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

International scientifc committee Comité scientifique international Annemie Adriaens Invited speakers Loïc Bertrand Orateurs invités Joris Dik Matthias Alfeld Koen Janssens Emilie Chalmin Apurva Metha Catherine Dejoie Jennifer Mass Trinitat Pradell Martin Radtke Ritimukta Sarangi Ina Reiche Marco Stampanoni Jean Susini Josefina Pérez-Arantegui Public session Robert van Langh Wednesday September 10, afternoon Louvre auditorium Session publique 10 septembre après-midi Auditorium du Louvre Uwe Bergmann Robert van Langh Philippe Sciau

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 (...) Depuis 2010, nous publions La Recherche au musée du à la recherche » sont deux missions fondamentales assignées Louvre, bulletin annuel de la recherche qui a pour objectif au musée du Louvre aux côtés de la conservation et l’accueil de recenser tous les projets et études menés au musée du des publics dans le décret de sa création en établissement Louvre. Il informe sur les nouvelles acquisitions de chaque public, en 1992. département, développe les principales restaurations Connaître au mieux les œuvres de nos collections, et présente les nouveaux espaces muséographiques. les hommes qui les ont créées, les techniques qui les ont Il reprend les temps forts des expositions in situ et hors les mises en forme, découvrir les innovations et les influences murs et propose un annuaire des acteurs de la recherche. des artisans et des artistes, enquêter sur les parcours des œuvres de la fouille au musée – pour les pièces archéo- A l’instar des grandes institutions de recherche, le musée logiques - ou depuis leur création, leur passage d’une du Louvre s’est doté depuis 2011 d’un Conseil scientifique collection d’amateur à un autre, mettre en relation les constitué de membres éminents de la recherche en ar- sources archivistiques et documentaires, les analyses phy- chéologie et histoire de l'art, issus des universités et des sico-chimiques, et le regard sur l’œuvre, ... c’est le travail musées nationaux et internationaux, ainsi que d'acteurs quotidien des chercheurs du Louvre. du musée, afin de bénéficier d’un regard extérieur sur sa politique de recherche. Cette recherche modifie parfois fondamentalement la Le développement de projets de recherche, en lien avec présentation même des œuvres du musée ; elle amène le les institutions de recherche du Ministère de la Culture public à découvrir ou redécouvrir un artiste, une culture, et du Ministère de l’Enseignement supérieur et de la une époque, grâce notamment aux quelque quarante ex- Recherche, fait partie de nos priorités. Souhaitant s’impli- positions ou actualités des salles au Louvre ou hors les murs. quer dans les nouveaux développements technologiques Avec la trentaine de publications d’ouvrages scientifiques associés aux recherches menées sur les collections, (catalogues raisonnés, catalogues d’expositions, monogra- le musée du Louvre s’est associé aux sept laboratoires du phies), les colloques et conférences consacrés à l’archéologie CNRS, du ministère de la Culture et du MNHN (IPANEMA et à l’histoire de l’art, le résultat de cette recherche est large- à SOLEIL, C2RMF, LAMS, département de préhistoire du ment diffusé auprès de tous. 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 Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

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 In 2010, we published the first edition of La Recherche decree that conferred on the Louvre the status of public au musée du Louvre (“Research at the Musée du Louvre”), institution charged the museum with two other core an annual bulletin that inventories all projects and studies missions: “ensuring scientific study of the collections” and carried out at the Musée du Louvre. The bulletin provides “promoting ... research”. Every day, the Louvre’s research team updates on new acquisitions for every department, gives a works to gain a deeper understanding of the pieces in our detailed presentation of main conservation works, and intro- collections, of their creators and of the techniques employed duces new exhibition spaces. It also contains a summary of in the creation process. Every day, they gain insight into onsite and offsite exhibition highlights, as well as a directory what influenced craftspeople and artists, and how they of research specialists. innovated in turn; they trace the trajectories of pieces from their excavation (in the case of archaeological artefacts) In 2011, following the example of leading research institutes, or from their creation to their arrival at the museum, and the Musée du Louvre set up a Scientific Council comprising, from one connoisseur’s collection to another. Every day, on the one hand, eminent figures in archaeological and art our researchers make connections between archival and history research, from universities as well as national and documentary sources, physicochemical analyses, and the international museums; and on the other hand, museum way artworks are interpreted from an art history perspective. stakeholders, who provide a welcome outside perspective on the Louvre’s research policy. In some instances, research radically changes the very pre- Developing research projects in collaboration with the re- sentation of the museum’s artworks, allowing the public to search institutes of the French Ministry of Culture and of the discover or rediscover an artist, a culture, or a time period French Ministry of Higher Education and Research is one of through some forty exhibitions and events taking place in- our priorities. Always eager to be involved in new technolo- side and outside museum walls. Research findings are made gical developments associated with research carried out on widely available through some thirty scientific publications its collections, the Musée du Louvre hosts within its walls the (catalogues raisonnés, exhibition catalogues, monographs), 2014 edition of the International Conference on Synchrotron as well as symposia and lectures dedicated to archaeology Radiation and Neutrons in Art and Archaeology. For the oc- and art history. casion, 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 Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Bienvenue !

Depuis 2005, la conférence internationale sur le Rayon- nement 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 Conservation et altération, Processus et chaînes opératoires, le Metropolitan Museum of Art de New-York en 2012, cette Nouvelles méthodes et processus analytiques, Paléontolo- sixième édition se tient cette année au cœur de la ville de gie et paléo-environnements. À une semaine des Journées Paris, dans l’environnement exceptionnel du musée du Louvre. européennes du Patrimoine, nous avons souhaité inclure Pendant trois jours, la conférence réunira près de 300 per- une composante inédite à cet événement en organisant sonnes venues des quatre coins du monde : archéologues, une session spéciale destinée à faire découvrir au public scientifiques en conservation, conservateurs, scientifiques du musée du Louvre la richesse des méthodes synchrotron et ayant l’expérience des techniques sur grands instruments neutrons pour l’étude du patrimoine culturel et archéologique. et d’autres techniques d’analyse, étudiants, historiens Autre innovation, des visites d’étude, associant conservateurs de l’art, restaurateurs, gestionnaires de patrimoine culturel, du musée et spécialistes des méthodes synchrotron, sont utilisateurs potentiels des synchrotrons, etc. organisées au Louvre.

Les méthodes synchrotron et neutron sont en plein L’événement a suscité un très vif intérêt puisque nous avons développement pour l’étude des objets patrimoniaux. reçu plus d’une centaine de résumés provenant de 23 pays Les conférences, tables rondes et séances de posters sont différents situés sur quatre continents (Amérique, Europe, ainsi programmées autour de quatre sessions thématiques Asie, Océanie). Les contributions à la conférence seront qui réuniront des conférenciers de notoriété internationale : 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 parti- culièrement 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 Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

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 oppor- tunity 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 Conservation and alteration, Processes and chaînes opéra- the Metropolitan Museum of Art in New-York in 2012, toires, New methods and analytical processes, Paleontology this sixth meeting is held this year at the heart of Paris, and palaeo-environments. A week before the European in the exceptional venue of the Louvre. Over three days, Heritage Days, we wanted to include a brand new compo- the conference will gather nearly 300 people from all over nent in the event, a special session to introduce the Louvre’s the world: archaeologists, conservation scientists, conser- visitors to the richness of methods employing synchrotron vators, researchers with experience in large-scale research and neutron radiation for the investigation of artistic and facilities and other analytical techniques, art historians, archaeological materials and artifacts. Study visits are ano- curators, cultural heritage managers, students, potential users ther innovation, bringing together curators and specialists of synchrotrons, etc. in synchrotron methods at the Musée du Louvre.

Synchrotron and neutron methods are developing fast The event has attracted great interest, and we have received for the study of historical artefacts. The seminars, round- over a hundred abstracts from 23 countries on four conti- table discussions and poster sessions will be scheduled nents (America, Europe, Asia and Australia). Contributions to around four themed sessions involving world-class speakers: 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 Mu- sée 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 Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

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 p. 204 ITINÉRAIRE DU MUSÉE DU LOUVRE AU MUSÉE D’ORSAY

PROCEEDINGS / ACTES p. 205

AUTHOR INDEX / INDEX DES AUTEURS p. 206

Loïc BERTRAND SR2A Local Organizing Committee

7

SESSION PLANNING / AGENDA DES SESSIONS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

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 Ofcial 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 Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

DETAILED PLANNING AGENDA DÉTAILLÉ From Tuesday 09 September 2014 at 18:30 to Friday 12 September 2014 at 19:00 (CET)

9 Sept. 2014

18:30 > 20:30 Welcome reception and preliminary registration 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’) 09:00 > 09:30 Registration 09:30 > 10:00 Ofcial Opening CONSERVATION AND ALTERATION I SESSION 10:00 > 10:30 O-01 Investigation of historical paintings by X-ray techniques Invited Speaker: Matthias Alfeld, Deutsches Elektronen-Synchrotron DESY, Hamburg, Germany

10:30 > 10:50 O-02 Synchrotron studies of the migration of lead soaps in old master paintings and model systems 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 12:00 > 13:40 Lunch (On Your Own)

NEW METHODS AND ANALYTICAL PROCESSES I SESSION 13:40 > 14:00 O-06 Detection of platinum in gold with D²XRF Speaker: Martin Radtke, BAM Federal Institute For Materials Research and Testing, Analytical Chemistry, Berlin, Germany 14:00 > 14:20 O-07 Spectroscopic pulsed neutron imaging and its application to metal cultural heritage Speaker: Yoshinori Shiota, Nagoya University, Graduate School of Engineering, Nagoya, Japan

th 14:20 > 14:40 O-08 A scanning nano-XRF study of a 19 century daguerreotype photograph Speaker: Edward Vicenzi, Smithsonian Institution, Museum Conservation Institute, Suitland, USA

14:40 > 15:00 O-09 In-situ time-lapse X-ray difraction of silver corrosion Speaker: Rosie Grayburn, Universiteit Gent, Department of Analytical Chemistry, Gent, Belgium 15:00 > 15:30 Break

10 DETAILED PLANNING / AGENDA DÉTAILLÉ Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

10 Sept. 2014 | Musée du Louvre (Auditorium) 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 fuorescence 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 Difraction 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 fring protocol Invited Speaker: Philippe Sciau, CNRS, CEMES, Toulouse, France 20:00 Adjourn 21:30 Museum Closes (Extended Hours for Wednesday)

11 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’) 09:30 > 10:00 O-16 Role of S K-edge X-ray absorption spectroscopy in conservation eforts 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 difraction 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

11:00 > 11:30 Break

CONSERVATION AND ALTERATION II SESSION 11:30 > 11:50 O-20 Degradation mechanisms of reinforcement iron rebars in monuments: infuence 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 DETAILED PLANNING / AGENDA DÉTAILLÉ Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

11 Sept. 2014 | Musée du Louvre (Auditorium) SUITE

11:50 > 12:10 O-21 De Colorando Auro: revealing diferent 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 Speaker: Nicholas Edwards, University of Manchester, School of Earth, Atmospheric and Environmental Sciences, Manchester, UK

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: 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 16:00 > 16:30 Break

PALAEONTOLOGY AND PALAEO-ENVIRONMENTS II SESSION

16:30 > 16:50 O-28 Confocal X-ray fuorescence 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 mummifed tissues Speaker: Bart van Dongen, University of Manchester, School of Earth, Atmospheric and Environmental Sciences, Manchester, UK 17:10 > 17:40 O-30 Rock art pigments: alteration and weathering processes in caves and open sites 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 20:30 (entrance includes access to museum before the dinner)

12 Sept. 2014 | Musée du Louvre (Auditorium)

08:45 Recommended arrival time at the Richelieu ‘group entrance’ 09:00 Museum Opens

th th 09:30 > 10:00 O-31 Materials, techniques and conservation of 15 to 19 centuries stain glass “grisailles” Invited Speaker: Trinitat Pradell, Universitat Politecnica de Catalunya, Fisica, Castelldefels, Spain

12 DETAILED PLANNING / AGENDA DÉTAILLÉ Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

12 Sept. 2014 | Musée du Louvre (Auditorium) SUITE

PROCESSES AND CHAÎNES OPÉRATOIRES II SESSION 10:00 > 10:20 O-32 Deciphering ancient ceramic fring conditions through replication Speaker: Ilaria Cianchetta, Getty Conservation Institute, Los Angeles, USA

CONSERVATION AND ALTERATION III SESSION

10:20 > 10:40 O-33 Diference 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

11:00 > 11:30 Break

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 diferences 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

12:00 > 13:40 Lunch (On Your Own)

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 fat 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 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 DESY, Hamburg, Germany

Uwe Bergmann LCLS, Stanford, USA

Emilie Chalmin Trinitat Pradell EDYTEM, Universitat Politècnica de Catalunya, Le Bourget du Lac, France Castelldefels, Spain

Catherine Dejoie Ritimukta Sarangi ETH Zurich, SLAC, Switzerland 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 Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

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 En parallèle des présentations orales et de la session the richness of methods employing synchrotron and poster, la sixième édition du SR2A comprend plusieurs neutron radiation for the investigation of artistic and événements : archaeological materials and artifacts; Un accueil de bienvenue pour délivrer aux Study visits organised with the Musée du Louvre participants des informations sur la conférence will associate a curator and an analytical scientist et leur permettre de se rencontrer autour d’un verre ; with a group of participants to the conference who will discuss about research on an artefact from Un dîner, élaboré par le chef Yann Landureau, the Louvre collection; le jeudi 11 septembre dans le restaurant du presti- gieux musée d’Orsay, classé Monument historique. A Stand with books for young and old in connection Il sera précédé d’une visite du musée ; with the themes on which the Conference focuses in the Louvre bookshop. 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.

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Matthias Alfeld1 10 sept. 2014 10:00 > 10:30 O-01 1 Deutsches Elektronen-Synchrotron DESY, 22607, Hamburg, Germany Investigation of historical paintings by X-ray techniques

The use of synchrotron radiation (SR) based techniques tion of historical paintings too large to be investigated at a for the analysis of historical paintings and other cultural SR source. Given the comparably low effort of these in-situ heritage objects has undergone a steep increase in the investigations with mobile scanners, MA-XRF can also be last 10-15 years [1]. Paintings are investigated on diffe- used in studies of more routine naature, e.g. those aimed at rent length scales: the better part of a painting’s surface supporting the planning of conservation treatments. can be investigated in a non-destructive fashion by scan- In this contribution the development and perspective ning macro-XRF (MA-XRF) with a lateral resolution of a few of scanning macro-XRF for the investigation of historical hundred micrometers, while small samples taken from a paintings will be discussed. Further, it will be shown how painting are often studied at a sub-micrometer length scale. the capabilities of beamline P06 at DESY can contribute to The macroscopic investigation of paintings by MA-XRF allows the investigation of samples taken from historical paintings. the study of surface and sub-surface paint layers, which may With its state-of-the-art KB mirror system and the highly sen- visualize changes of concept (pentimenti) and discarded sitive Maia detector system [7] the beamline allows for a fast and overpainted works [2]. The study of paint samples aims acquisition of elemental distribution images by micro-XRF in general at the identification of pigments and their degra- with dwell times of a few milliseconds per pixel and a lateral dation process by techniques such as scanning micro-XRF, resolution in the sub-micrometer range. It also allows for XRD and XANES [3, 4]. a fast acquisition of large stacks of elemental distribution While no technique of same effort was found to provide re- images with variable primary energy for XANES imaging sults comparable to that of SR based ones for small samples, as well as for XRF tomography. Microscopic X-ray diffraction mobile, X-ray tube based MA-XRF scanners provide results imaging and tomography is also feasible. only slightly inferior to SR instruments. Mature in-house built Finally, the value of advanced data evaluation procedures, scanners [5], as well as commercial instruments [6], allow for such as non-negative matrix approximation, for the interpre- the investigation of large areas (several thousands of square tation of data sets obtained from historical paintings will centimeters) in a few hours. They also permit the investiga- 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).

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Annelies van Loon1 - Katrien Keune1 - Mathieu Thoury2 O-02 10 sept. 2014 10:30 > 10:50 Joen Hermans1 - Christophe Sandt3 - Solenn Réguer4 Petria Noble5 - Klaas Jan van den Berg6 - Alysia Sawicka7 Aviva Burnstock7 - Loïc Bertrand2 1 University of Amsterdam, Van ‘t Hoff Institute for Molecular Sciences / PAinT, Synchrotron studies 1098 XH, Amsterdam, Netherlands 2 Ipanema, 91192, Gif sur Yvette, France 3 Synchrotron SOLEIL, SMIS beamline, 91192, Gif sur Yvette, France of the migration 4 Synchrotron SOLEIL, Diffabs beamline, 91192, Gif sur Yvette, France 5 Royal Picture Gallery Mauritshuis, Paintings Conservation Studio, 2501 CM, The Hague, Netherlands of lead soaps in old 6 Cultural Heritage Agency of the Netherlands, Research and Knowledge Centre, 1071 ZC, Amsterdam, Netherlands 7 T he Courtauld Institute of Art, Conservation and Technology, WC2R ORN, master paintings London, United Kingdom and model systems

If and how lead soaps migrate in aged oil paintings are two compared with data from 16 replica paint films constructed to important and challenging questions. The formation of lead- simulate the lead soap migration and aggregation processes. rich surface deposits and lead soap aggregates that affect Synchrotron experiments were carried out at Synchrotron many Old Master paintings indicates that lead soaps (reaction SOLEIL near Paris, at the SMIS and Diffabs beamlines, which products of lead-containing pigments and fatty acids from allowed performing FTIR, XRF, XRD and XANES (Pb L3-edge) the oil medium) are mobile and that they may travel through respectively. Methodology was optimized to prepare poli- the paint. Previous SEM-EDX studies have shown lead-rich shed cross-sections, using micromesh polishing cloth (dry), deposition bands and finely dispersed lead-rich particles in and 2 to 6 µm thick thin-sections, using ultra-microtome, the paint medium and at layer interfaces that are not confined allowing measurements in reflection and transmission modes. to pigment particles [1, 2]. This paper discusses the application Areas of interest were identified through pre-characterization of synchrotron-based analyses, with FTIR and X-ray techniques, on a bench-top FTIR imaging microscope. to obtain structural information about the various lead com- pounds present and their spatial distribution in the paint layers In Rembrandt’s Homer, the dark passages of paint are disfi- at the micro-scale. gured by the presence of a whitish insoluble surface crust rich in lead. A similar surface crust was observed on the surface We selected a coherent corpus of samples from a traditional of dark paints of the painted ceiling in the Johan de Witthuis. oil painting by Rembrandt van Rijn, Homer, 1663 (Mau- This unique case-study is of significance as it survives unvar- ritshuis) and an original painted ceiling dating from c.1650 nished and the lead salts have developed on the surface (Johan de Witthuis, The Hague). The results of analyses were 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 Bibliography XANES throughout the entire multi-layer paint build-up, [1] Keune, K., van Loon, A., Boon, J., 2011, ‘SEM backscattered-electron images which supports our hypothesis of their mobility. The high of paint cross-sections as information source for the presence of the lead signal-to-noise ratios of the FTIR spectra allowed us to observe white pigment and lead-related degradation and migration phenomena in oil paintings’, Microscopy and Microanalysis Vol 17, Issue 5: 696-701. pronounced differences in the carboxylate profiles of the [2] Van Loon, A., Noble, P., Boon, J., 2012, ‘The formation of complex crusts paint layers and reference samples of pure lead soap crystals. in oil paints containing lead white and smalt: dissolution, depletion, diffusion, deposition’, in Historical Technology, Materials and Conservation: This points to different chemical environments of the lead SEM and Microanalysis, ed. N. Meeks, C. Cartwright, A. Meek, A. Mongiatti, carboxylate group, and is comparable to observations on zinc London, The British Museum/Archetype: 207-209. [3] O smond, G., Boon, J.J., Puskar, L., Drennan, J., 2012, ‘Metal stearate soap distributions in modern oil paint layers [3]. These results distributions in modern artists’ oil paints: surface and cross-sectional will be further discussed in the paper, as they provide impor- investigation of reference paint films using conventional and synchrotron tant clues about the mechanisms regarding the formation and infrared microspectroscopy’, Applied Spectroscopy Vol 66, Number 10: 1136-1144. migration of lead soaps in aged oil paintings.

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Roel Hendrickx1 - Ester S.B. Ferreira1 - Jaap J. Boon1 O-03 10 sept. 2014 10:50 > 11:10 Anders Kaestner2 1 SIK-ISEA, Kunsttechnologie, CH-8032, Zürich, Switzerland 2 Neutron radiography PSI, ICON beamline, CH-5232, Villingen, Switzerland for the quantitative analysis of water uptake and swelling of painting canvases and preparation layers

This contribution concentrates on the moisture uptake of Neutron radiography is very well suited to follow up the water painting canvases and preparation layers. Many chemical uptake of these complex layered systems because of the high reactions and material transport phenomena in paint layers attenuation of water molecules, which leads to a relatively high lead to changes in surface appearance and to deformations contrast in the images of humid materials when compared or mechanical stresses in paintings. These chemical reactions to the surrounding materials. In collaboration with SIK-ISEA, and material mobility are linked to or driven by the presence of AMOLF, has developed a moisture reaction chamber which moisture. It is our goal to elucidate and quantify the water mo- is relatively transparent for neutrons and which can hold a bility and storage in the paint multiplex using historically accu- 1 cm2 sample of primed canvas and in which a high relative rate replicas of known paintings and original painting samples. humidity can be generated during a dynamic water uptake ex- The focus is on materials used in late 19th century and early 20th periment [4]. Experiments are executed in the ICON beamline century painting, which have been characterised in previous at PSI, Switzerland. The resulting images are 2D arrays of 16 bit work using synchrotron X-ray tomography and SEM [1,2], grey values, 2048×2048 pixels with a resolution of about 14 in the context of the study of the early oeuvre of the Swiss micron/pixel. Comparison of the images in humid condition painter Cuno Amiet (1868-1963). It appears that the ground (taken every 100 seconds for a period up to 10 hours) to those layers, which were usually handmade in the cases under of the dry state, allows the assessment of the evolution of study and are mostly composed of animal glue and chalk, the quantity of moisture. An important challenge is to take have an important number of pores in the capillary range [1]. into account the movement of the sample and its changing The glue itself is known to have a pronounced hygroscopic shape. A methodology for a quantitative analysis is proposed behaviour [3]. using Matlab for image processing. This involves a specific segmentation of the image with a morphological reconstruc- tion, which allows to use relative distance to the edges in the Bibliography analysis, rather than fixed points. [1] Gervais, C., Boon, J.J., Marone, F., and Ferreira, E.S.B. (2013). Characterization The first results confirm the hypothesis that water transport is of porosity in a 19th century painting ground by synchrotron radiation governed by diffusion and increases linearly with the square X-ray tomography. Appl. Phys. - Mater. Sci. Process. 111, 31–38. [2] SIK-ISEA (in preparation for publication). Technologische Forschungen root of time. The experimental method itself is shown to be zur Malerei von Cuno Amiet (1883–1914), Zürich: Scheidegger & Spiess. feasible and versatile. A new set of experimental data is cur- [3] Mecklenburg, M.F. (2007). Determining the Acceptable Ranges of Relative Humidity And Temperature in Museums and Galleries. Part 1. Structural rently being investigated. Further analyses currently under response to Relative Humidity, Unpublished report, Maryland: study include the variation of several parameters such as the Smithsonian Museum Conservation Institute. [4] Boon, J.J., Eijkel, G., Cerjak, I., Ferreira, E.S.B., Gervais, C., and Kaestner, coarseness of the weave, the preparation method of the sizing A. (2012). Monitoring Water Uptake and Proton Exchange in Painted and the presence and composition of a ground layer. 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.

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Letizia Monico1 - Koen Janssens2 - Costanza Miliani1 O-04 10 sept. 2014 11:10 > 11:30 Ella Hendriks3 - Frederik Vanmeert2 - Geert van der Snickt2 Muriel Geldof4 - Luc Megens4 - Marine Cotte5 Brunetto Giovanni Brunetti1 1 CNR- ISTM/Centre SMAArt, Chemistry Department, Perugia University - Via Elce di Non-invasive in situ Sotto 8, I-06123, Perugia, Italy 2 Antwerp University, Chemistry Department - Groenenborgerlaan 171, B-2020, Antwerpen, Belgium spectroscopic techniques 3 Van Gogh Museum, Conservation Department - Paulus Potterstraat 7, 1070 AJ, Amsterdam, The Netherlands and synchrotron 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, radiation-based X-ray Grenoble, France methods to examine In keeping with our previous studies [1], preliminary non-invasive in situ Raman, reflection mid-FTIR investigations and MA-XRF the state of conservation scanning analysis of this painting revealed that Van Gogh made of chrome yellow 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 pigments in Van Gogh’s its high tendency to undergo photo-reduction.[2,3] Depending on the shade investigated, these different forms of Sunfowers 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 Ongoing technical examination aims to appraise the current orange ” pigment was also identified. These mixtures were fre- condition of Vincent van Gogh’s Vase with Sunflowers (Arles, quently applied by Van Gogh in his later works.[4] January 1890), now in the collection of the Van Gogh Museum Similar results were also obtained by laboratory FTIR, Raman in Amsterdam, with a view to possible conservation and resto- and SEM-EDX investigations as well as SR µ-XRD analysis ration treatment. of related paint samples. This paper focuses on one aspect of the research involving color Cr K-edge µ-XANES and µ-XRF analysis of a selection of mi- change due to the alteration of certain types of the chrome cro-samples taken from the most representative chrome yellow paints used by the artist. yellow-paint areas of the painting provided a detailed characteri- zation of the distribution of the Cr species within the paint layers.

A methodological approach based on the combination of In those samples containing the pigment in the PbCr1-xSxO4 form, non-invasive spectroscopic methods and advanced synchrotron we found an amount of 40-100 % Cr(III) species in the non-origi- radiation (SR)-based X-ray investigations now provides direct nal varnish layer and/or at the paint surface in close contact with evidence for the fact that the darkening of some chrome yellow it. The concentration of reduced Cr decreases with depth in the paint areas in Vase with Sunflowers may in part be ascribed to bright yellow paint down to values of about 15 %. a reduction process of the original chromate. Based on these results we consider it reasonable to pose that the darker Cr(III)-based compounds originated through reduction of Bibliography the original chromate pigment. This agrees with the alteration mechanism previously obser- [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, ved in darkened chrome yellow samples taken from other Hendriks E, Geldof M, van der Loeff L, Salvant J, Menu M. Anal. Chem. 2013, paintings by Van Gogh, such as Bank of the Seine (Van Gogh 85, 851-859. Museum) and Falling leaves (Les Alyscamps) (Kröller-Müller [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. Museum, Otterlo) [5,6]. [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. This paper will present detailed information about the che- [4] Geldof M, Megens L, Salvant J. Van Gogh’s palette in Arles, Saint-Rémy mical composition and conservation state of the chrome 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. yellow paint areas in the Amsterdam version of Vase with [5] Monico L, Van der Snickt G, Janssens K, De Nolf W, Miliani C, Dik J, Radepont Sunflowers, discussing results gained through a combined M, Hendriks E, Geldof M, Cotte M. Anal. Chem. 2011, 83, 1224-1231. used of non-invasive and laboratory analytical techniques [6] T an H, Tian H, Verbeeck J, Monico L, Janssens K, Van Tendeloo G. Angew. Chem. Int. Edit. 2013, 52, 11360–11363. as well as SR-based X-ray methods.

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Carolina Barata1 - Carolina Barata2 - Fernando Rocha1 O-05 10 sept. 2014 11:30 > 11:50 Antonio João Cruz3 - Antonio João Cruz4 Slavka Andrejkovičova1 - Solenn Réguer5 1 Universidade de Aveiro, Geosciences Department, Geobiotec Research Unit, 3810-193, Aveiro, Portugal SR-XRD analysis 2 Universidade Católica Potuguesa, Conservation Department, 4169-005, Porto, Portugal 3 I nstituto Politécnico de Tomar, Conservation Department, 2300-313, of bole layers Tomar, Portugal 4 Hercules, Research Unit, 7000-809, Évora, Portugal in popular and erudite 5 Synchrotron SOLEIL, Diffabs, 91190, Saint-Aubin, France Portuguese gilded Baroque retables

Very little is known about the materials and techniques The high consumption of boles in the Baroque period was used in Portuguese gilded retables from the Baroque. mainly due to the fact that they were healing clays adminis- The studies based on a scientific approach are very scarce [1] tered mainly orally as antacids, gastrointestinal protectors and focused particularly on works with erudite features and and antidiarrhoeaics [4]. on the characterization of the superficial gold leaf. In order to clarify the origins of the boles used in Portu- Although the thin gold leaf is what stands out on gilded guese retables and to understand the differences between retables, its appearance is conditioned by the layer which materials used in works with different artistic quality, lies immediately beneath it, which is usually described as microsamples collected from two different groups of eru- the bole layer, essentially composed of clay minerals agglu- dite and popular gilded retables, respectively belonging to tinated in a proteinaceous glue. The bole contribution to the city of Oporto and its rural surroundings, were selected the final effect derives mainly from its colour and its texture, for elemental and mineralogical characterization. These parameters that depend on its mineralogical composition. samples show a bole layer with a thickness of 30 µm in The bole has usually red or yellow tones and traditionally average, but its minute size do not allow the use of regular is designated as Armenian bole, in accordance with the micro-XRD equipment for phase identification. For this origin where it is supposed to be obtained the material reason it was necessary to use SR-XRD, performed with a of best quality (Armenia). However it was frequently adul- six circles diffractometer at the DIFFABS beam line at SOLEIL terated due to its high cost [2]. Furthermore, it is known Synchrotron, on 34 samples previously analysed through that the bole was also extracted in other regions, namely SEM-EDS [5]. The analysis was performed in reflection mode in Portugal where good quality boles were obtained [3]. since the samples are very friable and do not allow the pre- paration 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 Bibliography and provenance were also analysed. The results, which are presented in the communication, sug- [1] Cardoso, I.P.; Infocus. 2006. 41 (4), 64-86. [2] Cruz, A.J.; Artis. 2009, 7-8, 385-405. gest that boles of the erudite and the popular retables have [3] Biringuccio, V.; The Pirotechnia, Dover Publications: New York, 1990, 117; similar composition, both qualitative and quantitative. Most Costa, E. M.; A Natural History of Fossils, London, 1757, 20; Hill, J.; A history of the materia medica, editora: London, 1751, 188-189. boles are mainly composed of kaolinite (usually the predo- [4] Gomes, C.; Silva, J.; Minerals and Human Health: benefits and risks. minant clay mineral), illite and smectite and feldspars, quartz C. Gomes e J. Silva: Aveiro, 2006, XI-XII. [5] Barata, C.; Cruz, A. J.; Rocha, F.; I Encontro Luso Brasileiro de Conservação and gypsum as well. This composition is consistent with e Restauro, UCP/CITAR: Porto, 2012, 40-50. the composition of the common red Portuguese clays [6] [6] Gomes, C.; Argilas: aplicações na indústria. C. Gomes: Aveiro, 2002, 251-255. and is also similar to the composition of most geo- [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. phagic materials [7].

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Martin Radtke1 - Günter Buzanich1 - Uwe Reinholz1 O-06 10 sept. 2014 13:40 > 14:00 Heinrich Riesemeier1 - Oliver Scharf2 - Maria Guerra3 1 BAM Federal Institute For Materials Research And Testing, 1.3 Analytical Chemistry, 12489, Berlin, Germany 2 I fG Institute For Scientific Instruments GmbH, 12489, Berlin, Germany Detection of platinum 3 ArchAm - UMR 8096 CNRS - Univ. Paris 1 Pantheon-Sorbonne, 92023, Nanterre in gold with D²XRF Cedex, France

The only realistic chance for non-destructive gold prove- geometries like the Rowland circle. Here we describe a nance is the determination of the trace element pattern. new approach, that is based on a flat crystal geometry for Among the most characteristic elements of gold are Sn, Pd wavelength dispersion and an additionally energy dispersive and Pt kept in the metal along the metallurgical process [1]. system for detection, the so-called Double Dispersive X-Ray The non destructive determination of Pt with energy dis- Fluorescence (D2XRF). persive X-ray fluorescence is especially challenging because While even with a simple SDD detector the detection limit the weak fluorescence lines of the Pt traces are overlapping can be lowered significantly, the full advantage of this with the strong Au fluorescence or, depending on the exci- set-up can be achieved by using an array detector like the tation energy, the Au Raman scattering [2]. To resolve peak Color X-ray Camera (CXC) [3]. In this case no collimating ele- overlaps the use of a wavelength dispersive system (WDX) ments are necessary and a high efficient detection scheme is mandatory. is realized. Depending on the set-up, a whole energy re- While the much better energy resolution of a WDX is a clear gion of around 1000 eV can be measured simultaneously, advantage, there are as well drawbacks. Compared to an which is an additional benefit. We carried out measurements energy dispersive system the measurement time is higher, on various gold standards with known Pt concentrations. because each element must be measured separately and We could demonstrate the highly reliable conversion the efficiency is restricted due to the used slits which are between measured count rates and Pt concentrations and defining the geometry in traditional WDX systems. lowered with this setup the detection limit for platinum These disadvantages can be overcome, by using several in gold to less than 1 ppm in 1000 s, which is the best value detection channels in parallel and more sophisticated 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..

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Yoshinori Shiota1 - Takashi Kamiyama2 - Syota O-07 10 sept. 2014 14:00 > 14:20 Nagashima2 - Sasiphan Khaweerat3 - Yoshiaki Kiyanagi1 1 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, Spectroscopic pulsed Sapporo, Japan 3 T hailand Institute of Nuclear Technology, Nuclear Science, 10900, 16 Vibhavadi neutron imaging Rangsit, Chatuchak, Bangkok and its application to metal cultural heritage

In research on precious cultural heritage, non-destructive of the technique coupled with a position sensitive neu- measurement of its material structure is one of important tron detector is possible to obtain microstructural in- technique to investigate age, region, material composition formation depending on the position of a bulk material and production technology. The spectroscopic pulsed with one neutron transmission imaging measurement. neutron imaging technique offers non-destructive method Sometimes elemental composition in the material obtained to reveal internal crystallographic structure and elemental from resonance absorption or activation analysis provides distribution in bulk metal, due to the high penetration significant information. of neutron beam. The spatial distributions are useful in order to investigate At a pulsed neutron source, the neutron energy can be ana- mechanical properties, working process, elastoplastic de- lyzed by using time-of-flight method and the transmission formation and composite phase characteristics in the metal spectra with specific Bragg-edges of a crystalline material materials. As a result, the method was used for our metal are obtained from transmission measurement. We have cultural heritages analysis [3,4]. After Japanese swords were developed quantitative evaluation technique of micros- measured as a traditional transmission imaging, they were tructural information such as crystal lattice plane spacing, evaluated distributions of martensite steel phase, crystallite crystallographic texture, crystallite size and crystalline phase size and texture. Such a microstructural factor is due to steel by analyzing the Bragg-edges [1]. Spectroscopic analysis material and production technology. Besides, the method of the Bragg-edges is performed by using the RITS code that was introduced to the analysis of some authentic Thai coins is based on the Rietveld theory [2]. In addition, the application produced during A.D.1874-1919. In this study, we will introduce the principle of the spectros- copic pulsed neutron imaging and the results on Japanese swords and coins. In the Japanese swords, the differences of microstructural factors were observed among swords pro- Bibliography duced in different region and age. Meanwhile, the analysis of [1] Y. Kiyanagi, H. Sato, T. Kamiyama and T. Shinohara, J. Phys. Conf. Ser. 340 Thai coins shows slightly differences in the crystallographic (2012) 012010. structure varied by date of production. [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, This work was partially supported by a Grant-in-Aid for F. Grazzi, A. Scherillo, S. Uno and A. S. Tremsin, Application of a pulsed Scientific Research (S) from Japan Society for the Promotion neutron transmission method to a cultural heritage study,1st International Conference on Neutron Imaging and Neutron Methods in Archaeology of Science (No. 23226018). 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

31 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

NOTENOTES

32 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Edward Vicenzi1 - Benjamin Stripe2 - Volker Rose2 O-08 10 sept. 2014 14:20 > 14:40 1 Smithsonian Institution, Museum Conservation Institute, 20746, Suitland, USA 2 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 Some microanalytical information has been derived from daguerreotype photographs have been characterized scanning electron microscopy-based studies of daguer- by nano-X-ray fluorescence spectrometry (nano-XRF). reotypes [e.g. 2]. However, given the scale of the particles, The examined features include photo contrast-inducing detailed microchemical analysis of image-forming nano- nanoparticles, a gilding layer, and sulphide corrosion within particles requires sample preparation that involves feature 19th century photographic images. removal from the object followed by thinning of material to minimize particle/photon scattering. Such sample prepara- In 1839, the daguerreotype photographic process was first tion technology has only been widely available in the past presented to the scientific community in France. The techno- decade via focused ion beam (FIB) microscopy. This effort logy spread rapidly and was widely used around the globe seeks to determine the elemental make-up of nanoparticles until roughly 1860. Image formation can be generalized in as well as the protective nanofilm that coats daguerreotypes four steps: by way of synchrotron nano-XRF imaging and analysis. Ad- 1) exposing silver-plated copper to an iodine vapor, ditionally, this study aims to produce the first quantitative 2) further exposing the sensitized plate to visible light within chemical measurements of 19th century daguerreotype a camera, nanostructures using a standards-based methodology. 3) development of an image after the plate is treated with heated mercury vapor, and finally The hard X-ray nanoprobe at Argonne National Laboratory’s 4) deposition of a gold gilding layer [1]. 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 Bibliography processed using a package of software routines designed [1] Y. Kiyanagi, H. Sato, T. Kamiyama and T. Shinohara, J. Phys. Conf. Ser. 340 specifically for XRF data sets [6]. (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, Nano-XRF imagery reveal nanoparticle cores are nearly F. Grazzi, A. Scherillo, S. Uno and A. S. Tremsin, Application of a pulsed completely encapsulated by the Au gilding layer, instead neutron transmission method to a cultural heritage study,1st International Conference on Neutron Imaging and Neutron Methods in Archaeology of simply being coated only on upper surfaces. Fitting and and Cultural Heritage Research (NINMACH 2013), Munchen, Germany, quantification of the nano-XRF spectra for daguerreotype September, 2013. [4] Y. Shiota, T. Sato, H. Hasemi, A. S. Tremsin, T. Kamiyama and Y. Kiyanagi, particles and gilding layers establishes that sulphur is an Non-destructive Measurement of Microstructural Factor of Japanese Sword important player with regard to the chemistry of the interior by using Neutron Transmission Spectroscopy, The international conference on “ the Beginnings of the Use of Metals and Alloys ” (BUMA VIII), Nara, of daguerreotype HgAg nanoparticles and it is not restricted Japan, September, 2013 to the atmosphere/object interface.

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34 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Rosie Grayburn1 - Rita Wiesinger2 - Mark Dowsett3 O-09 10 sept. 2014 14:40 > 15:00 Paul Thompson4 - Manfred Schreiner2 - Annemie Adriaens1 1 Universiteit Gent, Department of Analytical Chemistry, 9000, Gent, Belgium 2 Academy of Fine Arts, Institute of Science And Technology, 1010, Vienna, Austria 3 University of Warwick, Department of Physics, CV4 7AL, Coventry, United Kingdom In-situ time-lapse 4 European Synchrotron Radiation Facility, XMaS (BM28), 38000, Grenoble, France X-ray difraction of silver corrosion

Several heritage systems have been studied using state- The design of the experiment meant that pressurised gases of-the-art synchrotron techniques [1–4] developed by the could be used as source gases with minimal safety concerns Electrochemistry and Surface Analysis (ESA) group at Uni- in the hutch. The eCell itself was not kept above atmospheric versiteit Gent, Belgium, and the Analytical Science Projects pressure as the gases flowed through the cell from the top (ASP) group at Warwick University, UK. In this presentation (sample height) to the base, and the effluent was extracted we show how the eCell [5] (and associated control software) at low outlet velocity (max. 1 L min-1) using the vacuum line can be used to study the time-lapse corrosion of pure silver in the hutch. The hydrogen sulphide source gas contained by anthropogenic gases alongside newly designed equip- 10 ppm H2S in synthetic air. This was diluted to 500 ppb ment for analysis of multiple samples. This work was carried using synthetic gas in the gas-mixing manifold. The ozone out on the XMaS [6] beamline at the European Synchrotron was generated by running synthetic air through an ozone Radiation Facility, Grenoble. generator. The concentrations of both the source gas and The cultural heritage value of silver is documented in output gas were well below the safety limits and presented museum collections across the globe. However, the silver no danger to the users. surface is not as chemically stable as that of other precious The time-lapse XRD data shows that when pure silver is metals, and is susceptible to corrosion by gases such as H2S exposed to 500 ppb H2S, 500 ppb O3 and RH >50 % crystal- and O3. In order to study the initial corrosion of silver in the line corrosion products start to form after only 30 minutes presence of these gases, a customized gas-mixing set-up of gas flow. Silver sulfide, silver oxides, intermediates and (designed by the Institute of Science and Technology, mixed species formed over the duration of the experi- Academy of Fine Arts, Vienna) delivered the required hu- ment. The data can start to give us an idea as to the exact midity and gas concentration to the cell under turbulent mechanism of degradation by this gas mixture as we track flow conditions to the silver sample surface placed under the transformation from one crystalline species to another. the X-ray transparent Kapton window. 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 Bibliography who wish to study time-lapse gaseous corrosion at ambient [1] R. Grayburn, M. Dowsett, M. De Keersmaecker, E. Westenbrink, temperature and pressure. 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.

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Elisa Barzagli1 - Francesco Grazzi1 - Alan Williams2 O-10 10 sept. 2014 15:30 > 15:50 David Edge2 - Antonella Scherillo3 - Marco Zoppi1 1 Istituto Dei Sistemi Complessi, CNR, research, 50019, Firenze, Italy 2 T he Wallace Collection, Museum and Conservation, W1U 3BN, London, United Kingdom Non-invasive 3 Science and Technology Facility Council, ISIS Facility, research, OX11 0QX, Didcot, characterization of two United Kingdom Japanese swords from the Wallace collection

The metallurgy of historical combat weapons (swords, (X-XVI century), in different ways, by five schools of sword- in particular) is one of the most interesting topics of archaeo- smithing, each aiming to provide what was believed to be metallurgy because they were manufactured using the the optimum mechanical characteristics for each part of highest quality materials and the most advanced technology the blade, according to its function [6,10] available throughout the ages [1,2]. The work presented is part of a long-term project aimed at In order to achieve a good level of characterization of metal the characterization of the processing techniques in different artifacts, by traditional analytical methods, a destructive ap- traditions and their evolution over time. proach is usually necessary. However, this method is strictly Samples object of this work are two blades, with different forbidden for well conserved museum exhibits. Neutron shape and characteristics, belonging to the collection of techniques have already been demonstrated to be among arms and armour of the Wallace Collection (London, UK): the most suitable methods to characterize qualitatively 1) a long sword (Tachi) of the 15th Century (Koto period be- and quantitatively the composition and the microstructural longing to the Yamato Tradition). The Tachi is a long sword properties of metal artifacts in a non-destructive way [3-5]. used by horsemen, that needed to be hard enough to Ancient Japanese swords represent one of the best examples cut armours and elastic enough to sustain a hard impact. in this field. Hence, they are one of the most interesting 2) a long knife (Tanto) or double edged straight sword used classes of artifacts that can be studied in order to better mainly as a piercing weapon. It is dated to the 17th century understand the evolution of metallurgy [6,7]. (Shinto period). All the Japanese swords, so far investigated by neutron The measurements were carried out using the diffractometer diffraction, have shown distinctive inner structures and INES (Italian Neutron Experimental Station) at the ISIS spal- manufacturing procedures [4,5,8,9]. These procedures have lation neutron source (UK). been refined across the years starting from the Koto period 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. Bibliography The characteristics are in agreement with the data found in [1] A. Williams, The knight and the blast furnace, Brill, Leiden (2003). the literature: high hardness in the edge, and high resilience [2] V. F. Buchwald, Iron and steel in ancient times, Historisk-filosofiske Skrifter 29, The Royal Danish Academy of Sciences and Letters (2005). in the back. [3] F. Grazzi et al., J. Anal. At. Spectrom. 27, 293 (2012). The good quality of the results obtained is combined with [4] F. Grazzi et al., J. Anal. At. Spectrom. 26, 1030 (2011) [5] F. Grazzi et al., Anal. Bioanal. Chem. 400,1493 (2011). the privilege of being able to analyze objects belonging to [6] K. Nagayama, The Connoisseur’s Book of Japanese Swords, Kodansha one of the best collections of arms and armour in Europe. 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).

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38 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Myrtille Hunault1 - Fanny Bauchau2 - Claudine Loisel2 O-11 10 sept. 2014 15:50 > 16:10 Michel Herold3 - Matthew Newville4 - Georges Calas1 1 University Pierre and Marie Curie, Paris 6, IMPMC, 75252, Paris Cedex 5, France 2 Museum National d’Histoire Naturelle, CRC-LRMH, 77420, Champs-Sur-Marne, France 3 University Paris Sorbonne, Centre Andre Chastel, 75004, Paris, France Reducing 4 University of Chicago, Advanced Photon Source, GSECARS, 60409, Argonne, Il, USA manufacturing conditions of medieval blue glass revealed by µ-XANES

Transition metal ions are widely used as colorant in glass In the framework of the study of the 13th century stained manufacturing. In the Middle Age, glassmakers were able to glass color of the Sainte-Chapelle of Paris, four contempo- control the glass production conditions in order to obtain a rary samples dating from 12th-13th centuries were analyzed wide range of colors. The blue color relies on the presence of with synchrotron radiations. As a comparison, for each Co2+, Fe2+ and Cu2+. The main blue colorant is Co2+, which only sample, a fragment was re-melted at 1200°C in air. K-edge occurs in this oxidation state in the glass. On the contrary, micro-XANES was performed at the beamline 13-ID-E at the Fe, Cu and Mn can happen in several oxidation states. These Advanced Photon Source (Chicago, IL, USA) to determine elements can interact in their redox equilibriums, which the oxidation state of Mn, Fe and Cu. The measurement influences the glass color. The oxidation state is also sensi- was performed across the glass thickness and compared to tive to the temperature and to the oxygen partial pressure the re-melted glass fragment. The results revealed that the of the furnace. The exact processing conditions have been four ancient glasses are reduced compared to the re-melted investigated according to ancient textbooks but suffer from equivalent glass. In ancient glasses, Mn is mainly present terseness and their impact on final glass color is not yet as Mn2+, Fe as Fe2+ and Cu as Cu+, whereas more oxidizing understood. 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). Bibliography These results inform us on the sensitivity of the blue color to [1] M. Schvoerer, Conserv. Restaur. Vitr. Actes Journées Détudes Cent. Int. Vitr. the relative coloring role of each species and the influence (1993) 131. [2] B. Cochain, D.R. Neuville, D. de Ligny, J. Roux, F. Baudelet, E. Strukelj, P. Richet, of the glass processing. The correlation with the optical ab- J. Phys. Conf. Ser. 190 (2009) 012182. sorption signature of these glasses provides a starting point [3] L. Grodecki, Comptes-Rendus Séances Académie Inscriptions Belles-Lettres 120 (1976) 345. for further analyses and interpretations of the color of the [4] K. Boulanger, M. Hérold, Le vitrail et les traités du Moyen Âge à nos Jours: Sainte-Chapelle stained glass windows. 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)

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Jennifer Mass1 - Arthur Woll2 - Alyssa Hull3 - Patricia Favero4 O-12 10 sept. 2014 16:10 > 16:30 Adam Finnefrock5 - Robin Kirkham6 - Anthony Kuczewski7 Catherine Matsen1 - Gareth Moorhead6 - Chris Ryan6 1 Winterthur Museum, Conservation Department, 19735, Winterthur, USA 2 Cornell University, Cornell High Energy Synchrotron Source, 14853, Ithaca, USA Pablo Picasso’s The 3 University of Delaware, Department of Chemistry, 19716, Newark, USA 4 T he Phillips Collection, Conservation Department, 20009, Washington DC, USA 5 Janssen R&D, 19002, Spring House, USA Blue Room (1901): 6 CSIRO, Materials Science and Engineering, 3168, Clayton, Australia an intensive technical investigation of a blue period painting

Pablo Picasso’s 1901 painting, The Blue Room, in The Phillips entire painting. The SR-XRF maps were obtained at the Cor- Collection, Washington, DC, is considered a major turning nell High Energy Synchrotron Source using a new version of point in this artist’s work during a seminal year in his stylistic the 384-sensor Maia detector. The goals of this measurement development. With The Blue Room and other works, Picasso were to determine the elemental distribution of the com- transitioned into his Blue Period, abandoning earlier colorful bined painting, and the feasibility of distinguishing features depictions of belle époque nightlife in fin-de-siècle Paris for of the presentation surface and buried works in this and a more subdued, primarily blue palette that would continue other, similar Picasso works of the same period. Due to the to dominate his paintings into 1904. high concentration of zinc throughout the painting, as well Despite extensive research into various aspects of Pablo as Picasso’s use of a lead-based ground, the painting was Picasso’s working methods and materials, and detailed scanned in its entirety twice: once with an incident energy analyses of a handful of his later paintings, comprehensive of 12.6 keV to excite mercury L-edge fluorescence but not technical analysis of a work from the Blue Period, and of one lead, and a second time with an energy of 9.37 keV, below of Picasso’s reused canvases, has not been carried out. The the zinc K edge. Both scans were performed with a pixel Blue Room has been known for several years to have another size of 0.2×0.2 mm2, and took approximately 11 hours to painting, a portrait, beneath the presentation surface, also complete. Despite the thickness of zinc and barium—based thought to have been carried out in 1901. It is well known fillers and similarity in composition between the two images, that Picasso reused his canvases, one major example of several features of the buried portrait are distinguishable in which is the Art Institute of Chicago’s Blue Period painting the XRF maps, which are assisting the ongoing curatorial The Old Guitarist (1903-4), which has been shown to have at work on this painting. least three different hidden figures. Questions addressed will include: what palette and painting Here we describe initial results of a comprehensive analysis of methods did Picasso use for the two works? What is the rela- The Blue Room. We describe combined results from portable tionship between the two palettes? Were the works painted X-ray fluorescence (XRF), Raman spectroscopy, FTIR, and wet-into-wet? The combination of the cross-section studies, scanning electron microscopy X-ray microanalysis, along molecular analyses, and XRF imaging provide a wealth of with synchrotron-radiation (SR) based XRF mapping of the new information about this important work.

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42 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Uwe Bergmann1 O-13 10 sept. 2014 17:00 > 20:00 1 SLAC National Accelerator Laboratory, LCLS, 94025, Menlo Park, USA X-ray fuorescence imaging: from Archimedes to Archaeopteryx and beyond

In an attempt to uncover the hidden writings in the In the field of cultural heritage we will present examples in- Archimedes Palimpsest some years ago the technique cluding the imaging of a leaf from a seventh-century Qur’an of rapid-scan X-ray fluorescence (XRF) was developed at palimpsest and a section of the original score of the opera the Stanford Synchrotron Radiation Lightsource. After its Médée believed to be over-painted by its composer Luigi successful application in that project, XRF has been refined Cherubini. Other examples presented include the recent over the last years, leading to numerous new studies discovery of soft-tissue residue in fossils of Archaeopteryx, of large objects of cultural, archaeological and paleonto- as well as the work that has successfully resolved the rem- logical importance. nants of pigment in Confuciusornis sanctus, a 120-million- year-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)

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Robert van Langh1 O-14 10 sept. 2014 17:00 > 20:00 1 Rijksmuseum, museum, 1071 XX, Amsterdam, The Netherlands What have we learned from Neutron Transmission Radiography and Time-of-Flight Neutron Difraction on Renaissance bronzes?

In November 2005 the Rijksmuseum showed 13 different nal neutron sensitive device, based on a highly sensitive neutron tomographic reconstructions of Renaissance CCD-camera looking via a mirror onto a scintillation screen. bronzes during an exhibition at the Daniel Katz Gallery in About 300 single projections of the object are needed for London. Within art history the project was widely perceived one tomography run, where the object is rotated around as a project where science can truly bring new information its vertical axis in steps from 0° to 180°. within the authentication of art objects. A reconstruction algorithm calculates from these 2D projec- tion data the 3D volume matrix, which can be forwarded for In 2010 a continuation of the project took place where further analysis to the visualisation tools, where animation, 12 bronzes more were studied at the PSI installation for slices and segmentation can be obtained. neutron tomography at the beam line NEUTRA located at the spallation neutron source SINQ. The setup consists Using the data from neutron imaging, neutron diffraction on a quasi-parallel beam with up to 40 cm annual diame- was used to analyse the inside of the sculptures based ter directed to the object of interest. Behind the object, on the apparent difference of attenuation shown in the the transmitted beam is detected with a two-dimensio- 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 Bibliography completely new insights in the manufacturing of Renais- sance bronzes. [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. During the presentation various insights into the bronze [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 sculpture will be given and put in an art historical context fluorescence spectometry’, Metal 2010, ICOM-CC metal working group. and it will show that collaboration between scientists, Charleston 2010, pp. 204-209. [3] Langh, R. van, L. Bartoli, J.R. Santisteban, and D. Visser, ‘Casting technology curators and conservators is essential for obtaining results of Renaissance bronze statuettes: the use of TOF-neutron diffraction that are reliable for the authentication of works of art. for studying afterwork of Renaissance casting techniques’, Journal of Analy- tical 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.

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46 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Philippe Sciau1 O-15 10 sept. 2014 17:00 > 20:00 1 CNRS, CEMES, 31055, Toulouse, France How to use the hierarchical heterogeneous structure of ancient ceramics to trace their fring protocol

In archaeological investigations, ceramics are one of the ad- information concerning the firing process. Also, the physi- vance technological products. Not only are they identifying co-chemical study of sherds is often the best way to obtain markers, but often also indicator of technological prowess of information concerning the manufacturing process. Through a civilization and/or an archaeological period. Consequently, the example of the black and/or red high gloss coatings they have been a major focus of archaeometric research of Greek and Roman potteries, we will try to show how to from the beginning of the field in the 1950s. Among the deduce precise information using synchrotron facilities and investigation fields, the manufacturing process held and still other advanced materials science investigation techniques. holds an important place and in particular the identification The approach used the heterogeneous and complexity of the firing protocol. A whole study includes the study of of these artifacts. It is based both on a multi-scale analysis firing structure survey found during the excavations, the and a decomposition in sub systems of materials. From the physico-chemical analyses of ceramic fragments, experi- confrontation of the results obtained for each sub-system mental firings and making replications, but unfortunately and at different scales, we will show how the various steps of in many cases the firing structures were not identified or firing protocol can be traced as well as information concer- the conservation state was not enough to deduce from them ning the raw materials used in the manufacturing process.

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48 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Eleanor Schofeld1,2 - Ritimukta Sarangi1 O-16 11 sept. 2014 09:30 > 10:00 1 The Mary Rose Trust, HM Naval Base, PO13LX, Portsmouth, UK 2 SLAC National Accelerator Laboratory, Stanford University, 94025, Menlo Park, USA Role of S K-edge X-ray Absorption Spectroscopy in Conservation Eforts of the Mary Rose

Sulfuric acid production is a pervasive problem in wooden earth metal carbonates. The efficacy of the treatment plan archeological artefacts and has been shown to significantly is followed with S K-edge X-ray absorption spectroscopy, damage these cultural heritage relics. The problem is aggra- which is an excellent tool for the determination and differen- vated in the case of waterlogged wooden artefacts, in which tiation of the different types of sulfur species present in the sulfur accumulation is accelerated due to the presence of wooden artefacts. It is observed that the treatment is success- sulfur metabolizing bacteria. Finding a common solution ful in converting the dangerous low-valent sulfur species in to all waterlogged wood acidification is impossible due to the wooden artefacts into more benign forms of sulfur, the variation in the type of wood, acidification and extent in the process neutralizing the formed acid. The benefits of damage. In this study a treatment plan for the sulfur and limitations of this treatment plan will be addressed. rich wood of the Mary Rose is developed based on alkaline

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

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50 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Pauline Martinetto1 - Sophie Cersoy1 - Pierre Bordet1 O-17 11 sept. 2014 10:00 > 10:20 Jean-Louis Hodeau1 - Elsa van Eslande2 - Philippe Walter2 1 Univ. Grenoble Alpes, CNRS-UJF, Institut Néel, 38000, Grenoble, France 2 Combined structural Sorbonne Universités, CNRS-Univ Paris 06, LAMS, 75000, Paris, France analysis of ancient ill-ordered carbon-based cosmetics and inks

Carbon black materials are easy to get by combustion of DSCT experiments requiring moving the sample with a organic matter and were thus often used since prehistory, precise translation - rotation system and involving data as pigments or drawing, writing, dyeing materials or even acquisitions of few hours per sample, enabled us to localize as cosmetics components. Black carbon-based powders and extract the signal of the various phases present. These from the roman site of Pompeii were analyzed. The six first promising results are being completed by micro-beam analyzed samples come from ink and cosmetic containers data collected on Diffabs at SOLEIL, as some heterogeneities made of bronze or glass. Ancient recipes as well as preli- within the sample seems to be a few dozen microns in size. minary studies in laboratory revealed the complexity of The treatment of data acquired at thirty increasing 2the- these precious materials containing both ill-ordered phases ta positions to reach a high Q-range has been achieved. (mostly carbonaceous ones) and well-crystallized ones. Assessment of the weight proportion of each crystallized Diffraction patterns thus show diffuse scattering signatures phase in the archaeological samples using Rietveld refine- (broad oscillations from non-graphitic carbon) with Bragg ments was first achieved. PDF calculations were compared reflections superimposed. with structural models taking into account the presence and proportion of each crystallized phase obtained in the pre- Therefore the following two-steps strategy involving vious step. For the amorphous part, differences with graphite non-destructive techniques and analysis of reference structure could be visualized and proved to be relevant for carbon-based materials was chosen and set up on D2Am short range order arrangements. Other models mentioned in beamline at ESRF: literature (turbostratic piles and/or curved-graphitic-sheets) 1- Selective extraction of the total scattering signal of each are still under tests. phase present using X-ray Diffraction Scattering- Computed Moreover quantitative comparison of the PDF of references tomography (DSCT) and and archaeological samples, combined with Raman spec- 2- Structural characterization of amorphous phases by Pair troscopy analysis performed in the laboratory, enabled to Distribution Function (PDF) analysis using X-ray scattering discriminate carbon blacks according to their starting ma- data collected on a wide 2 theta-range with a good statistic. terial (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. 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.

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52 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Frederik Vanmeert1 - Koen Janssens1 - Matthias Alfeld2 O-18 11 sept. 2014 10:20 > 10:40 Gerald Falkenberg2 - Geert van der Snickt1 - Wout de Nolf1 1 University of Antwerp, Department of Chemistry, AXES Research Group, 2020, Antwerp, Belgium X-ray powder 2 DESY, PETRA-III, P06 Beamline, 22607, Hamburg, Germany difraction mapping and tomography for analysis of (degraded) paint layer systems

X-ray powder diffraction is a general method for highly The paint multilayer systems to be discussed as examples specific phase identification and quantitative analysis. originate on the one hand from 15th C. panel paintings by When employed with synchrotron micro beams in two-di- H. Memling; their complexity, sometimes involving more mensional scanning mode, it allows for quantitative than 10 individual layers of different thicknesses and strongly mapping of the crystalline phases present in complex, different compositions reflects the extensive craftmanship heterogeneous materials [1]. of this ‘Flemish primitive’ painter. In some cases, the original A variant of scanning SR-XRPD is XRPD tomography [2] complexity of the stratigraphy has been increased further where the sample under investigation is rotated along one due to the formation of degradation products. As such, axis and translated along a second axis perpendicular to these paint layer systems are a challenge and interesting the first. This method allows to record phase maps in virtual test case for analysis by XRPD mapping and tomography. planes inside the sample under investigation without the need for physically sectioning the material. The elimination Stratigraphically more simple paint layer systems can on of the physical sectioning step has the advantage that the the other hand be found is paintings by the late 19th C. integrity of (brittle or fragile) samples [3] is preserved while painter V. Van Gogh. These sample materials, however, often also any contamination or phase transformations due contain traces of (ongoing) degradation processes that to sample preparation are avoided. have given rise to the in situ formation of layered systems of primary and secondary phases. Analysis of these systems In this paper we describe the results of examining several paint by highly-specific methods such as XRPD mapping and layer systems by means of conventional 2D scanning XRPD tomography allows to extract information on the nature of and by means of XRPD tomography using a (sub) microsco- the alteration mechanisms involved and experimentally test pic X-ray beam (0.4×0.4 μm2) of 21 keV energy, produced at some hypotheses. The case of the alteration of red lead will PETRA-III beamline P06 and compare the results critically. be treated as an example.

Bibliography

[1] D e 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.

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54 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Fauzia Albertin1 - Alberto Astolfo2 - Marco Stampanoni2 O-19 11 sept. 2014 10:40 > 11:00 Eva Peccenini3 - Yeukuang Hwu4 - Frederic Kaplan5 Giorgio Margaritondo1 1 École Polytechnique Fédérale de Lausanne (EPFL), Faculté des Sciences de Base, CH-1015, Lausanne, Switzerland Virtual X-ray reading 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 (VXR) of ancient 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 administrative d’humanités digitales, CH-1015, Lausanne, Switzerland handwritten documents

The study of ancient documents is too often confined We present here positive tests of this approach. First, to specimens of high artistic value or to official writings. we systematically analyzed the ink composition of a sample Yet, a wealth of information is often stored in administrative of Italian handwritings spanning over several centuries. records such as ship records, notary papers, work contract, Then, we performed X-ray imaging with different contrast tax declaration, commercial transactions or demographic ac- mechanisms (absorption, scattering and refraction) using counts. One of the best examples is the Venice Time Machine the differential phase contrast (DPC) mode of the TOM- project that targets a massive digitization and information CAT beamline of the Swiss Light Source (SLS). Finally, we extraction program of Venetian archives. The Archivio di Stato selected cases of high contrast to perform tomographic in Venice holds about 80 kms of archival documents spanning reconstruction and demonstrate page-by-page handwri- over ten centuries and documenting every aspect of Venetian ting recognition. Mediterranean Empire. If unlocked and transformed in a digital The experiments concerned both black inks from different information system, this information could change significantly centuries and red ink from the 15th century. For the majo- our understanding of European history. rity of the specimens, we found in the ink areas heavy or We are exploring new ways to facilitate and speed up this medium-heavy elements such as Fe, Ca, Hg, Cu and Zn. broad task, exploiting X-ray techniques, notably those based This eliminates a major question about our approach, on synchrotron light. Specifically, we plan to use X-ray tomogra- since the documentation on the nature of inks for ancient phy to computer-extract page-by-page information from sets administrative records is quite scarce. As a byproduct, of projection images. The raw data can be obtained without the approach can produce valuable information on the opening or manipulating the bounded administrative registers, ink-substrate interaction with the objective to understand reducing the risk of damage and accelerating the process. and prevent corrosion and deterioration.

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56 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Mathieu Jacot-Guillarmod1 - Claire Gervais1 O-20 11 sept. 2014 11:30 > 11:50 Olivier Rozenbaum2 - Valerie L’ Hostis3 - Philippe Dillmann4 Delphine Nef4 1 Bern University of Applied Sciences, 3027, Bern, Switzerland 2 I nstitut des Sciences de la Terre d’Orléans, CNRS-BRGM-Université Degradation d’Orléans, 7327, Orléans, France 3 Laboratoire d’ Etudes du Comportement des Bétons et des Argiles, CEA Saclay, 91191, Gif Sur Yvette, France mechanisms 4 LAPA; NIMBE-SIS2M UMR 3299 and IRAMAT UMR 5060, CNRS/CEA Saclay, of reinforcement iron 91191, Gif Sur Yvette, France rebars in monuments: infuence of porosity on the formation of corrosion products the bars are embedded in the binder or do they form due to the mechanical constraints induced by the precipitation studied by X-ray of the corrosion layer? To answer to these questions this study focuses on samples tomography 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 or- der to investigate the transformed medium and the distribu- tion of the corrosion products and of the porosity in it samples Gothic cathedrals have been building thanks to metallic rein- of 2×2 mm² have been prepared for X-ray tomography. forcement metallic chains and rebars. These elements can be Acquisitions were realized on a laboratory set-up and under embedded in lime, mortar or hydraulic binders and corrode synchrotron radiation on ID19 at the ESRF. Laboratory sys- in contact with these media. The mechanical resistance of tem enabled voxel sizes between 2 and 4 µm while images the metallic elements is affected by the corrosion processes obtained at the ESRF were acquired with a 0.7 µm voxel size. endangering the structure. In order to assess the possible The collected tomography images were filtered by an inverse damage and establish a reliable conservation diagnosis the scale space method and the corrosion products, porosity knowledge of the corrosion mechanisms is required. In pre- and binder were segmented by a local Otsu thresholding vious studies [1,2] the formation of a corrosion layer consti- procedure. Visualized analysis of the segmented images tuted of iron oxide and oxi-hydroxides has been characte- reveals that corrosion products and porosity form two rized. Besides, elementary iron is detected in a micrometer to highly connected and percolating networks. These two millimeter zone in the binder, heterogeneously distributed networks are linked together and tend to be continuous, and can locally reach concentration of few tenth wt %. which agrees with the hypothesis of a gradual filling of the This zone of the corrosion system is called the transformed porosity network by the corrosion products. Their connec- medium. Mappings on samples prepared on cross section tivity, shape, tortuosity, and their spatial distribution were reveal that the distribution could correspond to the mi- further characterized and quantified by means of chord dis- gration of iron along the cracks formed in the medium, at tribution functions, Betti numbers and diffusion simulations. the interface with the corrosion products. The presence of This procedure combining image processing and simulations these cracks partially filled with corrosion products raise was found particularly powerful to investigate the corrosion questions: are these cracks present at the beginning when 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.

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58 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Amandine C. Crabbé1 - Marie-Angélique Languille2 O-21 11 sept. 2014 11:50 > 12:10 Cristian Mocuta3 - Helena J. M. Wouters4 - Herman Terryn1 Isabelle Vandendael1 1 VUB, SURF, 1050, Brussels, Belgium 2 CNRS, IPANEMA, 91192, Saint Aubin, France De Colorando Auro: 3 Synchrotron SOLEIL, DiffAbs, 91192, Saint Aubin, France 4 revealing diferent KIK-IRPA, Laboratory, 1000, Brussles, Belgium surface treatments of the silver gilded statuettes of a 13th century shrine using XANES

In 2005 the Holy Lady Shrine of Huy, Belgium (13th century Depending on the applied recipe the colour modified model masterpiece of Mosan art [1]) went to the Royal Institute for samples present variations in the copper concentration or Cultural Heritage (IRPA) for its third restoration. In order to deposition of iron in the top layer of the gilding. The oxida- restore the gilded silver statuettes of the shrine, it is of ma- tion state and geometry of these two chemical signatures is jor importance to acquire knowledge about which surface determined using XANES, enabling us to differentiate colour treatments these statuettes might have undergone during treated surfaces from untreated surfaces on model samples [5]. their history. In previous publications we demonstrated The XANES analyses of the historical samples reveal the that it is possible to modify the surface colour of a 24 carat presence of iron and copper at their surfaces implying that gilding on a silver substrate by applying interpreted medie- some colouring treatments might have been applied to val recipes [2-4] on model samples. In order to characterise them. Finally, some differences in chemical composition are both the treated model samples and the statuettes from detected between the statuettes of the apostles and the the shrine, a non-destructive and non-invasive surface ana- Christ, indicating that different statuettes might have been lytical technique is needed. We analysed both the model treated differently by the metal craftsmen. samples treated in the lab and the real historical samples chemically with XANES. This communication presents a In conclusion, XANES proves to be a very useful tool to reveal short overview of the research project focussing particularly the chemical state of iron and copper at the surface of the on the chemical characterisation of our model samples and historical samples, leading to some important recommen- the historical samples performed with XANES. dations 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 Bibliography 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.

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60 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Florian Kergourlay1 - Sophie Grousset2 - Jean-Louis Gallias1 O-22 11 sept. 2014 12:10 > 12:30 Delphine Nef2 - Solenn Réguer3 - Albert Noumowe1 Philippe Dillmann2 1 University de Cergy-Pontoise, Laboratoire de Mécanique et Matériaux du Génie Civil, F-95000, Cergy-Pontoise, France Degradation 2 CNRS-CEA, NIMBE-SIS2M/LAPA, 91191, Gif/Yvette, France 3 mechanisms Synchrotron SOLEIL, Diffabs, 91190, Saint-Aubin, France of reinforced concrete monuments study of initial corrosion processes in chlorinated environments

Since the Antiquity, monuments have been reinforced by the dology has been carried out to (I) determine the corrosion use of steel bars or reinforcements embedded in binders such pattern formed in the early stages and (II) monitor the ferrous as lime mortar or cement concrete. The understanding of cor- species transport within the binder porous system. rosion mechanisms of these reinforcements at a microscopic The first step consisted in the design of a dedicated cell scale is therefore a crucial step to set up more efficient conser- replicating the binder / iron (steel bar or archaeological vation treatments. The initial alkaline conditions within most iron reinforcement) system allowing in situ analysis during of the binders allow the formation of passive and protective the corrosion processes. Before and after the in-situ expe- layer at the surface of the metal, slowing corrosion rates. riments, characterizations of the system were performed However, a decrease of the interstitial solution pH because of thanks to complementary multi-scale tools including optical the natural binder carbonation or the penetration of aggres- and scanning electron microscopy (OM and SEM), Energy sive chemical species as chloride ions from the environment Dispersive and micro-Raman Spectroscopies (EDS and µRS). to the steel surface can lead to the destabilization of the Then, the in situ elementary and structural evolution of the passive layer with a significant increase of the kinetics. These corrosion system were monitored thanks to X-ray diffraction processes imply formation of corrosion products that can and fluorescence mapping under synchrotron microbeam generate cracks and binder spalling by high tensile stresses. (µSXRD and µSXRF) realized on the DiffAbs beamline at This is strongly linked to the way Fe ions will migrate in SOLEIL synchrotron. the porous network of the binder or precipitate locally. Firstly, it has been underlined that corrosion processes are ini- Besides, it is known that corrosion induced by chloride leads to tiated at the metal/cement interface flaws such as porosities a random pit formation [1]. However, the exact initial mecha- or pre-existing cracks. Secondly, thanks to the in situ approach nisms are not completely understood at microscopic scale. the formation of a transcient Fe(II)-Fe(III) corrosion product, To better understand the first stages of corrosion processes the green rust [2,3] and its evolution on several days have in chlorinated environments a four step experimental metho- 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 chlo- ride induced corrosion processes helping to evaluate rein- Bibliography forced concrete durability and hereafter upgrading modeling. [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

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62 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Marco Stampanoni1 O-23 11 sept. 2014 14:10 > 14:40 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, either by their X-ray absorption or their induced phase small source size and low divergence, synchrotron radiation shift. Fine tunability of the probe energy is another key has been increasingly used for a plethora of investigations feature of synchrotron radiation, which enables high sen- assessing the physico-chemical properties of materials. sitive chemical spectroscopic investigations. In my talk I The non-invasive character of such probe makes it particularly will review the most relevant X-ray techniques applied suited for the study of ancient, unique and historical materials. nowadays for the study of ancient and historical materials. This principle is at the basis of tomographic microscopy I will discuss in particular tomographic applications by investigations which aim at revealing the microscopic presenting existing methods, discussing their limits and structure of samples by exploiting the contrast generated 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

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64 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Giliane Pauline Odin1 - Véronique Rouchon1 O-24 11 sept. 2014 14:40 > 15:00 Frederick Vanmeert2 - Koen Janssens2 - François Farges3 Delphine Vantelon4 1 MNHN, CRC, 75005, Paris, France 2 University of Antwerp, Department of Chemistry, B-2020, Antwerp, Belgium Conservation 3 MNHN, IMPMC, 75005, Paris, France 4 of lignitized pyritic SOLEIL, LUCIA, 91190, Saint Aubin, France woods in the light of synchrotron measurements

Because of simultaneous presence of oxygen, water, For a reason so far unknown, sulfones were poorly present reduced carbon and sulfur species (such as pyrite), ligni- even though expected as oxidation products. Carbon-XAS tized woods are highly susceptible to oxidize after their measurements demonstrate the presence of aromatic, excavation, which often results in distorting significantly carboxylic and alkyl carbons, but no change could be the specimen. To improve their conservation, we have highlighted during treatments. experienced some conservator’s methods such as water washing and slow drying under plastics, in order to evaluate Washing treatments in water has no significant effect on their efficiency and potential side effects. sulfur speciation, even after five months. Sulfates are ne- vertheless released in the bath, pointing out a decrease of Lignitized pyritic woods coming from Angeac-Charente sulfur content. In peroxide hydrogen solution, this release (Charentes, France, 130 Ma) and Rivecourt (Oise, France, is stronger and sulfates are identified in both woods and 60 Ma) were submitted to several drying (with different solution. Comparison of drying protocols shows that oxi- oxygen and humidity levels) or washing (in pure water dation largely depends on humidity and to a lesser extent or 1 % hydrogen peroxide) treatments. We then monitored on oxygen: in dry air, sulfur is mostly present in its reduced their oxidation on LUCIA and TEMPO beamlines (SOLEIL) form. In wet air, sulfates grow within the first days of expo- by XAS, XPS and XANES measurements, to enhance the sure, after which, no more is produced. mechanism awareness. These data incline conservative protocol towards fast condi- These experiments showed that reduced sulfur is not only tioning of the samples, in humidity controlled environment present as pyrite but also as organic sulfides. Sulfur K-edge rather than anoxic ones. These conclusions are noticeable XANES spectra were modeled satisfactorily, considering as the control of humidity is easier and cheaper to achieve a mixture of pyrite and dibenzothiophene, a compound than that of oxygen. known to be present in bitumen. The oxidation of sulfur compounds products sulfoxides, sulfites and sulfates.

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66 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Nicholas Edwards1 - Phillip Manning1 - Victoria Egerton1 O-25 11 sept. 2014 15:00 > 15:20 William Sellers2 - Uwe Bergmann3 - Roy Wogelius1 1 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 When photons meet 3 SLAC National Accelerator Laboratory, Linac Coherent Light Source, 94025, fossils: the chemistry Menlo Park, USA of ancient life

It was generally perceived by the palaeontological commu- One avenue of research, currently being led by the Uni- nity that “ soft-tissue ” fossils (such as plants, skin, fur, feathers) versity of Manchester (UK), is the use of chemical imaging are little more than highly altered and/or replicated traces techniques to identify and map the chemical inventory of the living organisms. Indeed, such soft-tissues degrade of fossil tissues in-situ within their geological matrices. rapidly in most environments and so it was believed that Three primary non-destructive techniques: Synchrotron their preservation over tens and hundreds of millions of X-ray Fluorescence imaging, X-ray Absorption Spectroscopy years could only be the result of a unique combination of and Fourier Transform Infrared Spectroscopy imaging have post-mortem bio- and geochemical processes that altered shown that remnants of both the trace metal (organometal- their composition into something that could be preserved. lic) and organic (protein) inventory within soft-tissue fossils Consequently, it was also believed that any chemical analy- may be preserved, detected and mapped within discrete sis of these fossil tissues would reveal little useful informa- biological structures over entire organisms after hundreds of tion about the original organism, let alone something as millions of years. Key results from this work include the iden- distant as their original biochemistry. However, many recent tification of remnant skin protein and dental chemistry in studies on a range of fossil tissues have shown that rem- 50 million year old reptile fossils [1,2], and the identification nants of the original biochemistry may well be preserved. 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 . L a r s o n , 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.

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68 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Pierre Gueriau1 - Loïc Bertrand2,3 O-26 11 sept. 2014 15:20 > 15:40 1 Muséum national d’Histoire naturelle, CR2P UMR 7207, 75005, Paris, France 2 SOLEIL synchrotron, 91192, Gif-Sur-Yvette, France 3 IPANEMA USR 3461, 91192, Gif-Sur-Yvette, France 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 Presence of strontium, yttrium and REEs is attributed to their scanning approaches shed light on the chemistry of fossi- long-term isomorphous substitution within bone bioapa- lized plant and animal remains [1-5]. They particularly fo- tite and the authigenic apatite that replicated soft-tissues. cused on organics and metal distributions (at minor-to-trace Furthermore, we will discuss about the speciation and pre- levels) but other trace elements such as strontium and rare ferential incorporation of the more informative elements, earth elements (REEs), which are used in palaeoenvironmen- studied using microscopic X-ray absorption near edge spec- tal and taphonomic studies, can also be easily mapped using troscopy (XANES) and UV-Visible luminescence spectrosco- this technique [6]. We will show that the distributions of py, which provide relevant information on the microscale these trace elements are informative at histological scales in fossilization, diagenetic and preservation conditions in this well-preserved fossils from the Upper Cretaceous of Morocco. 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 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

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70 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Roy Wogelius1 - Nicholas Edwards1 - Arjen van Veelen1 O-27 11 sept. 2014 15:40 > 16:00 Victoria Egerton1 - Jennifer Anne1 - William Sellers2 Uwe Bergmann3 - Roberto Alonso-Mori4 Konstantin Ignatyev5 - Phillip Manning1 1 University of Manchester, SEAES, M13 9PL, Manchester, UK Remnants of life: 2 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 integrated geochemical 5 Diamond Light Source, I18, OX11 0DE, Didcot, UK methods for the analysis of exceptionally preserved specimens

Recently published research has shown that the chemical several different techniques in order to fully constrain the residue of biochemical processes can, under exceptional chemistry [1-4]. We will discuss the application of several circumstances, be preserved in-situ even in samples that complementary methods to the analysis of a range of fossils have been buried over long periods of geological time [1-4]. including bone and soft tissue. In particular, we show how Soft tissue chemistry can now be resolved even after over advances in synchrotron rapid scanning X-ray fluorescence, 150 million years of aging [2]. Analysis of such specimens microfocus imaging, X-ray absorption spectroscopy, and presents a number of obstacles. Along with the difficulties infra-red mapping can be combined for the study of the inherent in analyzing minute quantities of remaining ma- distribution of organometallic complexes within residual terial, such objects are typically rare and valuable hence organic-rich regions of large specimens. We will also show destructive sampling is often precluded. Furthermore, how these methods can be used to select small regions for a range of geochemical processes may alter the specimen pinpoint destructive analysis in order to maximize chemi- in unpredictable ways. Specimen size may make it impos- cal results but minimize damage to precious material and sible to use standard techniques that require high vacuum. how overprinting geochemical processes may be resolved Therefore, new analytical methods have been developed to via thorough analysis of the embedding matrix. Examples make chemical analysis of large fossil specimens possible. In involving different biological tissues (skin, hair, feathers, this talk we will show how synchrotron methods can serve bone, leaves) from a range of locations and ages will be dis- as a spearhead in leading the analysis of such challenging cussed within the context of analytical approach, specimen material [3]. However, given the complex nature of the constraints, desired data, and final outcome. Special atten- analytical problem, it is almost always necessary to combine tion 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.

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72 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Treena Swanston1 - Tamara Varney2 - Ian Coulthard3 O-28 11 sept. 2014 16:30 > 16:50 Reg Murphy4, David Cooper1 1 University of Saskatchewan, Department of Anatomy & Cell Biology, S7N 5E5, Saskatoon, Canada 2 Lakehead University, Department of Anthropology, P7B 5E1, Thunder Bay, Canada Confocal X-ray 3 Canadian Light Source, Experimental Facilities Division, S7N 2V3, Saskatoon, Canada 4 fuorescence and National Parks Antigua, Heritage Resources, P7B 5E1, St. John’s, Antigua, W.I. the biogenic uptake of strontium in colonial Antigua

Strontium (Sr) is a non-essential trace element with tiple individuals associated with the Royal Naval Cemetery properties similar to calcium. Trace element analyses (1793-1822) in Antigua plus a sample from a pre-European in the past have included Sr as an element of interest contact site (Muddy Bay) as part of a larger project with the because its presence within modern bone is directly goal of identifying the social determinants of lead poisoning. related to the diet of that individual. Until recently, it Two of the samples indicating differential strontium uptake was difficult to determine whether Sr in archaeologi- during bone remodelling events were from individuals with cal samples was a result of biogenic uptake or diage- European ancestry as determined by the cranial features. nesis. Confocal X-ray fluorescence is a valuable tech- In this paper we will discuss the advantages of using nique for differentiating between these two modes. synchrotron radiation to identify the biogenic uptake of This technique was utilized at the Advanced Photon Source strontium, which suggests geographic and/or seasonal va- on Beamline 20-ID where we analyzed samples from mul- riation 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.

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74 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Bart van Dongen1 - Natalie Mccreesh1 - Holly Barden1 O-29 11 sept. 2014 16:50 > 17:10 Campbell Price2 - Tristan Lowe3 - Nicholas Edwards1 Jennifer Anne1 - Victoria Egerton1 - Phillip Manning1 Roy Wogelius1 1 University of Manchester, School of Earth, Atmospheric and Environmental Pigment preservation Science and Williamson Research Centre for Molecular Environmental Science, M13 9PL, Manchester, United Kingdom 2 University of Manchester, Manchester Museum, M13 9PL, Manchester, in Egyptian mummifed United Kingdom 3 University of Manchester, Henry Mosley X-Ray Imaging Facility, M13 9PL, tissues Manchester, United Kingdom

The image we have of ancient Egyptians mostly comes from Here we apply state-of-the-art synchrotron-based imaging how they depicted themselves in brightly coloured tomb and spectroscopy to analyse a sample of mummified hair paintings. Men and women are illustrated with jet-black hair. encased in a ball of clay from the New Kingdom (c. 1295 B.C), Mummified remains however tell a different story, the hair opened by Egyptologists a century ago [6] and currently found almost always appear to have a reddish-brown colour part of the Egyptology collection held at The Manchester and the same is true for animal remains. This uniformity of Museum (University of Manchester). Although having the colour has been attributed to partial oxidation of melanin same reddish-brown colour as most Egyptian mummified pigments [1,2] although red dyes may also have been ap- material, we identify original pigment composition and plied [3]. Our international research effort has recently de- discuss the impact of mummification on possible pigment veloped the ability to non-destructively image, analyse and preservation. Our approach provides a unique opportunity quantify chemical residues within palaeontological samples to study the effects of preservation methods widely applied with unprecedented speed and sensitivity. The work under- in antiquity with the potential to reconstruct the pigmenta- taken by a team from the University of Manchester, working tion of a suite of mummified tissue types. Our ultimate goal at both Stanford Synchrotron Radiation Lightsource and is to begin to restore the colour of Ancient Egypt. 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].

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.

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76 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Émilie Chalmin1 O-30 11 sept. 2014 17:10 > 17:40 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 art of the Australia due to archaeological and geomor- known thanks to its preservation in limestone caves in SW phological studies, which reveal the presence of the first Europe and in open sites (South of Africa, Tassili, Australia...); humans on the Australian continent (45-5000 years BP)[1,2]. however, this art is threatened by numerous alteration and However, in the absence of radiometric dates relating to the weathering phenomena. These phenomena could lead art (paintings, rock crusts), our aims are: to the damage or the total disappearance of the paints. (I) to systematically assess whether the painting could have Environmental parameters, meteorological and anthropic been done ~ 40,000 years ago and effects could be involved in these processes. (II) to characterize the painting matter. Due to the rock Understanding these phenomena involving physico-che- substrate weathering and the very thin layer of remaining mical and/or biological processes is essential to preserve pigment, the characterization is particularly challenging our cultural heritage and requires specific methodological and enables to understand the weathering process [3]. development adapted to the complex, delicate and pre- Secondly, the Lascaux cave, well known for the impact of the cious samples. The use of synchrotron-based methods is biocide treatment [4,5], is also threatened by the presence now well known to answer to this problematic of mixture of vermiculation, small aggregates of particles, bound by a of phases, heterogeneity of these kinds of samples. Through matrix of clay and precipitated calcite and often found in examples of rock art studies in France and Australia, the karstic environments. New vermiculations were reported investigation of natural and biosynthetic samples by means in some spots nearby paints. A protocol was proposed in of combined laboratory and synchrotron methods enables order to understand the formation mechanisms of vermicu- to reach 3 processes: lations, in order to prevent any impact of this phenomenon The first example is coming from Jawoyn rock art, in Arnhem on rock art [6]. Land (North Australia) considered as the most ancient rock 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 mas- Bibliography ked by a white opaque calcite layer [7]. The role of the bac- teria in the sensitive equilibrium of the cave environment [1] D avid, B., Geneste, J.-M., Whear, R. L. et al. (2011). Australian Archaeology 73: 73. seems to be non-negligible [5]. In the case of the Large cave, [2] D avid, B., Barker, B., Petchey, F. et al. (2013). Journal of Archaeological we attempt to determine if bacteria are playing a role in this Science 40(5): 2493-2501. [3] Chalmin E., Castets G., Delannoy J.J. et al. (submitted) coédition ERAUL opaque calcite layer supposed to be due to biomineraliza- (université de Liège) - Service géologique de Belgique tion. Two questions are addressed (i) Is it possible to find one [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): or several biogenic tracers in the natural neoformed calcite 644-652. phases? And (ii) can we find such biogenic tracers in natural [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. white opaque calcite from the Large cave and get clues on [8] Chalmin, E. & Reiche, I. (2013). Microscopy and Microanalysis 19: 1523-1534. the role of bacteria in their formation [8]?

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78 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Trinitat Pradell1 - Gloria Molina1 - Sonia Murcia2 O-31 12 sept. 2014 09:30 > 10:00 Judit Molera3 1 Universitat Politècnica de Catalunya, Dpt. Física, 08860, Castelldefels, Spain 2 Univrsidad de Valencia, 3Instituto de Ciencia de los Materiales, 46980, Paterna, Spain Materials, 3 Universitat de Vic, Escola Politècnica Superior, 08500, Vic, Spain techniques and conservation of 15th to 19th centuries stain glass “ grisailles ”

A grisaille is a brown-blackish paint applied onto the inner all over Europe becoming a fundamental decorative ele- surface of stain glass to draw the contours and details of the ment of the new esthetic movements; in this period stain figures and generate shades and volumes in the faces, hair, glass also incorporated technical innovations and a general hands and clothing. Grisailles were traditionally made of reformulation of the materials used, that seems to have finely ground oxides of iron but also of copper, zinc, lead or negatively influenced its stability. However, the micrometric manganese mixed with lead ground glass, Arabic gum and a layer structure of the grisailles (typical layer thicknesses vary medium such as vinegar or urine and fixed onto the flat glass between 10 and 100 µm) together with the low amount by firing. The lead glass is known to have a lower melting and diverse nature of the compounds (pigment particles, temperature than the window glass softening temperature crystalline and amorphous reaction compounds, aging and therefore, can be fixed without affecting its stability. and weathering compounds) have limited their identifica- Grisailles are consequently a mixture of unreacted subs- tion. The high brilliance, collimation, energy selection and tances, crystalline and amorphous compounds produced monochromacity of the SR beam are ideal to obtain 2D during firing but also resulting from their weathering and micro-XRD maps from thin cross sections of the grisailles. aging. Grisailles were applied between the 13th century XRD-patterns with a high signal to noise ratio and angular (Gothic) and the first half of the 16th century (Renaissance) resolution were obtained using a 20 µm × 20 µm spot size, together with yellow stains on either transparent or coloured 28 kV energy and a CCD camera, SX165 (Rayonix) area detec- bulk glass and also later with enamels and plaqué glass. tor in MDPD beamline at Alba-Cells. The analyses are com- During the second half of the 16th century the new religious plemented with SEM-EDX analyses of the cross sections of Calvinism Iconoclasm and the Reformation in the North the grisailles. A selection of grisailles from several cathedrals of Europe but also the Trento Council in the Catholic in Spain (Avila, Burgos, Alcalá de Henares, Segovia) a dating Church resulted in a mass destruction of stain glass and from 15th to the 19th century and belonging to several master its substitution by transparent glass in Religious buildings glaziers are studied. Changes in the methods of production and, consequently in a progressive loss of old stained glass and materials in the different historical periods are obtained techniques. Stain glass was rediscovered in the 19th century and also related to the conservation state of late materials.

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80 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Ilaria Cianchetta1 - Karen Trentelman1 - Brendan Foran2 O-32 12 sept. 2014 10:00 > 10:20 Marc Walton3 - Apurva Mehta4 1 T he Getty Conservation Institute, 1200 Getty Center Dr., 90049, Los Angeles, USA 2 T he Aerospace Corporation, 2350 E. El Segundo Blvd., 90245-4691, El Segundo, USA 3 Art Institute of Chicago, 111 S Michigan Ave., 60603, Chicago, USA Deciphering ancient 4 SLAC National Accelerator Laboratory, 2575 Sand Hill Road, 94025-7015, Menlo Park, USA ceramic fring conditions through replication

The decorated ceramics produced in ancient Athens from refined illitic clay and fired using a three-stage (oxidation-re- the 6th through the 4th centuries BCE, also known as Attic duction-oxidation) firing protocol, systematically varying the pottery, are considered a benchmark technological achie- temperature, and duration of the stages. The resulting gloss vement of the pre-industrial world. The iconic black-figure samples ranged in color from bright red to deep black, as vessels (black figures painted on red reserve), and the later, well as “ misfired ” samples in which both red and black gloss more refined, red-figure vessels (figures left in reserve on is formed, all similar in appearance to examples found on a black background), demonstrate a sophisticated control ancient Athenian pottery. The body and slip of the samples of particle morphology, porosity and firing conditions. were characterized by colorimetry, ICPMS, micro-XRF and Both techniques achieved the production of smooth XANES to determine the chemistry, color and mineralogy and glossy black surfaces layers – called black gloss – by of the gloss. Statistical analysisof the data indicate that the alternating the high-temperature kiln between oxidative temperature and duration of each of the oxidative steps – and reductive environments during firing. Areas painted the first and third stages in the canonical three step firing with a refined slip turned from red (due to the presence of sequence– is critical for controlling the color and the density 3+ Fe compounds: hematite, α-Fe2O3 and maghemite, γ -Fe2O3) of the glosses produced. 2+ to black (Fe iron compounds: magnetite, Fe3O4, hercynite, In order to understand the state of black gloss production

FeAl2O4) depending on the atmospheric condition of each technology and how it evolved over four centuries - from stage. Although a basic understanding of their production the Corinthian production of the 7th century BC, through the has been developed [1], details regarding the painting and Athenian production of the 6th and 5th century BC, ending firing schemes employed are still not completely understood with Faliscan and Apulian production of the 4th century BC - In order to understand the technological foundations of we examined and analyzed the color and mineralogy of 25 Athenian pottery production [2,3], we have examined each original Greek and Italian sherds belonging to the collection step of the black gloss production individually to understand of the J. Paul Getty Museum. This materials characterization the role of thermodynamics and kinetics in controlling the approach is beginning to provide very detailed glimpses overall process. This presentation will focus on the effects into not only how this benchmark technology evolved, but of firing conditions on the density and color of the gloss also the variations in the production processes practiced by produced. Over 50 replicate samples were painted with contemporary workshops.

Bibliography

[1] J.V. Noble, T he 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

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82 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Marie Albéric1,2 - Aurélien Gourrier3,4 O-33 12 sept. 2014 10:20 > 10:40 Wolfgang Wagermaier2 - Peter Fratzl2 - Ina Reiche1,5 1 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 Diference between Biomaterials Department, 14424, Potsdam, Germany 3 UMR 5588 CNRS Université Grenoble Alpes, Laboratoire Interdisciplinaire de Physique (LIPHY), 38000, Grenoble, France sub-microscopic 4 European Synchrotron Radiation Facility, Grenoble, FRANCE5 BESSY II; Helmholtz-Zentrum Berlin für Materialien und Energie, 14476, Berlin, Germany and macroscopic 5 Rathgen-Forschungslabor, Staatliche Museen zu Berlin, 14059, Berlin, Germany preservation states of marine archaeological elephant tusks revealed by micro-SAXS/WAXS analysis

Elephant ivory used to manufacture art objects from prehis- Micro-SAXS/WAXS profiling [4,5] performed under syn- toric to contemporary times is a biological nano-composite chrotron radiation at the MySpot beamline (BESSY II, Berlin) material subjected to complex physico-chemical alteration allowed us to characterize the structural features of three ele- mechanisms occurring over time [1,2]. Ivory, the dentin part phant tusks recovered from a 17th century Dutch shipwreck of elephant tusks is composed of an organic collagen-based in Brittany seawaters. By comparison to modern elephant matrix at 20 % with embedded Mg-rich carbonated hy- tusks, the structural changes have been identified and lin- droxyapatite (HAP) at 70 wt. % and 10 % water. It presents ked to different mechanisms, which slightly varies from one a highly hierarchical structure [3]. The proper conservation tusk to another depending on the very specific local marine of valuable ivory artefacts needs the understanding of environment of each tusk. The most surprising result is that the mechanisms responsible for structural modifications, the macroscopical preservation states of the surfaces do including the HAP crystal size, organization and collagen not always reflect the microscopical preservation states of fiber orientation. 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

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Daniela Saviello1 - Austin Nevin2 - Émeline Pouyet3 O-34 12 sept. 2014 10:40 > 11:00 V. Capogrosso4 - S. Bellei2 - A. Cesaratto4 - Sara Goidanich1 Lucia Toniolo1 - Marine Cotte3 1 Politecnico di Milano – Dipartimento di Chimica Materiali e Ingegneria Chimica, Via Luigi Mancinelli 7, 20131, Milano, Italy The use 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 of synchrotron 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, radiation for 3 rue Galilée 94200 Ivry-sur-Seine, France the analysis of the distribution of additives in ABS spectra, this study allowed comprehensive analysis, providing 2D images associated with molecular information about the design objects polymer composition and the presence of additives. It allowed the identification of protein-based additives as microscopic and model samples 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]. Acrylonitrile Butadiene Styrene (ABS)-based plastics are found Some of the aged model samples had been treated with op- in numerous design objects in museums collections and are tical brighteners and agar gel in order to improve the appea- widely used today for the excellent mechanical, chemical, rance of yellowed ABS. As a matter of fact, the yellowing of the and physical properties. However, ABS is susceptible to polymer was reduced in this way and at our knowledge this is photo-oxidative degradation and this instability often leads the first approach that does not involve the use of aggressive to the loss of properties, chemical modifications, worsening products. In this work, SR based µ-FTIR will allow mapping of mechanical performance and color changes, mainly the distribution of such added chemicals and evaluating the yellowing [1]. This is particularly tricky for the conservation of chemical modifications in the polymeric blend following the historical objects and there are currently no ethical methods treatment, a key issue in the assessment of treated samples. to reverse the yellow appearance. The assessment of the In a historical object analyzed, microscopic inclusions contai- role of additives in polymers degradation is a critical point ning Cd and S were identified through preliminary SEM for the conservation and preservation of artefacts made in analyses. SR-based μ-FTIR, µ-XANES and µ-XRF spectroscopies plastics. Natural polymers, organic additives and inorganic will be soon used to map traces of such Cd-based pigments colorants are usually found in historical ABS; these materials in thin sections. While CdS-based are well-known as colorants are heterogeneously distributed in plastics and are present as and stabilizers in ABS used in the past, there are now significant microscopic inclusions, requiring spatially resolved analysis for concerns regarding the leaching of toxic Cd ions from plastics. their complete characterization. In the context of the degradation and stability of historical SR-Fourier Transform Infrared Spectroscopy (SR-FTIR) analyses plastics, it is not clear if Cd-based colorants improve long-term were carried out on historical design objects at the ID21 stability of ABS to photo-oxidation or if CdS based colorants beamline of the European Synchrotron Facility (ESRF). Com- present on the surface of the objects are sensitive to oxidation bining high spatial resolution with high signal to noise ratio 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)

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Farideh Jalilehvand1 - Magnus Sandström2 O-35 12 sept. 2014 11:30 > 11:50 Yvonne Fors3 - Vicki Richards4 1 University of Calgary, Department of Chemistry, T2N 1N4, Calgary, Canada 2 Stockholm University, Department of Materials and Environmental Chemistry, 10691, Stockholm, Sweden X-ray spectroscopic 3 D epartment of Conservation, University of Gothenburg, 41320, Göteborg, Sweden 4 characterization Western Australian Museum, Shipwreck Galleries, 6160, Fremantle, Australia of sulfur compounds in marine archaeological wood

Conservation of marine archaeological wood from histo- rical shipwrecks increasingly relies on modern analytical techniques to obtain insights into improving specifically designed treatments [1]. Synchrotron radiation plays an of different types of functional sulfur groups are evaluated, important role in allowing characterization of many types while the total sulfur and iron concentrations are obtained of sulfur and iron compounds accumulated in the wood on by calibrating their X-ray fluorescence in XRF experiments. the seabed, which is important in assessing the long-term High resolution X-ray spectromicroscopy at the sulfur K-edge detrimental processes associated with their post treatment. shows that organically bound sulfur (mainly thiols, disulfides) Generally, the incorporated sulfur compounds originate from accumulates in lignin-rich parts of the wood cell walls. Of hydrogen sulfide produced by sulfate-reducing bacteria in special interest for the conservation treatment regime are, wood buried under the seabed [2-4]. Analyses of the amount however, the iron sulfides including pyrite, which form in and speciation of the sulfur compounds can be performed the presence of corroding iron objects. The iron sulfides by X-ray spectroscopic methods, in particular sulfur K-edge are subsequently easily oxidised at post treatment under XANES (X-ray Absorption Near Edge Structure), combined atmospheric conditions with high humidity. Sulfur K-edge with elemental analyses by scanning X-ray fluorescence XANES spectra often show iron sulfides to be present in (XRF) of wood cores. By fitting normalized sulfur K-edge treated museum artefacts affected by acidity problems and XANES spectra of structurally known sulfur compounds as formation of iron sulfate salts. Laboratory experiments show models to spectra of wood samples, the relative amounts 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 Bibliography Skuldelev Viking ships, Denmark, the Vasa, Sweden) will be [1] Y. Fors, F. Jalilehvand, M. Sandström, Analytical Aspects of Waterlogged compared with timber samples recovered from the seabed Wood in Historical Shipwrecks, Anal. Sci., 2011, 27, 785-792. [2]. Y. Fors, T. Nilsson, E. D. Risberg, M. Sandström and P. Torssander, Sulfur (e.g. from the Pandora, Australia, the Mary Rose, UK, the Ghost accumulation in pine wood (Pinus sylvestris) induced by bacteria ship and Kronan, Sweden) to discuss the effects of various in simulated seabed environment: implications for marine-archaeological wood and fossil fuels, Int. Biodeterior. Biodegrad., 2008, 62, 336-347. conservation treatments. [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.

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Chris McGlinchey1 - Felisa Berenguer2 - Kevin G. Yager3 O-36 12 sept. 2014 11:50 > 12:10 Rebecca Ploeger4 - René de la Rie5 1 The Museum of Modern Art, 11 West 53Rd St, 10019, New York, Ny, USA 2 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 Synchrotron X-ray 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, scattering Amsterdam, The Netherlands of ethylene vinyl acetate copolymer based art conservation adhesives: elucidation of morphological diferences

The ethylene vinyl acetate copolymer based art conservation polyethylene component of the copolymer to recrystallize adhesives BEVA 371 and BEVA 371b are dry to the touch at upon cooling. Pure EVA copolymers at 20 ºC indicate a crystal room temperature and become highly tacky soft solids ca- structure (peak at Q ~ 0.055 nm–1) that is nearly eliminated in pable of adhesion between 60 and 65 ºC, the recommended formulation 371, but retained in 371b. This indicates that the activation temperature for both adhesives. These two for- polyethylene phase is mostly amorphous in 371 at room tem- mulations have the same semicrystalline components (two perature which helps explain the gradual tack development ethylene vinyl acetate (EVA) copolymers and paraffin wax) but as the material is heated. When heated to 65 ºC both show have different low molecular weight additives (amorphous a peak at Q ~ 0.03 nm–1 but in formulation 371b it is much ketone resins). Recent published findings (Ploeger 2014) stronger, indicating greater crystallinity. Formulation 371, have found that the formulations vary in tack below the re- examined by wide angle X-ray diffraction at beamline X27C commended activation temperature: 371 begins to develop at Brookhaven National Lab, exhibited diffraction peaks some tack above 45 ºC while 371b achieves tack more abrup- corresponding to the -CH2- (orthorhombic) unit cell, which tly between 55 and 60 ºC. This is significant because 371, were retained at the activation temperature, 65 ºC. Polarized the original formulation, is no longer available yet having light microscopy at 65 ºC also shows a weak crystal structure gradual tack development can sometimes be exploited by evenly dispersed throughout the material in both formu- conservators if the object is temperature sensitive or a wea- lations and helps explain why neither acts as free-flowing ker adhesive bond is desired. Small angle X-ray scattering liquid at the recommended activation temperature. The (SAXS) studies help reveal the structural differences that are findings demonstrate that SAXS is a useful tool to study likely responsible for the change in activation properties. resin-copolymer compatibility for this class of adhesives and These studies carried out at the SWING beamline at SO- may help guide the development of future formulations LEIL indicate the ketone resins influence the ability of the when specific activation properties are desired.

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Domagoj Mudronja1 - Frederik Vanmeert2 O-37 12 sept. 2014 12:10 > 12:30 Kevin Hellemans2 - Stjepko Fazinic3 - Darko Tibljas4 Koen Janssens2 1 Croatian Conservation Institute, Government research institute, 10000, Zagreb, Croatia Optimization of 2 University of Antwerp, Government University, 2610, Antwerp, Belgium 3 Rudjer Boskovic Institute, Government Research Institute, 10000, Zagreb, Croatia an ammonium oxalate 4 Institute for Mineralogy and Petrology, Government University, Zagreb, Croatia treatment for the protection of monumental limestone and marble surfaces

Stone samples have been treated with two application me- less porous (2 %) Carrara marble there is only a small difference thods (poultice and brushing) using a solution of ammonium between the shorter and longer treatment. The oxalate layer oxalate (AmOx) and varying treatment time. Limestone and thickness, consisting of both weddellite and whewellite, marble model samples with different porosity were selected, is between 30 and 40 µm. The measured diffraction intensity and attention was specifically focused to study brushing of both calcium oxalates is approximately the same for both treatment, which is economically more feasible on large treatments. On the more porous (7 %) Veselje limestone the surfaces than the poultice method for creating an acid-resis- difference between the shorter and longer brushing treat- tant calcium oxalate (CaOx) layer. The distribution/contrast ment is more visible. The thickness of the weddellite layer is between calcite and the two Ca-oxalate forms (weddellite approximately the same for both treatment times (roughly and whewellite) on treated stone samples was visualized using 50 µm). Whewellite reaches a depth of around 400 µm with synchrotron-based micro analytical techniques (SR-µXRD the 3h treatment compared to 150 µm for the 1h treatment. in transmission geometry with 10.5 × 6.5 µm2 (hor. × vert.) The measured intensity of both calcium oxalates is higher on probe size and SR-µFTIR with 10×10 µm2 probe size). SR-µXRD stones treated with the longer treatment time. provided information on the layer thickness of the two oxalate SR-µFTIR comparison of the CaOx distribution on surfaces forms while SR-µFTIR was used to visualize the distribution of treated by brushing on two model stones showed that on calcium oxalate on the stone surface. a less porous Carrara marble there is no difference between SR-µXRD results of two brushing treatments (1 and 3 hours shorter and longer treatments. This difference is more visible treatment time) on two different stones showed that on the 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 Bibliography brushing treatment the layer of CaOx is more homogeneous, so [1] D e Nolf, W., Janssens, K., Surface and Interface Analysis, 2010, 42, 411 there is no more CaCO left on the surface to react with AmOx. [2] D oherty, B., Pamplona, M., Selvaggi, R., Milliani, C., Matteini, M., Sgamellotti, 3 A., Brunetti, B., Applied Surface Science, 2007, 253, 4477 On the more porous stone after one hour of treatment, there is [3] D oherty, B., Pamplona, M., Matteini, M., Sgamellotti, A., Brunetti, B., Journal still some CaCO on the surface that reacts during subsequent of Cultural Heritage, 2007, 8, 186 3 [4] Mairani, A., Matteini, M., Rizzi, M., OPD Restauro, 2000, 12, 146 application of AmOx. [5] Matteini, M., Moles, A., Lanterna, G., Nepoti, M.R., International Symposium II: Both analytical methods confirmed that on less porous stones The Oxalate Films in the Conservation of Works of Art, 1996, 425 [6] Matteini, M., Conservation Science in Cultural Heritage, 2008, 13 (<2 %) there is actually no difference between different ap- [7] Mudronja, D., Vanmeert, F., Hellemans, K., Fazinic, S., Janssens, K., Tibljas, plication methods and treatment times, since a protective D., Rogosic, M., Jakovljevic, S. Applied physics. A, Materials science & processing, 2013, 111, 108 CaOx layer has been homogeneously formed after 1 hour of [8] Pinna, D., Salvadori, B., Porcinai, S., Construction and Building Materials, brushing or ten hours of poultice treatment. Stones that are 2011, 25, 2723 more porous need a longer brushing treatment to create [9] Vanmeert, F., Mudronja, D., Fazinic, S., Janssens, K., Tibljas, D., X-ray

spectrometry, 2013, 42, 256 a similar CaOx layer.

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Catherine Dejoie1 - Philippe Sciau2 - Weidong Li3 O-38 12 sept. 2014 14:10 > 14:40 Laure Noe2 - Apurva Mehta4 - Kai Chen5 - Hongjie Luo6 Martin Kunz7 - Nobumichi Tamura7 - Zhi Liu7 1 ETH Zurich, Lab. of Crystallography, 8093, Zurich, Switzerland 2 CEMES, 31055, Toulouse, France Learning from 3 Chinese Academy of Sciences, Shanghai Institute of Ceramics, 200050, Shanghai, China 4 Stanford Synchrotron Radiation Lightsource, 94025, Menlo Park, USA the past: the formation 5 Xi’an Jiaotong University, Center for Advancing Materials Performance from the Nanoscale, 710049, Xi’An, China 6 Shanghai University, 200436, Shanghai, China process of rare ε-Fe2O3 7 Lawrence Berkeley National Lab, Advanced Light Source, 94720, Berkeley, USA in the ancient black-glazed Jian (Tenmoku) wares

Ancient Jian wares are famous for their lustrous black glaze the presence of ε-Fe2O3, a rare metastable polymorph of that exhibits unique colored patterns [1,2]. Some striking Fe2O3 with unique magnetic properties [4], in both HF and examples include the brownish colored « Hare’s Fur » (HF) OS samples. The micro-XRD results also indicate that there are strips and the silvery « Oil Spot » (OS) patterns. The Black differences between ε-Fe2O3 crystallites in the HF sample and glazed “ Jian ware ”, also known in Japan as “ Temmoku ware ”, the OS sample. The ε-Fe2O3crystallites in HF are nanometer was mainly produced in Jian Kiln located in Jianyang of Fujian size and randomly oriented, while the ε-Fe2O3 crystallites in Province. The surface patterns of the Jian wares such as Hare’s the OS sample grow to larger micron size with a dentritic tex- Fur and Oil Spot are believed to originate from the crystal- ture. This is a direct indication that the firing conditions of ce- lization of iron oxides. It is currently believed that hematite ramics significantly affect the formation of iron oxide crystals.

(α-Fe2O3) crystals are formed on the HF surface and mixtures OS firing conditions are clearly more favorable to the for- of magnetite (Fe3O4) and hematite crystals are precipitated mation and stabilization of ε-Fe2O3 crystallites of larger size, on the OS surface [3]. However few mineralogical studies which are significantly larger than nano-sized ε-Fe2O3 crystals have been carried out to confirm this theory. To reveal the that can be synthesized today. These results shed new lights crystallographic nature of the iron oxides and their formation on the actual mechanisms and kinetics of polymorphous mechanism, we have investigated the microstructure and transitions of Fe2O3. Deciphering technologies behind the local chemical composition of ancient Jian bowl samples fabrication of ancient Jian wares has the potential to provide through a combination of X-ray based and electron based new pathways for the industrial synthesis of the metastable characterization techniques. For the first time, we identified ε-Fe2O3 phase.

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] T ronc, 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).

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Lukas Helfen1 - Peter Reischig2 - Arie Wallert3 - Joris Dik4 O-39 12 sept. 2014 14:40 > 15:00 Tilo Baumbach2 1 ESRF, ID19, 38000, Grenoble, France 2 KIT, IPS, 76021, Karlsruhe, Germany 3 Rijksmuseum, Restoration and Research, 1070 DN, Amsterdam, The Netherlands Synchrotron 4 TU Delft, 3mE, 2628 CD, Delft, The Netherlands laminography for µm-scale three-dimensional region-of-interest imaging of fat artwork

Synchrotron laminography is presented as a non-destructive We will point out the potential of synchrotron laminography for tool to obtain three-dimensional (3D) information about 3D region-of-interest imaging of flat artwork. Synchrotron lami- paintings and other flat artwork. Information on the genesis nography, initially developed for the non-destructive high-resolu- and decay of historical paintings usually lies hidden under tion imaging in microelectronics and microsystem technology [1], the paint surface. Traditional methods for the study of hidden allows one to zoom with varying spatial resolution into the paint layers (like radiography and different microscopy tech- paint layer system and to image more representative parts of niques) have shortcomings in the lack of depth information / a painting. It has recently been shown to yield complementary separation and destructiveness. Confocal methods (e.g. information about paint stratigraphy and substructure on mock- based on X-ray fluorescence) are restricted to investigate up specimens [2-4]. Additionally, we will present first results rather limited 3D regions due to the dwell time required at obtained at the ESRF X-ray imaging beamline ID19 on historical each scanning point. 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, “ T hree-dimensional Imaging of Paint Layers and Paint Substructures with Synchrotron Radiation Computed µ-Laminography ”, J our nal 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)

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Émeline Pouyet1 - Marine Cotte2 - Barbara Fayard3 O-40 12 sept. 2014 15:00 > 15:20 Anna Lluveras-Tenorio4 - Jennifer Mass5 Daniela Saviello6 - Austin Nevin7 - Philippe Sciau8 1 European Synchrotron Radiation Facility, 38000, Grenoble, France 2 LAMS UMR-8220, 94200, Ivry-Sur-Seine, France Combined 3 Laboratoire de Physique des Solides, 91405, Orsay, France 4 D epartment of Chemistry and Industrial Chemistry, 56100, Pisa, Italy 5 Scientific Research and Analysis Laboratory, Conservation Department, synchrotron-based 19735, Winthertur, USA 6 Politecnico di Milano, Dipartimento di Chimica Materiali e Ingegneria Chimica, 20133, Milano, Italy micro-spectroscopic 7 Consiglio Nazionale delle Ricerche, Dipartimento di Fisica, 20133, Milano, Italy 8 analyses of painting CEMES, 31055, Toulouse, France thin-sections

The complex and heterogeneous structure of paint samples I) asian historical leanly bound gilded sculpture fragments, and compromises their chemical characterization. Spectral-ima- II) samples from polymeric design objects from the 1960’s. ging techniques, combining microscopy and spectroscopy, The first set of samples shows complex multi-step gilding are very well suited to achieve full 2D chemical descriptions of techniques based on the use of saponified oil as a mordant. fragment sections. Both the composition and the stratigraphy The polymer samples present a degraded surface due to of the multilayered complex mixtures in samples are probed. photo-oxidation processes, which could be studied analyzing Access to a multi-modal and non-invasive platform able to artificially aged model samples. These results could not have perform both X-ray and FTIR micro spectroscopies is very been obtained without the development of dedicated sample promising for the characterization of painting samples. In this preparation. context, user communities are pushing towards an improved The development of new micro-spectroscopy tools for im- and easier combination of these techniques [1]. For successful proving and diversifying the capabilities imaging beamlines application of both FTIR and X-ray analysis it is necessary to are also in progress. In particular, a new micro-spectroscopy improve i) sample preparation and ii) instrumental capabilities. tool based on a 2D full-field XANES set-up was developed at Indeed, the full exploitation of both micro-FTIR and X-ray ID21, ESRF, combining XAS with full-field X-ray microscopy [3]. techniques through transmission measurements can open In this set-up a series of radiographies are acquired over new avenues for hyper-spectral characterization of historical millimetric field of view (up to 2 mm2) with sub-micron re- paintings. The most standard sample preparation approaches solution (down to 0.3×0.3 µm2), while scanning the energy will be discussed and the related possible analytical and of the incoming beam around the absorption edge of the chemical interferences will be illustrated and solved using element of interest. Millions of XAS spectra are thus acquired two examples [2]: within few minutes in low dose configuration. This technique is therefore very well-suited for the 2D study of multilaye- red and heterogeneous samples such as artistic materials. The new XANES full-field imaging end-station will be intro- duced and its capabilities will be illustrated with the first ex- periments carried out on historical painting samples. As long as samples can be prepared as thin-sections of micrometric

Bibliography thickness, the set-up is largely applicable to a broad range of materials, and successful analyses will be presented on [1] M. Cotte et al., Journal of Analytical Atomic Spectrometry, 23, p. 820-828 (2008) samples from ancient glasses, papers and ceramics [4]. [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)

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98 ABSTRACTS FOR ORAL PRESENTATIONS Synchrotron radiation and neutrons in art and archaeology Conference RÉSUMÉS DES PRÉSENTATIONS ORALES Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Matthieu Réfrégiers1 - Mathieu Thoury1,2 O-41 12 sept. 2014 15:20 > 15:40 Bertrand Cinquin1 - Frederic Jamme1 1 Synchrotron SOLEIL, DISCO, 91192, Gif Sur Yvette, France 2 New developments IPANEMA, DISCO & IPANEMA, 91192, Gif Sur Yvette, France and opportunities in synchrotron ultraviolet luminescence microscopy

Use of synchrotron deep ultraviolet (DUV, below 350 nm) for samples. In addition, to record full field UV luminescence images, exciting luminescence opens up new possibilities in historical a full field DUV microscope with only one transmission optic has samples studies because, it does not need external specific been installed on the DISCO beamline imaging branch. Due to probes or labeling, but instead allows taking profit of the intrinsic diffraction limit the lateral resolution is always increased when properties of the materials studied. looking in the UV range allowing nanometric spatial resolution. It is possible to track at the same time, semi-conductors locali- New developments are underway on the beamline for better zation and embeding biomaterials. flexibility: UV monophotonic excitation does present real spec- We have developed two DUV fluorescence microscopes set-up tral excitation, paving the way to excitation imaging for better for luminescence coupled to a synchrotron beamline, providing selectivity of the chromophores. Moreover, we are installing a fine tunable excitation from 200 to 600 nm and full spectrum semi structured illumination scheme in order to perform HiLo acquired on each point of the image, to study DUV excited microscopy for full-resolution optically sectioned images of fluorescence emitted from nanovolumes directly inside complex 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] T awil, 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] Z ubkovs, V., Jamme, F., Kascakova, S., Chiappini, F., Le Naour, A., & Refregiers, M. Analyst, on line first [6] T houry, 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.

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ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Eleanor Cato1 - Jaap J. Boon1 - Camelia Borca2 P-01 Rouge/Red 10 sept. 2014 17:00 > 20:00 Daniel Grolimund2 - Luca Quaroni2 - Ester S. B. Ferreira1 1 SIK-ISEA, Art technology, 8032, Zurich, Switzerland 2 Characterisation, Paul Scherrer Institute, Synchrotron radiation, 5232, Villigen, Switzerland distribution and origin of mixed Tutton salt eforescence in early 20th century degraded cadmium yellow paint in the oeuvre of Cuno Amiet (1868-1963)

A total of 70 paintings by the Swiss artist Cuno Amiet (1868-1963) cross section for study by light microscopy and SEM-EDX, were examined within the context of a technological study of and finally the subsequent preparation of a thin section for his early oeuvre from 1883-1914. Several paintings exhibit sur- micro-XRF and micro-XRD (approx. 35 micron thickness) and face efflorescence on the cadmium yellow containing paint. micro-FTIR by polishing down to 5 microns. The 3D rendering Cuno Amiet used cadmium yellow as such or in pigment mix- of the different phases obtained from on the XTM data demons- tures in paintings throughout the period studied but it is the trate that the crystalline efflorescence was present in different dominant yellow in his palette after 1908. Particularly interesting depths of the sample and is not only a surface phenomenon. is his work from 1913. While preparing a series of paintings for The efflorescent growth is the physical cause of the delamination a Kunsthaus Zürich commission, he extensively used light cad- of the paint layer. The analysis of this crystalline efflorescence mium yellow - a CdS/ZnS pigment with significant amounts of by FTIR indicates the presence of Tutton salts as an ammonium cadmium carbonate and cadmium oxalate. Four of the 8 pain- sulphate double salt of zinc and/or cadmium. Comparison tings from this series were studied and the examination of the with synthesised references shows that the FTIR spectroscopy remaining four is planned. All exhibit a similar formation of a Zn can’t discriminate between Cd(NH4)2(SO4)2 and Zn(NH4)2(SO4)2. and Cd containing efflorescence despite different ownerships However, the synthesised double salts produce different XRD and conservation histories. We infer that the original pigment patterns. The high spatial resolution of the micro-XRF and quality or paint mixture is a determining factor in the reactivity. micro-XRD setup at the microXAS beamline at PSI enabled the A multistep analytical approach was developed involving X-ray mapping of the two phases in the thin section. The micro-XRF tomography (XTM) followed by production of a suitable target 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

Bibliography Amiet’s 1913 painting series. Cd(NH4)(SO4) efflorescence has been detected before in a 1921 painting by James Ensor [1] [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 but its origin remained unclear and was thought to be possibly Radiation Based X-ray Techniques. » Analytical Chemistry 81(7): 2600-2610. associated with conservation treatments.

103 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Jacopo Corsi1 - Alessandro Lo Giudice1 P-02 Rouge/Red 10 sept. 2014 17:00 > 20:00 Alessandro Re1 - Angelo Agostino2 - Antonella Scherillo3 Francesco Grazzi4 - Zsolt Kasztovszky5 - Boglarka Maroti5 Laszlo Szentmiklosi5 - Federico Barello6 1 Università di Torino and INFN, Dipartimento di Fisica, Via Giuria 1, 10125, Torino, Italy Characterisation 2 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 of silver pre-Roman 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, coins from Northern 10122, Torino, Italy Italy with neutron-based techniques

During the last two years, several pre-Roman coins from northern with the INES diffractometer [4] at the ISIS facility (Rutherford Italy have been analysed thanks to neutron-based techniques Appleton Laboratory, UK) on coins coming from the Biandrate such as neutron diffraction (ND) and prompt gamma activation (NO), Casale Monferrato (AL) and Serra Riccò (GE) hoards and analysis (PGAA). This coinage is a collection of several series of from some numismatics collections in Turin. The analysis of dif- silver coins, called drachmas, produced by different Celtic and fraction patterns has been carried out with the GSAS software to non-Celtic tribes settled in northern Italy between the 4th and determine phase weight fractions through Rietveld refinement. the 1st century B.C. They are all characterized by the imitation of Other pre-Romans coins, kept at the Hungarian National Museum [5], the lion depicted on Massalia’s heavy drachm, whose different have been measured at the PGAA station [6] of the Budapest styles have been used by numismatists to group them in typo- Neutron Centre. The possibility to analyse these coins has been logies. Many issues still remain unsolved, such as chronology, a unique chance, because of the richness of the collection and attributions and relationships within the emissions [1-2]. the presence of several typologies not previously analysed. To provide new data for this study, a selection of specimens The results obtained on around 100 coins show a clear silver coming from different hoards and museum collections, re- debasement occurring among the first and latter drachmas presentative of different emissions, has been analyzed with emissions, due to inflation processes which can be related with non-destructive neutron based techniques, which allowed the the increasing economic power of the Roman republic in the problem of the silver surface enrichment [3] to be overcome. Po valley. The silver loss can be also used to establish a relative We performed time-of-flight neutron diffraction measurements 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 Bibliography Roman republican currency. Finally, a comparison between ND [1] Pautasso, A., 1966. Le monete preromane dell’Italia settentrionale, and PGAA measurements will be presented, providing results Sibrium, 7: 1-162. [2] Arslan, E.A., 1995. La monetazione celtica cisalpina. Un nuovo both on standards and coins, in order to combine the results quadro generale, Sibrium, 22: 179-215. obtained with the two techniques. [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 Acknowledgements: in Physics Research B, 226: 153-162. [4] Grazzi, F., Celli, M., Siano, S., Zoppi, M., 2007. Preliminary results of the Italian This project has been supported by the Cooperation Agree- neutron experimental station INES at ISIS: Archaeometric applications, ment no. 06/20018 between CNR and STFC. The financial Il Nuovo Cimento C, 30: 59-65. support by CHARISMA Grant Agreement n. 228330 is grate- [5] Arslan, E.A., 1991-1992. Le monete padane preromane a Budapest, Numizmatikai Közlöny, XC-XCI: 9-33. fully acknowledged. We kindly acknowledge Dr. M. Torbágyi [6] Révay, Zs., Belgya, T., Kasztovszky, Zs., Weil, J.L., Molnár, G.L., 2004. for the loan of coins of the Hungarian National Museum Cold neutron PGAA facility at Budapest, Nuclear Instruments and Methods in Physics Research B, 213: 385-388. and Dr. A. Guerrini for those from the Armeria Reale in Turin.

104 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Milene Gil1 - Jose Antonio Pestana2 - Luis Dias1 P-03 Rouge/Red 10 sept. 2014 17:00 > 20:00 Lucia Tobias1 - Ana Cardoso1 - Catarina Miguel1 Jose Mirão1 - Antonio Candeias1

1 Analytical HERCULES Laboratory, 7000-809, Évora, Portugal characterisation of gilding techniques in secco 16th century murals at the Convent of Christ (Tomar, Portugal)

A combined analytical approach has been adopted for the Acknowledgments study of the gilded decorations, presumably from the 16th The authors wish to acknowledge the Fundação para century, of the Convent of Christ Charola in Tomar. The main a Ciência e Tecnologia for financial support (Pós-doc goal was to compare the gilded materials and techniques grant SFRH/BPD/63552/2009) and projects ONFINARTS used in six murals pannels with angels. Thirteen microsamples (PTDC/EAT-HAT/115692/2009) and PRIM’ART (PTDC/CPC- from the clothes, bases and frames paint layers were collected EAT/4769/2012), funded by FCT/MEC and co-funded by in order to attest originality and contemporaneity. Fundo Europeu de Desenvolvimento Regional (FEDER) The analytical setup comprised optical microscopy (normal through the program COMPETE. 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 imme- diatly 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.

105 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Prayoon Songsiriritthigul1 - Markus Kleine2 P-04 Rouge/Red 10 sept. 2014 17:00 > 20:00 Josef Hormes3 1 Institute of Science, Suranaree University of Technology, Korat, Thailand 2 Glasmalerei Peters Gmbh, Paderborn, Germany 3 Center for Advanced Microstructures and Devices (Camd), Louisiana State Corrosion products University, Baton Rouge, USA from window 116 of the Cathedral of Chartres: a combined study using X-ray fuorescence and X-ray absorption near edge structure spectroscopy

The corrosion of glass is a very complex process as it depends monochromatic radiation of 10 keV and detected using a on external conditions (e.g. micro-climate, pollution) as well 13-element Ge-detector. For the assignment of elements as on the composition of the glass (color, content of potas- and a rough calibration of fluorescence intensities NIST stan- sium etc.). While the basic mechanisms of the degradation dard glass samples (NIST 610 and NIST 612) were measured. process are known, there are still some open questions that The fluorescence spectra of all 6 samples are dominated by have be answered for finding the “ best ” method for clea- the signals from 5 elements: Ca, Mn, Fe, Cu, and Zn with a ning and protecting historic glass. The Chartres Cathedral very clear additional signal from sulfur. There are unexpecte- (UNESCO World Heritage Site) is famous for its stained glass dly strong variations in the Ca/K – ratio between the samples windows. The majority of the windows (about 150 out of indicating that the leaching process is strongly influenced the 176) were made and installed between 1205 and 1240. by the other constituents of the glass. Based on the Mn/Fe The samples for this investigation were taken from one ratio one can distinguish at least two groups of samples: for of the clerestory windows (window 116) of the cathedral samples coming from “ blue ” glasses, the Mn/Fe-ratio is < 1; (dated to the period 1228–31) that was recently restored at for samples from yellow/skin colored and reddish samples the Glasmalerei Peters in Paderborn. By using a spatula six the Mn/Fe ratio is ~ 1. Also the sample coming from a corrosion samples were taken from differently colored fields green field of the window has a Mn/Fe ratio < 1, but here of the window. The corrosion products had different colors the general fluorescence pattern is changed by very strong (from beige to dark brown) and varied in their structure Cu Kα and Cu Kβ lines. The K-XANES spectra that have been between powdery and flaky. Experiments were carried out recorded for the major elements indicate that in opposition at Beamline 8 at the Synchrotron Light Research Institute to general expectation not all elements in the corrosion layer (SLRI) in Korat (Thailand). Fluorescence was excited using are present just as sulfates.

106 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Katrien Keune2 - Jennifer Mass1 - Florian Meirer3 P-05 Rouge/Red 10 sept. 2014 17:00 > 20:00 Carol Pottash4 - Annelies van Loon4 - Alyssa Hull5 Apurva Mehta6 - Arthur Woll7 - Robert Gordon8 Adam Finnefrock9 - Émeline Pouyet10 - Marine Cotte10 th 1 Winterthur Museum, Conservation Department, 19735, Winterthur, USA Early 18 c. 2 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 arsenic pigments 5 University of Delaware, Department of Chemistry, 19716, Newark, USA 6 SLAC National Accelerator Laboratory, Stanford Synchrotron Radiation Lightsource, 94025, Menlo Park, USA in the old and new 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 worlds: tracking the 10 ESRF, 38043, Grenoble, France transformation and migration of arsenic 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 mi- sulfde pigments in croanalysis and Raman microspectroscopy. Confocal microspec- troscopy was carried out at APS. This presentation will focus on a Dutch golden age results from X-ray microspectroscopy: X-ray fluorescence mode (XRF scanning) allowed precise mapping of local elemental dis- still-life and new tribution, while X-ray Near-Edge Absorption Structure (XANES) in combination with multi-energy XRF mode allowed identification England polychromed and mapping of the gross chemical speciation. chest on stand 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

Arsenic sulfide pigments orpiment (As2S3) and realgar (As4S4), 1 eV from 11867 to 11877, clearly indicate the presence of mul- are well known to shift color under exposure to visible light. tiple As species. The Coorte contains still intact AsSx species as Realgar undergoes photo-induced polymorphism and turns bri- well as oxidized As species, while Saybrook contains oxidized ght yellow (pararealgar) to colorless (As2O3, arsenolite), whereas As species only. Confocal XRF of the As species in the Coorte orpiment photo-oxidizes and becomes colorless (arsenolite). ground layer confirmed that only oxidized species are present. Here we report on this transformation as well as the charac- Comparison of the Coorte XANES spectra and their prinicipal terization of the reaction products and their mobilities, based components with published spectra and As reference com- th on investigation of two works of art from the early 18 century: pounds were carried out. These analysis suggest As2S3 (most

Still life with five apricots by Adriaen Coorte (1704) (Royal reduced), Ca3(AsO4)2 (most oxidized), and As2O3 can adequately Picture Gallery Mauritshuis, The Hague, The Netherlands) and represent the majority of the As speciation in the sample. The an colonial American polychromed chest on stand attributed to arsenate and arsenite products are very mobile. The arsenate

Charles Guillam painted in Saybrook, Connecticut c. 1710-1727 species seems to have reacted with the gypsum (CaSO4) in the

(Winterthur Museum, Wintherthur, USA). 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Phillip Manning1 - Roy Wogelius1 - Nicholas Edwards1 P-06 Rouge/Red 10 sept. 2014 17:00 > 20:00 William Sellers1 - Bart van Dongen1 - Sam Webb2 Victoria Egerton1 - Rodolfo Coria3 - Tristan Lowe1 Uwe Bergmann2 1 University of Manchester, ML39PL, Manchester, UK Synchrotron-based 2 Slac National Accelerator Laboratory, 94025, Menlo Park, USA 3 imaging fossilised Conicet – Universidad Nacional De Río Negro, 00000, Plaza Huincal, Argentina dinosaur skin

Integument colour is controlled by both the chemical and Edge Structure spectroscopy to provide detailed information structural characteristics of a material, whether it is skin, hair, on the trace-metal inventory and oxidation state of elements feathers or any other biological tissue. Colour is crucial in the within these fossils, and demonstrates that organically derived evolution of species through multiple selective advantages endogenous compounds are present. The results support that might include camouflage or display. The combination earlier work that showed both structure and macromolecular of morphology (structural) and biomarkers (chemical) has composition of dinosaur skin can be conserved for over 66 been used to infer colour and pigment patterns in a range million years [3]. Additional infrared spectroscopy mapping of extant and extinct organisms, including iconic fossils indicates the presence of key functional groups within the such as Archaeopteryx [1]. Melanin is the most widely used skin of both samples, indicative of the breakdown pro- pigment in vertebrates and consists of several covalently ducts (amide groups) from endogenous structural proteins linked indoles and is considered an unusually large polymer (comparable to keratin) [4]. When combined with the results compared to most natural pigments. The sheer size and com- from the synchrotron-based imaging in this study we show plexity of these molecules determines their precise structure clear evidence for the presence of Cu-O/Cu-N complexa- and physical properties and also controls their bonding to tion, indicative of endogenous pigments still being present other components (e.g. proteins, metal ions) [2]. Here we within discrete biological tissue samples from exceptionally analyse two key specimens of fossilised dinosaur skin using preserved fossil integument. The trace-metal coordinated non-destructive chemical analysis in order to investigate the biochemistry of melanin-type pigments in dinosaur skin po- potential for pigment preservation in the integument; one tentially played key roles both in life and death. Melanin, rich sample from an embryonic sauropod dinosaur (~90 million in trace-metals, functioned as a ‘natural-biocide’ protecting key years old) and the other skin from a mummified hadrosaur soft-tissues in life. The very same trace-metals inhibited the dinosaur (~66 million years old). Synchrotron Rapid Scanning natural processes of decay after death, resulting in rare and X-ray Fluorescence is combined with X-ray Absorption Near remarkable fossils that display soft tissue structures.

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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Mirta Santos1 - Margarida Nunes1 - Catia Relvas1 P-07 Rouge/Red 10 sept. 2014 17:00 > 20:00 Marta Manso2 - Maria Luisa Carvalho2 - Ana Teresa Caldeira1 Francisca Figueira3 - Teresa Ferreira1 1 Laboratório HERCULES & CQE, Universidade de Évora, Largo Marquês de Marialva 8, 7000-804, Évora, Portugal Analytical 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, and microbiological Rua das Janelas Verdes 37, 1249-018, Lisboa, Portugal studies on paper exhibiting foxing

Foxing spots emerge on paper as stains of reddish-brown, oxidation or fungal digestion. Elemental mapping under brown or yellowish color, generally of small dimensions, micro-EDXRF spectrometry was carried out to identify any with sharp or irregular edges, most of which, when excited possible metal contamination on the spot and surrounding with UV light, show fluorescence [1]. Despite the formation areas. VP-SEM/EDS analysis took into account fibers state mechanisms of foxed areas have been studied since 1930, of conservation and it permitted to distinguish different there are still no conclusive results. Metal contamination, typologies of the foxing stains. Additionally, VP-SEM/EDS fungi and moisture condensation processes are suggested contribute to estimate the fillers used in the papermaking as possible causes of foxing [2]. Metals found in foxing process. Micro-XRD, ATR-FT-IR and micro-Raman studies spots, may arise either from the papermaking process or were develop to complete the study of the fillers and sizing from airborne dust, include potassium, iron, tin, copper, materials used in paper production and to evaluate the copper–mercury or copper–zinc or brass [2,3]. degradation status of cellulose fibers in the foxing stains. In this study a contribution on the formation of foxing stains ICP-MS analyses were carried out in order to estimate the on papers from 18th and the 20th century will be presented. total amount of metals in the foxing stains and compare Fluorescence of foxing stains under ultraviolet light was it with unstained areas. Biological colonization was also registered as a first indication of permanent change in the studied in order to evaluate the possible influence of biotic cellulose and indication on degradation by metal-induced attack in foxing.

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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Isabel Tissot1 - Lore Troalen2 - Marta Manso1 P-08 Rouge/Red 10 sept. 2014 17:00 > 20:00 Matthew Ponting3 - Ian Shaw3 - Martin Radtke4 Uwe Reinholz4 - Maria Luisa Carvalho1 Maria Filomena Guerra5 1 Centro de Física Atómica da Universidade de Lisboa, Av. Prof. Gama Pinto 2, Gold in ancient Egypt: 1649-003, Lisboa, Portugal 2 National Museums Scotland, 242 West Granton Road, EH5 1JA, Edinburgh, UK 3 Garstang Museum, University of Liverpool, 12-14 Abercromby Square, L69 7WZ, studies on provenance Liverpool, UK 4 BAM FIMRT, Richard-Willstaetter-Strasse 11, 12489, Berlin, Germany & corrosion 5 ArchAm - UMR 8096 CNRS, MAE, 21 allée de l’Université, 92023, Nanterre, France

The multi-disciplinary project CNRS PICS 5995 intends to The results obtained show that the composition of the provide with science-based techniques new evidence on Egyptian gold foils from Abydos is typical of placer gold the technologies used in the Egyptian workshops producing with Ag ranging between 0.2 and 14 % and Cu from 05 gold work during the Bronze Age, and to shed more light and 1.5 %. Contrary to expectation, the presence of Pt could on the origin of the gold [1,2]. This project also revealed: be detected in all the analysed foils but at contents that (1) the presence of surface atmospheric corrosions; and could only be determined by D2XRF, which evidences the (2) the almost continuous use of placer gold in all types use of placer gold for their manufacture. of objects except gold foils, detected by the presence of For the study of the corrosion products found on the Egyp- whitish platinum group element (PGE) inclusions. tian gold foils, several ternary and binary gold alloys were In this work 20 gold foils from the excavations of John Garstang produced and artificially aged in a corrosive environment at Abydos, on behalf of the Liverpool Institute of Archaeology, containing high concentrations of S2-. The results obtained were analysed to identify the corrosion products found on the for the artificially aged coatings and for the corroded foils and the metal composition. As would be expected from Egyptian gold foils were compared. We could show the the earlier work, no whitish PGE inclusions could be observed presence on the corroded surfaces of different corrosion on the foils. The use of placer gold can only be detected by the phases revealed by the heterogeneous distribution of Ag, Cu, presence of Pt in gold. The foils from Abydos were analysed by in spite of the homogeneous distribution of S which can be SEM-EDS, by µ-PIXE with 3 MeV proton beam, and by µ-XRF associated to a strong adsorption on the metallic surface using a M4 Tornado. To determine the Pt contents, we used the and to the presence of early corrosion stages. Double Dispersive X-ray Fluorescence (D2 XRF) setup recently developed in the BAMline at BESSY [3].

Bibliography

[1] T roalen, 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Octaviana Marincas1 - Daniel Timpu2 P-09 Rouge/Red 10 sept. 2014 17:00 > 20:00 1 University of Arts George Enescu, Univ. Lecturer, 700451, Iasi, Romania 2 I nstitute of Macromolecular Chemistry Petru Poni, Senior Researcher, Iasi, Romania 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 Today the state of conservation requires urgent mural pain- the Ist invited the french architect André Lecomte du ting restoration. Samples have been collected and analyzed Noüy to restore five important churches from the country. in order to establish the painting technique, the morpho- Two of them are located in Iasi. One of them have been logy of alterations, and the state of conservation. Different totally reconstructed and the other one have been par- imaging and analytical techniques like optical microscopy, tially changed. The original indoor mural painting have SEM-EDX, FTIR spectrometry and X ray diffraction have been been removed and a new decoration have been applied. 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 Bibliography occured. Explanations on the causes of the specific deterio- [1] C. Gervais, M.-A. Languille, S. Réguer, M. Gillet, S. Pelletier, C. Garnier, rations could be established. Thus the results are useful for 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. the future mural painting restoration projects. [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

111 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Jennifer Mass1 - Émeline Pouyet2 - Florian Meirer3 P-10 Rouge/Red 10 sept. 2014 17:00 > 20:00 Marine Cotte2 - Apurva Mehta4 - Alyssa Hull5 - Erich Ufelman6 - Barbara Buckley7 - Frederik Vanmeert8 1 Winterthur Museum, Conservation Department, 19735, Winterthur, USA 2 ESRF, ID21, 38043, Grenoble, France Cadmium carbonate’s 3 Utrecht University, Inorganic Chemistry and Catalysis, 3584 CG, Utrecht, Netherlands 4 Stanford University, SSRL, 94025, Menlo Park, USA 5 University of Delaware, Department of Chemistry, 19716, Newark, USA role in the synthesis 6 Washington and Lee University, Department of Chemistry, 24450, Lexington, USA 7 The Barnes Foundation, Conservation Department, 19130, Philadelphia, USA and alteration of 8 University of Antwerp, Department of Chemistry, 2020, Antwerp, Belgium cadmium yellow paints: evidence from the works of Henri Matisse and Edvard Munch

Cadmium carbonate (CdCO3) has for several years been To address this question of CdCO3’s role, a flake of apparently identified in the altered cadmium yellow (CdS) paints found non-degraded cadmium yellow paint was removed from

in Impressionist, early modernist, and post-Impressionist Henri Matisse’s Flower Piece to study the CdCO3 distribution works. When concentrated at the surface of the paint layer, both as a function of depth in the paint layer and in individual

CdCO3 appears to result from the photo-alteration of CdS, pigment particles. X-ray microspectroscopy and microdiffrac-

likely through a CdSO4-containing phase. However, in other tion were respectively carried out at ESRF ID21 and Petra III,

cases no clear stratigraphy is present and CdCO3 is distributed supplemented by light microscopy, backscattered electron

throughout the paint layer. This is significant because CdCO3 microscopy with X-ray microanalysis, and Fourier transform is highly insoluble (Ksp = 1.0 ×10-12), and if it formed solely infrared spectroscopy. This presentation will focus on results due to photo-alteration it would not be expected to migrate from X-ray microspectroscopy: µX-ray fluorescence (XRF away from the painting’s surface. In cadmium yellow paints in scanning) allowed precise mapping of local elemental distri- works such as Edvard Munch’s c. 1910 The Scream (The Munch bution, and Full Field X-ray Near-Edge Absorption Structure

Museum, Oslo), Plahter et al. have proposed that CdCO3 is (FF-XANES) [2] allowed for mapping the chemical speciation present because it was used in the indirect wet process syn- using the Cd-L3 and S-K edges.

thesis of CdS (e.g., the reaction of CdCO3 and Na2S) [1]. Thus,

the CdCO3 would be a residual starting reagent rather than a FF-XANES imaging of a 15 µm thin section at the Cd-L3 edge

photo-alteration product. The identification of CdCO3 in the revealed the presence of three Cd-based phases: CdS, CdSO4,

unaltered cadmium yellow paints of early modernist works and CdCO3. The CdSO4 was concentrated on only one surface such as Pablo Picasso’s The Blue Room (The Phillips Collection, of the sample, suggesting its role as a photo-alteration product

1901) and Henri Matisse’s Flower Piece (The Barnes Foundation, rather than a synthesis starting material. CdCO3 comprised 1906) supports the Plahter interpretation. 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 Bibliography the thin CdS coating.

[1] Plahter, U. and Topalova-Casadiego, B. Cadmium Yellow in « T he 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Mehdi Moini1 - Christopher Rollman1 - Loïc Bertrand2 P-11 Rouge/Red 10 sept. 2014 17:00 > 20:00 1 George Washington University, Academic, 20007, Washington, USA 2 SOLEIL Synchrotron Facility, 91192, Gif-sur-yvette, France 3 IPANEMA, 91192, Gif-sur-yvette, France Impact of synchrotron X-ray irradiation on proteinaceous specimens

Synchrotron radiation (SR) has become a preferred tech- level modifications were observed with free amino acids as nique for the analysis of a wide range of archeological well as with proteinaceous specimens. Aspartic acid (Asp), samples, artwork, and museum specimens. While SR is wool, parchment, and rabbit skin glue showed increased called a “non-destructive” technique, its effect on protei- racemization upon increasing X-ray irradiation time with naceous art objects has not been fully investigated at the rabbit skin glue showing the greatest increase in D-Asp. molecular level. To investigate the molecular level effects However, silk, cystine, and asparagine (Asn) did not show of X-ray on proteinaceous specimens, samples ranging signs of racemization at the irradiation times studied. In from amino acids to proteinaceous objects such as silk, addition to Asp racemization, parchment and rabbit skin wool, parchment, and rabbit glue were irradiated by syn- glue also showed racemization of isoleucine (Ile) and chrotron X-ray. Specimens were irradiated with two X-ray phenylalanine (Phe) after 100 s of X-ray irradiation using a energies (8 keV and 22 keV) and two photon fluxes (fo- focused beam. In general, focused and low energy (8 keV) cused or unfocused) under various lengths of time. At the beams induced more damage than unfocused and higher macroscopic level, color change, brittleness, and solubility energy (22 keV) beams. The results demonstrate that X-ray enhancement were observed for several samples within radiation can induce significant molecular level damage 100 s of X-ray irradiation. In addition, significant molecular after a few seconds of X-ray irradiation.

Bibliography

[1] D ating Human Bone; Is Racemization Dating Species Specific? Mehdi Moini, Christopher Rollman, and Christine France, Anal Chem. 2013, 85, 11211-5. [2] D ating 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Letizia Monico1 - Koen Janssens2 - Matthias Alfeld3 P-12 Rouge/Red 10 sept. 2014 17:00 > 20:00 Frederik Vanmeert2 - Marine Cotte4 - Gerald Falkenberg3 Chris Ryan5 - Daryl Howard6 - Costanza Miliani1 1 CNR-ISTM/Centre Smaart, Chemistry Department - Via Elce Di Sotto 8, I-06123, Perugia, Italy Cr K-edge full spectral 2 Antwerp University, Chemistry Department - Groenenborgerlaan 171, B-2020, Antwerpen, Belgium 3 D ESY, Hard X-Ray Micro/Nanoprobe Beamline P06 - Notkestraße 85, D-22607, XANES imaging Hamburg, Germany 4 ESRF, X-Ray And Ftir Microspectroscopy Beamline ID21 - Avenue des Martyrs 71, F-38000, Grenoble, France of alteration process 5 CSIRO, Earth Sciences and Resource Engineering - 26 Dick Perry Avenue, WA 6151, Kensington, Australia 6 Australian Synchrotron, X-Ray Fluorescence Microscopy Beamline - in chrome yellow Blackburn Road, Vic 3168, Clayton, Australia pigments by means of the Maia X-ray detector

During the last decade, synchrotron radiation (SR)-based micro Nowadays, technological research perspectives are driven X-ray fluorescence (µ-XRF) and X-ray absorption near edge by the need for shorter dwell times, not only to render the structure (XANES) methods (in point analysis or mapping 2D or 3D mappings of large areas more feasible but also to mode) has been succesfully used for the study of the degra- overcome problems due to beam induced damage to sample dation pathways of artists’ pigments due to their valuable materials. capabilities to provide information at the microscale level on In this regard, “ fast ” detectors are providing valuable solu- the valence states of the same metal and on the distribution tions due to their capabilities of process high count rates of the secondary compounds [1]. that result from an XRF signal collected in an extended solid angle without significant dead time. The Maia X-ray detector In this context, Cr K-edge µ-XANES and µ-XRF experiments [developed by CSIRO (Australia) and the Brookhaven National conducted at the X-ray and FTIR Microspectroscopy beamline Laboratory (USA)] [4], installed at the Australian Synchrotron ID21 of ESRF allowed us to elucidate that the darkening X-ray fluorescence microscopy (XFM) beamline and at the phenomenon of the originally bright chrome yellow paint Hard X-ray micro/nano-probe beamline P06 of DESY falls into

(PbCrO4, PbCr1-xSxO4) in a number of Vincent van Gogh this category. This system already has found application in the paintings and in a series of photochemical aged paint mi- painting conservation field [5]. cro-samples is ascribable to a reduction reaction from Cr(VI) to Cr(III) and that this process is related to the crystalline struc- In the present paper, the advantages and drawbacks of the ture and the chemical composition of the pigment itself [2-3]. latest generation of X-ray semiconductor type detectors that are implemented at the ID21, XFM and P06 beamlines in the Bibliography specific context of SR-based XANES/XRF imaging of Cr-based [1] M. Cotte, J. Susini, J. Dik, K. Janssens, Acc. Chem. Res. 43, 705 (2010). painting materials, will be discussed. [2] L. Monico, G. Van der Snickt, K. Janssens, W. De Nolf, C. Miliani, J. Dik, For this purpose, recently obtained results at these three SR 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, stations from a series of photochemical aged paint model M. Cestelli Guidi, M. Radepont, M. Cotte, Anal. Chem. 85, 851 (2013). samples and micro-samples taken from several Van Gogh [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, paintings, such as for example Falling leaves (Kröller-Müller G. De Geronimo, L. A. Fisher, A. Halfpenny, M. J. Lintern, E. Lombi, K. A. Dyl, Museum, Otterlo) and The Bedroom (Van Gogh Museum, 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, Amsterdam), will be presented. 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Katharina Müller1 - Marie Albéric1 - Andreas Staude2 P-13 Rouge/Red 10 sept. 2014 17:00 > 20:00 Heinrich Riesemeier2 - Ina Reiche1,3 1 Laboratoire d’Archéologie Moléculaire et Structurale, UPMC - UMR 8220 CNRS, 75005, Paris, France 2 Bundesanstalt für Materialforschung und -prüfung, 12205, Berlin, Germany Application of microCT 3 Rathgen-Forschungslabor, Staatliche Museen zu Berlin, 14059, Berlin, Germany for archaeological ivory identifcation and a better comprehension of its alteration phenomena

Human and animal bones and teeth play an important role visible at macroscale, the so-called Schreger pattern, allow a as precious key witnesses of ancient societies. Amongst them quite straightforward ivory identification for objects of ade- ivory, the dentine part of animal tusks, can be considered as quate size. But surface treatments, decorations or diagenetic a very precious biomaterial, which continuously was used alterations lead to the disappearing of these characteristic for the manufacture of excellent objects at least since the patterns and make the application of more sophisticated Palaeolithic period. Ivory is a complex nano-composite ma- methods necessary. terial possessing a specific structure, highly organised from The potential of microCT for the study of bone materials the macro- to the nano-scale and not yet fully understood. has been shown in numerous works ranging from anatomic Archaeological ivory is even more complex due to alteration studies to biomedical research on pathologies and bone processes occurring over time. Non-destructive investiga- implants. MicroCT allows the three-dimensional (3D) study tions of modern and archaeological ivory artefacts by micro of morphological features with a high spatial resolution in X-ray tomography (microCT) contribute to a better compre- the micrometer range. MicroCT setups installed at synchro- hension of the structural organisation of the material and of tron sources provide even higher spatial resolution (< 1 µm), structural alteration phenomena. Furthermore, characteristic needed to image the specific characteristics of the ivory features of the ivory structure can be used for the identi- microstructure (tubules of about 2 µm in diameter). fication of ivory used as raw material for ancient objects. By microCT analysis we were able to identify the raw materials This is a key point in archaeological interpretations as the used for the manufacture of a bishop’s crozier (15th century, choice of material may depend either on the availability, the Cathedral of Angers, France) and of Palaeolithic beads production techniques or the context in which the objects from three archaeological key-sites in Southwest-France were used. The characteristic morphological features of ivory (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]. Further- more, 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 Bibliography site conditions (rock shelters, marine environments) and [1] Reiche, Müller, Staude, A., J. Goebbels, H; Riesemeier, Journal of Analytical of different ages (middle age to Paleolithic). Characteristic Atomic Spectrometry, 26, 1802-1812. [2] C. Vercoutère, K. Müller, L. Chiotti, R. Nespoulet, A. Staude, H. Riesemeier alteration phenomena observed are the increase of porosity, and I. Reiche 2011, ArcheoSciences, 35, 259-271. (2012). the formation of fissures or cracks and inclusions.

115 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Gert Nuyts1 - Simone Cagno2 - Koen Janssens3 P-14 Rouge/Red 10 sept. 2014 17:00 > 20:00 1 University of Antwerp, PHD Student, B-2020, Antwerp, Belgium 2 Norwegian University of Life Sciences, Researcher, N-1432, AS, Norway 3 University of Antwerp, Professor, B-2020, Antwerp, Belgium Micro-XANES study on Mn browning: identifcation of the formed Mn compounds

Under influence of environmental conditions, historical glass, giving proof of their presence. We have employed micros- especially non-durable mediaeval glass, can undergo corrosion. copic XANES spectroscopy in an attempt to identify the This is a complex process governed by several factors and Mn-compounds present in Mn-stains found in historically involving various transformations. One of the most disfiguring corroded glass samples. For this purpose several glass frag- corrosion phenomena is the formation of dark-coloured Mn ments were analysed that originate from an excavation at a enrichments or stains that reduce glass transparency and former Franciscan friary and are dated to the 14th century, all can cause macroscopic browning/blackening of the glass of which contain Mn (0.5-1.6 wt %; expressed as MnO). Glass surface. As described elsewhere in more detail by Schalm fragments, visually showing Mn browning, were cut, polished et al. [1], Mn-stains can be formed during glass corrosion and their composition was determined via SEM-EDX analysis. when a Mn source is present. It can originate e.g. from the Similar cross-sections were analysed at beamline ID21 at the groundwater surrounding a buried glass fragment. However ESRF, Grenoble, France. Prior to XANES analysis, elemental historical glass often contains a small amount of Mn, which distribution maps were recorded to localise the Mn stains. can either be deliberately added as decolourising agent (in XANES spectra were recorded at different points across the

the form of pyrolusite, MnO2) or present as an impurity of the stains and linear combination fitting was performed on these raw materials (e.g. wood ash). [2] In unaltered bulk glass Mn is unknown spectra, expressing the latter as a combination of mainly present as Mn(II), and a minor fraction as Mn(III), due to series of Mn reference spectra. The expected presence of

its stability during the glass production. Previous studies have pyrolusite (MnO2) was not observed, while the best fits were

suggested the presence of MnO2 in the Mn stains [1], and a obtained using a fitting model including Mn2O3 and hollandite

hypothesis for its formation was proposed: in the presence of (black/gray Mn-bearing mineral BaMn(IV,II)8O16). This suggests

water and oxygen, Mn(II) and/or Mn(III) ions can be oxidised that the model by Schalm et al. [1] where an oxidation to MnO2

to higher oxidation states, giving rise to, e.g., insoluble MnO2 needs to be refined as (a) Mn is not completely oxidised to from which the Mn stains are formed[1,3,4]. In addition to +IV while (b) not only pyrolusite is formed. It appears that

pyrolusite (MnO2), Watkinson et al. [5] suggested the presence the blackening of the glass can also be caused by other dark of several dark black/brown coloured Mn bearing minerals coloured Mn-bearing minerals such as hollandite or related leading to the discolouration phenomena, however without compounds/minerals with varying Mn(IV):Mn(II) ratios.

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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Giliane Pauline Odin1 - Véronique Rouchon1 P-15 Rouge/Red 10 sept. 2014 17:00 > 20:00 Frederick Vanmeert2 - Koen Janssens2 - François Farges3 Delphine Vantelon4 1 MNHN, CRC, 75005, Paris, France 2 University of Antwerp, Department of Chemistry, B-2020, Antwerp, Belgium S-XANES study of 3 MNHN, IMPMC, 75005, Paris, France 4 Autunian pyritic fossils: SOLEIL, LUCIA, 91190, Saint Aubin, France infuence of organic matter on degradations

The collections of the Muséum national d’Histoire naturelle S-XANES measurements were performed on artificially aged (MNHN, Paris, France) and the Muséum d’Histoire natu- shale and collection specimens (LUCIA, SOLEIL). On these ones, relle d’Autun (MHNA, Autun, France) include many fossils spectra show a different speciation of the sulfur between the preserved within Autunian shale. They contain unstable shale and the fossil itself. The shale contains oxidized sulfur sulfur compounds, such as pyrite, whose oxidation results in species (mostly sulfates) whereas the organic matter of the fos- efflorescence, mainly related to iron sulfates [1]. sil is composed of reduced species as organic sulfides, which may reflect the future potentiality of the fossil to oxidize. On To understand the key factors of the degradation, newly artificially aged shale, the efflorescence of sulfates is promoted excavated shale samples were collected in the Autunian of by the increase of temperature and humidity, giving spectra the Autun Basin, place of origin of the damaged specimens. very similar to those of collection specimens. Gypsum (calcium They were artificially aged at 50 % or 80 % relative humidity sulfate dihydrate) is the major crystalline phase growing on (RH) and at 40°C or 90°C, in order to reproduce the alterations the shale, whereas iron sulfates mainly crystallize around observed on specimens [2]. A special attention was paid on fragments of organic matter. These observations suggest a a currently excavated fossiliferous level called “ the Muse possible link between the presence of organic matter and Fishes Layer ”, which contains pyritic fishes (actinopterygians the formation of iron sulfates. Complementary ageing are attributed to Aeduella). currently performed in order to validate this hypothesis.

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] O din G. P. et al., 2014. Accelerated ageing of shale of palaeontological interest: Impact of temperature conditions. Annales de Paléontologie, in press.

117 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Janbade Prafulla Tarachand1 P-16 Rouge/Red 10 sept. 2014 17:00 > 20:00 1 Chandigarh College of Architecture, Sector 12, 160012, Chandigarh, India Identifcation, analysis of the building stones used in the historical period with Ardhanareswar temple provides the opportunity to study the medieval stone against the stone from the restored work and quantifcation and fresh sample from the quarry. The thin sections, chemical analysis along with SEM analysis and X-ray diffraction analysis of decay were used to understand the character and mineralogical com- position of the stone along with various properties of the stones. The pro-conservation situation demands an appropriate and deterioration: mechanism for meaningful understanding of the materials for managing treatments & conservation activities in historic cities Comparative study and monuments. Surface Area based approach to quantification of the stone of a substituted decay model: case study of Trilokeenath temple, Mandi, India The documentation for the conservation and restoration project antique stone with remains most crucial stage as lot of decision making are based on the accuracy and authenticity of it. The documentation restored stone using provides the professional a framework to analysis and logical decisions. The policy makers and fund allotters face a different SEM and XRD technique 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 process of identification of the material, including the the quantification of the decay and deterioration of the stone stones used in construction, is the first step in any architectural monuments like the fitzner and zezza. These models are either conservation and restoration project. The process of identi- over simplified or too complicated. fication and classification of stone involves many different We have tried to bring the balance by using the simple method techniques, like Physical examination, thin section analysis, che- for the classification of the damage categories and used simple mical investigations, electron microscopy, X ray diffraction etc. area calculations methods for the quantification of the decay These investigation forms the crucial backbone of information and damage. The preliminary application of the proposed mo- for deciding the strategy for conservation and restoration plan del to the Trilokeenath temple, Mandi, India has been tried for and further treatment. This information is also useful in unders- its appropriateness. The pro-conservation situation demands tanding the cause and methods of decay and deterioration. an appropriate mechanism for meaningful understanding, A group of state listed monument of the mediaeval temple of the extent and degree of the damage objectively, of the architecture in Nagari style was selected for understanding each monument and also each part of the monuments. This the nature of decay and deterioration and evolving an appro- helps in the rationality in resource allocation. This paper tries to priate methodology. These are situated in Mandi, Himachal identify those techniques and methods and analyze them for Pradesh, a northern Himalayan state of India. These temples conservation aspects. The analysis is qualitative and attempt were completely destroyed in major earthquake of 1905 and has been made to quantify it and thus making it objective and the restoration work was carried out at intermittent stages. As not liable to subjective interpretations, this could be the first per the practice of the time, locally available stone of similar step towards the goal of having explicitly described strategy for quality from the same live quarry Thus Trilokinath temple along future course of suitable actions in use for conservation project.

118 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Solenn Réguer1 - Carlotta Santoro2 - Anne-Solenn Le Hô3 P-17 Rouge/Red 10 sept. 2014 17:00 > 20:00 François Mirambet3 - Sandrine Pagés-Camagna3 Didier Gourier4 - Laurent Binet4 - Karim Zarkout3 Sigrid Mirabaud5 - Nadège Lubin-Germain2 - Michel Menu3 1 SOLEIL Synchrotron, L’orme des Merisiers, BP 48, 91192, Gif Sur Yvette Cedex, France Determination 2 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 of the alteration 5 INP, Restoration department, 93210, Saint Denis la Paline, France mechanism of green copper based pigments by a multi- analytical approach

Among the various painting materials used during the XVth To better understand the degradation process, the present and XVIth centuries, some green copper-based pigments approach is based on the comparison of data collected as verdigris and resinate have been widely used for their on both model samples simulating the ancient paintings transparent and pure green tones. Unfortunately chromatic and real samples issued from Old masters paintings. modifications like browning or darkening can be observed Model samples have undergone artificial ageing (RH, T, on those green painted layers. The understanding of the light) to reproduce the color change effect. They were degradation process is the key factor to evaluate potential characterised before and after accelerated ageing tests by evolution of the damages through time. a complementary set of analytical investigation techniques Despite several previous studies pursued on this question as UV-visible, EPR and SEM-EDS [4]. Among them, X-ray ab- during the last 20 years, the mechanism responsible for sorption spectroscopy was realized on the DiffAbs beamline the darkening of green copper-based pigments remains at SOLEIL synchrotron. unknown. Several contradictory hypotheses were formu- The darkening is clearly promoted by the unsaturation lated: oxidation of binders due to a high chemical reactivity degree of the siccative oil. XANES experiments have de- of copper when present in the form of verdigris or resinate, monstrated that incorporation of copper acetate or resi- poor stability with other pigments, reduction of Cu(II), nate pigments in the linseed oil binder and the following formation of inorganic copper oxides, effects of outer SO2 accelerated ageing induces a rearrangement of the bridge and NO2 pollutants, diffusion of copper ions from verdigris binuclear structure of the copper atoms generally observed by fatty and resin acids, variation in the hydration of Cu for the pure pigments. The chromatic change has been complex [1-3]. Up to now, no clear and definite explanation evidenced and characterized by UV-visible spectroscopy. of the degradation process has been proposed and the Moreover EPR experiments allowed us to demonstrate debate remains still unsolved. that incorporation of copper acetate in oil favours the monomeric copper-carboxylate structure due to the labi- lity of Cu-carboxylate ligand bonds. Nevertheless, it is not responsible for the browning mechanism. The formation of Bibliography Cu(I) in the copper complexes of the pigment/oil system is

[1] Altavilla C., Ciliberto E., Appl. Phys.A, 83, 699-703 (2006). considered. It could be initiated by ambient light absorption [2] Gunn M., Chottard G., RivièreE., Girerd J., Chottard J.-C, Studies in Conservation, through LMCT leading to the reduction of Cu(II) into Cu(I) 47, 1, 12-23 ( 2002). [3] I oakimoglou E., Boyatzis S., Argitis P., Fostiridou A., Papapanagiotou K., and a drastic change in the optical properties. The partially Yannovits N., Chem. Mater., 11, 2013-2022 (1999). decarboxylated Cu(I)-Cu(I) pairs are thought to react with [4] Santoro C., Zarkout K., Le Hô A.-S., Mirambet F., Gourier D., Binet L., oxygen, promoting the formation of copper bridged by Pagès-Camagna S., Reguer S., Mirabaud S., Le Du Y., Griesmar P., Lubin-Germain N., Menu M., Appl. Phys.A, 114, 637, (2014) peroxide bonds and a darkening of samples.

119 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Nati Salvado1 - Salvador Buti1 - Gianfelice Cinque2 P-18 Rouge/Red 10 sept. 2014 17:00 > 20:00 Jordi Juanhuix3 - Carme Clemente4 - Victoria Beltran1 Trinitat Pradell5 1 Universitat Politècnica de Catalunya, Departament d’Enginyeria Química, 08800, Vilanova i la Geltrú, Spain Synchrotron radiation 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 based techniques 5 Universitat Politècnica de Catalunya, Departament de Física i Enginyeria for the study of altered Nuclear, 08860, Castelldefels, Spain metal foil coatings in Baroque altarpieces

Baroque artists applied metal foils on altarpieces to produce The samples extracted are very complex, to the original colourful sparkling and shining light effects. Additionally, materials (bole, adhesives, metal foils, resins, drying oils, pigments or dyes were mixed with oils and resins and pigments/dyes, fillers and binders), reaction, weathering applied over the silver or gold foils to create also colour and aging compounds (i.e. metal carboxylates and oxalates) shades. However, the effect intended by the artist appears we have to add those materials incorporated by historical distorted by the alterations occurred over the years re- restorations and dirtiness. Furthermore, those substances are sulting from the chemical reactions among the materials present in variable concentrations, and often in extremely themselves and with the environment. Besides, these low concentrations. Finally, the location and distribution of processes are favoured by the environmental conditions the reaction and aging substances in the different layers is in which the materials are kept. The silver foil itself reacts also important and consequently, homogenizing and dissol- with the environment through the micro fissures open in ving the samples is not adequate since this valuable infor- the organic protection coatings producing silver sulphides mation is lost. Synchrotron radiation based micro-sensitive and chlorides, which, while crystallizing, produce themsel- techniques such as µFTIR, µXRD and µXRF,are outstanding ves stresses that enlarge the cracks resulting in a gradual to overcome the difficulties involved in the analysis. loss of the metal layer. Generally speaking, the metal foils coatings become fragile and more vulnerable making their The cathedral of Tortosa, a few kilometres inland from the restoration more complex and risky. The study of the reac- mouth of the Ebro river in Catalonia, contains a set of Baroque tivity and stability of the metal foils, coating layers and the altarpieces made over a prolonged period of about one hun- adhesives which fix the foils onto the ground layers (often dred years, the oldest dating 1671 and the newest, 1775. a bole) is essential to define restoration strategies. During this extended period the materials used and the techniques employed changed and those changes are ma- nifested 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.

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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Olivier Schalm1 - Patrick Storme1 - Vitaliy Feyer2 P-19 Rouge/Red 10 sept. 2014 17:00 > 20:00 Amandine Crabbé3 - Stefano Voltolina4 Alessandro Patelli4 - Herman Terryn3 1 University of Antwerp, Conservation Studies, 2000, Antwerp, Belgium 2 Peter Grünberg Institute, Research Center Jülich, 52425, Jülich, Germany Evaluation 3 Vrije Universiteit Brussel, Research Group of Electrochemical and Surface Engineering, 1050, Brussels, Belgium of the atmospheric 4 Veneto Nanotech, Nano Fabrication Facility, 30175, Venezia-Marghera, Italy plasma afterglow cleaning performance of tarnished gies the Cu-rich sulfides are almost impossible to remove. Therefore, atmospheric plasma afterglows are able to remove silver-copper the black tarnish layer from some silver objects while visually similar tarnish layers on other objects cannot be removed at surfaces by means all, making the cleaning behaviour unpredictable. In order to understand this difference in cleaning behaviour, of synchrotron X-ray the surface of polished and sulphidized pure silver (Ag999), sterling silver (Ag925) and copper coupons (Cu999) before photoelectron and after plasma treatment were characterized at the µm-level using optical microscopy and scanning electron microscopy. 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 Silver sulphide compounds are rather easily reduced to me- depth investigation, we used photoelectron microscopy at tallic silver when they are treated with an atmospheric plasma the NanoESCA beamline of the Elettra synchrotron. The set-up afterglow obtained from a gas mixture of 5 vol % H2 in He. includes a non-magnetic, electrostatic photoelectron emission Therefore, it is a promising technique for the cleaning of tarni- microscope (PEEM) and a double-pass hemispherical analyser, shed silver objects, especially silver in combination with other allowing the mapping of core-level photoemission signatures materials such as gelatin (e.g., photographic glass negatives) with the lateral resolution of about 100 nm. or organic fibers (e.g., silver threads in textiles). However, most historical silver objects are alloyed with a small amount This investigation has shown that atmospheric plasma treat- of copper (e.g., Sterling silver contains 92.5 w % Ag and ments on sulphidized Ag999, Ag925 and Cu999 were able to 7.5 w % Cu) and this copper appears to oxidize preferentially reduce some corrosion compounds. The surface of sulphi- during the sulphidation process. The resulting black sulphide dized Ag999 consisted of a granular layer of sulphide particles. layer is composed of complex mixtures of Cu-rich and Ag-rich The XPS analyses suggested the presence of a monosulphide sulphides. Unfortunately, with the current plasma technolo- layer covered by a layer rich in polysulphides. The afterglow was able to reduce all the polysulphide S-S bonds and most Bibliography of the monosulphides. The resulting surface consisted of a porous aggregate of metallic silver particles with on top [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 some isolated monosulphide Ag2S particles. At a µm-level, and OCS, Corrosion Science, 25(12) (1985) 1163-1180 the sulphidized Ag925 comprised Cu-rich sulphide islands. [2] Hayez V., Franquet A., Hubin A., Terryn H., XPS study of the atmospheric corrosion of copper alloys of archaeological interest, Surface and Interface However, this microstructure could not be observed with analysis, 36 (2004) 876-879 XPS, due to the presence of a thin but homogeneous Ag2S [3] Patelli A., Favaro M., Simon S., Storme P., Scopece P., Kamenova V., Kamenarov Z., Lorenzon A., De Voeght F., PANNA Project – Plasma top layer. The afterglow was able to reduce this Ag2S film into and Nano for New Age Soft Conservation. Development of a Full-Life metallic silver. For sulphidized Cu999, the afterglow was able Protocol for the Conservation of Cultural Heritage, in Progress in Cultural to transform some sulphide compounds, resulting in a thin Heritage Preservation, Lecture Notes in Computer Science, Springer, Heidelberg, Volume 7616, 2012, pp 793-800 metallic Cu film on top of the surface.

121 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Eleanor Schofeld1 - Mark Jones1 - Alan Chadwick2 P-20 Rouge/Red 10 sept. 2014 17:00 > 20:00 1 Mary Rose Trust, Charity, PO1 3LX, Portsmouth, United Kingdom 2 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 corroded artefacts or fixtures. Since excavation, the ship Dockyard, has been undergoing conservation since its has been kept wet with water and various concentrations excavation in 1982. The Tudor ship sank in 1545 off the of Polyethylene Glycol, a polymer used to gradually replace south coast of England during confrontation with the the water within the wood to ensure mechanical stability invading French fleet. The starboard side was covered in upon drying. In April 2013 the sprays were turned off and protective silt whilst the portside gradually eroded away. the ship is now drying under environmentally controlled The burial environment, with limited Oxygen, reduced the conditions. Sulfur X-ray Absorption Spectroscopy has been activity of traditional wood eroding bacteria. However, used to determine the change in sulfur speciation as a it also promoted the activity of sulfur reducing bacteria, function of drying time and depth into the timbers of the which reacted with sulfate ions in the seawater to produce Mary Rose hull. This is the first time sulfur development reduced sulfur compounds. These gradually diffused into has been measured real-time as function of air-drying. the wood, often reacting with iron ions available from Initial results will be presented here.

122 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Alicja Rafalska-Łasocha1 - Marta Grzesiak-Nowak2 - P-21 Rouge/Red 10 sept. 2014 17:00 > 20:00 Dominika Sarkowicz3 - Wiesław Łasocha1,2 1 Jagiellonian University, Faculty of Chemistry, Kraków, Poland 2 Institute of Catalysis And Surface Chemistry Pas, Kraków, Poland Investigation 3 National Museum in Krakow, Poland of historic pigments and painting materials in works by Henryk Siemiradzki

Antiquity and Bible were the main inspiration for Henryk In the second part of this project samples taken from Siemi- Siemiradzki (1843-1902). His paintings depict scenes from radzki paintings: The Ruins of the Roman villa, A Scene from the Greco-Roman world e.g. Roman Orgy in the Time of Caesars life of the first Christians, Portrait of Son Leos and Self-Portrait (1872) and from the life of first Christians e.g. Christian with a Palette were investigated by means of XRPD with Dirce (1897). Siemiradzki’s works show also scenes from the use X-rays from laboratory and synchrotron sources. everyday life of ancient people, beautiful landscapes and We wanted to identify brown pigment in the first painting portraits. Exact knowledge of the chemical composition of and blue pigments in last three paintings. The obtained pigments used by Henryk Siemiradzki − one of best Polish results show that the brown paint contained the mixture of artists − is important for enrichment of the data concerning red, white and yellow pigments while blue paints contained his workshop and is also useful in conservation and preser- iron cobalt aluminum oxide (FeCoAlO4) or artificial ultramarine vation of his works representing mainly Academic art [1]. (Na7Al6Si6O24S3) or Prussian blue Fe4[Fe(CN)6]3 with some ad- At the beginning of this study the components of several mixtures of other painting materials. powdery pigments (which belong now to the collection of X-ray powder diffraction measurements were carried out in the National Museum in Krakow) inherited from Siemiradzki DESY Hamburg or at Faculty of Chemistry Jagiellonian Uni- were examined and compared with the results obtained versity with the use of X’PERT PRO MPD diffractometer, Cu Kα by XRF analysis. 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 compa- rison 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Mathieu Thoury1,2 - Marika Spring3 - Loïc Bertrand1,2 P-22 Rouge/Red 10 sept. 2014 17:00 > 20:00 Serge Cohen1 - Marie-Angélique Languille1 Alessandra Vichi1,2 1 IPANEMA, F-91192, Gif-Sur-Yvette Cedex, France 2 SOLEIL Synchrotron, F-91192, Gif-Sur-Yvette Cedex, France Methodology 3 Scientific Department, National Gallery, Trafalgar Square, WC2N 5Dn London, UK in practice: workshop on sample preparation for FTIR analysis at IPANEMA - SOLEIL synchrotron

In the framework of the networking activities of the CHA- trated effort on this aspect of analytical methodology, RISMA European project (funded under FP7, GA no. 228330, which can sometimes be neglected, with habitual practice www.charismaproject.eu) an innovative initiative was being continued without an assessment of whether it is co-organized by IPANEMA and the National Gallery London, adequate. In fact sample preparation is far from routine, to foster collaborative exchange of knowledge on scientific and can have a strong influence on the quality of the data methods applied to cultural heritage within the consortium, and results and has become more important with the advent and to communicate the outcomes of this work externally, of new chemical imaging techniques. with the objective of raising standards more generally across Those based on FTIR are of special interest because over this research area. The workshop Sample preparation and the last two or three years several of the institutions within analytical methodology for synchrotron FTIR microscopy, CHARISMA have acquired imaging or mapping systems. was held at the IPANEMA laboratory, SOLEIL synchrotron, They are therefore keen to re-assess and refine their pro- 5-6 July 2012, with three associated days of beamtime on tocols, to achieve a more sophisticated understanding of the SMIS synchrotron FTIR beamline. This was formulated as the factors influencing their analyses with these systems, a practical ‘hands on’ counterpart to a survey and literature and to evaluate the place of FTIR imaging/mapping within review on sample methodology and preparation practices. the examination of individual cross-sections with multiple Coupling a ‘hands-on’ workshop – where participants with complementary analytical techniques. A range of samples various levels of expertise on differing topics could exchange were prepared in different ways and the effect on FTIR ideas – with experimental time, where the same partici- analysis in various modes was tested: transmission, reflec- pants actually worked together on a pre-selected corpus of tance, transflectance or ATR – in the lab or on the beamline. samples, was a valuable and fruitful event. The experiments explored included different embedding The workshop brought together a small number of scien- media and systems, improving polishing techniques with tists who had specific expertise in this area. It proved to both traditional and new methods (e.g. argon ion polishing, be a stimulating forum for a direct exchange of ideas and through the Ilion+ kindly loaned by Gatan) and microtomy, knowledge, through working together very closely in a either to make thin sections (for transmission and transflec- practical way, discussing hints and tips, and learning from tance FTIR) or for ‘resurfacing’ of thick sections. This poster will each other’s experience. It served as a pretext for concen- present the main observations and conclusions of this work.

Bibliography

[1] Blak H., Małkiewicz B., Wojtałowa E., Malarstwo polskie XIX w. Katalog zbiorów pod redakcją Zofii Gołubiew, Kraków 2001.

124 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

David Agyeman-Budu1 - Arthur Woll2 P-23 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Sanjukta Choudhury3 - Ian Coulthard4 - Robert Gordon5 Emil Hallin4 1 D epartment of Materials Science and Engineering, Cornell University, 14853, Ithaca, USA Fabrication of spoked 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 channel arrays for 3D 5 PNCSRF, Aps Sector 20, 60439, Argonne, USA micro confocal X-ray fuorescence

We report the development and practical demonstration of optics at APS beamline 20-ID-B for confocal XRF mapping spoked channel arrays (SCAs), a novel X-ray collection optic and XAFS of an 11th century stained glass sample from the for confocal X-ray fluorescence microscopy (CXRF). The optic Paderborn Cathedral, a paint sample from an 18th century consists of micron-scale, lithographically-fabricated arrays oil painting by Adriaen de Coorte and most recently, an ar- of collimating channels, all directed towards a single source chaeological bone sample excavated from a cemetery near position. In contrast to polycapillaries, SCAs exhibit nearly English Harbor, Antigua. Here, we report key details required energy-independent resolution and collection efficiency. to design and fabricate SCAs, including limitations imposed For example, a nearly energy-independent depth resolution by the substrate material and factors that determine useful below 2 microns has been achieved from 3-10 keV, degra- channel dimensions. The optics reported in refs. 1-2 were ding slightly to 3±0.5 microns at 1.7 keV. Our original SCA fabricated from silicon, and were thus expected to operate design, described in Ref. 1, exhibited limited working dis- well only below about 12 keV. Recently, we have fabricated tance and efficiency. An improved design [2] has effectively new optics from germanium, which should operate well solved both limitations, resulting in a practical optic that has up to 30 keV. In addition, we are currently fabricating SCAs now been used for a wide range of art and archaeological with channel widths up to 50 μm, which we may be suitable applications. In particular, we have employed 1 µm and 7 µm for use in non-synchrotron based CXRF systems.

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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Jennifer Anne1 - Roy Wogelius1 - Nicholas Edwards1 P-24 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Arjen van Veelen1 - Victoria Egerton1 - William Sellers2 Uwe Bergmann3 - Dimosthenis Sokaras4 Konstantin Ignatyev5 - Phillip Manning1 1 University of Manchester, School of Earth, Atmospheric and Environmental Bone physiology 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, through particle Menlo Park, USA 4 SLAC National Accelerator Laboratory, Stanford Synchrotron Radiation Lightsource, 94025, Menlo Park, USA physics 5 Diamond Light Source, OX11 0DE, Didcot, UK

Most palaeontological studies that use synchrotron tech- In this study we focus on mapping and quantifying trace niques apply tomographic methods in order to obtain fine elements that are crucial for the maintenance and repair morphological details that cannot be distinguished using of bone within both extant and extinct organisms by using conventional CT scanning. However, there is considerably a combination of Synchrotron Rapid Scanning-X-ray Fluores- more information to be gleaned from fossil material cence (SRS-XRF) and microfocus elemental mapping. through the sensitivity and tunability of a synchrotron light source. Most notably, the use of fine scale composi- Zinc was found to be differentially distributed within: 1] the tional mapping and the quantification of trace elements fracture callus of a large carnivorous dinosaur (Allosaurus can be critical for resolving key biochemical structures fragilis: ~146 million years old), 2] the secondary osteons of and thereby improve our understanding of biological an extinct dugong (Metaxytherium sp.: ~17 million years processes and pathways [1,2]. For example, the processes old), and 3] within the plexiform tissue of an extinct hyena behind bone remodeling and healing recapitulate bone (Crocuta crocuta spelaea: ~40 thousand years old). These development. Thus the ability to determine trace ele- tissues all consist of actively remodeling or ossifying bone ment patterns associated with such processes can lead at the time of death. The distributions and concentrations of to a better understanding of bone development within zinc match those found in modern tissues from comparable different vertebrate groups, and perhaps may even help species [3]. As zinc is crucial for the ossification and mine- uncover details about the evolutionary development of ralization of bone [4], we propose that zinc may be used as the skeleton. a biomarker for active ossification within the fossil record.

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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Felisa Berenguer1 - Andrew King2 - Timm Weitkamp2 P-25 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Sebastian Schöder2 - Pascal Mercere2 - Philippe Janvier3 Thierry Moreno2 - François Polack2 - Loïc Bertrand1 Serge Cohen1 - Pierre Gueriau3 - Didier Merle3 Jean-Sébastien Steyer3 - Florent Goussard3 Tomography Stéphanie Gastou3 1 IPANEMA, CNRS, Ministère de la Culture et de la Communication, USR 3461, 91192, Gif-sur-Yvette, France for cultural heritage 2 SOLEIL SYNCHROTRON, Division Experiences, 91192, Gif-sur-Yvette, France at Synchrotron SOLEIL 3 CR2P, Muséum National d’Histoire Naturelle, UMR 7207, 75005, Paris, France

In the past decade, synchrotron-based microtomography specimens, and will be optimized for fast tomographic data (SR-µCT) has become a central tool for investigating the mor- acquisition with white beam (0.1 sec per full tomograph) phology of cultural heritage samples. SR-µCT accesses the 3D and in-situ experiments. PUMA will be opening to the users inner structure in a non-invasive way for obtaining images with in the second half of 2015. The beamline tomography setup, a higher resolution (voxel sizes ranging from a few hundreds designed for exploiting phase contrast imaging, will deliver of nanometers to a few microns) and far shorter acquisition a 20×10 mm2 (H×V) beam in the energy range from 15 to times than a conventional tomograph. After the pioneering 60 keV. The key development will be automation of data acqui- work at the ESRF in palaeontology and palaeo-anthropology, sition and analysis in order to measure large sets of specimens synchrotron facilities such as SLS, Diamond and SOLEIL join (high throughput corpus studies) combined with high-defi- the development of SR-µCT for cultural heritage specimens. nition, up to 12k×12k sections. Both PUMA and PSICHE will At SOLEIL, the PUMA beamline will be devoted to investigation give access to spatial resolution of 1 to a few microns, whereas of ancient materials with tomography and scanning X-ray higher resolution will be available at ANATOMIX (open end imaging methods in the context of the development of the 2015): pixel sizes down to 200 nm (for parallel-beam tomogra- European research platform for ancient materials IPANEMA. phy) and 30 nm (for microscopy) will be available. ANATOMIX PUMA will join two tomography beamlines at SOLEIL: PSICHE will offer various phase-contrast imaging modalities (including and ANATOMIX. grating interferometry) and will be optimized to perform fast acquisition experiments in the energy range from 5 to 25 keV. The three SOLEIL tomography beamlines, fed by insertion devices, have complementary characteristics, as each one With these three beamlines, SOLEIL will cover a wide spectrum of them is tailored for different needs of tomography experi- of possibilities for tomographic study of ancient materials, ments. PSICHE, already available to the users, is a high-pressure from small to medium size fossil specimens to archaeological diffraction and tomography beamline working at 15-80 keV, artifacts (tools, ceramic and metallic objects). We will also with a maximum beam size of 15×6 mm2 (H×V). PSICHE is present test experiments that have already been performed prepared for hosting large sample environments and heavy at the beamline METROLOGY.

127 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Mathieu Thoury1 - Sébastien Ancelin1 - Felisa Berenguer1 P-26 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Serge Cohen1 - Marie-Angélique Languille1 Regina Oprandi1 - Sebastian Schoeder2 - Loïc Bertrand1 1 IPANEMA, CNRS, MCC, 91192, Gif-sur-Yvette cedex, FRANCE The European research 2 Synchrotron SOLEIL, PUMA beamline, 91192, Gif-sur-Yvette cedex, FRANCE platform on ancient materials IPANEMA at Synchrotron SOLEIL

The building hosting the IPANEMA European research plat- research, among which half were selected for beamtime and form on ancient materials (CNRS, Ministère de la Culture et the team has supported users by participating to project de la Communication) was inaugurated in September 2013 definition and implementation, experiment preparation, at the SOLEIL synchrotron, France. The activities of IPANEMA complementary characterisation and data processing. are centred on two areas: interdisciplinary research in metho- dology and medium-term support to synchrotron proposals, The new building hosts facilities for sample preparation, for four fields of application: archaeology, cultural heritage, X-ray, infrared and UV/visible and SEM characterisation and palaeontology and palaeo-environmental sciences. an instrumentation workshop. Offices and user facilities allow hosting researchers working on ancient materials at the site. IPANEMA fosters new methodological concepts and de- Specific research partnerships were set up with leading velopments, in particular in synchrotron X-ray imaging international institutions, in particular the Smithsonian Ins- (development of the PUMA beamline, microtomography), titution of the USA and NWO, the Netherlands organisation UV/visible microimaging, and statistical analysis of data. for scientific research. At the European level, IPANEMA is part Since the initiation of IPANEMA, more than 200 proposals of the European Research Infrastructure network IPERION-CH were submitted to the SOLEIL facility on ancient materials and was supported as part of FP7 CHARISMA (2009–2014).

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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Olga Otero1 - Renaud Boistel2 - Anthony Herrel3 P-27 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Lukas Helfen4 - Lukas Helfen5 1 Université de Poitiers - UFR SFA, iPHEP UMR CNRS 7262, 86073, Poitiers, France 2 CNRS, iPHEP UMR CNRS 7262, 86073, Poitiers, France 3 CNRS, UMR7179 MNHN, 75231, Paris, France 3D X-ray imaging 4 European Synchrotron Radiation Facility (ESRF), id19, 38043, Grenoble, France 5 ANKA Light Source / Institute for Photon Science and Synchrotron reveals hidden hearing Radiation, Karlsruhe Institute of Technology, D-76021, Karlsruhe, Germany apparatus of ancient fshes

Synchrotron X-ray imaging of fossilized fishes is helping Apart from the established technique of synchrotron one to better understand how sound transmission in the tomography, a novel X-ray imaging modality is helping course of evolution developed. Otophysan fish represent to study fossils embedded in flat stone. Synchrotron lami- more than half of the freshwater fish today, and include well- nography was developed at the ESRF beamline ID19 [2] known members such us piranhas, catfish and minnows. and serves for reconstruction of regions of interest on flat They show an astonishing wide range of morphologies, in stone specimens, like fossils [3]. The laminography instru- relation with the variety of habitats that they occupy in all ment installed at ID19 provides a unique opportunity to use continents with the exception of Antarctic. This evolutionary phase contrast [4] for highly sensitive imaging compared to success story is often related to the evolutionary advantage its laboratory counterparts. This along with the high spatial brought by their Weberian Apparatus (WA), an original resolution provided is particularly suited for truly non-des- complex structure compound of an ossicular complex and tructive imaging of the Weberian regions in the fossils em- soft tissue, which allows acute reception and transmission bedded in flat stone. of sounds and vibrations. If only otophysan fish have a WA, each of the four extant lineages (Characiformes, Cyprini- We use X-ray laminography at the ESRF to describe accurately formes, Gymnotiformes and Siluriformes) shows a particular the WA structures in extant and extinct fish, with the aim to organisation. Although the anatomy of the WA in extant fish help and resolve the heated debate about the origin of WA. has been accurately described [e.g. 1], the modalities of the In our presentation, we focus on the 3-D images obtained apparition of this complex remain rather dull. Notably, the and the details of the bony anatomical architecture of WA anatomy of the various WA patterns in early otophysan fish revealed in fossils. 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.

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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Antonio Brunetti1- Anna de Palmas2 - Claudio Bulla2 P-28 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Nick Schiavon3 - Giampaolo Piga1 1 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 An XRF/Monte Carlo Formazione, 07100, Sassari, Italy 3 University of Evora, Hercules Laboratory and Evora Geophysical Centre, study of Nuragic 7000/809, Evora, Portugal samples from Sardinia, Italy

Sardinia is the second largest island in the Mediterranean latter represents an important factor for the classification and is well-known for its Nuragic civilisation, which thrived of the production site and technology used. XRF analysis is in the Bronze and Early Iron Ages from XX to VII centuries BC. a powerful non destructive tool for Cultural heritage sample Metallurgy developed greatly during this period, and this analysis. It is based on the interaction of the X-ray with the provides us with important information on the technolo- matter producing, besides others effects, characteristic gy used in the economic activities of the Nuragic people. X-ray photons which represents a unique marker of the A great variety of bronze artefacts have been found: axes, presence of a chemical element inside the sample. Howe- chisels, awls, wedges, drills, files and saws used for wor- ver, the presence of the two outer layers, patina and pro- king wood, and scrapers, blades, borers and punches for tective ones, alters the number of the photons produced working leather. The importance of these unique bronze making very difficult to obtain a quantitative estimation productions is so far not supported by in-depth knowledge at least with standard approach such as the Fundamental about the qualitative and quantitative chemical com- Parameters one. Here this problem will be addressed by a position of the alloys. Moreover, many of these bronze new, innovative approach based on a fast Monte Carlo si- samples show corrosion signs and also the presence of mulation of the experiment performed [1-4]. This approach the so-called patina and a protective layer. Thus, from the allows to consider any kind of multilayer structures as well archaeometric point of view, their surface can be conside- as to take in account the presence of rough surfaces that red as a multilayered structure that makes it hard to obtain is typical in Cultural Heritage samples. Some results will be reliable quantitative data on the bronze composition. The reported and discussed.

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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Valentina Capogrosso1 - Anna Cesaratto1 - Sara Bellei2 P-29 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Francesca Gabrieli3 - Francesca Rosi3 - Laura Cartechini3 Nicolas Trcera4 - Caroline Tokarski5 - Herve Vezin5 Aviva Burnstock6 - Austin Nevin2 1 Politecnico Di Milano Physics, Departement Piazza Leonardo Da Vinci, 32 20133, Milan, Italy Multi-analytical 2 Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133, Milan, Italy 3 IFN-CNR, Piazza Leonardo da Vinci 32, 20133, Milan, Italy 4 I nstitute of Molecular Science and Technologies, Via Elce di Sotto, 8, 06123, study of historical 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, semiconductor Lille, France pigments 7 The Courtauld Institute of Art, Somerset House Strand, WC2R 0RN, London, Great Britain for the detection of impurities and trace metal ions

During the mid 19th century a new class of pigments, based In this work, we present the application of synchrotron-based on semiconductors including ZnO, ZnS, and CdS, substituted analysis of the impurities in historical samples of ZnO, ZnS the pigments used by painters in earlier periods. Despite their and CdS-based pigments. The necessity of a micrometric improved properties in terms of hiding and handling power with spatial resolution and sub-ppm sensitivity for investigating respect to traditional materials, early formulations of synthetic trace and heterogeneous impurities in semiconductor based pigments have proven to be chemically unstable. Many impu- pigments required the access to synchrotron radiation rities were introduced unintentionally during manufacturing, as sources. Analysis was performed at the LUCIA beamline at has been highlighted by recent results obtained in our research the SOLEIL synchrotron for the simultaneous detection of group based on luminescence spectroscopy of Zn-based the atomic distribution and the oxidation state of the specific pigments [1]. In parallel, spectroscopic investigations on both metal impurities in our samples. We revealed the presence pure ZnO and paint models have demonstrated that physical of trace metal ions in powder samples by means of micro- and chemical interactions affect the UV and visible emissions, X-ray Fluorescence (XRF) mapping [5] and we investigated leading to the observation of considerably different emission the oxidation states and coordination of metallic inclusions profiles [2]. Fluorescent inclusions in paint samples containing by means of micro-X-ray Absorption (XAS) spectroscopy. ZnO have been also investigated at DISCO beamline at SOLEIL The mapping of metal impurities within pigment particles synchrotron through the use of raster-scanning microspectros- provides data which can allow us to discriminate different copy and full-field microimaging [3]. From Fluorescence imaging manufacturing routes and to better understand the chemi- and Fluorescence spectroscopy measurements of ZnO and ZnS cal reactivity of pigments in the presence of most common samples [4], we suspected the presence of metallic impurities organic binders. This work is focused to obtain markers for including traces of Pb, Fe, Mn and Cu. The presence of some of future in situ analysis of paint-samples with evident impli- these impurities has been confirmed by Electron Paramagnetic cations for the conservation and treatment of early 20th (EPR) measurements performed at the University of Lille. 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Sanjukta Choudhury1 - Arthur R. Woll2 P-30 Bleu/Blue 10 sept. 2014 17:00 > 20:00 David Agyeman-Budu2 - Treena Swanston3 Tamara Varney4 - David M. L. Cooper3 - Robert A. Gordon5 Emil Hallin6 - Graham N. George1 - Ian Coulthard7 Ingrid J. Pickering1 Microchannel array 1 University of Saskatchewan, Geological Sciences, SK S7N 5E2, Saskatoon, Canada 2 Cornell University, Cornell High Energy Synchrotron Source, NY 14853, Ithaca, USA 3 University of Saskatchewan, Anatomy and Cell Biology, SK S7N 5E5, Saskatoon, Canada derived high resolution 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 confocal X-ray 7 Canadian Light Source, Bioxas, SK S7N 2V3, Saskatoon, Canada fuorescence imaging for art and archaeology

X-ray fluorescence imaging (XFI) is a nondestructive tool or diagenic. Remarkably improved lateral spatial resolution for studying trace element distribution. Confocal XFI, a less (3 × 5 microns μm2) for fluorescence emission ranging from 3.6 common variant, enables higher spatial resolution imaging to 14.1 keV) is achieved when microchannel arrays [1], recently and depth information of fragile or valuable objects for which developed at Cornell High Energy Synchrotron, were em- sectioning is challenging or undesirable. This presentation ployed in confocal detection. Microchannel array derived high compares results from several art and archaeology samples resolution confocal detection was also used to investigate studied at scan-probe microscopy station 20-ID-B at the APS the nature of the iron containing corrosive layers in ancient synchrotron using different fluorescence detection modes. stained glass samples, obtained from Paderborn Cathedral, Standard and confocal modes of XFI were used to obtain Germany (13th Century), in order to aid the study regarding the elemental distribution images from archaeological bone efficacy of various cleaning methods used in the restoration samples excavated from the Royal Naval Hospital Cemetery (c. process. Initial imaging and spectroscopy results obtained in A.D. 1793-1822) near English Harbor, Antigua. These samples this study will be presented. Due to the energy-independent were investigated to answer key questions about whether lead nature of the microchannel array derived confocal probe poisoning played a role in the demise of the British military volume, correlations among different elemental features can in West Indies, and whether the observed lead is biogenic be unambiguously identified.

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:10.1088/1742- 6596/493/1/012028

132 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Phil K. Cook1,2 - Marie-Angélique Languille3 P-31 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Élise Dufour4 - Cristian Mocuta4 - Delphine Vantelon5 Loïc Bertrand1,2 1 IPANEMA, 91192, Gif-Sur-Yvette, France 2 Synchrotron SOLEIL, 91192, Gif-Sur-Yvette, France Micro-X-ray 3 CNRS, CRCC, 75005, Paris, France 4 Muséum National d’histoire Naturelle / CNRS, Archéozoologie, fuorescence Archéobotanique, 75005, Paris, France evidences elemental fuctuation on a short time scale in fsh otoliths

Archaeological fish otoliths, “ ear stones, ” composed of ara- From the high lateral resolution elemental maps, concen- gonite (CaCO3) and an organic template, are increasingly tration fluctuations in strontium content along the growth employed for palaeoenvironmental reconstructions [1]. An axis can be seen with lengths as short as a few micrometres. individual’s life history (salinity and temperature of water in- Measurements in the medium-energy X-ray range show habited) is encoded within the elemental composition of daily homogeneous increments, but the higher lateral resolu- (~5 µm thick) and seasonal (300–400 µm) growth increments. tion tender X-ray maps reveal heterogenities in elemental Among the minor and trace elements present is Sr at a typical content within isochronous increments on a length scale concentration of 5–50 µmol/g [2]. Measurement of Sr content of several micrometres. Contamination on the edge of the can reveal the fish’s environment at the time of deposition otoliths can be identified from handling and preparation. with a temporal resolution proportional to lateral resolution. Surface contamination from sample preparation can be Laser ablation (LA) mass spectrometry (MS) and high-current detected and does not prevent analysis of the otolith overall. electron microprobe (EPMA) analyses are often employed After X-ray analysis, the samples were examined under for such elemental measurements. However, both of these visible, UV fluorescence, and electron microscopy for radia- techniques produce significant ablation of the sample. tion-induced side effects (RISE). Medium-energy X-rays re- The multi-element, sensitive, fast, and non-destructive analysis sulted in a barely noticeable impact, but using tender X-rays, promised by synchrotron micro-X-ray fluorescence (µXRF) more significant RISE was observed. These RISE appear to makes it an attractive technique [3]. Elemental quantification be primarily dose dependent and are hypothesised to be has been carried out on 6 archaeological otoliths along with in the organic fraction. SR-µXRF is often labelled non-des- modern counterparts in order to study their small-scale tructive, but these observations highlight the need for study elemental variation. Experiments were performed using me- and consideration of potential side effects resulting from dium-energy and tender X-rays with on-sample spot size as analyses. SR-µXRF provides a powerful tool for laterally re- small as 4×3 µm2 (H×V). Maps have been obtained for full core- solved elemental quantification of biomineral palaeoproxies, to-edge sections of otoliths up to 3.2×0.8 mm2. Using tender but requires reflection on its true resolution limits and po- X-rays permits a lateral resolution equivalent to the spot size. tential sample side effects.

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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Marine Cotte1 - Paul Taforeau1 - Émeline Pouyet1 P-32 Bleu/Blue 10 sept. 2014 17:00 > 20:00 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 spectroscopy can be combined to infrared spectrosco- Radiation Facility, Grenoble, France is composed of 5 py to obtain a full identification of components, with a beamlines, which offer a very wide range of accessible beam ranging from a few microns in the infrared domain, lateral resolution and corollary field of view, as well as an to ~40 nm in the hard X-ray domains. extended set of imaging and analytical tools. The ID17 These beamlines, in particular ID19 and ID21, are regularly beamline is primarily dedicated to biomedical applications, successfully used for the analysis of ancient materials, the and delivers a very large beam (~150×6 mm²) suitable word “ ancient ” covering fragments from design objects for the tomography of large samples. The ID19 beamline of the 50’s and 60’s, to fossils of about 600 million years. offers versatile capabilities for 3D imaging, with different At ID21, X-ray and IR micro-analyses are applied to a large contrast modes, acquisition times, sample environment... range of materials (paintings, glasses, inks, ceramics, metals, The beamsize is slightly lower (~75×15 mm²), but the spatial biological remains, polymers...) with the two-fold objec- resolution is improved (from 100 to ~0.3 µm). The ID16A tives of rediscovering ancient artistic technologies, and beamline, currently in construction, will provide ultimate understanding degradation processes. At ID19, paleonto- capabilities for imaging at the nano-scale (down to 10 nm). logy is a major field of research, where 3D imaging reveals These three beamlines focus mainly on a morphological non-invasively fundamental information hidden in the characterization, with some chemical information limited micro-structure of bones, teeth, fossils of animals, of plants... to elemental composition and mapping. Conversely, This talk will aim both at giving an overview of these ap- the ID21 and ID16B beamlines offer multi-analytical plications as well as at presenting the different imaging platforms for a more precise chemical characterization capabilities, in particular the most recent ones developed of samples. X-ray fluorescence, diffraction, absorption in the context of the ESRF upgrade programme.

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] T afforeau, 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Pisutti Dararutana1 P-33 Bleu/Blue 10 sept. 2014 17:00 > 20:00 1 T he 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, espe- chrotron radiation was used to analyze elemental distribution cially glasses. Due to the complex nature of materials, extremely of the Lanna-style glass. Scanning electron microscope coupled sensitive, spatially resolved, multi-elemental and versatile analyti- with X-ray fluorescence spectroscopy and Proton-induced cal instruments were needed. The techniques employed should X-ray emission spectroscopy were also carried out to detect be as a noninvasive as possible and able to give complementary composition and structure. Compositional analysis showed information from macroscopic to nanometer scales. Lanna-style that the main contents were SiO2 and PbO. K2O and CaO were decorative glass which called ACG/ABG is one of decorative as minor contents. The differences in color were affected from glasses which are found throughout Thailand in special places, the addition of iron, copper and manganese. Cross-sectional such as, Buddhist temples, which, for centuries, have served SEM observations of ACG/ABG showed three different layers as community centers for the locals. It is found mostly in the including metal substrate, binder and coated glass. The glasses northern and northeastern Thailand, and some parts of Laos, were mostly transparency with plenty and bubbles. It is mostly Burma and China. As the glasses have kept deteriorating over lead-silica based glasses. Their colors resulted from metal ions. time, restorations must be performed routinely to preserve these It can be concluded that these techniques in combination are cultural crafts for later generations to appreciate.In this work, powerful for the investigation of heterogeneous glassy materials micro-beam X-ray fluorescence spectroscopy based on syn- 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Rafaela Debastiani1 - Rolf Simon1 - Andrea Wähning2 P-34 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Tilo Baumbach1 1 Karlsruhe Institute of Technology, IPS-ANKA, D-76344, Eggenstein-Leopoldshafen, Germany 2 Analysis of Roman Badisches Landesmuseum Karlsruhe, 76131, Karlsruhe, Germany mural paintings from Wössingen (Germany) using synchrotron radiation

From 1st to 3rd centuries AD, Roman province in Germany lived a Badisches Landesmuseum Karlsruhe’ collection and provide us peaceful and prosper epoch. In this epoch, there was a culturally a big color palette. blossoming, towns were founded and buildings were decorated X-ray fluorescence (XRF), X-ray diffraction (XRD) and infrared with mural paintings. The study of mural paintings helps to spectroscopy (IR) are providing data about chemical com- obtain information about the origin of the pigments (by trace position, mineral phases and molecular information of the elements), possible changes and restaurations in the mural pigments. Preliminary XRF analysis identify some possible paintings and the building function (private, public baths, etc). pigments for each color. S, Ca, K, Mn, Fe, Cu, Zn, As, Rb, Sr, Hg, Fragments of Roman mural paintings from Wössingen, Pb are some of the elements present in the pigments. For a Germany, from 1st to 3rd centuries AD, are being analyzed at ANKA complete identification of the pigments, XRD and IR analysis Synchrotron, in Karlsruhe, Germany. These fragments are from are being performed.

136 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Giulia Festa1,2 - Enrico Perelli Cippo3 - Daniela di Martino1 P-35 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Roberto Senesi2 - Carla Andreani2 - Erik Schooneveld4 Winfried Kockelmann4 - Nigel Rhodes4 - Katalin Biro5 Giuseppe Gorini1,6 1 University of Milano-Bicocca, Physics Department, I-20126, Milan, ITALY Neutron resonance 2 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 transmission imaging 5 Hungarian National Museum, Department of Archaeology, H-1088, Budapest, HUNGARY for 3D elemental 6 CNISM, Unita’ di Ricerca di Milano Bicocca, I-20126, Milan, ITALY mapping at the ISIS spallation neutron source

Neutrons have been widely applied in archaeometric lation neutron source was used for the experiments [4,5]. research since 1960, with a growing number of innovative Transmission spectra were obtained by measurement of methods allowing for non-destructive or non-invasive the flight time of epithermal neutrons passing through the analysis [1,2]. A recent application concerns neutron re- sample, an early mediaeval disk fibula [6] from the Hunga- sonances that can be used as fingerprints to identify and rian National Museum in Budapest. The same object had quantify elements within the bulk of different objects. previously been analyzed through 2D NRTI [3] and other 3D Indeed, Neutron Resonance Transmission Imaging (NRTI) has elemental imaging techniques, like PGAI (Prompt Gamma been successfully applied to the 2D elemental mapping of Activation Imaging) [7]. archaeological samples [3]. The methodology and analysis procedures used in the Here we report on the first three-dimensional elemental reconstruction of the 3D NRT elemental image will be des- imaging by NRT. A dedicated set-up at the INES (Italian cribed. Our results will be compared with previous results. Neutron Experimental Station) beamline of the ISIS spal- 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., “ T he 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Renfei Feng1 - Jason Maley2 - Ruth Hofemyer2 P-36 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Tom Ellis1 - Don Brinkman3 - Ramaswami Sammynaiken2 1 Experimental Facilities Division, Canadian Light Source, S7N 2V3, Saskatoon, Canada 2 Saskatchewan Structural Sciences Centre, University of Saskatchewan, S7N 5C9, Saskatoon, Canada Reading about the life 3 Preservation & Research, Royal Tyrrell Museum, T0J 0Y0, Drumheller, Canada of Dinosaurs recorded on the enamel of teeth

The enamel of teeth is mainly calcium hydroxyl apatite which and whether or not the teeth were worn down and shed. itself does not undergo much structural change after millions High doses of UV or gamma radiation induce different types of years. Dinosaur teeth have a fossilized core and an almost of defects in enamel. intact enamel. Over the period of 60 million years, chemical changes in the enamel are influenced by the environment in Our investigation employs several advanced instrumental which the fossil was preserved, e.g., metal ion diffusion into methods to read the information present in the microana- available structural sites and ion replacement. The fossilized tomy of enamel on dinosaur teeth. The results from Micro core would represent a reasonable template of the dentine X-ray Fluorescence Mapping (XRFM), X-ray Absorption Spec- structure. troscopy (XAS) and Micro Laue Diffraction Mapping (LDM) will be presented, which show a very good snap shot of Studies on the teeth of mammals show that the structure the environment, ion substitutions projected structure and and ordering of the enamel in teeth represent the hardness ordering for the different types of dinosaurs. Diet, migration or types of food eaten. Hunter-Schreger Bands (HSB) was patterns, ecosystem type, radiation exposure and stage of observed in human and other mammals but not in insec- dental evolution could be revealed and would support to tivores and multituberculates. The rate of growth of teeth future studies on the biology, physiology, and ecology of and size of enamel crystallites indicate the age of animal, extinct animals.

138 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Marine Gay1 - Matthias Alfeld2 - Michel Menu3 P-37 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Éric Laval3 - Pablo Arias4 - Ina Reiche1,5 1 Laboratoire d’Archéologie Moléculaire et Structurale, CNRS-UMR8220, UPMC, 75005, Paris, France 2 Deutsches Elektronen-Synchrotron DESY, PETRA III, 22607, Hambourg, Allemagne Palaeolithic paint 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 palette used at Prehistóricas de Cantabria, 39005, Santander, Spain 5 Rathgen-Forschungslabor, Staatliche Museen zu Berlin, 14059, Berlin, Germany La Garma cave (Cantabria, Spain) investigated by means of complementary in situ and synchrotron analytical methods

Understanding the meaning of Palaeolithic graphical sation of the rock art in this cave, to explain its singularities, expression is one of the key issues of Prehistoric research. looking for various hands that potentially performed the It includes the study of the painting matter which provides decorations of distinct figures in the different rooms. significant sources of information in the quest of the com- A preliminary analysis by energy dispersive X-ray spectrome- prehension of the technical skills of prehistoric artists and try coupled to a scanning electron microscope (SEM-EDS) the “ chaîne opératoire ” of the painting activities. La Garma has been carried out on twenty-five samples taken from the cave, listed as World Heritage by UNESCO in 2008, is part of medium and lower gallery of the cave. Different types of th the most exceptional sites discovered at the end of the 20 hematite (Fe203) and goethite (FeOOH) have been distingui- century in the North of the Spain. It offers over 500 graphical shed, revealing the use of different paint “ pots ” by prehistoric units covering a wide chronological range, dating from the artists [2]. In order to improve this issue, a speciation analysis Aurignacian to the Magdalenian period, and spread on the of Fe was performed at the P06 beamline of PETRA at DESY wall of numerous rooms. This rock art is connected with large (Hamburg’s synchrotron) by high-resolution micro X-ray ab- surfaces rich in occupational remains, conferring to this cave sorption near edge structure (XANES) measurements at the an important position in the study of the Upper Palaeolithic Fe K-edge. It will allow giving more detailed insights into the in this region. oxidation state and the coordination environments for Fe [3]. This cave gathers a large assortment of colours (red, yellow, Complementary, to have a global comprehension of the purple and black), associated to different mineral phases rock art repartition inside the cave, an on-site systematically (iron and/or manganese oxides, charcoal and mixtures). study of the prehistoric representations have been initiated A detailed characterisation of the mineral pictorial matter by the implementation of a self-built X-ray fluorescence used for a same colour is crucial to understand the organi- (XRF) portable and non-invasive spectrometer. This spec- troscopic study allows illustrating the strong potential of such in situ analyses to acquire statistically relevant data in

Bibliography a cave environment while preserving the integrity of these representations. In a wider perspective, the combination of [1] P. Arias, C. González Sainz, A. Moure Romanillo and R. Ontañón, T.P. 57, 41-56 (2000) such complementary analytical methods will bring a better [2] P. Arias, E. Laval, M. Menu, C. González Sainz and R. Ontañón, Anthropologie understanding of the symbolic practices of past societies 115, 425-445 (2011). [3] M. Wilke, F. Farges, P. E. Petit, G. E. Brown Jr. and Fr. Martin, Am. Min. 86, and the cultural relationships within the Cantabrian region 714-730 (2001). at the Upper Palaeolithic.

139 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Claire Gervais1 - Marie-Angélique Languille2 P-38 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Solenn Réguer3 - Valerie Briois3 - François Baudelet3 1 Bern University of Applied Sciences, 3011, Bern, Switzerland 2 IPANEMA, CNRS, 91191, Gif sur Yvette, France X-ray absorption 3 Synchrotron SOLEIL, 91191, Gif sur Yvette, France spectroscopy of the photosensitive pigment Prussian Blue: a multi-beamline approach to study that must be considered for sensitive artefacts. This was the case for Prussian blue, which in some cases underwent a its fading process reduction induced by the synchrotron light.

We will report here on our experience concerning the analy- sis of Prussian blue model samples during X-ray absorption X-ray absorption spectroscopy (XAS) has been widely used to spectroscopy performed at three bending magnet beamlines study the local structure of pigments. The high brilliance now of the synchrotron SOLEIL, that differ by their optics scheme, available at third-generation synchrotrons coupled with the use beam size, photon density and acquisition time: Step by of efficient focusing optics and detectors gives access to high step XAS at the DiffAbs beamline [1] with meso-beam photon density, micro-spatially resolved XAS measurements and (200 µm×300 µm), Energy-dispersive XAS at ODE beamline sub-seconds to min time-resolved XAS experiments. [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 for- In the case of the photosensitive Prussian blue, an iron-based mer the typical time resolution for one high-quality spectrum pigment known to fade under daylight or under anoxia, state is 20 min whereas for the two latter ones, sub-seconds time of the art XAS beamlines have been successfully used to cha- resolution is available and requires averaging over several racterize the pigment when embedded in different substrates spectra to get sufficient statistics for our diluted PB samples. [1], study the reduction of Fe(III) at the origin of the fading, and follow the fading kinetics in different environments (such as Through various examples of Prussian blue samples (cyano- low-oxygen atmosphere or high relative humidity) and for types, Prussian blue on paper, in gelatin and dyed textiles), different substrates [2]. However, “ every rose has its thorn we will discuss the choice of the XAS experimental condi- ” and the high density of photons at the sample position for tions, that is often a subtle balance between the goal of the micro scale characterizations may lead to radiation damages 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 Bibliography three beamlines are complementary in their approach and [1] C. Gervais, M.-A. Languille, S. Réguer, M. Gillet, S. Pelletier, C. Garnier, allow to tackle the mechanisms behind Prussian blue fading E. P. Vicenzi, and L. Bertrand, “ Why does Prussian blue fade? Understanding in a most profitable way. 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, We will also show that radiation damage can have different F. Baudelet, and L. Bertrand, “ Live ”Prussian blue fading by time-resolved X-ray absorption spectroscopy, ” Appl. Phys. A, vol. 111, no. 1, pp. consequences, such as pigment excitation leading to pho- 15–22, Jan. 2013. toreduction and fading, or irremediable deteriorations of the [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 substrate. We will finally discuss the strategies we have deve- XMCD studies at SOLEIL ”, High Pressure Research, 31(1):136-139, 2011. loped to estimate radiation damage by calculating the dose [4] E. Fonda, A. Rochet, M. Ribbens, L. Barthe, S. Belin, and V. Briois, “ T he SAMBA quick-EXAFS monochromator: XAS with edge jumping., ” J. Synchrotron absorbed by the sample, and... use it to study the mechanisms Radiat., vol. 19, no. Pt 3, pp. 417–24, May 2012. behind Prussian blue photoreduction [2].

140 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Victor Gonzalez1 - Gilles Bastian1 - Thomas Calligaro1 P-39 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Myriam Eveno1 - Bruno Mottin1 - Élisabeth Ravaud1 Gilles Wallez2 - Michel Menu1 1 C2RMF, Recherche, 75001, Paris, France Sr-XRD characterization 2 IRCP, PCMTH, 75005, Paris, France of lead white in Goya’s paintings

This work focuses on the composition and microstructure Historical sources indicate that the lead white used by Goya of the lead white pigment employed in historical paintings was not produced in Spain but rather imported, mainly from by means of SR-XRD combined with Rietveld refinement. Holland. Ancient inventory records mention various quali- The objective is to relate the samples precise compositions ties of this pigment (albayalde fino, entrefino, ordinario, de with historical texts, and ancient fabrication processes. The tabletas, de Holanda, de Venecia) sold at different prices that studied materials are a set of 15-20 micro-samples collected the painter could select according to the expected pictorial on masterpieces painted by Goya (1746-1828). The very small result. The advanced characterization of the constitutive size of the samples (<100 µm) and the complexity of the materials of the lead white based paint layers should consti- chemical system motivates the use of synchrotron beam in tute a precious tool for a better understanding of the artist order to quantify the crystalline phases by SR-XRD. technique, and the pigment fabrication process.

Easel paintings contain various pigments dispersed in an Samples were first analyzed by SEM-EDX. All preparation organic matrix. Lead white was the most common pigment, layers appear to be lead white based, most of the time mixed present in the preparation layers as well as in the paint layers, with earth-based pigments. Most pictorial layers also contain sometimes mixed with other colors. Lead white is composed lead white. SR-XRD will permit the precise identification and of two main lead carbonates phases, i.e. cerussite PbCO3 and quantification of the various mineral phases: it will then be hydrocerussite 2PbCO3.Pb(OH)2, sometimes associated with possible to connect those results to the use Goya made of plumbonacrite Pb5O(OH)2(CO3)3. In addition, the pigment this pigment in his work. is often combined with several crystalline extenders such as calcite CaCO3. The phase proportions are related to the This research is part of a Ph.D. work started at the C2RMF manufacture processes and the post-synthesis treatments in 2013 bearing on the fine characterization of lead white applied by the manufacturers. 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. Bibliography

[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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Axelle Hubert1,2 - Alexandre Simionovici2 P-40 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Laurence Lemelle3 - Ivo Zizak4 - Alexei Erko4 Frances Westall1 1 Centre de Biophysique Moléculaire, CNRS, 45071, Orléans, France 2 Institut des Sciences de la Terre, Université Jospeh Fourier, 38041, Grenoble, France Synchrotron radiation 3 Laboratoire de Géologie de Lyon, CNRS-ENS, 69622, Villeurbanne, France 4 Institute of Nanometre Optics & Technology, HZB, 12489, Berlin, Germany µXRF and µXANES: in search of oxygenic photosynthesis in archean and proterozoic samples

One approach to understanding the appearance and evolu- forms of life and the blossoming of biodiversity. However, tion of life on Earth is to travel as far back in time as possible, the evolution of oxygenic photosynthetic bacteria has still to study the most primitive forms of life. This can be achieved to be constrained in time. by the study of the geological record, only witness of Earth One approach to this problem is the study of the chemical ancient history. Sedimentary rocks of the Archean geological and mineralogical signatures of OxPh at various scales to eon (from 4.0 to 2.5 billion years (Ga) in the past), hold the determine the local to global impact of oxygen on the most ancient fossils known today. chemistry of the oceans and atmosphere in the Archean We focus our work on the evolution and the spread of oxygenic and Paleoproterozoic geological record (from 4.0 to 1.8 Ga). photosynthesis (OxPh), sometime between 3.5 and 2.4 Ga ago. Within this context, we are investigating the signatures of OxPh, whereby oxygen is released to the environment as OxPh at the local scale within the immediate (mm-μm) a metabolic by-product, developed from anoxygenic pho- vicinity of fossilized photosynthetic microbial mats and cells. tosynthesis which, although primitive, was already itself a In order to cover the period of time assigned to the evo- complex form of metabolism. A widely accepted theory lution of OxPh, we prepared samples of cherts of Archean puts the evolution of oxygenic photosynthetic bacteria in (Josefsdal) and Paleoproterozoic (Gunflint) sedimentary the front row to explain the Great Oxidation Event (GOE) [1], rocks, ranging from 3.47 to 1.9 Ga, containing fossilized relics which records an appreciable rise in the concentration of of putative photosynthetic activity, sectioned using Fast Ion oxygen in Earth’s oceans and atmosphere around 2.4 billion Beam techniques to optimized dimensions of 15×10×2 μm. years (Ga) ago [2], prior to which the oceans were most likely We conducted Synchrotron radiation X-ray Fluorescence anoxic [3]. The GOE marked a key point in the history of the spectrometry (XRF) and X-ray Absorption Near-Edge biosphere, as the increase of oxygen concentration in oceans Structure spectroscopy (XANES) analyses at the MySpot and atmosphere allowed the development of more complex 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,

Bibliography Ba, La, Ce, Nd, Sm, Eu), which bring crucial information on the micro-organisms and their environment. To do so, we [1] Buick R. (2008). When did oxygenic photosynthesis evolve?, Philosophical Transactions of the Royal Society B, 363, 2731-2743. have developed a new absolute quantification method for [2] Bekker A., et al. (2004). Dating the rise of atmospheric oxygen, Nature, 427, SR-XRF analyses by indirectly quantifying the light elements, 117-120. undetected by XRF, but nonetheless present in the samples [3] Holland H. D. (2006). The Oxygenation of the atmosphere and oceans, Philosophical Transactions of the Royal Society B, 361, 903-915. (e.g. H, C, N, O, Na).

142 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Frederic Jamme1 - Mathieu Thoury1,2 P-41 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Bertrand Cinquin1 - Matthieu Réfrégiers1 1 Synchrotron SOLEIL, DISCO, 91192, Gif sur Yvette, France 2 DISCO beamline: IPANEMA, 91192, Gif sur Yvette, France new developments and applications in art and archaeology

UV luminescence techniques have been used by conservators Indeed, the luminescence spectra obtained at high spectral and museum scientists for decades, providing a analysis of and spatial resolutions have made it possible to identify pre- art and heritage materials. viously hard-to-identify constituents of musical instruments DISCO beamline, which monochromatic beam supplies two and pictorial works. DUV-visible microscopes, provides a new and unique ap- We will present recent and future developments at the DISCO proach to characterize the luminescence of ancient materials. 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] T awil, 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] Z ubkovs, V., Jamme, F., Kascakova, S., Chiappini, F., Le Naour, A., & Refregiers, M. Analyst, on line first [6] T houry, M., Echard, J. P., Réfregiers, M., Berrie, B., Nevin, A., Jamme, F., & Bertrand, L. Analytical Chemistry, 2011, 83(5): 1737–1745.

143 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Zsolt Kasztovszky1 - Katalin T. Biro2 - Veronika Szilagyi3 P-42 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Andor Hajnal4 - Karoly Özvegy5 - Ágnes Szekeres5 1 Centre for Energy Research, Hungarian Academy of Sciences, Nuclear Analysis and Radiography Department, 1121, Budapest, Hungary 2 Hungarian National Museum, 1088, Budapest, Hungary Provenance study 3 Isotoptech Ltd, 4026, Debrecen, Hungary 4 Grafoproduct Ltd, 24000, Subotica, Serbia 5 Municipal Museum of Subotica, Department of Archaeology of archaeological and Numismatics, 24000, Subotica, Serbia obsidian using non-destructive Prompt Gamma Activation Analysis

Obsidian was one of the most popular raw materials to beam is a non-destructive analytical method enables us to produce prehistoric stone tools. Thanks to the very specific quantify most major components and some characteristic geological pre-conditions of its formation, the main geological trace elements in a few cm3 volume [3, 4]. The method does sources are well localized worldwide. The classical geological not require any sampling or preparation; almost any size of sources of obsidian in Central Europe can be found in the objects can be placed into the neutron beam. Furthermore, Tokaj-Eperjes Mountains and in the SE foreland of the Car- any impairment of the object is caused by the investigations. pathians in Ukraine, while other sources used in prehistory In this paper, we discuss the provenance of archaeological are known in the Mediterranean region (e.g. Sardinia, Lipari, obsidians found in Subotica (Szabadka, North Serbia) region, Melos). Sources in Anatolia and in Armenia are also well known applying PGAA. and well characterized. According to the literature [1], three The stone implements found at the coast of the Ludas lake main types of Carpathian obsidians exist, denoted as C1 for the constitute the substance of the examination.The lake is si- North-Tokaj (Slovakian) origin, C2 for the South-Tokaj (Hunga- tuated nearby Subotica (Szabadka) in northern Serbia, in the rian) origin, and C3 for the Sub-Carpathian (Ukrainian) origin. Autonomous Province of Vojvodina, about 20 km from the Moreover, C2 group can be subdivided to C2T (Tolcsva), C2E Hungarian-Serbian border in the Southern part of the Great (Mád- Erdőbénye) and C2Tr (Tolcsva “ red ”) types. Hungarian Plain, situated in the heart of a terrestrial sedimen- Since 2003, prompt-gamma activation analysis (PGAA) at the tary area. No exploitable lithic raw material can be found in Budapest Neutron Centre has been successfully used for charac- the neighbouring areas (cca. 100 km radius), thus imported terisation and for provenance research of obsidian artefacts [2]. lithic raw materials had to be obtained for everyday use. The PGAA that utilizes a guided external cold or thermal neutron 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 Bibliography out the commercial contacts of the area in the prehistoric age, [1] Williams-Thorpe, O., Warren, S. E., Nandris, J., 1984. The distribution i.e., where was the raw material of their tools obtained from? and provenance of archaeological obsidian in Central and Eastern Europe. Journal of Archaeological Science 11, 183-212. Would it support or refute the trade routes and contacts set up [2] Kasztovszky, Z., Biró, K. T., Markó, A., and Dobosi, V., 2008. Cold neutron by the archaeologists and based on the previous excavations? prompt gamma activation analysis—a non-destructive method for characterization of high silica content chipped stone tools and raw Obsidian is only one element of this system here which is not materials, Archaeometry, 50(1), 12-29. numerous but very important as trade and contact marker. For [3] Révay, Z., 2009, Determining Elemental Composition Using Prompt Gamma Activation Analysis, Analytical Chemistry, 81, 6851-6859. these purposes, the composition of the Serbian archaeologi- [4] Szentmiklósi, L., Belgya, T., Révay, Z., and Kis, Z., 2010, Upgrade cal obsidian pieces have been compared with our database of the prompt gamma activation analysis and the neutron-induced of PGAA results about more than 300 archaeological and prompt gamma spectroscopy facilities at the Budapest Research Reactor, Journal of Radioanalytical and Nuclear Chemistry, 286, 501-505. geological samples.

144 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Ziga Smit1 - Mateja Kos3 - Sasa Rudolf3 - Zora Zbontar3 P-43 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Tina Lah3 1 Faculty of mathematics anf physics, University of Ljubljana, Jadranska 19, 1000, Ljubljana, Slovenia 2 Jožef Stefan Institut, Jamova 39, 1000, Ljubljana, Slovenia Datatreasure - a new 3 National Museum of Slovenia, Prešernova 20, 1000, Ljubljana, Slovenia 4 tool for dissemination Faculty of Arts, University of Maribor, Koroška 160, 2000, Maribor, Slovenia of scientifc analytical results

From 2001- 2006 an action, dealing with non-destructive Our main idea derives from the concept of sharing knowledge analysis of museum objects (COST G8) was taking place in for gaining knowledge. We think that it is necessary to make the scope of European COST actions. all the results of expensive scientific procedures available It is COST G8 legacy that gave us the idea of preparing an to users. We plan to create an online database of results of European project which should connect natural scientists analytical methods, equipped with a search engine that will and museum professionals. After the action ended, we dis- allow quick and efficient gathering of data. The data will also covered that only a small amount of the results of expensive be useful for comparison. scientific analyses of artifacts were published and dissemi- Because of this, it will be possible to get maximum effect nated. Vast majority of the results never saw the daylight and from EDS, ICP AES, LA ICP MS, PIGE, PIXE, RAMAN, XRF and were lost to other researchers. We also noted that there is a many other analytical methods and enrich our knowledge strong tendency to limit the usage of the data to only one in the fields of basic and advanced art research. field of expertise, for instance conservation – restoration. Our idea is to gather as many as possible of various types of We expect the project DataTreasure to have following scientific analytical results (elemental and oxide quantities, impacts: published and unpublished) and make them available to the t

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the most part of valuable information is lost to the researchers. publication

145 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

L.K. Herrera1 - A. Justo2 - M. Salome3 - G. Martinez-Criado3 P-44 Bleu/Blue 10 sept. 2014 17:00 > 20:00 A. Muñoz-Paez1 1 Universidad de Colombia, Education, 11001, Bogota, Colombia 2 I nstituto de Ciencia de Materiales de Sevilla, Consejo Superior de Investigaciones Científicas-Universidad de Sevilla, Research, 41092, Sevilla, Spain Metal pipes of Spanish 3 European Synchrotron Radiation Facility, Research, BP 220, 38043, Grenoble, France Baroque organ: an elemental analysis

This paper describes the distributions and correlations of This study reveals the different minor and major elements and elemental distributions present in the tin and lead phases their localization in the two microsized segregated areas using of a pipe from a Spanish baroque organ. The composi- micro-XRF, knowledge of relevance in the construction of new tion and microstructure of the pipe were studied using a organs. Ancient organ builders used the lead available in the combination of laboratory techniques and microanalytical 17th century, and they produced a unique sound that now methods at a synchrotron radiation source. The soft and might be reproduced by adding the impurities that came na- hard X-ray microprobes allowed for elemental imaging of turally in old “ pure ” lead and have been discovered now. These the main phases and low concentrated elements at (sub-) results are important for the new organ builders because the micrometer scales. X-ray microscopy beamline ID21 was lead casted today is totally pure. So, that new builders may used to record µXRF and µXANES data at low excitation reproduce antique technology to make better organ pipes energies, 4.05 and 7.3 keV. As expected, it was found that by adding low concentrated elements. Our findings indicate the main components of the metal pipe, tin (80 %) and lead that the main corrosion product formed in the upper layer was (20 %), formed segregated phases. The presence of Hg, Ni, laurionite, PbCl(OH), unexpected compound since chlorine Fe and Cu was detected into the lead phase, being their was not present in the initial alloy. This result corroborated concentration within the range of 0.05-0.01 %. 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Sara Sa1 - Manuel Pereira2 - Sonia Domingos3 P-45 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Antonio Candeias3 - Agnes Le Gac1 1 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 Thai mask under Ambiente / Centro de Petrologia e Geoquímica, Instituto Superior Técnico, 1049-001, Lisboa, Portugal 3 Universidade de Évora, Laboratório Hércules, Centro de Química de Évora, scrutiny: combined use 7000-809, Évora, Portugal of X-ray spectroscopic techniques Because very little is known on this specific mask from a material and mid-infrared and technological viewpoint, this study aimed at getting a first insight into the support and polychrome coating implementa- spectroscopy tion 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 This study focuses on a mask used in modern Khon performance, digital X-ray Radiography (XRR) was carried out in situ in an a classical dance drama from Thailand originally performed as attempt to put in evidence specific aspects of the headdress a court entertainment but evidencing nowadays a popular inner structure and assembly [3]. style for common folk. The mask under study is an elaborate Scanning Electron Microscopy coupled with Energy Dispersive polychrome headdress, 42 cm high, depicting a peacock in the X-ray Spectroscopy (SEM-EDS) was used on a well selected round, called ‘Nokyoonh’ and used in specific episodes from the set of samples, on planar and cross sections for providing SEM Ramakien, the Thailand’s national epic. Dated from the 1960s, imaging at high magnifications, elemental composition and this headdress was brought from Bangkok by Francisco Capelo mapping, and allowing the assessment of the type of gold alloy in 2013, and joined the Museu da Marioneta (Puppet Museum) used and its fineness. collection, in Lisbon, this very year. As a non-destructive imaging technique, X-ray Micro-Computed According to the available information on the current manufac- Tomography (µCT) was also implemented on the aforesaid turing process, Khon masks are made of fibers from the sa rice samples for yielding 3D static and dynamic visualization of their paper applied on a top clay model, and after being removed morphology and microstructure [4]. It was useful to compare from the mold, painted with acrylic paints [1]. Depending on the density, porosity and texture of the fibrous substrates joined the character that is being represented, gold leaf can be applied, together and of all the pictorial layers too. as it seems to be the case regarding the golden tiara which X-ray Diffraction (XRD) was particularly well adapted to assess completes the headdress. 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 in- formation and obtain spectra from a very wide range of ancient Bibliography and modern substances, Attenuated Total Reflectance (FTIR-ATR) [1] N. Chandavij, P. Pramualratana. Thai Puppets & Khon Masks. River Books, as an IR technique complemented the other ones with further Michigan, 1998. [2] A. Le Gac, R. Estrompa, J.C. Frade, S. Pessanha, T.I. Madeira, A. Cardoso, information on the binder used in the paint films [6]. 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 The overall data allowed not only to have a better understanding [3] J. Lang and A. Middleton, Radiography of cultural material, Elsevier, Oxford, of the construction techniques and final touches applied to this 2005, 20-48 [4] S.R. Stock. MicroComputed Tomography: Methodology and Applications, contemporary Thai mask, but also to compare the gathered CRC Press, 2008 results with the literature content [1]. [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 Acknowledgements: [6] O . Chiantore, D. Scalarone, T. Learner. Characterisation of artists’ acrylic To Maria José M. Santos & Maria Carrelhas, Directors of Museu emulsion paints, Journal of Polymer Analysis and Characterisation, 8, 2003, 67-82 da Marioneta.

147 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Agnes Le Gac1 - Teresa Madeira2 - Marco Pereira3 P-46 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Joana Santos3 - Isabel Nogueira4 - Marta Manso5 Jean Bleton6 - Stéphane Longelin5 - Antonio Candeias7 Maria Luisa Carvalho5 1 Universidade Nova de Lisboa, Departamento de Conservação e Restauro, Technological aspects Faculdade de Ciências e Tecnologia, 2829-516, Caparica, Portugal 2 Universidade de Lisboa, Departamento de Física, Faculdade de Ciências, 1649-003, Lisboa, Portugal of a pair of wax-cast 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 Mate- fgurines unveiled by riais e Superfícies, Instituto Superior Técnico, 1049-001, Lisboa, Portugal 5 Universidade de Lisboa, Centro de Física Atómica, Faculdade de Ciências, 1640-003, Lisboa, Portugal multi-analytical 6 Université Paris-Sud, Laboratoire d’Études des Techniques et Instruments d’Analyse Moléculaire, Institut Universitaire de Technologie d’Orsay, 91400, Orsay, France techniques 7 Universidade de Évora, Laboratório Hércules, Centro de Química de Évora, 7000-809, Évora, Portugal

Seven complementary techniques were successfully applied to light, under visible and ultraviolet light, to document their specific study a pair of very alike colored wax figurines belonging to Mu- shape, textures and state of preservation. seu Nacional Machado de Castro, Coimbra (Portugal): Examina- As non-destructive technique particularly suitable to visualize tion under visible and ultraviolet light, Neutron Tomography (NT), hydrogen rich substances and organic artifacts, NT was used for X-ray Radiography (XRR), Energy Dispersive X-ray Fluorescence assessing different densities within wax and material thickness (EDXRF), Scanning Electron Microscopy coupled with Energy and the joint techniques. Dispersive X-ray Spectroscopy (SEM-EDS), Gas Chromatography Non-invasive portable digital XRR offered the possibility of looking with Mass spectrometry (GC-MS) and Raman spectroscopy (RS). through the inner structure of both objects. Front and side views These eighteenth-century figurines in the round, 30 cm high, were taken aiming at looking for eventual metallic elements that depict Francis of Assisi in a very naturalistic way, as an emaciated ensure the figurine and pedestal adequate holding [1]. “ Lesser Brother ” living in poverty, clad in a rough homespun and In a preliminary approach, portable EDXRF was also used in situ to barefoot. Each statuette stands on a marble-like cylindrical base search for elemental composition of all the constitutive parts [2]. decorated with rococo motifs. SEM imaging (Backscattering Electron and Secondary Electron modes) was undertaken on well representative samples, for While very little is known about the circumstances under which high magnification records (×25-5,000), chemical contrast and these artworks were brought together, what makes the connection topographical aspects. Area and point analyses were carried out between them so singular is that they were cast from the same by SEM-EDS, equipped with mapping facilities, to provide data model. Their study offers the unique opportunity to verify aspects on all materials employed to achieve the plastic and chromatic inherent to the production of multiples copies in wax casting. effects: pigments, gilding and fibers. Furthermore semi-quanti- The figurines were examined in situ with normal and racking tative 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 Bibliography foundation material. [1] J. Lang and A. Middleton, Radiography of cultural material, Elsevier, RS was useful as complementary molecular technique to accu- Oxford, 2005, p. 20-48. [2] B. H. Stuart, Analytical Techniques in Materials Conservation, John Wiley & rately determine the inert and coloring agents employed to give Sons Ltd, Chichester, 2007, Chapter 6.3 “ X-ray fluorescence spectroscopy ”, the statuettes their final appearance. 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 The gathered data allowed for a systematic comparison to be for the assessment of consolidant impregnation efficiency in Portuguese glazed tiles (XVII century), Journal of Archaeological Science 39 (4) 2012, drawn between the two figurines and verify how far their ma- 964-969. nufacturing process was the same. It also gave an opportunity [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: to establish a parallel between the concrete reality of this case a production of painter-gilders or sculptors?, in S. Eyb-Green (Ed.), study and the theoretical content of historical art technological Technology and Interpretation Reflecting the artist’s Process, sources on wax-casting [4]. 4th International Symposium of the ICOM-CC ATSR Working group, Archetype Publications, London, 2012, p. 90-111.

148 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Agnes Le Gac1 - Sara Sa1 - Wantana Klysubun2 P-47 Bleu/Blue 10 sept. 2014 17:00 > 20:00 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 Thai mask 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, under scrutiny: 1049-001 Lisboa, Portugal 4 Universidade de Evora, Laboratorio Hercules, Centro de Quimica De Evora, Combined use 7000-809 Evora, Portugal of X-ray spectroscopic Dated from the 1960s, the headdress under study was brought from Bangkok by Francisco Capelo in 2013, and joined the techniques Museu da Marioneta (Puppet Museum) collection, in Lisbon, that very year. and infrared 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 implementa- spectroscopy tion 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 This study focuses on a Thai mask which is strictly speaking illumination, and optical microscopy [3], non-invasive portable an elaborate polychrome headdress (42 cm high) depicting a digital X-ray Radiography (XRR) was carried out in situ in an peacock in the round, called ‘Nokyoong’ in Thai. This mask may attempt to put in evidence specific aspects of the headdress have been worn in two traditional Thai costumed dance-dramas inner structure and assembly [4]. based on the ‘I-Knao’ narrative. The first dance, called ‘Yarun in Scanning Electron Microscopy coupled with Energy Dispersive pursue of the peacock’, is based on an I-Knao poem by King X-ray Spectroscopy (SEM-EDS) was used on a well selected Rama II and practiced since 1817. It consists of two dancer-actors set of samples, on planar and cross sections for providing SEM only, one enacting the hunter role of ‘Yarun’ and the other one, a imaging at high magnifications, elemental composition and peacock role [1]. It is also classified as ‘Lakorn Nai’, a performance mapping, and allowing the assessment of the type of gold alloy excusively displayed in the Royal precincts. The second dance used and its fineness. ‘Rabum Mayurapirom’, consists of multiple performers dressed as As a non-destructive imaging technique, X-ray Micro-Computed peacock characters. While the choreography of this play was in- Tomography (µCT) was also implemented on the aforesaid vented by Peaw Sanitwongsenee and its melody was composed samples for yielding 3D static and dynamic visualization of their by Montree Tramoch, the premiere of Rabum Mayurapirom took morphology and microstructure [5]. It was useful to compare place in 1961 [2]. 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 Bibliography ground and pigments were used, and whether they were em- [1] S. Pothiwhetchakul. Master of Arts Thesis. Chulalongkorn University, ployed as single matter or in admixtures [6]. Bangkok, 1996. For its ability to improve reproducibility, provide molecular in- [2] I . Boonprakob, an online article (accessed 2014): http://taopuyimbunhotmail.blogspot.com/2009/01/blog-post_15.html. formation and obtain spectra from a very wide range of ancient [3] A. Le Gac, R. Estrompa, J.C. Frade, S. Pessanha, T.I. Madeira, A. Cardoso, and modern substances, micro Fourier Infra Red spectroscopy L. Piorro, J. Mirão, A. Candeias, M.L. Carvalho. Multianalytical approach for the authenticity of an eighteenth-century Pascal Taskin harpsichord, (µ-FTIR) analysis complemented the other ones with further Journal of Analytical Atomic Spectrometry, 27, 2012, 626-643 information on the binder used in the paint films [6]. [4] J. Lang and A. Middleton, Radiography of cultural material, Elsevier, Oxford, 2005, 20-48 The overall data allowed to have a better understanding of [5] S.R. Stock. MicroComputed Tomography: Methodology and Applications, the construction techniques and final touches applied to this CRC Press, 2008 [6] N.C. Debnath, S.A. Vaydia. Application of X-ray diffraction technique contemporary Thai mask. for characterisation of pigments and control of paints quality, Progress in Organic Coatings, 56 (2-3), 2006, 159–168 Acknowledgements: To Maria José Santos, Director of the Puppet [7] C. Selwitz. Cellulose Nitrate in Conservation. The Getty Conservation Institute, Los Angeles, 1988. Museum, and Maria Carrelhas.

149 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Heinz-Eberhard Mahnke1,2 - Verena Lepper3,4 P-48 Bleu/Blue 10 sept. 2014 17:00 > 20:00 1 Freie Universität Berlin, FB Physik and TOPOI, 14195, Berlin, Germany 2 Helmholtz-Zentrum Berlin, 14109, Berlin, Germany 3 Staatliche Museen zu Berlin, Ägyptisches Museum und Papyrussammlung, 10117, Berlin, Germany Virtual unfolding 4 Humboldt-Universität zu Berlin, 10178, Berlin, Germany and unrolling of papyri – identifcation of hidden texts

In collections in various museums around the world, We report the development of a procedure for sorting there are numerous objects of folded and rolled ancient out proper objects for tomographic inspection. With X-ray papyri and other manuscripts often inscribed with texts of fluorescence possible objects are first screened for metal historic and archeological value. To make such texts readable, containing ink like iron or copper from iron gall or copper tedious procedures (and sometimes totally unsuccessful) vitriol. Only objects with positive metal signals are then are necessary for unfolding and unrolling these delicate and chosen for tomographic scans. brittle objects. With recent progress in X-ray tomography Samples prepared for demonstration from modern material CT with respect to resolution (i) and sensitivity (ii) it is now (papyrus and ink) with written symbols and without have possible to develop procedures for a virtual solution: been tested and nicely support the chosen procedure. In (i) T he recent reading by X-ray CT of a Mandaic text im- the case of iron, however, one has to expect surprises since pressed onto a thin pure lead foil and rolled [1] nicely the sensitivity for revealing writings is blurred by Fe inherent illustrated the achievements in resolution. already in the papyrus material itself. (ii) A demonstration on a parchment role from the Norfolk archive dating from the year 1778 as an example for or- ganic 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Annalaura Restivo1 - Sandro Jurinovich1 - Ilaria Degano1 P-49 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Erika Ribechini1 - Simone Bugani2 Josefna Perez-Arantegui3 1 Università di Pisa, Dipartimento di Chimica e Chimica Industriale, 56126, Pisa, Italy Micro X-ray 2 Università di Bologna, Dipartimento di Chimica Industriale e dei materiali, 40136, Bologna, Italy 3 Universidad de Zaragoza, Instituto Universitario de investigación fuorescence with en Ciencias Ambientales, 50009, Zaragoza, Spain synchrotron radiation (SR µ-XRF) and energy dispersive X-ray microanalysis coupled to feld-emission scanning electron Microscopy (EDX-FESEM). Elements present in the wool matrix (like S) and others added in the mordanting process microscopy (EDX-FESEM) (Fe) were investigated. The employment of SR µ-XRF allowed us to obtain elemental mapping in the threads with high for studying spatial resolution, whereas EDX-FESEM was used to study the spatial variation of the light elements. the degradation of wool The results highlighted the advantages of working with complementary analytical techniques. Iron, one of the historical textiles dyed elements more actively involved in the redox degradation processes, was spatially confined to the external part of the with iron-tannin dyes 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 Historical textiles are an important part of our cultural the core to the cuticle. EDX-FESEM quantitative data dis- heritage, but such fragile textiles are subjected to several closed three different degrees of degradation on the basis types of degradation that damage their integrity and rea- of C/S ratios along the fibre section; the low C/S ratio in the dability. The knowledge of their degradation mechanisms cuticle (high S content) corresponded to non-degraded is a matter of importance to improve the conservation of fibres. The presence of sulphur-rich proteins is extremely these materials. Textile dyeing is one of the main sources of important due to their influence on the mechanical and fibre damage and, among the different dyeing techniques, thermal properties of wool, and the disulphide bonds are iron-tannin dyestuffs are known to cause specific and intense fundamental in maintaining the three-dimensional structure damage to textiles. In particular our study was focused on of wool. Also two different trends were identified for C/O the deteriorating effects of tannins on wool threads, and ratio by EDX-FESEM, and the high C/O ratio in the cuticle was specifically on the chemical characterization of the dyed assigned to non-oxidized fibres. The oxidative mechanisms wool cross-sections. may have affected the external lipid layer of the wool, and Two different analytical methods were applied to fully the surface C/O ratio was identified as a good indicator of characterise the chemical composition and the elemental fibre degradation, highlighting the occurrence of oxidation distribution in the dyed cross-sections of reference wool reactions. In general, both morphological and elemental samples and historical textiles: micro X-ray Fluorescence with analysis of wool specimens showed that the dyeing process Synchrotron Radiation (SR µ-XRF) and Energy Dispersive X-ray (addition of mordants and tannins) increased the rate of wool microanalysis coupled to Field-Emission Scanning Electron damage, irrespectively of the type of raw materials exploited.

151 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Sofa Pessanha1 - Mario Costa1 - Maria Ines Oliveira1 P-50 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Maria Estrela Jorge2 - Maria Luisa Carvalho1 1 Centro de Fisica Atomica da Universidade de Lisboa, Av. Prof Gama Pinto, 2, 1649-003, Lisboa, Portugal 2 Centro de Quimica e Bioquimica da Faculdade de Ciencias Analysis of the silver da Universidade de Lisboa, Campo Grande, 1649-010, Lisboa, Portugal content in “ dinheiros ” minted during the reign of D. Fernando of Portugal (1367- 1383) – debasement or mineral impurity?

“ Dinheiros ” are the first Portuguese coins, minted with a bil- very sensitive to changes introduced by a corrosion layer. This lon alloy (copper and silver). In this work, a set of “ dinheiros ” way, “ clean ” spots were identified and quantitative analysis from D. Fernando of Portugal (reign 1367-1383) was analyzed carried out. The obtained results are similar to the ones and the composition of the alloy was compared with other obtained in a previous study [1] where a clear decrease of “ dinheiros ” from previous reigns (from 1223 to 1367). By the Ag content was determined: from 8-9 % in the previous using the X-ray Fluorescence (XRF) analysis, a problem for reigns to 0.2-0.3 % in the coins attributed to D. Fernando. The an accurate quantification may arise from their preservation silver contents determined is very well comparable to the state: usually a corrosion layer appears on the original surface silver content determined in other copper or bronze artifacts of the object, which is composed by a variety of copper or analyzed, even in a copper counting bead, leading us to silver based compounds. Although the coins were in good believe that this low amount of silver was not intentionally state of conservation and no active corrosion was macros- introduced to create a billon alloy but relates to impurities copically observable, the surface of the coins was further present in the original mineral specimen. evaluated by means of X-ray Diffraction (XRD). In order to overcome this hindrance, the silver K/L intensity ratios were Acknowledgments: determined and compared for the analyzed samples - K/L M. E. M. Jorge would like to thank the project PEst-OE/QUI/ intensity ratios are constant for different Cu-Ag alloys but are UI0612/2013 for the funding.

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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Giampaolo Piga1 - Antonio Brunetti1 P-51 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Assumpcio Malgosa2 1 University of Sassari, Scienze Politiche, Scienze della Comunicazione e Inge- gneria dell’Informazione., 07100, Sassari, Italy 2 Universitat Autonoma de Barcelona, Unitat de Antropologia Biologica, Interdisciplinary Departament de Biologia Animal, Biologia Vegetal i Ecologia, 08193, Bellaterra study of cremation (Barcelona), Spain urns from the iron age necropolis of Sebes (Flix, Tarragona, Spain).

In recent decades, research and experience of cases have the cristallinity and the fire temperature] with the aim to im- greatly increased the ability to recognize and interpret the prove the methodology used by different authors [1,2] for burnt bones. The ability to preserve the bones during the better understand funerary practices and customs within micro-excavation, to distinguish between burned human archaeological contexts. In addition to traditional research remains and other materials, and the determination of the methods, the application of chemical and physical tech- combustion temperature, time duration and intensity distri- niques such as XRF, XRD and FT-IR is increasingly accepted bution throughout the body after focusing on microscopic in archaeological and forensic studies [3]. X-ray diffraction changes in the bone may be important for understanding fu- and FT-IR analysis have several significant advantages neray practices and customs within archaeological contexts. which are complementary for our full understanding of Thus, new experimental methods are needed to better cla- the firing process whether in anthropological and forensic rify the variety of factors that involves the study of funerary contexts [3,4]. urns. In this work we present a interdisciplinary study of Computed tomography (CT) has been recognized by cremation urns belonging to the necropolis of Sebes (Flix, scientists as a very efficient tool for non-destructive study Tarragona, Spain) through various processes [CT-computed of archaeological artefacts, fossil/no fossil skeletal materials tomography, micro-excavation, skeletal anthropology study; and especially for mummies studies. Comprehensive studies X-ray Diffraction (XRD), X-ray Fluorescence (XRF) and Fourier of the contents of archaeological cremation urns with CT are transform infrared spectroscopy (FT-IR) analysis to determine 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.

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Alicja Rafalska-Lasocha1 - Marta Grzesiak-Nowak2 P-52 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Justyna Olszewska-Swietlik3 - Bozena Szmelter-Fausek3 Wieslaw Lasocha1 1 Jagiellonian University, Faculty of Chemistry, 30-060, Krakow, Poland 2 Jerzy Haber Institute of Catalysis And Surface Chemistry, PAS, µ-XRPD investigations 30-239, Krakow, Poland 3 Nicolaus Copernicus University, Institute for the Study, Conservation of the pigments And Restoration of Cultural Heritage, 87-100, Torun, Poland in 17th century panel paintings from Gdansk and the northern region of Poland

Proper recognition of artists’ technology and techniques yellow type I (Pb2SnO4) and lead tin yellow type II (PbSnO3). often requires applying a broad range of interdisciplinary Their powder diffraction patterns are different and each of research methods based on the study of written sources them can be easily detected by XRPD. (treatises and manuscripts), old painting workshops, practical The investigations of red paint layers with the use of µ-XRPD reconstruction of formulas, artistic experience and physical excluded existing in the paintings crystalline red pigments, and chemical investigations [1]. The panel paintings by which suggests that red lakes were used by the masters. In

Anton Möller (1563/65-1611), Isaak van den Blocke (1589- one sample µ-XRD revealed aluminum oxide Al2O3, whereas 1628) and Hermann Han (1580-1627/28) who lived in Gdańsk from the reaction between alkali and alum hydrated alumina

(Poland) were investigated in this study. Al(OH)3 should be obtained. In practice, it is difficult to cha- Chemical composition of grounds and pigments used by 17th racterize this substrate, partly because it is amorphous and

century masters in several panel paintings were identified by highly variable [2]. The presence of Al2O3 in the sample will means of µ-XRPD technique. Calcite and lead white were de- be the subject of further studies on production and chemical tected in ground and white layers. Due to the fact that XRPD characterization of dyestuff used by 17th century masters. is one of the best methods to identify chemical compounds Described above results clearly show that contrarily to the with similar elemental composition we were able to identify microdiffraction on not easily accessible synchrotron beams, two kinds of lead white: cerrusite and hydrocerrusite in the microdifraction technique with the use of laboratory X-ray investigated samples. source is suitable for analysis of typical for panel paintings In blue paint layers we have identified azurite and ultrama- thin paint layers and this technique can be widely used to rine. What is interesting, thanks to µ-XRPD technique we were enrich the knowledge about cultural heritage objects. able to identify two different blue pigments used by the All measurements were carried out on X’PERT PRO MPD master in the same blue paint layer. The results obtained for diffractometer, Cu Kα radiation, 40 kV and 30 mA, a graphite one of the paintings suggest that smalt or other amorphous monochromator and PIXCEL PSD detector. The apparatus blue pigment was used. was equipped with a collimator (output beam diameter In the case of yellow paint we have identified lead tin yellow 0.1 mm). Phase analysis and pigment identification were type I. Old masters used two types of lead tin yellow: lead tin 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Paula R. P. Allegro1 - Marcia A. Rizzutto1 - Tiago F. Silva1 P-53 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Nemitala Added1 - Jessica F. Curado1 - Ana G. Guimarães2 Marcia Barbosa2 1 Institute of Physics, University of São Paulo, 05508-090, São Paulo, Brazil ED-XRF and PIXE 2 Museum of Contemporary Art, University of São Paulo, 05508-900, São Paulo, Brazil analysis of a modern Italian painting

Energy Dispersive X-ray Fluorescence (ED-XRF) [1] and in-air Par- Those paintings in the back part are not recognized as painted ticle induced X-ray emission (PIXE) [2,3] are physical techniques by the same artist who painted the front part. Our group have used to determine the elemental constituents of a material. To already studied two of these five paintings recently and deter- perform PIXE and ED-XRF it is not necessary to take a sample of mined the authorship of the compositions on their verso [7,8]. the material, so they suit very well to determine the elemental constituents of Cultural Heritage objects, like paintings, with very In this work, ED-XRF and PIXE analysis have been carried out to good results, as seen in [4,5]. The main advantage of ED-XRF ana- determine the elemental constituents of the painting entitled “ Il lysis is that this technique can be done in situ, while PIXE allows pittore all’aria aperta ” (62.5 × 50.3 cm), oil on canvas, produced measurements of different layers of the material. in 1919 by Virgilio Guidi. This painting is of particular interest due to an incomplete composition of an unknown artist on its verso. The Museum of Contemporary Art of the University of São Paulo ED-XRF measurements in both sides of the painting were done (MAC-USP), Brazil, has a collection of Italian paintings, which at MAC-USP using a miniature Ag X-ray tube system and a SSD constituted a panorama of the main trends of Modern painting detector. PIXE measurements in the front composition were in Italy from the 1920s to the 1940s [6]. Inside this collection, five performed at Laboratório de Análises de Materiais por feixes paintings are subject of interesting research in the museum, iônicos (LAMFI), belonging to the University of São Paulo, Brazil, because they have another composition on their verso, exceptio- using a proton external beam with an incident energy about nal phenomenon of the artistic practices of the interwar period. 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, Bibliography iron oxides and cobalt blue pigments by the artist. Some traces [1] E. P. Bertin, “ Principles and practice of X-ray spectrometric Analysis ”, elements detected, like S, Cr, Pb, Se and Sr, are still under analy- Plenum Press, Londres, (1975) 1079. sis and can help in the determination of the authorship of the [2] S. A. E. Johansson, J. L. Campbell, « PIXE, A Novel Technique for Elemental Analysis », John Wiley and Sons (1988). verso composition. [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.

155 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Alessandro Re1 - Jacopo Corsi1 - Debora Angelici1 P-54 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Alessandro Lo Giudice1 - Alessandro Borghi2 Emanuele Costa2 - Antonella Scherillo3 - Francesco Grazzi4 - Lorenzo Mariano Gallo5 - Giovanni Pratesi6 1 Università di Torino and INFN, Dipartimento di Fisica, 10125, Torino, Italy Neutron difraction 2 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 on lapis lazuli: 5 Museo Regionale di Scienze Naturali, 10123, Torino, Italy 6 Università di Firenze, Dipartimento di Scienze della Terra and Museo characterisation di Storia Naturale, 50121, Firenze, Italy of rocks and artworks for a provenance study

Lapis lazuli is a semi-precious blue stone, being used for glyp- are in agreement with a Pamir Mountains and Chagai Hills tic as early as 7000 years ago: jewels, amulets, seals and inlays provenance, other than Badakhshan. Moreover, there is some are examples of objects produced using this material. Only evidences that also in Renaissance the Chagai Hills deposits few sources of lapis lazuli exist in the world due to the low was used as source of lapis lazuli to produce ultramarine probability of geological conditions in which it can be for- blue pigment [6]. Nevertheless a systematic and exhaustive med [1], so that the possibility to associate the raw material provenance study of the raw material used for artworks is to man-made objects is helpful to reconstruct trade routes. still lacking and lapis lazuli provenance is then a still open This is especially true for ancient contexts where there is an question. Since art and archaeological objects produced absence or scarceness of written evidences [2]. Although using lapis lazuli are valuable, only non-invasive techniques the Badakhshan mines in Afghanistan are widely considered can be used to identify the provenance of the raw materials. as the only sources of the lapis lazuli in ancient times [2-4] For this kind of investigation Prompt Gamma Activation other sources have been taken in consideration: Tajikistan Analysis (PGAA) was proposed and preliminary studies on (Pamir Mountains) [3,5], Pakistan (Chagai Hills) [5,6], Siberia rock samples were promising [8]. (near Lake Baikal) [3], Iran [3] and Sinai [7] (these last two not Our group started a provenance study of this material in geologically confirmed and their interpretations still debated 2007, using a protocol based on a multitechnique approach [4]). Results obtained using physico-chemical analysis (AAS) [9-11]. Due to the heterogeneity of lapis lazuli it is very dif- on limited quantities of cut wastes from Shahr-i-Sokhta [5] ficult 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 Bibliography to the high penetration of neutrons, it has been possible [1] Wyart J. et al, Gems & Gemmology 17 (1981) 184-190 to recognize the different phases composing several rocks, [2] T osi M., Gururajamanjarika, Studi in onore di G. Tucci, Ist. Univ. Orientale, Napoli (1974) 3-22 through the analysis of the diffraction patterns obtained at [3] Herrmann G., Iraq 30(1) (1968) 21-57 the time of flight (TOF) diffractometer INES (Italian Neutron [4] Herrmann G. et al, Reallexikon der Assyriologie und Vorderasiatischen Archäologisch, ed. W. de Gruyter, Berlin (1983), 6: 489-492 Experimental Station) operating at ISIS facility (RAL, UK). [5] Casanova M., South Asian Archaeology, World Archaeology, In this contribution the results obtained on 13 rocks from 4 Prehistory Press, 14 (1992) 49-56 [6] Ballirano P. et al, American Mineralogist, 91 (2006) 997-1005 different provenances and on 3 artworks from the XIX cen- [7] Nibbi A. “ Ancient Egypt and some Eastern Neighbours ”. Park Ridge, tury Savoy Collection (Museo Regionale di Scienze Naturali) Noyes Publication (1981) 2: 33-55 [8] Z öldföldi J. et al, Proceeding of 34th Int. Symp. on Archaeometry [12] will be presented. The differences among the sources (Zaragoza, Spain, 2004), (2006) 353-360 can be used to have some indications about the provenance [9] Lo Giudice A. et al, Analytical and Bioanalytical Chemistry 395(7) (2009) 2211-2217 of artworks and objects made in lapis lazuli whose origin is [10] Re A. et al, Nuclear Instruments and Methods in Physics Research not known. These results can be extended to archaeological B 269(20) (2011) 2373-2377 samples and can be a good starting point to answer still [11] Re A. et al, Applied Physics A 111(1) (2013) 69-74 [12] Gallo L.M., Cataloghi, XVI, Torino, (2004) 287pp debated archaeological questions.

156 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Solenn Réguer1 - Cristian Mocuta1 - Filipe Alves1 P-55 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Dominique Thiaudière1 - Delphine Vantelon2 Nicolas Trcera2 - Benedikt Lassalle2 - Damien Roy2 Pierre Lagarde2 1 Synchrotron SOLEIL, DiffAbs beamline, 91192, Gif sur Yvette, France DifAbs and LUCIA 2 Synchrotron SOLEIL, LUCIA beamline, 91192, Gif sur Yvette, France beamlines complementarity to study ancient materials.

The diagnosis of the degradation state and the development combination of such techniques offers the possibility of com- or improvement of conservation strategies for different ma- plementing the local structure information by data on the terials as metals [1-3] and paintings [4,5], are of great interest long range order, which is essential for a full characterization for the preservation of the historical or artistic artefacts. of the studied material. All the measurements are perfor- Thus, it is crucial to characterize (structure, elementary com- med on the 6/8 circle kappa diffractometer using different position) and locate (at micrometric scale) the constitutive well-adapted detectors, ensuring that all experiments are phases of the studied materials, according to their key role carried out on the same zone of the sample, in absolutely in the alteration processes. identical physico-chemical conditions (temperature, reactive These studies make the most of the available comple- solution, etc.). mentarities of the DiffAbs and LUCIA beamlines at SOLEIL The LUCIA beamline is a tender (0.8-8 keV) X-ray microprobe synchrotron. These beamlines are actually complementary with capabilities for chemical speciation by µ-XAS and for in the energy range, the beam size and the techniques they elemental mapping by µ-XRF with a spot size of 2.5×2.5 µm² offer. In addition, these two beamlines are part of the most obtained by two mirrors dynamically bendable in the Kirk- requested by users studying ancient materials running X-rays patrick-Baez configuration [6]. It allows the possibility to based synchrotron techniques. measure heterogeneous samples at the micrometric size and The DiffAbs beamline provides a monochromatic X-ray to combine these two element-specific and non-destructive beam, tunable in the 3-23 keV energy range. The multi-scale techniques for phase’s local structure characterization. beam size, standard (300 µm) and microbeam (10 µm), can Since they opened, DiffAbs and LUCIA beamlines proved be used in conjunction with all the analysis techniques avai- their competitiveness to study materials for various topics lable at the beamline: XRD, XAS and XRF. The simultaneous 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Marcia A. Rizzutto1 - Elizabeth A.M. Kajiya1 P-56 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Pedro H.O.V. Campos1 - Martha Aldred1 - Jessica F. Curado1 Suene Bernardes1 - Ana G. Magalhães2 - Marcia Barbosa2 1 Instituto de Física, Universidade de São Paulo, 05508-090, São Paulo, Brazil 2 Museu de Arte Contemporânea, Universidade de São Paulo, 05508-050, The Italian painting São Paulo, Brazil ‘‘A Adivinha’’ by Achille Funi analyzed using non destructive techniques

The painting A Advinha (The fortune-teller) by Achille Funi pigments that have the elemental composition of lead, was analyzed with non destructive techniques as energy zinc, chromium, iron, mercury, calcium, etc. The analysis of dispersive X-ray fluorescence, images and computed ra- the pigments used in a painting is extremely important for diography (CR). This painting, oil on wood of 46 × 46 cm, restoration and conservation process and can also allow belongs to the collection of the Museum of Contemporary the identifying the pigments that may suffer degradation. Art of the University of São Paulo (MAC USP). The museum This knowledge allows one to adopt specific practices for has a collection of Italian paintings [1], which constituted storage and/or exhibition of paintings, and, also the choice a panorama of the main trends of Modern painting in Italy of the most suitable treatments to reverse or to stop dete- from the 1920s to the 1940s [2]. This painting was analyzed rioration processes. aiming at the better characterization of the artist’s proce- The image (visible light, infrared reflectography, ultraviolet dures and his work, and also a construction of a data base photography, tangential light) and radiography techniques of the pigments of this artist. A portable X-ray Fluorescence used were useful to reveal internal details that are invisible (PXRF) system was employed to identify the pigments used the naked eye. In this painting, these analyses revealed by the artist and is composed of a Si-drift detector with an that the painting was in a good state of conservation and active area of 7 mm2 and a Be-window with 12.5 microns also allowed to identify the successive phases of the artist’s thickness. The system uses an Ag-anode X-ray tube wor- creation process. The analysis revealed hidden drawings per- king at 30 kV and 5 µA of voltage and current respectively. formed by the artist under the painting and the preparatory The PXRF analysis allow the identification of the different 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Laszlo Rosta1 P-57 Bleu/Blue 10 sept. 2014 17:00 > 20:00 1 Wigner Research Centre for Physics, Budapest Neutron Centre, H-1525, Budapest, Hungary Neutrons and complementary The Budapest Neutron Centre (BNC) has long traditions in application of neutrons for archaeology research. In particular, methods for the Prompt Gamma Activation Analysis (PGAA) group has made a pioneering work to apply this technique to archaeo- archaeometallurgy metry. Small Angle Neutron Scattering (SANS) and Neutron Diffraction (ND), Neutron and Gamma Radiography (NGR) investigations 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 mu- seums as well as provides access to a network of large scale The application of analytical tools in the investigations of facilities; BNC is one of the transnational access providers by the objects of Cultural Heritage usually concern dating, the services offered at its neutron facilities: diffractometers provenance, manufacturing techniques, workshop affinities, (ND), SANS, PGAA stations and imaging facilities. Complemen- as well as fake identification, conservation or preservation tary measurements are offered by the use of External Beam of objects. Neutrons are perfect tools of archaeometrical PIXE and compact XRF Spectrometers, microscopes, mass studies due to their non-destructive and non-invasive spectrometers etc. also at BNC site. nature. Various kinds of neutron techniques can be used Neutron methods and complementary techniques available at to explore the compositional or structural features of the BNC and their relevance to investigation of objects of Cultural samples. Based on the detection of characteristic γ-photons Heritage, in particular applications to archaeometallurgy will produced in (n, γ) reaction, one can determine the ‘bulk’ be presented. A review of case studies as comprehensive elemental composition of the objects. Or, investigation of analysis of artefacts by combined neutron techniques will neutron scattering patterns gives information on the atomic, be demonstrated. For example, manufacturing processes of molecular or nano-scale structural properties: crystalline/ the earliest Hungarian Bronze Age defensive armour such amorphous morphology, phase composition, mechani- as helmets, greaves and cuirass were studied by PGAA, PIXE cal strains, impurities, etc. Furthermore, neutron imaging and ToF-ND [1]. Medieval steel objects e.g. swords of Vikings, techniques (tomography/radiography) play an important knifes from India and Syria were investigated to reveal their role in the exploration of the deep bulk topology or in-side iron phase structure and composition relevant for the ancient content of artefacts. 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 inven- tion of bloomery smelting by nearly two millennia, they are commonly assumed to be made from meteoritic iron. Our set Bibliography of neutron measurements has provided unambiguous results [1] Kasztovszky Zs, Rosta L; How can neutron contribute to Cultural Heritage to offer a comprehensive interpretation of the origin and Research; Neutron News, 23, 25-28, 2012 [2] Káli Gy, Rosta L, Sánta S, Eszenyi G., Characterization of archaeological fabrication of these beads and their significance for the his- and museological metal-related artefacts by TOF-ND at Budapest Neutron tory of iron working development [3]. Objects of late Roman Centre, ICNS 2013, Edinburgh [3] Rosta L, Belgya T, Káli Gy, Kasztovszky Zs, Kis Z, Kovács I, Maróti B, silversmith activity attracts nowadays considerable interest Szentmiklósi L, Szőkefalvi-Nagy Z, Jambon A, Rehren Th; Proof of – the comparative analysis of various silver objects marked the Meteoritic Origin of Mankind’s Earliest Iron Artefacts through Neutron BOE
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with stamp of known imperial workshops and pieces of similar http://www.hungarianarchaeology.hu silversmith appearance without “ certificate ” can reveal the [4] Káli Gy, Horváth E, Kasztovszky Zs, Kovács I, Maróti B, Mráv Zs, Rosta L, same origin of these objects due to the identification of ar- Szőkefalvi-Nagy Z, Archaeometry Investigation of Late Roman Silversmith Objects, Research report 2014 (to be published) chaeometallurgical parameters by neutron measurements [4].

159 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Sebastian Schöder1 - Felisa Berenguer2 - Serge X. Cohen2 P-58 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Aurélien Delmotte1 - Thierry Moreno1 - François Polack1 Sébastien Ancelin2 - Françoise Deschamps1 - Didier Dallé1 Loïc Bertrand2 1 Synchrotron SOLEIL, PUMA beamline, 91192, Gif-Sur-Yvette, France The PUMA beamline 2 IPANEMA, 91192, Gif-Sur-Yvette, France

Researchers in the cultural heritage field have become an PUMA will be a high energy (4 to 60 keV) X-ray beamline that important group of the synchrotron community. However, will provide to its users both full field phase contrast tomo- the limited amount of beamtime available at 3rd generation graphy and scanning microbeam techniques with microme- synchrotron sources often restricts the research done to tric resolution. The robust optical setup will allow a simple “ exceptional ” or “ highlight ” samples and makes it difficult transition between the full field and microbeam modes of to investigate statistically meaningful numbers of typical the beamline. A double crystal monochromator with a Si 111 objects (corpus analysis). To overcome these problems, and and a Si 220 set of crystals will be used for energy selection. to provide tools specially adapted to the synchrotron com- In addition, experiments will be able to use the white beam. munities of archaeology, conservation, paleo-environments Focusing for microbeam operation will be done by a SOLEIL and palaeontology, the project to construct PUMA (“ Photons designed Kirckpatrick-Baez mirror system. A set of two high-in- used for Ancient Materials ”), a specially adapted beamline tensity pinholes will allow imaging users to isolate the cohe- at the synchrotron SOLEIL, was created. rent part of radiation for phase contrast experiments. A field of view of 20 mm (horizontal) and 10 mm (vertical) will be The construction of PUMA has been financed by the region available for full-field experiments. The setup will be optimized Île de France and the French ministry of research and higher for X-ray imaging, absorption and fluorescence spectroscopy education and will be operated by SOLEIL and the IPANEMA as well as diffraction and small angle scattering experiments. CNRS unit. While it will be open to users from all scientific fields, the beamline will be optimized for cultural heritage The beamline is currently under construction, commissioning science and a large part of the beamtime will be reserved will begin at the beginning of 2015. The beginning of user for these communities. operation is foreseen for the second half of 2015.

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, Development and trends in synchrotron studies of ancient and historical materials, Physics Reports. 519 (2012) 51–96.

160 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Tatiana Severin-Fabiani1,2 - Mathieu Thoury1,2 P-59 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Luc Robbiola3 - Benoit Mille4 - Matthieu Réfrégiers2 Loïc Bertrand1 1 IPANEMA, F-91192, Gif-sur-Yvette cedex, France 2 SOLEIL synchrotron, F-91192, Gif-sur-Yvette cedex, France Imaging 3 Laboratoire TRACES, UMR 5608, 31058, Toulouse Cedex 9, France 4 photoluminescence C2RMF, UMR171, 75001, Paris, France heterogeneity of corrosion products at sub-microscale in cultural heritage metallic artefacts

Novel imaging approaches based on synchrotron UV/visible We optimized synchrotron PL micro-imaging in order to photoluminescence (PL) allow studying a variety of ancient collect the relevant information on the nanoscale structure materials at a sub-microscale [1,2]: (a) deep UV excitation al- and PL properties of corroded bronze objects. We studied a lows probing luminophores not attainable with conventional corpus of 10 bronze artefacts from distinct burying environ- systems, while (b) decreasing the complex scattering effects ments (air, soils from various periods or regions) composed of encountered in the visible and IR. (c) High resolution spectral binary Cu–Sn, ternary Cu–Sn–Pb or tin-free alloys in several imaging enables accessing the complex heterogeneity of the advanced degradation states. The excitation tunability at the various phases which contributions are otherwise averaged DISCO synchrotron beamline (200–600 nm) and the emission when studied at a macroscopic scale [3]. Corroded layers in spectral selectivity allowed to detect PL from Sn- and Cu- copper-based archaeological artefacts are notoriously challen- based alteration products between 320 and 1100 nm. Copper ging to characterize because of their heterogeneous structure and tin oxides, often encountered in natural patinas, exhibit at the microscale due in particular to the presence of multiple semiconducting properties that were exploited for charac- phases and partial amorphous character during the long-term terisation in the 3.6 and 2.1 eV energy ranges, respectively. alteration processes [4]. In order to tackle both the great variability of corrosion layers dimensions, ranging from tens of micrometers to few milli- meters, 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.

Both morphology and PL properties of corrosion phases at Bibliography high resolution could inform on the original alloy nanoscale [1] L. Bertrand, M. Cotte, M. Stampanoni, M. Thoury, F. Marone, and S. Schöder. composition, the environment of the object that governed Development and trends in synchrotron studies of ancient and historical materials. Phys. Rep., 519(2):51–96, Oct 2012. long-term corrosion processes as well as preservation. Future [2] M. Thoury, J.-P. Echard, M. Refregiers, B. Berrie, A. Nevin, F. Jamme developments of the technique will aim at a better correlation and L. Bertrand. « Synchrotron UV-visible multispectral luminescence micro-imaging of historical samples ». Anal. Chem., 83(5), pp.1737-1745 (2011). between spatial and spectral information. [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.

161 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Salvatore Siano1 - Iacopo Osticioli1 - Maria Cristina Guidotti2 P-60 Bleu/Blue 10 sept. 2014 17:00 > 20:00 G. Capriotti3 - N. Kardjilov4 - A. Scherillo5 - Juri Agresti1 1 Istituto di Fisica Applicata “ N. Carrara ”, CNR, 50019, Firenze, Italy 2 Soprintendenza Per I Beni Archeologici Della Toscana, 50121, Firenze, Italy 3 I stituto di Studi Sul Mediterraneo Antico, CNR, I-00015, Roma, Italy Combined neutron, 4 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh, D-14109, Berlin, Germany X-ray, and laser 5 Isis Facility, Ral, OX11 0QX, Chilton-Didcot, United Kingdom techniques for technological and compositional investigations of hollow bronze fgurines

Here, a multi-analytical non-invasive investigation aimed at the high degree of corrosion and mineralisation of the latter, describing the execution processes and characterising the along with their small thicknesses and relatively strong curva- alloy compositions and deterioration phenomenologies of tures. On the other hand, the comparison between the inner small bronze artefacts has been carried out, which included and outer surfaces, along with the discrimination of the core neutron, X-ray, and laser techniques. These have been suc- nails and repairs, have a crucial importance in order to distin- cessfully applied in order to address archaeometallurgical guish between direct and indirect casting methods, as well as problems, which were encountered while investigating a set for interpreting the execution procedure of the wax model for of three similar figurines of different sizes representing Osiride casting and the joining techniques used. In general, in many (maximum height of about 37 cm) from the antiquarian col- cases the level of contrast provided by traditional X-ray ima- lection of Florence’s Egyptian Museum. The artefacts were hol- ging is insufficient for such thorough descriptions of the tech- low castings with almost intact casting cores and presented nological features of ancient copper alloy statuettes, which can interpretation problems concerning their manufacturing often be much more effectively derived by means of neutron procedures and state of conservation, which were not deci- tomography. Although application case studies of the latter pherable in a non-invasive way using traditional techniques. were previously reported [1], here, we exploit for the first time Thus, in particular, X-ray radiography did not allow a sufficient high-resolution neutron tomography, which was carried on image contrast at the inner metal wall contours because of 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 Bibliography on INES at ISIS-RAL (UK). All these techniques are non-inva- sive and provide a powerful complementary analytical set [1] R. Van Langh, E. Lehmann, S. Hartmann, A. Kaestner, F. Scholten, The study of bronze statuettes with the help of neutron-imaging for achieving reliable surface [2], depth profile [3], and bulk techniques, Anal Bioanal Chem 395 (2009) 1949–1959. analyses [4], thus allowing exhaustive characterisation of the [2] M. Ferretti, S. Siano, The gilded bronze panels of the Porta del Paradiso by Lorenzo Ghiberti: Non-destructive analyses using X-ray fluorescence, raw materials and corrosion phenomenologies. Their applica- Applied Physics A 90 (2008) 97-100. tion in combination with high-resolution neutron tomogra- [3] S. Siano, L. Bartoli, A. Mencaglia, M. Miccio, J. Agresti, J., Use of neutron diffraction and laser-induced plasma spectroscopy in integrated phy in order to solve the specific interpretation problems of authentication methodologies of copper alloy artefacts, Nuovo Cimento mentioned Egyptian figurines, allowed us to achieve metho- B 124 (2009) 671-686. dological results of general valence, which can be exploited [4] S. Siano, L. Bartoli, W. Kockelmann, M. Zoppi, M. Miccio “Neutron metallography’’ of archaeological bronzes, Physica B 350 (2004) 123–126. in similar archaeometallurgical investigation.

162 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Eric Silver1 - Ed Vicenzi2 - Ting Lin1 P-61 Bleu/Blue 10 sept. 2014 17:00 > 20:00 1 Harvard-Smithsonian Center For Astrophysics, 60 Garden St., 02138, Cambridge, MA, USA 2 Smithsonian Institution Museum Conservation Institute, 4210 Silver Hill Road, A new approach 20746, Suitland, MD, USA to X-ray microanalysis of museum specimens

One of the most fundamental methods for characterizing cation to microanalysis may seem far afield from astrophysics, many museum specimens involves performing an analysis its broad band, high resolution spectral performance enables that yields their elemental composition. Particularly when the spin-off application discussed here. The 2-D images gene- combined with two dimensional chemical mapping, this in- rated by the microcalorimeter/VPSEM combination yield high formation may yield clues to a specimen’s origin and history. resolution maps of the elemental constituents of the sample. We have developed an instrument that provides this data Examples of diverse specimens that require such spatial with unprecedented sensitivity and accuracy. It combines fidelity to fully understand their origin and history include: a Smithsonian Astrophysical Observatory (SAO) microca- early photographs (nineteenth century metal-based da- lorimeter spectrometer, that was originally developed for guerreotype plates), geological materials (asteroidal/Martian X-ray astronomy missions under NASA auspices, with a meteorites), archeological artifacts, objects of fine art, and commercially available variable pressure-scanning electron novel nano-technological coatings for the conservation of microscope (VPSEM). Although the microcalorimeter’s appli- 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Hanna M. Szczepanowska1 - Sabine Rolland du Roscoat2 P-62 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Jean-Francis Bloch4 - Thomas Mathia3 1 Smithsonian Institution, Research, Non-Profit, Government, 20746, Suitland, USA 2 ESRF, Research, Grenoble, France 3 LTDS, CRNS, Research, Ecully, France Synchrotron X-ray 4 Grenoble University, Research, Grenoble, France micro-tomography, SEM and CLSM applied to characterization of fungi induced stains on artworks on paper

Fungal biodeterioration of artworks on paper is mani- Materials and methods. The samples of fungal stains were fested by staining and structural polymer degradation obtained from a 1920 Engraving on paper and a 17th cen- of paper by fungal enzymatic activities. Fungal staining tury study sheet from the collection of Maltese Archives, of paper results from complex interactions of heteroge- Malta. The fiber of both papers was cotton. Low-vacuum nous cellular materials (paper) with living systems (fungi). environmental SEM Hitachi S3700N and S4700 were used for The pigments are bi-products of bio-chemical processes wit- back scattered electron imaging, in a range of 12-15kV and hin fungal cell structures defined as secondary metabolites. 1 kV-0.5 kV respectively. Confocal scanning laser microscopy Although fungal biodeterioration of cultural heritage has (CLSM), Keyence VX9700, captured spatial distribution of fun- been studied for number of years the focus was on visual gal spores on the surface of paper. X-ray tomography carried effects of biodeterioration or identification of fungal species; out on a designated beam line at the European Synchrotron no studies of interfaces of fungi and paper matrix have been Radiation Facility (ESRF), Grenoble, France, aimed to model undertaken. The black stains on paper caused by pigmented 3D visualization of fungal mycelium in the paper matrix. The mycelium and spores only recently received some attention voxel size of 0.7 µm3 was used to characterize paper fibers [1,2,3]. This investigation explores black stains on paper and fungal filaments. The 2 mm × 2 mm samples were ex- attributed to Dematiaceous, meristematic fungi and their posed to a homogenous and coherent beam at 17.6 keV at interactions with the paper matrix. X-ray tomography using different viewing angles. The X-ray absorption radiographs synchrotron radiation employed in this study visualized in were captured by CCD FReLon camera. 3D mode interaction of fungal mycelium with the paper matrix complementing surface morphology captured on Results and discussion. Scanning laser microscope image SEM micrographs and scanning laser microscopy of paper (Figure 2A) shows morphology of fungal thick-walled spores with fungal deposits. 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 Bibliography matrix. Our preliminary data shows that X-ray microtomo- [1] H. M. Szczepanowska, Th. Mathia and P. Belin. Morphology of fungal stains graphy might become a valuable technique in defining the on paper characterized with multi-scale and multi-sensory surface metrology”. Scanning 36 (2013), p.76-85. relationship between fungal growth and paper substrate, [2] H. M. Szczepanowska, Living systems on heterogeneous cellular substrate: complement data of bio-deposits morphology obtained by contribution to a better understanding of dynamic interfaces of fungal pigmentation and paper in biodeterioration of cultural heritage. SEM and CLSM imaging. The findings contribute to a better (Unpublished Doctoral Theses, LTDS, University of Lyon, France, 2012). understanding of fungi and paper interactions and patterns [3] K Sterflinger and W E Krumbein. Dematiaceous fungi as a major agent for biopitting on Mediterranean marbles and limestones. of fungal growth guiding modeling of fungal remediation Geomicrobiological Journal 14 (1997), p.219-230. and preservation strategy.

164 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Manako Tanaka1 - Kazuhiro Nagata2 - Masayoshi Ito3 P-63 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Maki Tokugawa4 1 T okyo University of the Arts, Art Innovation Center, 110-8714, Tokyo, Japan 2 T okyo University of the Arts, Conservation Science Laboratory, 110-8714, Tokyo, Japan Investigation 3 Japan Synchrotron Radiation Research Institute, Research and Utilization division, 679-5198, Hyogo, Japan of raw material 4 Tokugawa Museum, Director, 310-0912, Ibaraki, Japan and manufacturing technique of traditional Japanese matchlock guns using SR-XRF It is considered that the barrel of a Japanese matchlock gun was made mainly by hot forging, although the detailed fa- brication technique of the barrel is not clear as it was carried and synchrotron out in secret. In my doctoral study, I studied the metallurgical microstructure of Japanese matchlock guns using destruc- radiography tive 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 nondestruc- It is said that traditional Japanese iron has good workability tive methods. Those are the reasons why we started the non- and does not rust easily. The reasons of these characteristics destructive study of iron artifacts using the advanced analy- are derived from the raw materials, iron making technique tical instruments such as synchrotron radiation. Steel barrels and iron manufacturing technique in ancient Japan. In of traditional Japanese matchlock guns fabricated in the traditional Japanese iron making, Tatara smelting, iron middle Edo period (17-18th century) have been investigated. sand was used as a raw material. The temperature and the The purpose of this work is to analyze Japanese iron frequency of forging decide the aesthetic value and the matchlock guns by synchrotron radiation and to investigate mechanical value of Japanese iron artifacts. Matchlock the raw material and fabrication technique of the steel barrel. gun is one of the typical iron artifacts in Japan. Matchlock Another purpose is to contribute to the development of guns were introduced into Japan in the 16th century by the nondestructive study of iron artifacts. The compositions Europeans. It is said that steel made from domestic iron of trace heavy elements are determined by synchrotron sand and/or imported steel was used as the raw material X-ray fluorescence analysis (SR-XRF). The internal structure of the barrel. However, the details have not been clari- is investigated with synchrotron X-ray radiography. It was fied yet because of the limited number of investigations. 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 Bibliography for estimating the raw materials. It also became clear that [1] M. Tanaka and M. Kitada:Microstructure of Japanese Matchlock Gun by using synchrotron X-ray radiography, we can identify the Fabricated by a Kunitomo Gunsmith in the Edo Genroku Period, Journal of the Japan Institute of Metals Vol.76, pp. 489-495, (2012). joint area of the steel and the distribution of nonmetallic [2] M. Tanaka and M. Kitada: Material Analysis of Ornamental Metal inclusions. It was confirmed that by using nondestructive and Gunstock of Japanese Matchlock Guns and Percussion Lock Guns Fabricated in the Edo Period, Journal of the faculty of fine arts, methods such as synchrotron radiation, we can get some Tokyo University of the Arts Vol.8, 17-29, (2012). important information on the raw material and fabrication [3] M. Tanaka, M. Kitada and M. Nishijima: Microstructure and Nonmetallic Inclusions in Japanese Percussion Lock Gun Fabricated in the Late Edo technique of iron artifacts. We will continue our study on Period, Journal of the Japan Institute of Metals vol. 74, pp.779-787, (2010). iron artifacts using not only synchrotron radiation but also [4] M. Tanaka and M. Kitada:Composition and Microstructure of Nonmetallic neutron imaging to develop the nondestructive study of Inclusions of Japanese Matchlock Gun (Hinawaju) Fabricated in the Edo Period, Journal of the Japan Institute of Metalsvol.74, pp. 250-257, (2010). iron artifacts.

165 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Manako Tanaka1 - Yoshinori Shiota2 - Hiroyuki Hasemi3 P-64 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Takenao Shinohara4 - Anton Tremsin5 - Yoshiaki Kiyanagi2 1 T okyo University of The Arts, Art Innovation Center, 110-8714, Tokyo, Japan 2 Nagoya University, Graduate School of Engineering, 464-8603, Nagoya, Japan 3 Hokkaido University, Graduate School of Engineering, 679-5198, Hokkaido, Japan Investigation 4 Japan Atomic Energy Agency, J-Parc Center, 319-1195, Ibaraki, Japan 5 University of California at Berkeley, Space Sciences Laboratory, CA 94720, of traditional Japanese Berkeley, USA matchlock guns using pulsed neutron imaging

One of the characteristics of traditional Japanese iron is good Kiyanagi developed5. It’s getting clear that an image indicating workability and rust resistance. The reasons of these characte- the number density, the crystal structure, the preferred orienta- ristics are derived from the raw materials, iron making technique tion, and the strain of the material can be obtained by using the and iron manufacturing technique in ancient Japan. Japanese energy analysis at a pulsed neutron source. Concerning the non- match lock gun is representative of Japanese iron artifacts. destructive methods, physical quantity like this can be obtained It is said that the barrel of a Japanese matchlock gun was made only by neutron. The purpose of this study is to analyze precious mainly by hot forging. But the detailed fabrication technique Japanese matchlock guns using pulsed neutron imaging and of the barrel is not clear as it was carried out in secret. We have to evaluate those crystallographic texture and microstructure. been studying the metallurgical microstructure of Japanese The final goal of our study is to contribute to the development matchlock guns using destructive methods [1,4] and nondes- of the nondestructive study of iron artifacts. tructive methods such as synchrotron radiation. Furthermore, Experiment is carried out by pulsed neutron imaging using recently we have started the nondestructive study of Japanese the TOF method. Before analyzing, we checked the radioactive matchlock guns using neutron. In this poster, we will present the activation of impurities in Japanese matchlock guns by using nondestructive study of Japanese matchlock guns using pulsed handheld XRF. A 2D-PSD is used to get the spatial dependent neutron source at J-PARC in Japan. of TOF data. Distribution of nonmetallic inclusions and inlaid We analyzed Japanese matchlock guns by using the pulsed piece of the barrel are observed from spectrum transmission neutron time-of-flight (TOF) method which our collaborator, Prof. 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 Bibliography possibility that the muzzle is reinforced with higher carbon steel [1] M. Tanaka and M. Kitada:Microstructure of Japanese Matchlock Gun to resist a strong impact by the explosion of the gunpowder. Fabricated by a Kunitomo Gunsmith in the Edo Genroku Period, Journal From the strain calculated from 110 edge, the welding region 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 of the barrel is considered. It is concluded that by analyzing the Inclusions in Japanese Percussion Lock Gun Fabricated in the Late Edo crystallographic texture and microstructure by pulsed neutron Period, J. Jpn. Inst. Met. vol. 74, pp.779-787, (2010). [3] M. Tanaka and M. Kitada:Composition and Microstructure of Nonmetallic imaging, we can clarify the metallurgical characteristics of iron Inclusions of Japanese Matchlock Gun (Hinawaju) Fabricated in the Edo artifacts and reveal the traditional Japanese iron making and Period, J. Jpn. Inst. Met. vol.74, pp. 250-257, (2010). [4] M. Tanaka and M. Kitada: Microstructure of Japanese Matchlock Gun forging techniques. Our study shows the usefulness of the pulsed Fabricated in the Edo Period, J. Jpn. Inst. Met. vol. 73, pp. 778-785, (2009). neutron imaging and there is a possibility that this method can [5] Y. Kiyanagi, H Sato, T Kamiyama and T Shinohara: A new imaging method using pulsed neutron sources for visualizing structural and dynamical contribute to the development of the nondestructive study of information, Journal of Physics, Conference Series 340, 012010 (2012). metal artifacts.

166 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Wantana Klysubun1 - Prapong Klysubun1 - Yuying Huang2 P-65 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Nirawat Thammajak1 - Panidtha Sombunchoo1 Somdech Leelamanotham3 1 Synchrotron Light Research Institute, 111 University Ave., Muang, 30000, Nakhon Ratchasima, Thailand Investigating bronze 2 Shanghai Synchrotron Radiation Facility, 239 Zhangheng Rd., Pudong, 201204, Shanghai, China 3 T he 12th Regional Office of Fine Arts, Pimai-Chumpuang Rd., Pimai, 30110, ring fragments from Nakhon Ratchasima, Thailand Non Pa Cha Gao archaeological site with synchrotron X-ray techniques

Non Pa Cha Gao is located in Nakhon Rachasima, Thailand on cross-sectional areas of 4-9 mm2 shows non-uniformity provides an important evidence of secondary burial culture of constituent composition, i.e. copper, tin, lead, arsenic, in South East Asia, dating back 2400-1100 years in the past. and nickel. In addition, variation of copper concentration is The site, excavated in 2003, holds a large number of massive clearly in contrast to those of tin, lead, and arsenic. Microsco- ceramic vessels containing human bones, along with bronze pic visual inspection indicates that corrosion had penetrated rings and ceramic pieces buried as tribute for the deceased, deep into the bronze bodies. Alloy compositions determined were found 0.5-1 meter below the datum. In this work, we by SRXRF analysis from five fragments are 69-87 % Cu, 21- have investigated small bronze ring fragments with thickness 33 % Sn, 0.1-0.7 % Pb and 0.1-0.6 % As. Aluminum, silicon, varying from 3-6 mm and projected diameters varying phosphorous, sulfur, chlorine, calcium, and iron are also from 7-8 cm using synchrotron radiation X-ray fluorescence detected in the bronze bodies suggesting that segregation (SRXRF) mapping, quantitative SRXRF analysis, and X-ray and mineralization from the surrounding environment had absorption near edge spectroscopy (XANES). To the extent taken placed. Corrosion products were investigated by Cu of our knowledge, this is the first analytical study on bronze K-edge, Sn L3-edge, and P K-dege XANES measurements, artifacts found in Thailand that utilizes synchrotron radia- and it was found that the predominant species are copper tion techniques. Elemental mapping at 40 µm resolution chlorine, cuprite, stannic oxide, and phosphate.

167 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Lien van de Voorde1 - Eddy Verhaeven2 - Bart Vekemans1 P-66 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Robin de Wolf1 - Peter Vandenabeele3 - Laszlo Vincze1 1 Ghent University, Department of Analytical Chemistry, 9000, Ghent, Belgium 2 Antwerp University, Faculty of Design Sciences, 2000, Antwerpen, Belgium Use of a novel portable 3 Ghent University, Archaeometry Research Group, 9000, Ghent, Belgium XRF/XRD instrument for studying pigments and model paintings

The use of X-ray based spectroscopic techniques for the The Surface Monitor presented in this contribution is a investigation of cultural heritage objects provides valuable portable instrument which provides a simultaneous mea- compositional/structural information on the examined surement of X-ray Fluorescence (XRF) and X-ray diffraction materials in a non-destructive way. Due to the rapid evolu- (XRD) on cultural heritage materials. The instrument is tion of compact, portable X-ray instrumentation in the last commercially available, manufactured by Assing S.p.A. (Italy). 25 years it is now unnecessary to remove exhibited artefacts This study reports analyses based on simultaneously collec- from their original location, enabling the more preferable ted XRF spectra and XRD patterns using the Surface Monitor relocation of the instrument/researcher to the museums for retrieving elemental and crystallographic information on instead. While analytical methods using X-ray fluorescence pigments and model paintings. The primary goal of these is a preferred method of choice to obtain information on investigations was to obtain information about the perfor- the elemental composition, very often the elemental in- mance of this commercially available portable instrumen- formation only is insufficient and should be coupled with tation. Next to evaluating the instrumental figures of merit, crystallographic data on the art or archaeological object future perspectives of using the instrument in the research under investigation. This additional information can be ob- of paintings and other objects of art exhibited in museums tained by e.g. using the X-ray powder diffraction method. will be discussed.

168 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Angela Vasilescu1 - Bogdan Constantinescu1 P-67 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Daniela Stan1 - Martin Radtke2 - Uwe Reinholz2 Günter Buzanich2 - Daniele Ceccato3 1 Horia Hulubei National Institute for Nuclear Physics and Engineering, Applied Nuclear Physics department, RO-077125, Magurele (Ilfov), Romania Studies on ancient 2 Federal Institute for Materials Research and Testing, BAM, D-12489, Berlin, Germany 3 I NFN Laboratori Nazionali di Legnaro, Dipartamento di Fisica silver metallurgy using dell’Universita di Padova, I-35020, Legnaro (Padova), Italy micro-SR-XRF and micro-PIXE

The metallurgical aspects of silver adornments offer to the beam at INFN Legnaro, obtaining maps and point spectra. archaeologist important information about the provenance of As main results, we mention the identification of bismuth in these items – mines, metal production workshops, jewelry ma- the Agighiol samples - suggesting their provenance from Sou- kers, commercial relations. In the case of silver, gold, bismuth, thern Thrace or Northern Greece, a homogeneous distribution zinc and antimony can be used as fingerprint elements for of silver, copper and lead - indicating an advanced metallurgy East European geological deposits (e.g. Bi for South Thracian (for Antiquity) and the presence of bromine and chlorine and Greek silver). The presence of copper and lead is directly (well-known silver corrosion agents) - giving information on related to the metallurgy of silver, copper being used to in- soil characteristics for the place of recovery of the artifacts. crease the mechanical properties of the metal. For some Dacian bracelets from the Poiana Galati hoard we Some Thracian-Dacian adornments found on Romanian identified the use of copper, zinc and tin (most probably from territory from the Agighiol treasure (4th Century B.C.) and bronze and brass) in the metallurgical process, as components Poiana Galati (1st Century A.D.) were investigated in this work. of the silver alloy. This procedure increased the mechanical To determine the composition of major (Ag) and minor (Cu, Au, resistance of adornments, silver being a “ soft ” metal. In the Pb) elements, in-museum XRF analysis was performed initially. case of one bracelet, the elemental maps for the analysed With special permit, two series of sub-millimetre-sized samples area revealed strong inhomogeneity in the copper map and from some artifacts belonging to above mentioned treasures superposition of silver, gold and lead. Copper inhomogeneity (appliqués, beads and small bracelets) could be analyzed using reflects a quite primitive alloying procedure while gold and the micro-SR XRF beam at BESSY at the BAM-line, at 20 keV lead, accompanying silver, reflect the composition of the excitation energy, as well as in the 2 MeV proton micro-PIXE initial mineral.

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 me- tallurgy 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Louisiane Verger1,2 - Laurent Cormier2 - Olivier Dargaud1 P-68 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Nicolas Trcera3 1 Cité de la Céramique, Sèvres et Limoges, Laboratoire, 92310, Sèvres, France 2 I nstitut de Minéralogie, de Physique des Matériaux et de Cosmochimie (IMPMC), Université Pierre et Marie Curie (UPMC), Physique des Amorphes, Chromium in pigments Liquides et Minéraux, 75005, Paris, France 3 and enamels produced Synchrotron SOLEIL, LUCIA beamline, 91190, Saint-Aubin, France at the “ Sèvres Cité de la Céramique ”: a Cr K-edge X-ray absorption study

Chromium is at the origin of a wide variety of coloration Firstly, the analyses on a pigment rich in eskolaite Cr2O3 (green, pink and brown) on Sèvres porcelains. This element will be discussed. It is used to produce green empire was introduced for the first time at the “ Manufacture of decoration on porcelain. Observations under a scanning Sèvres ” in 1804, a few years after its discovery by Vauquelin. electron microscope (SEM) with EDX analyses highlight Since this period, Cr is the basis of most pigments synthe- heterogeneity of composition along the grains of pigment: sized at the “ Manufacture of Sèvres ”. The mixture of these Cr is more concentrated near the surface of the particle. pigments with a colourless frit is applied on the porcelain The micro-focused synchrotron beam enables us to and fired at high temperature to form an enamel, i.e. a mix characterize two different chemical environments of Cr, of crystalline and glassy parts. However the origin of colours eskolaite being at the periphery. This was not predicted by due to Cr in enamels and how it can be controlled by heating XRD measurements, as eskolaite was the only crystalline treatments is still not well understood. phase detected. Observations under a scanning electron microscope (SEM), Chromium is also used to obtain pink decoration, with a

UV-visible spectroscopy and X-ray diffraction analyses were pigment mainly composed of malayaite CaSnSiO5 doped combined to X-ray absorption spectroscopy (XAS) in order with Cr. A variability of Cr speciation and environment will to characterize the enamel layer, the structural environment be demonstrated using XAS. of Cr and its relation to coloration properties. Finally, the interactions of the grains of pigment and We have observed that the enamels are composed of small the uncoloured frit play a key role in colour changes.

grains of pigment (5–30 µm) embedded in a glassy matrix. For instance the enamel composed of the spinel ZnAl2O4:Cr In order to selectively probe the Cr environment and its oxi- evolves from pink to brown during the heating treatment. dation state in pigments and enamels, we have used X-ray Micro-XANES measurements reveal the formation of a absorption near edge structure (XANES) spectroscopy at the reactive layer between the grain of pigment and the glassy Cr K edge (LUCIA beamline, SOLEIL). This study is focussed on matrix, which explain the variation of colour. the investigation of the pre-edge feature which is sensitive This study is then a new approach of chromium oxides: to both redox and coordination. The spatial resolution of the through a patrimonial point of view, it also brings fun- X-ray beam on LUCIA beam line (4×4 µm2) was mandatory damental information about chromium environment in to characterize pigments embedded in the glassy matrix. spinels, solid solutions and glass matrices.

170 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Elizabeth A. Willnef1 - Bronwyn A. Ormsby2 P-69 Bleu/Blue 10 sept. 2014 17:00 > 20:00 Cherno Jaye3 - Daniel A. Fischer3 - Sven L.M. Schroeder4 1 University of Manchester, SCEAS, M13 9PL, Manchester, UK 2 T ate, Tate, SW1P 4RG, London, UK 3 NIST, NIST, 20899, Gaithersburg, USA Conservation 4 University of Manchester, Chemistry, M13 9PL, Manchester, UK of artists’ acrylic paints: application of near edge X-ray absorption fne structure (NEXAFS) spectroscopy to understanding the impact of wet cleaning treatments on paint flm surfaces

Artists’ acrylic paints make up a significant fraction of modern the fundamental surface processes resulting from cleaning and contemporary works-of-art. From a conservation pers- treatments has proved to be challenging. The primarily or- pective these paints, because of their relative youth, are less ganic layers (e.g. cleaning residues, pigment) present at low well understood than oil-based counterparts. As conservation concentrations at the uppermost paint surface following treatments of acrylic paints become more commonplace un- cleaning treatments are difficult to distinguish from a subs- derstanding the impact of wet cleaning treatments becomes trate with similar elemental composition. We have therefore more important, which has resulted in investigations with a applied near-edge X-ray absorption fine structure (NEXAFS) variety of analytical techniques including, for example, FTIR, spectroscopy to overcome these challenges by studying mass spectrometry and AFM [1]. Progress has been made model artists’ acrylic paint films as a function of paint brand, in identifying the causes of variations in pigment, gloss and pigment, cleaning treatment and age [4,5]. surfactant levels as a function of paint brand and cleaning treatment [2]. Novel cleaning treatments have been assessed NEXAFS measurements performed at beamline U7A of the for cleaning efficacy [3]. However, detailed examination of NSLS (Brookhaven, USA) in partial electron yield mode provi- ded surface sensitive molecular level chemical state informa- tion 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 Bibliography and changes in pigment levels at the surface were probed.

[1] Ormsby, B., Learner, T. Rev. Conserv. 2009, 29 - 41. In addition to single point measurements the complementary [2]. Kampasakali, E. et al. Stud. Conserv. 2011, 56, 14. benefit of NEXAFS imaging was investigated. These results [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, were used in conjunction with other spectroscopies (XPS, S.L.M. Surf. Interface Anal. DOI: 10.1002/sia.5376 (2014). ATR-FTIR), microscopy (SEM) and visual inspection to build up [5] Willneff, E.A., Ormsby, B.A., Schroeder, S.L.M., Spectroscopic Techniques a broader picture of how the surface chemistry of these paint and the Conservation of Modern Paints. In preparation for Heritage Science (4/2014) films responds to, and changes with wet cleaning treatments.

171 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

V. Danilovitcha1 - S. Dernovitcha1 - Z. Kharytanovitch1 P-70 Vert/Green 10 sept. 2014 17:00 > 20:00 V. Kochman1 - V. Lakiza1 - I. Groutso2 - C. Cardon3 Jerome Beaucour3 - B. Cubitt4 - C. Dewhurst4 - T. Pirling4 D. Atkins4 1 National Academy of Sciences Academy of Sciences of Belarus, Institute Characterisation of History, BY-220072, Minsk, Republic of Belarus 2 Maxim Tank Belarusian State Pedagogical University, BY-220050, Minsk, Republic of Belarus of excavated 3 Centre d’Études Napoleoniennes, F-92300, Levallois, France Napoleonic artefacts 4 Institut Max von Laue – Paul Langevin, F-38042, Grenoble Cedex 9, France from the Berezina battlefeld in Belarus using neutron techniques

An important collection of artefacts have been unearthed the Centre d’Etudes Napoleoniennes collaborated with during preventative archaeological surveys in 2012 and 2013 the Institute Max Von Laue Paul Langevin (ILL) in a series around the village of Stoudienka in Belarus – the site of the of experiments using non-destructive neutron diffraction Napoleonic army’s passage during the retreat from their techniques available at the ILL on selected artefacts: Small Russian campaign in November 1812. Recovered objects Angle Neutron Scattering on instrument D33 for material such as fragments of bronze eagles, brass plates and buttons characterization and surface examination and mechanical with faint outlines of inscriptions and several lead bullets deformation analysis on the strain imager SALSA, in order have resulted in historian’s needs for further characterization to better understand their importance and obtain clearer to reveal otherwise uncertain information, for example their knowledge of events which took place on the battlefield mode of destruction. The Belarus Academy of Science and more than 200 years ago.

172 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Audrey Cochard1 - Solenn Réguer2 - Joël Douin1 P-71 Vert/Green 10 sept. 2014 17:00 > 20:00 Marie-Hélène Mathon3 - Sébastien Joulie1 - Nicolas Ratel-Ramond1 - Jean-Marc Olivier4 - Philippe Sciau1 1 Université de Toulouse Paul Sabatier, Cemes, 31055, Toulouse, France 2 Synchrotron SOLEIL, DiffAbs beamline, 91192, Gif-sur-Yvette, France Study of “old ” 3 CEA Saclay, Laboratoire Léon Brillouin, 91191, Gif-sur-Yvette, France 4 Duralumin used Université de Toulouse Le Mirail, Framespa, 31058, Toulouse, France in airplanes by crossing laboratory analyses and archives researches

Aluminum-copper alloys were used a lot for aircraft from the Toulouse [3]. Up to now, no direct information concerning World War I until now for structural applications. A precise the nature of alloys used in the manufacturing Breguet 765 knowledge of the nature of these alloys begins to interest Sahara was available as most of Breguet company archives the industrial heritage field. However, although these mate- has been lost. However, first laboratory analyses revealed rials were processed less than a century ago and used in an that at least two different compositions were used for the industrial context, structural data are very limited. In many rivets, respectively the A-U3G and A-U4G alloys, as described cases their structure was not investigated on the nanometer in scientific literature by Tournaire and Renouard in 1955 [4]. scale, which is fundamental to understand the mechanical The A-U3G alloy, easier to use, was developed to substitute properties [1] and the corrosion behavior of age-hardenable the A-U4G alloy at the same time that the conception of the aluminum alloys. The link with archival documents from Breguet 765. These two types of rivets have been analyzed aircraft manufacturers is complex for the alloys made before using a combination of techniques: electron microprobe, 1960-70, because the existing archival data of manufacturers transmission electron microscopy, X-ray synchrotron diffrac- are fragmentary [2]. The best way to highlight these “ histori- tion and neutron diffraction. TEM investigations confirmed cal ” alloys is obtained by crossing the available archive data that these “ old ” alloys contain much more various precipi- and precise laboratory analyzes. tates in nature and in size that the actual equivalent alloys. The present study focuses on the Breguet 765 Saraha built in The nano-structure of these two alloys are also very different:

1958. This double-deck military aircraft was built during the the main precipitates of A-U4G rivets are CuAl2, Mg17Al12, post-Wold War II boost of the French aeronautical industry. It Al4MnSi0.7 and Al17(Fe3.2Mn0.8)Si2, while for A-U3G precipitates, is currently in renovation by the association Ailes Anciennes the main phase is Al7Cu2Fe. It should be noted that A-U3G composition, developed later, contains much less sub-micro- metric (10-1000 nm) and micrometric (1-10 µm) precipitates. Interesting structures linked to weak variations of Al/Cu ratio

Bibliography were observed in each composition. These wavy variations are rather regular with a periodicity of around 100 nm. [1] D ubost, B., Saintfort, P., Durcissement par précipitation des alliages d’aluminium, Dossier Techniques de l’ingénieur M240 (1991). Whether these structures are a consequence of aging over [2] Le Roux, M., L’entreprise et la recherche: un siècle de recherche industrielle several decades or not is under investigation. 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] T ournaire, M., Renouard, M., Alliages pour rivets de la famille du Duralumin, Revue de l’Aluminium 217 (1955).

173 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Anna Fedrigo1 - Francesco Grazzi1 - Alan Williams2 P-72 Vert/Green 10 sept. 2014 17:00 > 20:00 Francesco Civita3 - Antonella Scherillo4 - Joe Kelleher4 Floriana Salvemini1 - Marco Zoppi1 1 Consiglio Nazionale Delle Ricerche - Istituto Dei Sistemi Complessi, Research, 50019, Sesto Fiorentino, IT Phase composition 2 The Wallace Collection, Museum, W1u 3Bn, London, UK 3 Museo Stibbert, Museum, 50134, Firenze, IT and residual strain 4 STFC-ISIS, Research, OX11 0QX, Didcot, UK mapping of two Japanese helmets

Historical metallurgy is one of the most interesting fields of Here we present novel results from diffraction measurements of archaeometry, especially with regards to the production and two Japanese helmets attributed to the 17th century (Saotome use of steel for arms and armour components. Scientific and and Haruta school), performed by using the instrument Engin-x technological research into these kinds of artefacts has scarcely (ISIS-UK). The experiment allowed us to map the residual strain developed; in particular, a very limited amount of Japanese distribution inside a few single platelets along their section. armour has been investigated through metallography [1]. In This study completes the cycle of neutron measurements on addition, because of their generally excellent state of preserva- the samples and shed light on the last unresolved questions tion, the traditional methods of analysis do not suit these kinds raised by previous investigations. Both samples have been of objects because of their invasiveness. For these reasons, a joint already measured, using neutron diffraction on the INES research project among CNR-ISC (Florence, Italy), the Stibbert beamline (ISIS-UK), to obtain the quantitative phase com- Museum (Florence, Italy), and The Wallace Collection (London, position of selected parts. The shape of the ferrite diffraction U.K.) is carried out using a non-invasive approach, namely ther- peaks has been also thoroughly analysed and semi-quanti- mal neutron diffraction [2-5]. tative information was obtained about: (i) domain size of the The production of Japanese armours involves several complex crystallographic grains; (ii) texture intensity and distribution; steps that generally differ from one school (or tradition) to (iii) anisotropic residual strain distribution [3,4]. Considering the other [6,7]. The forging processes were orally transmitted the results obtained, the presence of a composite structure from one armourer to his pupil, thus the knowledge of most of steel and iron superimposed was suggested for the Haruta techniques was lost through time, leaving very few written helmet [9]. The morphology and construction method of the mentions, reported in a descriptive and non-scientific way [7]. Saotome helmet, identified by means of neutron tomography Documentary sources [7] suggest that, particularly with the performed at the NEUTRA beam-line (PSI, Switzerland), revealed introduction of firearms in 1542, the construction technique and the presence a novel arrangement of the lamellar plates, style of Japanese armourers changed to increase the protection that needed a more thorough understanding of the ancient art offered by their armour [8]. 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Christine Bläuer1 - Anja Diekamp2 - Jürg Gol3 P-73 Vert/Green 10 sept. 2014 17:00 > 20:00 Yongfeng Hu4 - Josef Hormes5 1 CSC Conservation Science Consulting Sarl, Fribourg, Switzerland 2 I nstitute for Structural Engineering and Material Sciences, Department of Engineering Science, University of Innsbruck, Innsbruck, Austria Mortar samples 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 from the Abbey of University, Baton Rouge, USA Saint John at Müstair: a combined spatially resolved X-ray fuorescence and X-ray absorption (XANES) study

Mortar is a very challenging system for any type of “chemical/ (hydraulic components in the Carolingian samples, pure mineralogical” analysis because of its composition from a Dolomite for the Gothic sample) as well as in the composi- broad range of crystalline - and sometimes non-crystalline- tion of the aggregates. compounds with a broad size distribution. Thus, hardly Synchrotron radiation based spatially resolved X-ray fluores- any synchrotron radiation based experiments have been cence (XRF) and X-ray absorption near edge structure (XANES) reported on the analysis of mortar. For this preliminary stu- experiments were carried out at the SXRMB beamline of the dy three mortar samples have been investigated from the Canadian Light Source covering the energy range between 1.7 Abbey of Saint John, in the Swiss village of Müstair (UNESCO and ~10 KeV with a spatial resolution of about 300 × 300 μm2. World Heritage Site since 1983). This abbey was established Fluorescence was excited with a monochromatic X-ray beam ca. 780 and there was basically just one major alteration of 9 keV. For each sample fluorescence spectra for at least when about 1500 the abbey church was modified from a 26 different positions were recorded. As expected the main single-nave Carolingian construction into a three-nave late elements that are detected at all positions with strongly Gothic church. Two samples were taken from Carolingian varying intensity ratios are Si, Ca, and Fe. Additional “ trace ”- plaster and the third one from a late Gothic plaster. All three elements are, for example, P, S, K, and Ti. For the determination samples were prepared as microsections and embedded into of the speciation of the elements K-XANES spectra of Ca and a synthetic resin (Araldite 2020). The samples were pre-cha- Fe were recorded at a few selected points of the samples: racterized by one of the authors (Ch.B.) using polarization at some “ dark ” spots and at some “ white ” spots – most likely microscopy and some standard wet chemical procedures limepops. The analysis of the Ca-K-XANES spectra shows that for determining in an indirect way the various chemical Ca exists in all samples mainly in the form of Calcite; howe- compounds in the samples. These experiments indicated, ver with significant contributions of other chemical forms. for example, differences between the samples from the The Fe-K-XANES spectra are different in the white and the different periods in the composition of the binder materials dark spots indicating a lower valency of Fe in the limepops.

175 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Alexandria Hunt1 - Barbara Stuart1 - Paul Thomas1 P-74 Vert/Green 10 sept. 2014 17:00 > 20:00 Daniel James2 - Bruno David2 - Jean-Michel Geneste3 Jean-Jacques Delannoy4 1 University of Technology, Sydney, School of Chemistry and Forensic Science, 2007, Sydney, Australia The characterisation 2 Monash University, School of Geography and Environmental Science, 3800, Clayton, Australia 3 Université de Bordeaux 1, Centre National de Préhistoire, 24000, Périgueux, France of Jawoyn rock art 4 Université de Savoie/CNRS, Laboratoire EDYTEM, 73376, Le Burget du Lac, France paintings in Arnhem Land, Australia using synchrotron infrared microspectroscopy

In 2006 remote rock art sites of the Jawoyn people in the Nor- traded across Australia in the past and it has been established thern Territory of Australia were rediscovered during an aerial sur- that the chemical composition of ochres is dependent on the vey of the Arnhem Land plateau. Subsequently, more than 4000 source [3,4]. A series of small paint specimens were collected rock art sites have been rediscovered, including the spectacular from the Little Barra site representing different colour types Nawarla Gabarnmang site, which dates back 45000 years making and ages. it one of the earliest human occupation sites in Australia [1,2]. An investigation of the specimens using synchrotron infrared The art at the sites depicts a history of the culture of the Jawoyn microscopy was carried out at the Australian Synchrotron in people, contain paintings of different generations and illustrate Melbourne, Australia. The study provides an understanding an array of pigment types. In 2010 an international team of ar- of the composition of the paints used at the Little Barra site. chaeologists were invited to document these extraordinary sites. Synchrotron FTIR microspectroscopy has enabled the minute The current project is a study of rock art at one of the Jawoyn samples to be examined in compression transmission mode, sites being documented known as ‘Little Barra’. The site thus avoiding the need to embed the specimens. Mapping contains a range of pigment types, with ochre colours ranging of the samples has been carried out to provide information from reds to yellows, and with white and black pigments also about the nature of both inorganic and organic components being observed. Ochre is an important component of paint in the paint specimens. An in-depth understanding of the used in traditional, as well as modern, Australian indigenous art. chemistry of the pigments is combined with archaeological This mineral-based material is mined from particular sites and information to build a clearer picture of the social practices is coloured by iron oxides. The source material was extensively 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Mark Jones1 - Andy Smith2 - Kevin Clancy3 P-75 Vert/Green 10 sept. 2014 17:00 > 20:00 Winfried Kockelmann4 1 Mary Rose Trust, College Road, PO1 3LX, Portsmouth, UK 2 STFC Daresbury Laboratory, Keckwick Lane, WA4 4AD, Warrington, UK 3 The Royal Mint, Llantrisant, CF72 8YT, Pontyclun, UK The minting of gold 4 STFC Rutherford Appleton Laboratory, Harwell, OX11 0QX, Didcot, UK coins in Tudor England explored by neutron difraction

Henry VIII of England’s flagship, the Mary Rose, was lost in This technique has been applied previously to show varia- action in 1545. Amongst the 19,000 historical artefacts re- tions employed in historical minting processes by providing covered from the wreck of the ship when she was raised in information on the orientation of the metal crystallites in 1982 were 29 gold coins. These coins came from the personal the bulk of a coin and we report here its application to the effects of the officers of the ship and were minted under four minting of gold coins in Tudor England as evidenced in the different monarchs of Tudor England. The minting process is collection from the Mary Rose. To confirm the details of the known to have changed during the reign of Henry VIII and Tudor minting processes we also had a selection of replicas the coins of the Mary Rose reflect this development. made using techniques based on written contemporary accounts and compare neutron diffraction patterns from Texture analysis by neutron diffraction data is non-destruc- these with those obtained from the historical coins. Finally, tive and reveals changes in the microcrystalline structure of our study was expanded to include an analysis of other his- metals related to the mechanical processes used in forging. torical coinage minted using later technologies.

177 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

György Kali1 - Eszter Horvath1 - Zsuzsanna Siklosi2 P-76 Vert/Green 10 sept. 2014 17:00 > 20:00 Maria Bondar3 - Viktoria Kiss3 1 Wigner Research Centre for Physics, Hungarian Academy of Sciences, Konkoly Thege Miklós út 29-33., 1121, Budapest, Hungary 2 I nstitute of Archaeological Sciences, Faculty of Humanities, Eötvös Loránd Non-destructive University Budapest, Múzeum körút 4/B, 1088, Budapest, Hungary 3 I nstitute of Archaeology, Center for the Humanities, Hungarian Academy and non-invasive of Sciences, Úri utca 49., 1014, Budapest, Hungary archaeometallurgical investigation In this study we present the non-destructive and non-invasive on Copper age archaeometallurgical investigation of three copper objects from the Copper Age Carpathian Basin. Two of them, a massive bra- artefacts from celet 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 the Carpathian Basin 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 Humankind’s earliest metalworking activities can be traced indispensable in this case. from the Neolithic. In this period the first wrought metal was still used to make ornaments only. Metal articles for further use Our research had two main objectives: 1) to deepen our (personal/utilitarian) appeared in large quantities in the Early knowledge about the Copper Age metalworking activity by Copper Age also in the territory of present-day Hungary [1]. identifying the manufacturing technique of the artefacts; Copper artefacts of the Carpathian Basin were probably 2) to determine the use value of the objects studying their made of South-Eastern European raw materials. Due to their function and supposed utility. geographical location Copper Age communities in the Car- pathian Basin played a principal role in the social network of In case of metals, the traces of the past mechanical (hamme- the South-Eastern and Central European cultural complexes. ring, drawing) or thermal (casting, annealing) treatment or The meeting point of these two “ worlds ” is located in the even the combination of these two processes are reserved in present-day Hungary. As a consequence, in order to be the crystallographic texture and microstructure. These features able to reconstruct European prehistory understanding the can be observed and analysed on the diffraction pattern [4, 5]. Hungarian Copper Age is essential. In order to reconstruct the metallurgical processes and to pro- vide 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) Bibliography applied in our study proved to be an appropriate and successful [1] N. Kalicz: Die terminologischen und chronologischen Probleme der method to characterise the phase composition, texture, stress Kupfer- und Bronzezeit in Ungarn. In: A. Aspes (ed.), Il passaggio dal Neolitico all’età del Bronzo nell’Europa Centrale e nella regione Alpina, and microstructure of the artefacts without any sampling and Problemi cronologici e terminologici, Atti del X Simposio Internazionale special treatment of the objects. sulla fine del Neolitico e gli inizi dell’età del Bronzo in Europa. Verona 1980, 117-137. [2] P. R a c z k y, Zs. Siklósi: Reconsideration of the Copper Age Chronology As a result of the TOF-ND measurements manufacturing pro- of the Eastern Carpathian Basin: a Bayesian Approach. Antiquity 87/336 (2013) 555-573. cess of the investigated artefacts could be reconstructed as a [3] J. Banner: Die Péceler Kultur. Archaeologia Hungarica 35. Budapest 1956. workflow. In case of the axe-adze, also traces of the intentional [4] G. Artoli: Chrystallographic Texture Analysis of Archaeological Metals: Interpretation of Manufacturing Techniques. Applied Physics A 98 (2007) and conscious increase of the use value could be identified. 899-908. It could be revealed that the base material of this tool has been [5] M. Mödlinger, P. Piccardo, Zs. Kasztovszky, I. Kovács, Z. Szőkefalvi-Nagy, hardened and annealed after the casting process, thus the axe Gy. Káli, V. Szilágyi: Archaeometallurgical Characterization of the Earliest European Metal Helmets. Materials Characterization 79. (2013) 22-36. has gained a special edge on its surface.

178 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Gloria Molia1 - Roberta Difebo2 - Judit Molera3 P-77 Vert/Green 10 sept. 2014 17:00 > 20:00 Trinitat Pradell1 1 Universitat Politècnica de Catalunya, Departament de Física i Enginyeria Nuclear, 08860, Castelldefels, Spain 2 Universitat de Barcelona, Dept. de Prehistòria, Història Antiga i Arqueologia, Manganese 08001, Barcelona, Spain 3 Universitat de Vic-Universitat Central de Catalunya, Escola Politècnica compounds in historical Superior, 08500, Vic, Spain glazes

Manganese oxides were to produce black decorations on Overglaze and underglaze applications of different man- glazes since ancient times. For a long time manganese was ganese compounds over a lead glaze and fired at tempe- thought being dissolved in the glaze, and not much effort was ratures between 875ºC and 1000ºC are analysed by means dedicated to the study of manganese decorations. However, of optical microscopy, Scanning Electron Microscopy (SEM), recent studies1 have demonstrated the presence of several Synchrotron radiation micro-XRD and Raman spectroscopy. manganese compounds in historical black decorations such as, SEM-EDX of polished cross sections of the samples gives infor- 2+ 2+ kentrolite (Pb2Mn3+2Si2O9), bustamite ((Ca ,Mn )Si2O6), brau- mation about the chemical composition and microstructure 2+ 3+ 2+ 3+ nite (Mn Mn 6(O8)SiO4), haussmanite (Mn Mn 2O4), among of the crystallites; in particular the morphology, size and distri- other. Their nature and presence/absence seems related to the bution of the crystallites. Synchrotron radiation micro-XRD on materials and processes followed in their production (firing thin cross sections of the glazes gives also information about conditions, raw materials, method of application, etc.). For this the nature and crystalline structure of the compounds; this reason, a set of replication experiments was designed to learn is particularly important to distinguish between the various about how the compounds found are related to the techno- manganese oxides (bixbite, haussmanite). Moreover, the small logy (methods of application, firing temperature, pigment size and low contrast typical of those compounds formed and glaze composition, etc.), and also to their appearance by elements of low atomic weight also strongly limits their and conservation state of the manganese based decorations identification by SEM. The advantage of synchrotron light in the historical samples. 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

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Lothar Lambacher1 - Martin Radtke2 - Jessica F. Curado2 P-78 Vert/Green 10 sept. 2014 17:00 > 20:00 Heinrich Riesemeier2 - Jochem Wolters3 - Ina Reiche4,5 1 Staatliche Museen zu Berlin, Kunstgewerbemuseum, 10785, Berlin, Germany 2 Bundesanstalt Für Materialforschung und -prüfung, Bamline, 12205, Berlin, Germany Non-destructive 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 Synchrotron XRF CNRS, 75005, Paris, France analyses of the so-called “ Gisela gold jewellery ” (end of the 10th c. AD)

The Gisela jewellery is the most important complex of pro- dieval techniques. To evaluate the old joining techniques fane jewellery from the Ottonian period originated from properly, the composition of the solder were another im- Western Germany (Mainz?), and is dating from the end of portant point of interest. the 10th century AD, that’s common research view [1,3]. But Concerning the Gisela pieces, an extensive microscopic a lot of questions are not yet answered, for example: How investigation was already carried out [4,5]. The Synchro- and why these different objects have been assembled in the tron-induced X-ray fluorescence analyses (Sy-XRF) were 19th c.? To answer these questions it is necessary to know, thus undertaken on determined, most interesting areas on whether the jewellery was worked as a real ensemble from the objects. We used the hard X-ray synchrotron beamline the beginning or not. The determination of the metal alloys (BAMline) operated by the BAM to determine major, minor and the significant contents of major and minor elements and trace element contents in the different treasury objects permit to establish an objective criterion to group or distin- by Sy-XRF. The special performances of the radiation ob- guish several objects of the treasury. This analytical criterion tained at the BAMline (hard X-rays) allow optimal analysis gives very valuable information for the interpretation of the of gold objects. At the BAMline, X-rays are produced by a origin of this exceptional find that cannot be gained from super conducting wavelength shifter (WLS) with a maxi- archaeological and technological observations alone. mum field of 7 Tesla. For XRF measurements of the major The main aim of the experiment was the determination and minor gold elements, a W/Si Double-Multilayer-Mono- of the major, selected minor and trace elements (Ag, Cu, chromator (DMM) was used to produce an X-ray beam with Sn, Pb) of the twenty golden objects and, by the precise an energy of 35 or 40 keV. The gold objects were mounted description of the metal alloys, to argue for or against an in air in a sample frame on a motorized xyz-stage with an either simultaneous or different processing of the jewellery. angle of 45° to the X-ray beam. Fluorescence signals were The objects are an outstanding example for the use of me- 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 Bibliography parts of the gold jewels. The analysed points on the objects were selected with the help of a long distance microscope. [1] O tto von Falke: Der Mainzer Goldschmuck der Kaiserin Gisela, Berlin 1913. [2] Mechthild Schulze-Dörrlamm: Der Mainzer Schatz der Keiserin Agnes. The analytical results obtained on the different gold pieces Neue Untersuchungen zum sogenannten «Gisela-Schmuck» of the treasury will be compared in this presentation in order (Römisch-Germanisches Zentralmuseum, Monographien, 24), Sigmaringen 1991. to clarify their origin. [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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Jessica Curado1 - Marcia Rizzutto1 - Martin Radtke2 P-79 Violet/Purple 10 sept. 2014 17:00 > 20:00 Günter Buzanich2 - Uwe Reinholz2 - Heinrich Riesemeier2 1 University of São Paulo, 05508-090, São Paulo, Brazil 2 Characterization BAM Federal Institute for Materials Research and Testing, 12489, Berlin, Germany of emeralds from Brazil and Colombia using µ-SRXRF technique

Emerald is one of the most important precious stone and Nowadays, Brazil is the largest producer of Emeralds but the most one of the most imitated gems. Their purity, in terms of valuable and beautiful gems are found in Colombia. The aim of mineral inclusions, is one of the factors that determine its the present study is therefore to characterize emeralds from diffe- commercial value and also serve as proof of its veracity. rent mines of Brazil and Colombia by using Synchrotron Radiation The green color is associated with the presence of minority X-ray Fluorescence Microanalysis (µ-SRXRF). The advantage of this elements like chromium, iron, and in some cases vanadium. technique is that the micro beam allows us to select a homoge- The identification and quantification of these elements al- neous, inclusion free area of the stone to distinguish the elemental lows the determination of their region of provenance. fingerprint according to the provenance of the emerald.

181 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Messaoud Harfouche1 P-80 Violet/Purple 10 sept. 2014 17:00 > 20:00 1 SESAME, Synchrotron, 19252, Allan, Jordan SESAME: a synchrotron facility ofering advanced tools for cultural heritage studies in the Middle East

Synchrotron radiation has become a powerful tool for mized for X-ray spectroscopic studies in all fields of science studying unique ancient artefacts in cultural heritage such and we expect a large demand from the cultural heritage as works of art and fossils. It has been shown, so far, that users’ community due to the wide research topics in the it is possible to obtain information about the chemical Middle-East region on different cultural heritage branches. state and local composition of analyzed objects, and to The XRF/XAFS beamline at SESAME is designed as an analyti- identify chemical elements that are harmful to them using cal facility dedicated to synchrotron-based X-ray absorption synchrotron-based techniques such as X-ray absorption spectroscopy (XAS) and X-ray fluorescence (XRF). Further, spectroscopy (XAS). a rudimentary diffraction setup can be implemented. BASEMA is a hard X-rays beamline, which will be constructed All three X-ray techniques represent key analytical methods at Synchrotron-light for Experimental Science and Applica- in environmental sciences, life sciences, cultural heritage, tions in the Middle East (SESAME) [1]. This beamline is opti- as well as in a broad range of industrial applications.

Bibliography

[1] http://www.sesame.org.jo

182 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Giuseppina Padeletti1 - Maria Pia Casaletto2 P-81 Violet/Purple 10 sept. 2014 17:00 > 20:00 Alessandro Longo3 - Luca Olivi4 1 CNR, ISMN, 00016, Monterotondo, Italy 2 CNR, ISMN, 90146, Palermo, Italy 3 ESRF, EXAFS station, 38000, Grenoble, France Further investigation 4 Elettra Sincrotrone Trieste, Beamline stectroscopy//scattering, 34149, of lustre-decorated Basovizza, Italy majolicas by using X-ray absorption spectroscopy

Lustre is characterised by a heterogeneous metal–glass nano- chemical composition and, in particular, the presence of bismuth composite film, some hundreds nanometers thick. Silver and in the form of cosalite (Pb2Bi2S5) in lustred majolicas produced copper nanoparticles are dispersed within the outer layers of during the Renaissance period in Central Italy. The presence of the glaze, conferring to the whole materials peculiar optical this phase was investigatedd by XRD and successively confirmed properties. In spite of recent studies [1-4], many questions by elemental analysis with ETAAS. regarding the chemical composition, the mechanism of metal By using X-ray Absorption Spectroscopy we intend to inves- reduction and the optical properties of lustre remain still open. tigate the Bi L3-edge to shed light into the bismuth chemical Synchrotron radiation techniques are suitable for detailed studies speciation and how this is influences by the presence of on metal-glass nanocomposites [5-6]. For example, X-ray ab- other metals such as lead and sulphur. In Furthermore we try sorption fine structure spectroscopy (EXAFS) can provide useful to get information on the chemical state and local environ- information on oxidized phases or atomic clusters dispersed in an ment of metal atoms in the glaze in order to achieve a better amorphous medium, otherwise not achievable with diffraction understanding of the mechanism of reduction of different techniques. As reported in previous studies [1-3], the Italian pro- metals and the manufacturing techniques corresponding duction of lustre-decorated majolicas can be discriminate from to different productions (Islamic, Hispano–Moorish or Italian the Hispano-Moresque or Islamic ones by using the different 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 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Thiago S. Puglieri1 - Dalva L.A. de Faria1 P-82 Violet/Purple 10 sept. 2014 17:00 > 20:00 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, The reasons for such behavior may lay in the fact that diffe- however, they cannot be replaced because of its cultural rent experimental setups were used, as well as different relevance. Preventive conservation strategies are essential characterization techniques, which may not be sensitive to for its preservation and, for the proposition of new or for the same compounds. For example, ordinary XRD probes the reassessment of the existent ones, a comprehensive large areas on the samples and is sensitive to long range characterization of artworks and their degradation products arrangements, while Raman microscopy is a short range is necessary, as well as investigations to understand the technique probing areas as small as 1 µm2. In such a mechanisms of the materials degradation, including synergic context, a comprehensive characterization of the corrosion effects. Since 2006, when participating in the SENSORGAN compounds necessarily demands a significant number of project, [1] our group is interested in the investigation of Pb complimentary techniques. corrosion [2-3] aiming the enlargement of the understanding We have also analyzed corroded artworks from museums [10] on their mechanisms and also the development of new and exposed metal coupons at churches and museums to technologies [4-5] for preventive conservation. explore how hazardous the environment was and although We are mainly focused on the effect of indoor pollutants, the experience was successful when the corrosion products particularly formaldehyde, an insidious organic compound. were present in large amounts, it was difficult to characterize [2-3,6-9] Studies of formaldehyde action on Pb reports diffe- thin layers. Ag, Cu and Pb coupons exposed during 3 months rent controlled ageing conditions, with controversial results, were analyzed by µ-Raman (532, 632.8, 785 and 1064 nm), XRD including the chemical composition of the corrosion layer. 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. Bibliography In situations like ours, the use of synchrotron-based techniques [1] http://goart.gu.se/cgi-bin/senslev1/sensorgan.taf, last accessed appear as an appealing option due to the much higher radia- in April 15 2014. [2] de Faria, D. L. A.; Cavicchioli, A.; Puglieri, T. S. Vib. Spectrosc., 54: 159-163, tion throughput that, consequently, enhances the chance of a 2010. successful use of the µ-FTIR and µ-XRD techniques, as well as [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. other X-ray based techniques (XANES and EXAFS, e.g.). [5] Cavicchioli, A.; de Faria, D. L. A. Sens. Actuators, B, 115:656-665, 2006. Considering the above presented comments, although we [6] Raychaudhuri, M. R. and Brimblecombe, P. Stud. Conserv., 45:226-232, 2000. [7] T etreault, J. et al. Stud. Conserv., 48:237-250, 2003. are not a current user of synchrotron-based techniques, [8] Eremin, K. Carbonyl Pollutants: A Museum Perspective, 1998. we can envisage the importance of such multi-technique 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. facility in the chemical characterization of systems like ours. http://iaq.dk/iap/iap1998/1998_05.htm, last accessed in April 15 2014. In fact, synchrotron radiation is being successfully applied to [10] de Faria, D. L. A.; Puglieri, T. S.; Souza, L. A. C. J. Braz. Chem. Soc., similar problems [11] justifying our interest in enlarging our 28:1345-1350, 2013. [11] Grayburn, R. et al. Corros. Sci., 82:280–289, 2014. knowledge on its potentiality in cultural heritage investigation.

184 ABSTRACTS FOR POSTERS / RÉSUMÉS DES POSTERS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Herman Winick1 P-83 Violet/Purple 10 sept. 2014 17:00 > 20:00 1 SLAC National Accelerator Laboratory, Stanford Synchrotron Radiation Light Source, 94025 Menlo Park, USA SESAME - a synchrotron light source in the Middle East

Developed under the auspices of UNESCO & closely mode- operations budget (~$3.7 million in 2014, expected to rise to led on CERN, SESAME (Synchrotron-light for Experimental $(5.7-8.5) million when research starts in 2016). Jordan provided Science & Applications in the Middle East) is an intergo- the site, building, & infrastructure. A staff of 35 is now installing vernmental research center now completing a synchrotron the greatly refurbished 0.8 GeV BESSY I injector system, a gift light source in Jordan, scheduled for first operation at the from Germany, including a pre-injector 22 MeV microtron which end of 2015. It will enable world-class research by scientists began operation in 2009. The facility will have the capacity to from the Middle East/neighboring countries, preventing or serve 25 or more simultaneous experiments. Seven Phase I reversing the brain drain. It will also build bridges between beamlines are planned; on day-one, four of them will be opera- diverse societies, contributing to a culture of peace through tional. These are beam lines optimized for protein crystallogra- international cooperation in science. It is anticipated that a phy, X-ray absorption fine structure and fluorescence, infra-red, major activity at SESAME will be studies relating to human and materials science. heritage, including art & archaeology. SESAME is already A training program on accelerator technology, beamlines, being viewed as a model project for Africa & other regions. & scientific applications, has been underway since 2000, The centerpiece of SESAME is a new 2.5 GeV 3rd Genera- funded by the International Atomic Energy Agency (IAEA), tion Electron Storage Ring/Light Source (133.2 m circu- the Abdus Salam International Centre for Theoretical Physics mference, 26 nm-rad emittance, 12 places for insertion (ICTP), the Japanese Society for the Promotion of Science devices), which will provide very intense light from infra-red (JSPS), the Portuguese Foundation for Science & Technology to hard X-rays for a wide range of basic & applied studies (e.g. (FCT), the US Department of Energy, & fellowships provided regional biomedical & environmental issues, local archaeo- by light sources around the world. Over 1000 scientists from logical objects). SESAME offers excellent opportunities to the region have benefited from SESAME training activities. train local scientists & attract those working abroad to return. The laboratory is managed by a Director, together with Scien- The project is governed by a Council which meets twice yearly tific, Technical & Administrative Directors. Three committees & presently has 9 Members (Bahrain, Cyprus, Egypt, Iran, Israel, advise the Council & work with the staff on the technical Jordan, Pakistan, Palestinian Authority, & Turkey). Members have design, beamlines, & scientific and training programs. collective responsibility for the project & provide the annual See www.sesame.org.jo

Bibliography

[1] http://www.sciencediplomacy.org/perspective/2012/synchrotron-light- and-middle-east

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199 PARTNERS / PARTENAIRES Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

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 INVITED SPEAKERS / ORATEURS INVITÉS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

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 Josefna 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 Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

MUSÉE DU LOUVRE PLAN PLAN DU MUSÉE DU LOUVRE

-2 | Hall Napoléon (Under the Pyramid)

DENON WING RICHELIEU WING SULLY WING - Islamic Art - 14th-17th-century French Paintings - 17th, 18th, 19th-century French Paintings - The East Mediterranean in the Roman Empire - German, Flemish and Dutch paintings - 17th, 18th and 19th-century Drawings and pastels - Italian and Spanish Paintings (Northern European schools) - 17th, 18th-century Decorative arts - 19th-century French Paintings - D ecorative arts (Middle Ages, Renaissance, - Greek, Etruscan, and Roman Antiquities - English Paintings 17th and 19th centuries) - Pharaonic Egypt - Gallerie d’Apollon, the Diamants de la Couronne - Napoleon III apartments - Ancient Iran, Arabia and the Levant jewelry collection - French sculptures - History of the Louvre and Medieval Louvre - Italian, Spanish and Northern European sculptures - Mesopotamia and ancient Iran - Greek, Etruscan, and Roman Antiquities - Coptic Egypt - Arts of Africa, Asia, Oceania and the Americas

202 MUSÉE DU LOUVRE PLAN / PLAN DU MUSEE DU LOUVRE Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Admission to the Conference

Welcome Reception - C2RMF

203 ITINERARY / ITINÉRAIRE Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

ITINERARY FROM THE MUSÉE DU LOUVRE TO THE MUSÉE D’ORSAY ITINÉRAIRE DU MUSÉE DU LOUVRE AU MUSÉE D’ORSAY

M Tuileries Palais Royal-Musée du Louvre M Quai des Tuileries Invalides M

Quai Anatole France Av. du Général Lemonnier RER Musée d'Orsay M Musée du Louvre Assemblée Nationale Pont Royal Quai François Mitterrand

Pont du Carrousel Quai Voltaire M

Solférino

Rue du Bac

M Varenne

Rue du Bac M

204 PROCEEDINGS / ACTES Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

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 pro- mouvoir les applications futures des rayonnements synchrotron et neutron pour l’art et l’archéologie.

Les manuscrits doivent être soumis par voie électro- Contributions to the Conference will be published in a Special nique via le site de soumission des manuscrits à JAAS Issue of Journal of Analytical Atomic Spectrometry (IF2013: et doivent se conformer aux instructions aux auteurs 3.2). All speakers and poster authors are strongly encouraged de JAAS. La même procédure d’examen que pour to contribute to this special issue. A joint publication of all les articles soumis par la voie standard sera sui- contributions to SR2A 2014 will strengthen the visibility of this vie par l’équipe de rédaction de JAAS. Les manuscrits research and promote future applications of synchrotron ne seront acceptés que s’ils sont conformes à la qualité et au and neutron methods for Art and Archaeology. contour thématique requis pour leur publication dans le journal. Manuscripts are to be submitted electronically via the JAAS La date limite pour la soumission des manuscrits est le manuscript submission site and should comply to the 15 octobre 2014. Instructions for Authors of JAAS. The same refereeing procedure as for regularly submitted papers will be followed Les articles seront en accès libre au téléchargement pendant by the JAAS editorial office. Papers will only be accepted 6 semaines à compter de leur publication. 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 Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

AUTHOR INDEX INDEX DES AUTEURS

P- POSTERS O- ORALS / ORAUX

A Bernardes Suene P-56 Cato Eleanor P-01 O-02/26 Ceccato Daniele P-67 P-22/25/26 Bertrand Loïc 31/58/59 Cersoy Sophie O-17 Added Nemitala P-53 11 Cesaratto Anna O-34 P-29 Adriaens Annemie O-09 Binet Laurent P-17 Chadwick Alan P-20 Agostino Angelo P-02 Biro Katalin T. P-35/42 Chalmin Émilie O-30 Agresti Juri P-60 Bleton Jean P-46 Chen Kai O-38 Agyeman-Budu David P-23/30 Bloch Jean-Francis P-62 Choudhury Sanjukta P-23/30 Albéric Marie O-32 P-13 Boistel Renaud P-27 Cianchetta Ilaria O-33 Albertin Fauzia O-19 Bondar Maria P-76 Cinque Gianfelice P-18 Aldred Martha P-56 Boon Jaap J. O-03 P-01 Cinquin Bertrand O-41 P-41 O-01/18 Borca Camelia P-01 Alfeld Matthias P-12/37 Civita Francesco P-72 Bordet Pierre O-17 Allegro Paula R. P. P-53 Clancy Kevin P-75 Borghi Alessandro P-54 Alonso-Mori Roberto O-27 Clemente Carme P-18 Brinkman Don P-36 Alves Filipe P-55 Cochard Audrey P-71 Briois Valerie P-38 Ancelin Sébastien P-26/58 P-22/25/26 Brunetti Antonio P-28/51 Cohen Serge X. 58 Andreani Carla P-35 Brunetti Brunetto G. O-04 Constantinescu Bogdan P-67 Andrejkovičova Slavka O-05 Buckley Barbara P-10 Cook Phil K. P-31 Angelici Debora P-54 Bugani Simone P-49 Cooper David M. L. O-28 P-30 O-27/29 Anne Jennifer P-24 Bulla Claudio P-28 Coria Rodolfo P-06 Arias Pablo P-37 Burnstock Aviva O-02 P-29 Cormier Laurent P-68 Astolfo Alberto O-19 Buti Salvador P-18 Corsi Jacopo P-02/54 O-06 Costa Mario P-50 Buzanich Günter P-67/79 Costa Sonia P-47 B Costa Emanuele P-54 C O-04/34/40 Barata Carolina O-05 Cotte Marine P-05/10/12 32 Barbosa Marcia Cagno Simone P-14 P-53/56 Coulthard Ian O-28 Barden Holly O-29 Calas Georges O-11 P-23/30 Crabbé Amandine Barello Federico P-02 Caldeira Ana Teresa P-07 O-21 P-19 Cruz Antonio João Barzagli Elisa O-10 Calligaro Thomas P-39 O-05 Cubitt B. P-70 Bastian Gilles P-39 Campos Pedro H.O.V. P-56 P-53/56/78 Bauchau Fanny O-11 P-03/45/46 Curado Jessica F. Candeias António 47 79 Baudelet François P-38 Capogrosso Valentina O-34 P-29 Baumbach Tilo O-39 P-34 Capriotti G. P-60 Beaucour Jerome P-70 D Cardon C. P-70 Bellei Sara P-29 Cardoso Ana P-03 Beltran Victoria P-18 Dallé Didier P-58 Cartechini Laura P-29 O-36 Dararutana Pisutti P-33 Berenguer Felisa P-25/26/58 P-07/08/46 Carvalho Maria Luisa 50 Dargaud Olivier P-68 Bergmann Uwe O-13/25/27 P-06/24 Casaletto Maria Pia P-81 David Bruno P-74

206 AUTHOR INDEX / INDEX DES AUTEURS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

de Faria Dalva L. A. P-82 Fischer Daniel A. P-69 Herrel Anthony P-27 de la Rie René O-36 Foran Brendan O-32 Herrera L. K. P-44 de Nolf Wout O-18 Fors Yvonne O-35 Hodeau Jean-Louis O-17 de Palmas Anna P-28 Fratzl Peter O-33 Hofemyer Ruth P-36 de Wolf Robin P-66 Hormes Josef P-04/73 Debastiani Rafaela P-34 Horvath Eszter P-76 Degano Ilaria P-49 G Howard Daryl P-12 Dejoie Catherine O-38 Hu Yongfeng P-73 Delannoy Jean-Jacques P-74 Huang Yuying P-65 Gabrieli Francesca P-29 Delmotte Aurélien P-58 Hubert Axelle P-40 Gallias Jean-Louis O-22 Dernovitcha S. P-70 O-12 Gallo Lorenzo Mariano P-54 Hull Alyssa Deschamps Françoise P-58 P-05/10 Gay Marine P-37 Hunault Myrtille Dewhurst C. P-70 O-11 Geldof Muriel O-04 Hunt Alexandria P-74 di Martino Daniela P-35 Geneste Jean-Michel P-74 Hwu Yeukuang O-19 Dias Luis P-03 George Graham N. P-30 Diekamp Anja P-73 Gervais Claire O-20 P-38 I Difebo Roberta P-77 Gil Milene P-03 Dik Joris O-39 Ignatyev Konstantin O-27 P-24 Goidanich Sara O-34 Dillmann Philippe O-20/22 Ito Masayoshi P-63 Gol Jürg P-73 Domingos Sonia P-45 Gonzalez Victor P-39 Douin Joël P-71 Gordon Robert A. P-05/23/30 Dowsett Mark O-09 J Gorini Giuseppe P-35 Dufour Élise P-31 Gourier Didier P-17 Jacot-Guillarmod Mathieu O-20 Gourrier Aurélien O-33 Jalilehvand Farideh O-35 E Grayburn Rosie O-09 James Daniel P-74 Grazzi Francesco O-10 Jamme Frederic O-41 P-41 Edge David O-10 P-02/54/72 O-04/18/24 Grolimund Daniel P-01 Edwards Nicholas O-25/27/29 Janssens Koen 37 P-06/24 Grousset Sophie O-22 P-12/14/15 Egerton Victoria O-25/27/29 Groutso I. P-70 Janvier Philippe P-25 P-06/24 Grzesiak-Nowak Marta P-52/21 Jaye Cherno P-69 Ellis Tom P-36 Guériau Pierre O-26 P-25 P-20/75 Erko Alexei P-40 Jones Mark P-50 Eveno Myriam P-39 Guerra Maria Filomena O-06 P-08 Jorge Maria Estrela Guidotti Maria Cristina P-60 Joulie Sébastien P-71 Guimarães Ana G. P-53 Juanhuix Jordi P-18 Jurinovich Sandro P-49 F Justo A. P-44

Falkenberg Gerald O-18 P-12 H Farges François O-24 P-15 K Favero Patricia O-12 Hajnal Andor P-42 Fayard Barbara O-40 Hallin Emil P-23/30 Kaestner Anders O-03 Fazinic Stjepko O-37 Harfouche Messaoud P-80 Kajiya Elizabeth A.m. P-56 Fedrigo Anna P-72 Hasemi Hiroyuki P-64 Kali György P-76 Feng Renfei P-36 Helfen Lukas O-39 P-27 Kamiyama Takashi O-07 Ferreira Ester S. B. O-03 P-01 Hellemans Kevin O-37 Kaplan Frederic O-19 Ferreira Teresa P-07 Hendrickx Roel O-03 Kardjilov N. P-60 Feyer Vitaliy P-19 Hendriks Ella O-04 Kasztovszky Zsolt P-02/42 Figueira Francisca P-07 Hermans Joen O-02 Kelleher Joe P-72 Finnefrock Adam O-12 P-05 Herold Michel O-11 Keune Katrien O-02 P-42

207 AUTHOR INDEX / INDEX DES AUTEURS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

Kharytanovitch Z. P-70 Mahnke Heinz-Eberhard P-48 Newville Matthew O-11 Khaweerat Sasiphan O-07 Maley Jason P-36 Noble Petria O-02 King Andrew P-25 Malgosa Assumpcio P-51 Noe Laure O-38 Kirkham Robin O-12 O-25/27/29 Nogueira Isabel P-46 Manning Phillip P-06/24 Kiss Viktoria P-76 Noumowe Albert O-22 Manso Marta P-07/08/46 Kiyanagi Yoshiaki O-07 P-64 Nunes Margarida P-07 Margaritondo Giorgio O-19 Kleine Markus P-04 Nuyts Gert P-14 Marincas Octaviana P-09 Klysubun Prapong P-65 Maroti Boglarka P-02 Klysubun Wantana P-47/65 Martinetto Pauline O-17 Kochman V. P-70 O Martinez-Criado G. P-44 Kockelmann Winfried P-35/75 O-12/40 Odin Giliane O-24 P-15 Kos Mateja P-43 Mass Jennifer P-05/10 Oliveira Maria Ines P-50 Kuczewski Anthony O-12 Mathia Thomas P-62 P-81 Kunz Martin O-38 Mathon Marie-Hélène P-71 Olivi Luca Olivier Jean-Marc P-71 Matsen Catherine O-12 Olszewska-Swietlik Justyna P-52 McCreesh Natalie O-29 L Oprandi Regina P-26 McGlinchey Chris O-36 Ormsby Bronwyn A. P-69 Megens Luc O-04 L’ Hostis Valerie O-20 Osticioli Iacopo P-60 O-32/38 Lagarde Pierre P-55 Mehta Apurva P-05/10 Özvegy Karoly P-42 Lah Tina P-43 Meirer Florian P-05/10 Lakiza V. P-70 Menu Michel P-17/37/39 O-21 P-25 P Languille Marie-Angélique P-22/26/31 Mercere Pascal 38 Miguel Catarina P-03 Łasocha Wiesław P-21 Miliani Costanza O-04 P-12 Padeletti Giuseppina P-81 Lassalle Benedikt P-55 Mille Benoit P-59 Patelli Alessandro P-19 Laval Éric P-37 Mirabaud Sigrid P-17 Peccenini Eva O-19 Le Gac Agnès P-45/46/47 Mirambet François P-17 Pereira Marco P-46 Le Hô Anne-Solenn P-17 P-45/47 Mirão Jose P-03 Pereira Manuel Leelamanotham Somdech P-65 O-21 Perelli Cippo Enrico P-35 P-40 Mocuta Cristian Lemelle Laurence P-31/55 Perez-Arantegui Josefna P-49 P-48 Lepper Verena Moini Mehdi P-11 Pessanha Sofa P-50 O-38 Li Weidong Molera Judit O-31 P-77 Pestana Jose Antonio P-03 P-61 Lin Ting Molina Gloria O-31 Piga Giampaolo P-28/51 O-38 Liu Zhi Monico Letizia O-04 P-12 Ploeger Rebecca O-36 Lluveras-Tenorio Anna O-40 Moorhead Gareth O-12 Polack François P-25/58 P-02/54 P-25/58 Lo Giudice Alessandro Moreno Thierry Ponting Matthew P-08 Loisel Claudine O-11 Mottin Bruno P-39 Pottash Carol P-05 Longelin Stéphane P-46 Mudronja Domagoj O-37 O-34/40 Pouyet Émeline P-05/10/32 Longo Alessandro P-81 Müller Katharina P-13 O-29 P-06 O-31 Lowe Tristan Muñoz-Paez A. P-44 Pradell Trinitat P-18/77 P-17 Lubin-Germain Nadege Murcia Sonia O-31 Prafulla Tarachand Janbade P-16 O-38 Luo Hongjie Murphy Reg O-28 Pratesi Giovanni P-54 Price Campbell O-29 N Puglieri Thiago S. P-82

M Nagashima Syota O-07 Nagata Kazuhiro P-63 Q Nef Delphine O-20/22 Madeira Teresa P-46 O-34/40 Magalhães Ana G. P-56 Nevin Austin P-29 Quaroni Luca P-01

208 AUTHOR INDEX / INDEX DES AUTEURS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

R Saviello Daniela O-34/40 Terryn Herman O-21 P-19 Sawicka Alysia O-02 Thammajak Nirawat P-65 Schalm Olivier P-19 Thiaudière Dominique P-55 Radtke Martin O-34/40 P-10/32 Scharf Oliver O-06 Thomas Paul P-74 P-21/52 Rafalska-Lasocha Alicja O-10 Thompson Paul O-09 Ratel-Ramond Nicolas P-71 Scherillo Antonella P-02/54/60 72 O-02/41 Ravaud Élisabeth P-39 Thoury Mathieu P-22/26/41 Schiavon Nick P-28 59 Re Alessandro P-02/54 Schoeder Sebastian P-25/26/58 Tibljas Darko O-37 O-41 Réfrégiers Matthieu P-41/59 Schofeld Eleanor O-16 P-20 Timpu Daniel P-09 O-02/05/22 Schooneveld Erik P-35 Tobias Lucia P-03 Réguer Solenn P-38/71/17 55 Schreiner Manfred O-09 Tokarski Caroline P-29 Reiche Ina O-33 Schroeder Sven L.M. P-69 Tokugawa Maki P-63 P-13/37/78 O-15/38/40 Toniolo Lucia O-34 Reinholz Uwe O-06 Sciau Philippe P-71 P-08/67/79 Trcera Nicolas P-29/55/68 O-25/27 Reischig Peter O-39 Sellers William P-06/24 Tremsin Anton P-64 Relvas Catia P-07 Senesi Roberto P-35 Trentelman Karen O-32 Rhodes Nigel P-35 Séverin-Fabiani Tatiana P-59 Troalen Lore P-08 Ribechini Erika P-49 Shaw Ian P-08 Richards Vicki O-35 Shinohara Takenao P-64 O-06 Shiota Yoshinori O-07 P-64 Riesemeier Heinrich P-13/78/79 U Siano Salvatore P-60 Rizzutto Marcia A. P-53/56/79 Siemiradzki Henryk P-21 Robbiola Luc Ufelman Erich P-10 P-59 Siklosi Zsuzsanna P-76 Rocha Fernando O-05 Silva Tiago F. P-53 Rolland du Roscoat Sabine P-62 Silver Eric P-61 Rollman Christopher P-11 V Simionovici Alexandre P-40 Rose Volker O-08 Simon Rolf P-34 Rosi Francesca P-29 Smith Andy P-75 van de Voorde Lien P-66 Rosta Laszlo P-57 Sokaras Dimosthenis P-24 van den Berg Klaas Jan O-02 Rouchon Véronique O-24 P-15 O-04/18 Sombunchoo Panidtha P-65 van der Snickt Geert Roy Damien P-55 van Dongen Bart O-29 P-06 Spring Marika P-22 Rozenbaum Olivier O-20 van Eslande Elsa O-17 Stampanoni Marco O-19/23 Rudolf Sasa P-43 van Langh Robert O-14 Stan Daniela P-67 Ryan Chris O-12 P-12 van Loon Annelies O-02 P-05 Staude Andreas P-13 O-27 P-24 Storme Patrick P-19 van Veelen Arjen Stripe Benjamin O-08 Vandenabeele Peter P-66 S Stuart Barbara P-74 Vandendael Isabelle O-21 O-04/18/24 Swanston Treena O-28 P-30 Vanmeert Frederik 37 P-10/12/15 Sa Sara P-45/47 Szczepanowska Hanna M. P-62 Vantelon Delphine O-24 Salome M. P-44 Szekeres Ágnes P-42 P-15/31/55 Salvado Nati P-18 Szentmiklosi Laszlo P-02 Varney Tamara O-28 P-30 P-42 Salvemini Floriana P-72 Szilagyi Veronika Vasilescu Angela P-67 Szmelter-Fausek Bozena P-52 Sammynaiken Ramaswami P-36 Vekemans Bart P-66 Sandrine Pagès-Camagna P-17 Verger Louisiane P-68 Sandström Magnus O-35 T Verhaeven Eddy P-66 Sandt Christophe O-02 Vezin Herve P-29 Santoro Carlotta P-17 Vicenzi Edward O-08 P-61 Santos Joana P-46 Taforeau Paul P-32 Vichi Alessandra P-22 Sarangi Ritimukta O-16 Tamura Nobumichi O-38 Vincze Laszlo P-66 Sarkowicz Dominika P-21 Tanaka Manako P-63/64 Voltolina Stefano P-19

209 AUTHOR INDEX / INDEX DES AUTEURS Synchrotron radiation and neutrons in art and archaeology Conference Conférence Rayonnement synchrotron et neutrons pour l’art et l’archéologie

W

Wagermaier Wolfgang O-33 Wähning Andrea P-34 Wallert Arie O-39 Wallez Gilles P-39 Walter Philippe O-17 Walton Marc O-32 Webb Sam P-06 Weitkamp Timm P-25 Westall Frances P-40 Wiesinger Rita O-09 Williams Alan O-10 P-72 Willnef Elizabeth P-69 Winick Herman P-83 O-25/27/29 Wogelius Roy P-06/24 Woll Arthur R. O-12 P-05/23/30 Wolters Jochem P-78 Wouters Helena J. M. O-21

Y

Yager Kevin G. O-36

Z

Zarkout Karim P-17 Žbontar Zora P-43 Zizak Ivo P-40 Zoppi Marco O-10 P-72

210

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