devices), which will provide very intense light from infra-red
to hard X-rays for a wide range of basic & applied studies (e.g.
regional biomedical & environmental issues, local archaeological objects). SESAME offers excellent opportunities to
train local scientists & attract those working abroad to return.
The project is governed by a Council which meets twice yearly
& presently has 9 Members (Bahrain, Cyprus, Egypt, Iran, Israel,
Jordan, Pakistan, Palestinian Authority, & Turkey). Members have
collective responsibility for the project & provide the annual
operations budget (~$3.7 million in 2014, expected to rise to
$(5.7-8.5) million when research starts in 2016). Jordan provided
the site, building, & infrastructure. A staff of 35 is now installing
the greatly refurbished 0.8 GeV BESSY I injector system, a gift
from Germany, including a pre-injector 22 MeV microtron which
began operation in 2009. The facility will have the capacity to
serve 25 or more simultaneous experiments. Seven Phase I
beamlines are planned; on day-one, four of them will be operational. These are beam lines optimized for protein crystallography, X-ray absorption fine structure and fluorescence, infra-red,
and materials science.
A training program on accelerator technology, beamlines,
& scientific applications, has been underway since 2000,
funded by the International Atomic Energy Agency (IAEA),
the Abdus Salam International Centre for Theoretical Physics
(ICTP), the Japanese Society for the Promotion of Science
(JSPS), the Portuguese Foundation for Science & Technology
(FCT), the US Department of Energy, & fellowships provided
by light sources around the world. Over 1000 scientists from
the region have benefited from SESAME training activities.
The laboratory is managed by a Director, together with Scientific, Technical & Administrative Directors. Three committees
advise the Council & work with the staff on the technical
design, beamlines, & scientific and training programs.
See www.sesame.org.jo
Bibliography
[1] http://www.sciencediplomacy.org/perspective/2012/synchrotron-lightand-middle-east
185
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195
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199
PARTNERS / PARTENAIRES
PARTNERS
PARTENAIRES
We thank the teams without which this Conference would not have been possible
Merci aux équipes sans qui cette conférence n’aurait pu avoir lieu
We also thank our partners for their continuous support
Nous remercions également pour leur soutien
200
COMMITTEES
COMITÉS
INTERNATIONAL SR2A SCIENTIFIC COMMITTEE
COMITÉ SCIENTIFIQUE INTERNATIONAL DU SR2A-2014
Annemie Adriaens, Chemistry Department, Ghent University, Belgium
Loïc Bertrand, IPANEMA, Saint-Aubin, France
Joris Dik, TU Delft, The Netherlands
Koen Janssens, Chemistry Department, University of Antwerp, Belgium
Apurva Metha, Stanford University, USA
Jennifer Mass, Winterthur Museum, USA
Martin Radtke, BAM Federal Institute for Materials Research and Testing, Berlin, Germany
Ina Reiche, LAMS, Ivry-sur-Seine, France and Rathgen-Foschungslabor Berlin, Germany
Jean Susini, ESRF, Grenoble, France
Josefina Pérez-Arantegui, Universidad de Zaragoza, Spain
Robert van Langh, Rijksmuseum Amsterdam, The Netherlands
SR2A-2014 LOCAL ORGANIZING COMMITTEE
COMITÉ LOCAL D’ORGANISATION DU SR2A-2014
Loïc Bertrand, Regina Oprandi, IPANEMA, Saint-Aubin
François Mirambet, C2RMF, Paris
Marie-Claire Le Bourdellès, Musée du Louvre, Paris
Philippe Walter, LAMS, Ivry-sur-Seine
Ina Reiche, LAMS, Ivry-sur-Seine, France and Rathgen-Foschungslabor Berlin, Germany
Philippe Dillmann, LAPA, Saclay
Marie-Angélique Languille, Claudine Loisel, CRC, Champs-sur-Marne / Paris
François Semah, Matthieu Lebon, MNHN Prehistory Department, Paris
Étienne Anheim, Stéphane Serfaty, PATRIMA
201
MUSÉE DU LOUVRE PLAN / PLAN DU MUSEE DU LOUVRE
MUSÉE DU LOUVRE PLAN
PLAN DU MUSÉE DU LOUVRE
-2 | Hall Napoléon (Under the Pyramid)
202
DENON WING
RICHELIEU WING
SULLY WING
- Islamic Art
- The East Mediterranean in the Roman Empire
- Italian and Spanish Paintings
- 19th-century French Paintings
- English Paintings
- Gallerie d’Apollon, the Diamants de la Couronne
jewelry collection
- Italian, Spanish and Northern European sculptures
- Greek, Etruscan, and Roman Antiquities
- Coptic Egypt
- Arts of Africa, Asia, Oceania and the Americas
- 14th-17th-century French Paintings
- German, Flemish and Dutch paintings
(Northern European schools)
- Decorative arts (Middle Ages, Renaissance,
17th and 19th centuries)
- Napoleon III apartments
- French sculptures
- Mesopotamia and ancient Iran
- 17th, 18th, 19th-century French Paintings
- 17th, 18th and 19th-century Drawings and pastels
- 17th, 18th-century Decorative arts
- Greek, Etruscan, and Roman Antiquities
- Pharaonic Egypt
- Ancient Iran, Arabia and the Levant
- History of the Louvre and Medieval Louvre
MUSÉE DU LOUVRE PLAN / PLAN DU MUSEE DU LOUVRE
Admission to the Conference
Welcome Reception - C2RMF
203
ITINERARY / ITINÉRAIRE
ITINERARY FROM THE MUSÉE DU LOUVRE
TO THE MUSÉE D’ORSAY
ITINÉRAIRE DU MUSÉE DU LOUVRE AU MUSÉE D’ORSAY
M
Tuileries
Anato
le Fra
M
nce
mon
nier
Quai
Tuile
r
ies
RER
M
al Le
i des
Invalides
Musée d'Orsay
Musée du Louvre
Assemblée Nationale
Pont
ac
M
Rue
du B
Solférino
M Varenne
Rue du Bac
M
Quai Fra
Roya
l
Quai
204
Palais Royal-Musée du Louvre
Géné
r
Qua
Av. d
u
M
Pont
Volta
ir
e
nçois M
du Ca
rrous
el
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d
PROCEEDINGS / ACTES
PROCEEDINGS
ACTES
Les contributions à la conférence seront publiées dans
un numéro spécial de la revue Journal of Analytical
Atomic Spectrometry (IF2013 : 3,2). Tous les intervenants
et les auteurs des posters sont fortement encouragés
à y contribuer. Une publication conjointe de toutes
les contributions à SR2A-2014 permettra de renforcer
la visibilité des recherches dans ce domaine et de promouvoir les applications futures des rayonnements
synchrotron et neutron pour l’art et l’archéologie.
Les manuscrits doivent être soumis par voie électronique via le site de soumission des manuscrits à JAAS
et doivent se conformer aux instructions aux auteurs
de JAAS. La même procédure d’examen que pour
les ar ticles soumis par la voie standard sera suivie par l’équipe de rédaction de JAAS. Les manuscrits
ne seront acceptés que s’ils sont conformes à la qualité et au
contour thématique requis pour leur publication dans le journal.
La date limite pour la soumission des manuscrits est le
15 octobre 2014.
Les articles seront en accès libre au téléchargement pendant
6 semaines à compter de leur publication.
Contributions to the Conference will be published in a Special
Issue of Journal of Analytical Atomic Spectrometry (IF2013:
3.2). All speakers and poster authors are strongly encouraged
to contribute to this special issue. A joint publication of all
contributions to SR2A 2014 will strengthen the visibility of this
research and promote future applications of synchrotron
and neutron methods for Art and Archaeology.
Manuscripts are to be submitted electronically via the JAAS
manuscript submission site and should comply to the
Instructions for Authors of JAAS. The same refereeing
procedure as for regularly submitted papers will be followed
by the JAAS editorial office. Papers will only be accepted
if they conform to the normal high standards and scope
required for publication in the journal.
The deadline for submission of proceedings is 15 October
2014.
Articles will be freely available to download for 6 weeks from
the date of publication.
205
AUTHOR INDEX
INDEX DES AUTEURS
P-
POSTERS
O-
ORALS / ORAUX
A
Added Nemitala
Adriaens Annemie
Agostino Angelo
Agresti Juri
Agyeman-Budu David
Albéric Marie
Albertin Fauzia
Aldred Martha
Bernardes Suene
P-53
O-09
P-02
P-60
P-23/30
O-32 P-13
O-19
P-56
Alfeld Matthias
O-01/18
P-12/37
Allegro Paula R. P.
Alonso-Mori Roberto
Alves Filipe
Ancelin Sébastien
Andreani Carla
Andrejkovičova Slavka
Angelici Debora
P-53
O-27
P-55
P-26/58
P-35
O-05
P-54
Anne Jennifer
O-27/29
P-24
Arias Pablo
Astolfo Alberto
O-19
P-37
Bertrand Loïc
Binet Laurent
Biro Katalin T.
Bleton Jean
Bloch Jean-Francis
Boistel Renaud
Bondar Maria
Boon Jaap J.
Borca Camelia
Bordet Pierre
Borghi Alessandro
Brinkman Don
Briois Valerie
Brunetti Antonio
Brunetti Brunetto G.
Buckley Barbara
Bugani Simone
Bulla Claudio
Burnstock Aviva
Buti Salvador
Buzanich Günter
B
Barata Carolina
Barbosa Marcia
Barden Holly
Barello Federico
Barzagli Elisa
Bastian Gilles
Bauchau Fanny
Baudelet François
Baumbach Tilo
Beaucour Jerome
Bellei Sara
Beltran Victoria
206
P-56
O-02/26
P-22/25/26
31/58/59
11
P-17
P-35/42
P-46
P-62
P-27
P-76
O-03 P-01
P-01
O-17
P-54
P-36
P-38
P-28/51
O-04
P-10
P-49
P-28
O-02 P-29
P-18
O-06
P-67/79
C
O-05
P-39
Cagno Simone
Calas Georges
Caldeira Ana Teresa
Calligaro Thomas
Campos Pedro H.O.V.
O-11
Candeias António
P-38
P-03/45/46
47
Capogrosso Valentina
Capriotti G.
Cardon C.
Cardoso Ana
Cartechini Laura
O-34 P-29
Carvalho Maria Luisa
P-07/08/46
50
Casaletto Maria Pia
P-81
P-53/56
O-29
P-02
O-10
O-39 P-34
P-70
P-29
P-18
Berenguer Felisa
O-36
P-25/26/58
Bergmann Uwe
O-13/25/27
P-06/24
P-14
O-11
P-07
P-39
P-56
P-60
P-70
P-03
P-29
Cato Eleanor
Ceccato Daniele
Cersoy Sophie
Cesaratto Anna
Chadwick Alan
Chalmin Émilie
Chen Kai
Choudhury Sanjukta
Cianchetta Ilaria
Cinque Gianfelice
Cinquin Bertrand
Civita Francesco
Clancy Kevin
Clemente Carme
Cochard Audrey
P-01
P-67
O-17
O-34 P-29
P-20
O-30
O-38
P-23/30
O-33
P-18
O-41 P-41
P-72
P-75
P-18
P-71
Cohen Serge X.
P-22/25/26
58
Constantinescu Bogdan
Cook Phil K.
Cooper David M. L.
Coria Rodolfo
Cormier Laurent
Corsi Jacopo
Costa Mario
Costa Sonia
Costa Emanuele
P-67
P-31
O-28 P-30
P-06
P-68
P-02/54
P-50
P-47
P-54
Cotte Marine
O-04/34/40
P-05/10/12
32
Coulthard Ian
O-28
P-23/30
Crabbé Amandine
Cruz Antonio João
Cubitt B.
O-21 P-19
Curado Jessica F.
P-53/56/78
79
O-05
P-70
D
Dallé Didier
Dararutana Pisutti
Dargaud Olivier
David Bruno
P-58
P-33
P-68
P-74
de Faria Dalva L. A.
de la Rie René
de Nolf Wout
de Palmas Anna
de Wolf Robin
Debastiani Rafaela
Degano Ilaria
Dejoie Catherine
Delannoy Jean-Jacques
Delmotte Aurélien
Dernovitcha S.
Deschamps Françoise
Dewhurst C.
di Martino Daniela
Dias Luis
Diekamp Anja
Difebo Roberta
Dik Joris
Dillmann Philippe
Domingos Sonia
Douin Joël
Dowsett Mark
Dufour Élise
P-82
O-36
O-18
P-28
Fischer Daniel A.
Foran Brendan
Fors Yvonne
Fratzl Peter
P-69
O-32
O-35
O-33
P-66
P-34
P-49
O-38
P-74
P-58
P-70
P-58
P-70
P-35
P-03
P-73
P-77
O-39
O-20/22
P-45
P-71
O-09
P-31
E
Edge David
O-10
Edwards Nicholas
O-25/27/29
P-06/24
Egerton Victoria
O-25/27/29
P-06/24
Ellis Tom
Erko Alexei
Eveno Myriam
P-36
P-40
P-39
G
Gabrieli Francesca
Gallias Jean-Louis
Gallo Lorenzo Mariano
Gay Marine
Geldof Muriel
Geneste Jean-Michel
George Graham N.
Gervais Claire
Gil Milene
Goidanich Sara
Gol Jürg
Gonzalez Victor
Gordon Robert A.
Gorini Giuseppe
Gourier Didier
Gourrier Aurélien
Grayburn Rosie
Grazzi Francesco
Grolimund Daniel
Grousset Sophie
Groutso I.
Grzesiak-Nowak Marta
Guériau Pierre
Guerra Maria Filomena
Guidotti Maria Cristina
Guimarães Ana G.
P-29
O-22
P-54
P-37
O-04
P-74
P-30
O-20 P-38
P-03
O-34
P-73
O-18 P-12
P-05/23/30
P-35
P-17
O-33
O-09
O-10
P-02/54/72
P-01
O-22
P-70
P-52/21
O-26 P-25
O-06 P-08
P-60
P-53
O-40
O-37
P-72
P-36
O-03 P-01
P-07
P-19
P-07
O-12 P-05
Hunault Myrtille
Hunt Alexandria
Hwu Yeukuang
P-44
O-17
P-36
P-04/73
P-76
P-12
P-73
P-65
P-40
O-12
P-05/10
O-11
P-74
O-19
I
Ignatyev Konstantin
Ito Masayoshi
O-27 P-24
P-63
J
Jacot-Guillarmod Mathieu
Jalilehvand Farideh
James Daniel
Jamme Frederic
Janssens Koen
Janvier Philippe
Jaye Cherno
Jones Mark
Jorge Maria Estrela
Joulie Sébastien
Juanhuix Jordi
Jurinovich Sandro
Justo A.
O-20
O-35
P-74
O-41 P-41
O-04/18/24
37
P-12/14/15
P-25
P-69
P-20/75
P-50
P-71
P-18
P-49
P-44
H
K
O-24 P-15
O-12
Hull Alyssa
P-27
P-39
F
Falkenberg Gerald
Farges François
Favero Patricia
Fayard Barbara
Fazinic Stjepko
Fedrigo Anna
Feng Renfei
Ferreira Ester S. B.
Ferreira Teresa
Feyer Vitaliy
Figueira Francisca
Finnefrock Adam
Herrel Anthony
Herrera L. K.
Hodeau Jean-Louis
Hoffemyer Ruth
Hormes Josef
Horvath Eszter
Howard Daryl
Hu Yongfeng
Huang Yuying
Hubert Axelle
Hajnal Andor
Hallin Emil
Harfouche Messaoud
Hasemi Hiroyuki
Helfen Lukas
Hellemans Kevin
Hendrickx Roel
Hendriks Ella
Hermans Joen
Herold Michel
P-42
P-23/30
P-80
P-64
O-39 P-27
O-37
O-03
O-04
O-02
O-11
Kaestner Anders
Kajiya Elizabeth A.m.
Kali György
Kamiyama Takashi
Kaplan Frederic
Kardjilov N.
Kasztovszky Zsolt
Kelleher Joe
Keune Katrien
O-03
P-56
P-76
O-07
O-19
P-60
P-02/42
P-72
O-02 P-42
207
Kharytanovitch Z.
Khaweerat Sasiphan
King Andrew
Kirkham Robin
Kiss Viktoria
Kiyanagi Yoshiaki
Kleine Markus
Klysubun Prapong
Klysubun Wantana
Kochman V.
Kockelmann Winfried
Kos Mateja
Kuczewski Anthony
Kunz Martin
P-70
O-07
P-25
O-12
P-76
O-07 P-64
P-04
P-65
P-47/65
P-70
P-35/75
Languille Marie-Angélique
Łasocha Wiesław
Lassalle Benedikt
Laval Éric
Le Gac Agnès
Le Hô Anne-Solenn
Leelamanotham Somdech
Lemelle Laurence
Lepper Verena
Li Weidong
Lin Ting
Liu Zhi
Lluveras-Tenorio Anna
Lo Giudice Alessandro
Loisel Claudine
Longelin Stéphane
Longo Alessandro
Lowe Tristan
Lubin-Germain Nadege
Luo Hongjie
Mahnke Heinz-Eberhard
Maley Jason
Malgosa Assumpcio
P-48
Manning Phillip
O-25/27/29
P-06/24
Manso Marta
Margaritondo Giorgio
Marincas Octaviana
Maroti Boglarka
Martinetto Pauline
Martinez-Criado G.
P-07/08/46
P-36
P-51
O-19
P-09
O-12/40
P-05/10
O-12
Mathia Thomas
Mathon Marie-Hélène
Matsen Catherine
McCreesh Natalie
McGlinchey Chris
Megens Luc
P-62
O-20
P-55
Mehta Apurva
P-71
O-12
O-29
O-36
O-04
O-32/38
P-05/10
Meirer Florian
Menu Michel
Mercere Pascal
Miguel Catarina
Miliani Costanza
Mille Benoit
Mirabaud Sigrid
Mirambet François
Mirão Jose
O-04 P-12
P-40
Mocuta Cristian
O-21
P-31/55
P-48
Moini Mehdi
Molera Judit
Molina Gloria
Monico Letizia
Moorhead Gareth
Moreno Thierry
Mottin Bruno
Mudronja Domagoj
Müller Katharina
Muñoz-Paez A.
Murcia Sonia
Murphy Reg
P-43
P-70
O-21
P-22/26/31
38
P-21
P-55
P-37
P-45/46/47
P-17
P-65
O-38
P-61
O-38
O-40
P-02/54
O-11
P-46
P-81
O-29 P-06
P-17
O-38
Madeira Teresa
Magalhães Ana G.
208
P-46
P-56
O-02
O-38
P-46
O-22
P-07
P-14
O
Odin Giliane
Oliveira Maria Ines
Olivi Luca
Olivier Jean-Marc
Olszewska-Swietlik Justyna
Oprandi Regina
Ormsby Bronwyn A.
Osticioli Iacopo
Özvegy Karoly
O-24 P-15
P-50
P-81
P-71
P-52
P-26
P-69
P-60
P-42
P-05/10
P-17/37/39
P-25
P-03
P-59
P-17
P-17
P-03
P-11
O-31 P-77
O-31
O-04 P-12
O-12
P-25/58
P-39
O-37
P
Padeletti Giuseppina
Patelli Alessandro
Peccenini Eva
Pereira Marco
Pereira Manuel
Perelli Cippo Enrico
Perez-Arantegui Josefina
Pessanha Sofia
Pestana Jose Antonio
Piga Giampaolo
Ploeger Rebecca
Polack François
Ponting Matthew
Pottash Carol
P-81
P-19
O-19
P-46
P-45/47
P-35
P-49
P-50
P-03
P-28/51
O-36
P-25/58
P-08
P-05
Pouyet Émeline
O-34/40
P-05/10/32
P-44
Pradell Trinitat
O-31
P-18/77
O-31
Prafulla Tarachand Janbade
Pratesi Giovanni
Price Campbell
Puglieri Thiago S.
P-16
P-13
O-28
N
M
O-11
P-44
Mass Jennifer
O-38
Newville Matthew
Noble Petria
Noe Laure
Nogueira Isabel
Noumowe Albert
Nunes Margarida
Nuyts Gert
P-02
O-17
P-43
L
L’ Hostis Valerie
Lagarde Pierre
Lah Tina
Lakiza V.
Nagashima Syota
Nagata Kazuhiro
Neff Delphine
O-07
Nevin Austin
O-34/40
P-29
P-63
O-20/22
P-54
O-29
P-82
Q
Quaroni Luca
P-01
R
Radtke Martin
O-34/40
P-10/32
Rafalska-Lasocha Alicja
Ratel-Ramond Nicolas
Ravaud Élisabeth
Re Alessandro
P-21/52
P-71
P-39
P-02/54
Réfrégiers Matthieu
O-41
P-41/59
Réguer Solenn
O-02/05/22
P-38/71/17
55
Reiche Ina
O-33
P-13/37/78
Reinholz Uwe
O-06
P-08/67/79
Reischig Peter
Relvas Catia
Rhodes Nigel
Ribechini Erika
Richards Vicki
Riesemeier Heinrich
Rizzutto Marcia A.
Robbiola Luc
Rocha Fernando
Rolland du Roscoat Sabine
Rollman Christopher
Rose Volker
Rosi Francesca
Rosta Laszlo
Rouchon Véronique
Roy Damien
Rozenbaum Olivier
Rudolf Sasa
Ryan Chris
O-39
P-07
P-35
P-49
O-35
O-06
P-13/78/79
P-53/56/79
P-59
O-05
P-62
P-11
O-08
P-29
P-57
O-24 P-15
P-55
O-20
P-43
O-12 P-12
S
Sa Sara
Salome M.
Salvado Nati
Salvemini Floriana
Sammynaiken Ramaswami
Sandrine Pagès-Camagna
Sandström Magnus
Sandt Christophe
Santoro Carlotta
Santos Joana
Sarangi Ritimukta
Sarkowicz Dominika
P-45/47
P-44
P-18
P-72
P-36
Saviello Daniela
Sawicka Alysia
Schalm Olivier
Scharf Oliver
Scherillo Antonella
Schiavon Nick
Schoeder Sebastian
Schofield Eleanor
Schooneveld Erik
Schreiner Manfred
Schroeder Sven L.M.
O-34/40
O-02
P-19
O-06
O-10
P-02/54/60
72
P-28
P-25/26/58
O-16 P-20
P-35
O-09
P-69
Sciau Philippe
O-15/38/40
P-71
Sellers William
O-25/27
P-06/24
Senesi Roberto
Séverin-Fabiani Tatiana
Shaw Ian
Shinohara Takenao
Shiota Yoshinori
Siano Salvatore
Siemiradzki Henryk
Siklosi Zsuzsanna
Silva Tiago F.
Silver Eric
Simionovici Alexandre
Simon Rolf
Smith Andy
Sokaras Dimosthenis
Sombunchoo Panidtha
Spring Marika
Stampanoni Marco
Stan Daniela
Staude Andreas
Storme Patrick
Stripe Benjamin
Stuart Barbara
Swanston Treena
Szczepanowska Hanna M.
Szekeres Ágnes
Szentmiklosi Laszlo
Szilagyi Veronika
Szmelter-Fausek Bozena
P-35
P-59
O-02
P-60
P-21
P-76
O-16
P-21
P-55
P-74
O-09
O-02/41
P-22/26/41
59
O-37
P-09
P-03
P-29
P-63
O-34
P-29/55/68
P-64
O-32
P-08
U
Uffelman Erich
P-10
P-53
P-61
P-40
P-34
P-75
P-24
P-65
P-22
O-19/23
P-67
P-13
P-19
O-08
P-74
O-28 P-30
P-62
P-42
P-02
P-42
P-52
T
Tafforeau Paul
Tamura Nobumichi
Tanaka Manako
Tibljas Darko
Timpu Daniel
Tobias Lucia
Tokarski Caroline
Tokugawa Maki
Toniolo Lucia
Trcera Nicolas
Tremsin Anton
Trentelman Karen
Troalen Lore
P-65
P-64
O-07 P-64
P-17
P-46
Thoury Mathieu
O-21 P-19
P-08
P-17
O-35
Terryn Herman
Thammajak Nirawat
Thiaudière Dominique
Thomas Paul
Thompson Paul
P-32
O-38
P-63/64
V
van de Voorde Lien
van den Berg Klaas Jan
van der Snickt Geert
van Dongen Bart
van Eslande Elsa
van Langh Robert
van Loon Annelies
van Veelen Arjen
Vandenabeele Peter
Vandendael Isabelle
P-66
O-02
O-04/18
O-29 P-06
O-17
O-14
O-02 P-05
O-27 P-24
P-66
O-21
Vanmeert Frederik
O-04/18/24
37
P-10/12/15
Vantelon Delphine
O-24
P-15/31/55
Varney Tamara
Vasilescu Angela
Vekemans Bart
Verger Louisiane
Verhaeven Eddy
Vezin Herve
Vicenzi Edward
Vichi Alessandra
Vincze Laszlo
Voltolina Stefano
O-28 P-30
P-67
P-66
P-68
P-66
P-29
O-08 P-61
P-22
P-66
P-19
209
W
Wagermaier Wolfgang
Wähning Andrea
Wallert Arie
Wallez Gilles
Walter Philippe
Walton Marc
Webb Sam
Weitkamp Timm
Westall Frances
Wiesinger Rita
Williams Alan
Willneff Elizabeth
Winick Herman
O-33
Wogelius Roy
O-25/27/29
P-06/24
Woll Arthur R.
O-12
P-05/23/30
Wolters Jochem
Wouters Helena J. M.
P-34
O-39
P-39
O-17
O-32
P-06
P-25
P-40
O-09
O-10 P-72
P-69
P-83
P-78
O-21
Y
Yager Kevin G.
O-36
Z
Zarkout Karim
Žbontar Zora
Zizak Ivo
Zoppi Marco
210
P-17
P-43
P-40
O-10 P-72
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