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Book of Abstracts

Third International Congress on Chemistry for Cultural Heritage

July 1 5, 2014Academy of Fine Arts

Vienna, Austria

http://www.chemch2014.org

ChemCH 2014

Third International Congress on Chemistry for Cultural Heritage

www.chemch2014.org

July 1 5, 2014Academy of Fine Arts

Schillerplatz 31010 Vienna, Austria

Book of Abstracts (edited by Rita Wiesinger and Manfred Schreiner)

http://www.chemch2014.org

Dear Participants of ChemCH 2014,

Scientific research on our cultural heritage, both for the study of its material aspects and for designing and controlling conservation and preservation strategies, faces a diversity of changes due to the complexity and intrinsic value of the materials and objects. Furthermore, environmental conditions all over the world have inflicted increasing damage or at least deterioration of surfaces that were meant to be created for eternity. By conventional techniques we are able to ameliorate most of the dangers, but new approaches of high technology must be explored to preserve the heritage of human civilization as well as art works of former generations.

Chemistry for Cultural Heritage is one important discipline meeting the requirements in material analysis, evaluation of degradation phenomena, and developing conservation-restoration treatments. In consonance with the rapid development of chemical analysis and synthesis new solutions are available for the study and preservation. The biennial conferences of ChemCH serve as a valuable opportunity to meet with colleagues and share their experiences, but also discuss new developments and possibilities in our interdisciplinary field.

In this context, it is a great honor and pleasure for the members of the Institute of Science and Technology in Art of the Academy of Fine Arts Vienna to host the Third International Conference on Chemistry for Cultural Heritage. On behalf of the organizing committee, we are delighted to welcome all ChemCH-members and guests at ChemCH 2014. Based on more than 120 abstracts submitted for this conference, a program with oral and poster presentations could be organized with the invaluable support of the members of Board of ChemCH and the Scientific Committee.

We want to express our sincere thanks to all authors and members of the committees for their unmatched enthusiasm and dedication to make ChemCH2014 a success meeting. Last but not least the institutions and companies are acknowledged for their support and sponsoring our meeting.

Prof. Dr. Manfred Schreiner & Dr. Rita Wiesinger(Chair of the ChemCH2014)

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ChemCH 2014, Vienna / AustriaCommittees

Committees

Board of ChemCH:

Rocco MAZZEO Chairman of ChemCH

National Representatives:

Austria Manfred SchreinerBelgium Jana SanyovaDenmark Kim P. SimonsenGermany Oliver HahnGreat Britain Brenda KeneghanItaly Rocco MazzeoRomania Elena BadeaSweden Yvonne ForsTurkey Hadi zbal

International Scientific Committee:

Bruno BRUNETTI University of Perugia, ItalyAntonio CANDEIAS University of Evora, PortugalFrancesca CASADIO The Art Institute of Chicago, USAMaria Perla COLOMBINI University of Pisa and Institute of Conservation

and Valorization of Cultural Heritage - National Research Council (ICVBC - CNR), Italy

Martina GRIESSER Kunsthistorisches Museum Wien, AustriaChristoph KLEBER Competence Centre for Electrochemical Surface

Technology, Wiener Neustadt, Austria

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ChemCH 2014, Vienna / Austria Committees

Qinglin MA Chinese Academy of Cultural Heritage, Beijing, ChinaLeopold PUCHINGER Vienna University of Technology, AustriaStefan SIMON Rathgen Forschungslabor Berlin, GermanyMatija STRLIC Centre for Sustainable Heritage, The Bartlett

School for Graduate Studies, University College London, UK

Kurt VARMUZA Vienna University of Technology, AustriaShuya WEI University of Science and Technology, Beijing,

China

Local Organizing Committee (Academy of Fine Arts Vienna):

Manfred Schreiner (chairman)Rita Wiesinger (co-chair)

Marta AngheloneFederica CappaMonica De BardiBernadette FrhmannDubravka Jembrih-SimbrgerIrene MartinaMichael MelcherValentina PintusGunn PllnitzWilfried Vetter

Christine Jiru (secretary) Ernst-Georg Hammerschmid (homepage)

History and Scope of ChemCH

Since the very beginning of investigation, preservation, and conservation-restoration of our cultural heritage chemistry has been playing an important role in documentation, studying ancient production of materials and art technology, understanding of degradation processes and present state of works of art, as well as developing and evaluating new materials and methods for interventions of both, movable and immovable art works. In the last decades the booming developments in chemical science, especially in analytical, organic or environmental chemistry, but also in the fields of electronics and computer sciences has brought us new instruments and methods of great perfection, which present new horizons in the analysis, diagnosis, and protection of art and cultural objects.

ChemCH 2014 is the 3rd International Congress on Chemistry for Cultural Heritage after previous symposia in Ravenna/Italy in 2010 and Istanbul/Turkey in 2012 and will particularly provide an international platform for presentation and discussion on the issues and topics - chemo-/nanotechnology - chemical imaging (e.g. immuno-chemistry) - chemometrics in cultural heritage interpretation of results for co-operation

with professionals in CH - modern materials in art and museums - new materials and methods in conservation-restoration - development of non-invasive techniques - sample preparation - degradation / corrosion: chemical interaction of environment with movable

and immovable art works - technical studies and authenticity (case studies) - concepts and methods in chemistry education and training for

professionals in CH

mailto:office%40chemch2014.org?subject=http://www.heritagesciencejournal.com/authors/instructions/researcharticlehttp://www.heritagesciencejournal.comhttp://www.springer.com

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ChemCH 2014, Vienna / Austria Table of Contents

Table of Contents

Program Overview 11

Abstracts of Oral Presentations

Session 1: Analytical Methods in Cultural Heritage I 34Session 2: Analytical Methods in Cultural Heritage II 49Session 3: Chemical Imaging 62Session 4: Degradation / Corrosion: Study of Chemical Processes

and Interaction of Environment with Different Materials I 73Session 5: Degradation / Corrosion: Study of Chemical Processes

and Interaction of Environment with Different Materials II 92Session 6: Chemometrics in Cultural Heritage 101Session 7: Chemo-/Nanotechnology 109Session 8: New Materials and Methods for Cultural Heritage I 115Session 9: New Materials and Methods for Cultural HeritageII 127Session 10: Technical Studies and Authenticity (Case Studies) I 141Session 11: Technical Studies and Authenticity (Case Studies) II 153

Abstracts of Poster Presentations 167

Sponsors 347

Index 353

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ChemCH 2014, Vienna / Austria Program

Program

Tuesday, July 1st, 2014

15.00 17.00 Registration

Wednesday, July 2nd, 2014

8.30 Registration

10.00 Opening: Welcome Addresses Manfred Schreiner, Chairman of ChemCH 2014 Rocco Mazzeo, Chairman of ChemCH in EuCheMS Herbert Ipser, President of GCH Ulrich Schubert, President of EuCheMS Eva Blimlinger, Rector of the Academy of Fine Arts Vienna

Session 1: Analytical Methods in Cultural Heritage I Chair: Rocco Mazzeo

10.30 Plenary Lecture 34 ORGANIC ANALYSIS IN ART AND ARCHEOLOGY FROM THE PAST TO THE FUTURE Maria Perla Colombini

11.00 ALMA FROM MATERIALS TO THE 36 PAINTING TECHNIQUE INVESTIGATION D. Hradil, J. Hradilov

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ChemCH 2014, Vienna / AustriaProgram

11.20 THE COMBINATION OF FTIR AND X-RAY MICRO 39 SPECTROSCOPIES FOR THE ANALYSIS OF THIN SECTIONS OF ARTISTIC MATERIALS AT THE ID21 BEAMLINE, EUROPEAN SYNCHROTRON RADIATION FACILITY E. Pouyet, M. Cotte, B. Fayard, A. Lluveras-Tenorio, F. Meirer, A. Nevin, D. Saviello, Ph. Sciau, M. Salom

11.40 MODELLING OF INDOOR PARTICULATE MATTER 42 DEPOSITION AND OF ITS DEGRADATIVE EFFECTS J. Grau-Bov, L. Mazzei, B. Budi, D. Thickett, M. Strli

12.00 DIRECT ON-TARGET MALDI-TOF MS ANALYSIS A FAST 45 PROTOCOL FOR LIPID/PEPTIDE IDENTIFICATION IN PAINT SAMPLES C. D. Calvano, I. D. Van Der Werf, F. Palmisano, L. Sabbatini

12.20 Lunch Break

Session 2: Analytical Methods in Cultural Heritage II Chair: Maria Perla Colombini

14.00 Plenary Lecture 49 SURFACE ENHANCED RAMAN SPECTROSCOPY A ROBUST NEW TECHNIQUE FOR THE IDENTIFICATION OF ORGANIC COLORANTS IN TEXTILES AND PAINTS F. Casadio

14.30 MeV SIMS VERSUS PY-GC/MS ANALYSIS OF 51 MODERN PAINT MATERIALS D. Jembrih-Simbrger, I. Bogdanovic-Radovic, M. Anghelone, N. Markovic, Z. Siketic, M. Schreiner, T. Tadic

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14.50 ORIENTAL LACQUERS HARDENING PROCESS 54 CHARACTERIZATION BY FTIR MICROSPECTROSCOPY AND PY-GC/MS J. C. Frade, J. C. Rodrigues, A. J. Candeias

15.10 DISCRIMINATING BONE, ANTLERS, IVORIES, HORN AND 56 TORTOISESHELL USING QUANTITATIVE FTIR G. Turner-Walker, B.-Y. Xu

15.30 IDENTIFICATION OF MICROBIAL VOLATILE ORGANIC 59 COMPOUNDS EMITTED BY MOULDS INFESTING OBJECTS MADE OF CELLULOSE T. Sawoszczuk, J. Sygua-Cholewiska

15.50 Coffee Break

Session 3: Chemical Imaging Chair: Antonio J. Candeias

16.20 Plenary Lecture 62 X-RAY BASED IMAGING AND SPECTROSCOPY OF PAINTINGS BY V. VAN GOGH FROM THE DM TO THE NM LEVEL Koen Janssens

16.50 PORTABLE BIOSENSORS FOR IN SITU DETECTION OF 64 PROTEINS IN ARTWORKS BY CHEMILUMINESCENT IMMUNOCHEMICAL CONTACT IMAGING G. Sciutto, M. Zangheri, M. Guardigli, M. Mirasoli, S. Prati, R. Mazzeo, A. Roda

17.10 XEOM 1 A NOVEL MICROSCOPY SYSTEM FOR THE 66 CHEMICAL IMAGING OF HERITAGE METAL SURFACES M. Dowsett, M. Hand, P.-J. Sabbe, A. Adriaens

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17.30 UNDRESSED! CHARACTERIZING DOCUMENTS AND 69 REVEALING THEIR HIDDEN TEXTS WITH TERAHERTZ T. Bardon, R. K. May, Ph. F. Taday, M. Strli

17.50 End of Session

Thursday, July 3rd, 2014

Session 4: Degradation / Corrosion: Study of Chemical Processes and Interaction of Environment with Different Materials I Chair: Rita Wiesinger

9.00 Plenary Lecture 73 ON DAMAGE, FITNESS-FOR-PURPOSE AND ISOCHRONES MATERIAL DEGRADATION THROUGH THE LENS OF HERITAGE STAKEHOLDERS Matija Strlic

9.30 ASSESSING THE IMPACT OF NOX ON PARCHMENT 76 SYNERGISTIC EFFECTS OF LIGHT AND TEMPERATURE E. Badea, C. Carsote, G. Della Gatta

9.50 IRRAS, SEM AND ToF-SIMS FOR GLASS SURFACE 79 ANALYSIS GLASS LEACHING AND PROTECTION M. De Bardi, H. Hutter, M. Schreiner, R. Bertoncello

10.10 THE SULFIDATION PROCESS OF STERLING 82 SILVER CHARACTERIZATION OF SULPHIDE FILMS AS A RESULT OF DIFFERENT CORROSIVE ATMOSPHERES P. Storme, O. Schalm, R. Wiesinger, Ch. Kleber, M. Schreiner

10.30 Coffee Break

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11.00 ELUCIDATING THE MOLECULAR STRUCTURE OF 85 METAL SOAPS IN OIL PAINTINGS J. J. Hermans, K. Keune, A. Van Loon, R. W. Corkery, P. D. Ledema

11.20 ELECTROCHEMISTRY AS A FAST METHOD TO 88 INVESTIGATE PIGMENT DEGRADATION K. De Wael, W. Anaf, K. Janssens

11.40 Poster Session I Chair: Elena Badea, Francesca Casadio

P01 NEW WATER-SOLUBLE AMINE-REACTIVE REAGENT FOR 168 LABELING MICROBIAL CELLS: APPLICATION TO CULTURAL HERITAGE A. T. Caldeira, S. Martins, R. Vieira, M. Gonzalez, A. Candeias, A. Pereira

P03 COMBINED ANALYTICAL TECHNIQUES FOR THE 173 INVESTIGATION OF DYES IN THE COPTIC COLLECTION OF THE EGYPTIAN MUSEUM OF TURIN M. Gulmini, A. Idone, M. Borla, C. Oliva, D. Gastaldi, F. Dal Bello, M. Aceto

P05 IDENTIFICATION AND CHARACTERIZATION OF COPPER 178 PHTHALOCYANINE POLYMORPHS IN UNAGED AND AGED PAINTS M. Anghelone, D. Jembrih-Simbrger, M. Schreiner

P07 ASSESSING SIDE-EFFECTS OF CONSERVATION TREATMENTS 183 USING HYPERSPECTRAL IMAGING T. ojewski, D. Chlebda, W. Zawadzki

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P09 SEC OF SILK: PROBLEMS AND SOLUTIONS 189 D. Pawcenis, M. A. Koperska, T. ojewski, J. ojewska

P11 THE RESEARCH PROJECT ON THE LAST JUDGEMENT 193 TRIPTYCHON BY HIERONYMUS BOSCH - COLLECTION OF THE GEMLDEGALERIE OF THE ACADEMY OF FINE ARTS VIENNA D. Colagrande, F. Cappa, A. Lehner, R. Trnek, M. Schreiner

P13 EXPLOITING REFLECTANCE FTIR SPECTROSCOPY FOR 198 THE IN SITU IDENTIFICATION OF PIGMENTS IN ILLUMINATED MANUSCRIPTS C. Zaffino, S. Bruni, V. Guglielmi, S. Faraone, A. Vinaccia

P15 IN SITU MULTI-ANALYTICAL STUDY OF PLASTER 204 SCULPTURES DEGRADATION FOR BETTER DIAGNOSIS OF THEIR STATE OF CONSERVATION M. Frade, D. Fragoso, A. M. Cardeira, St. Longelin, S. Costa, A. Candeia, M. L. Carvalho, M. Manso

P17 TEMPERATURE-RELATED DEGRADATION OF PIGMENTS 209 STUDIED BY HIGH TEMPERATURE X-RAY DIFFRACTION Z. ermkov, P. Bezdika, A. Lanok, D. Hradil

P19 DETERIORATION OF VEGETABLE-TANNED LEATHER 213 INVESTIGATED BY UNILATERAL NMR: EFFECTS OF HYDROLYSIS AND THERMAL TREATMENTS C. Sendrea, E. Badea, H. Iovu

P21 ARTIFICIALLY AGED PARCHMENT INVESTIGATED BY FTIR 219 I. Petroviciu, C. Carsote, W. Vetter, L. Miu, M. Schreiner

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P23 ANALYTICAL STUDY OF A CHROMATIC DETERIORATION: 223 LEAD PIGMENTS FADING IN 18TH CENTURY MURAL PAINTINGS BY SEM-EDS, -XRD AND -RAMAN M. Gil, T. Rosado, A. T. Caldeira, M. D. Botto, S. Longelin, M. L. Carvalho, C. Souto, A. Candeias, J. Miro

P25 FADED SHINE. USE AND DEGRADATION OF METAL BRASS 226 POWDER IN TWO 19TH CENTURY PAINTINGS E. S. B. Ferreira, D. Gros, N. C. Scherrer, St. Zumbhl

P27 CHEMICAL ANALYSIS AND INNOVATIVE SOLUTION FOR 232 CHALK STONE RESTORATION WITH HYDROXYAPATITE NANOPARTICLES R. M. Ion, D. Turcanu-Carutiu, R.-C. Fierascu, I. Fierascu

P29 BIOACTIVE NANOCOMPOSITES FOR PREVENTIVE 238 CONSERVATION OF STONE MONUMENTS L. Mondelli, N. Ditaranto, G. Germinario, I. D. Van Der Werf, A. Mangone, L. Sabbatini

P31 CALCIUM HYDROXIDE NANOPARTICLES PREPARED BY 244 SOL-GEL METHOD FOR PAPER DEACIDIFICATION O. Daranova, M. Bagoite, A. Beganskiene, A. Kareiva

P33 ELECTROCHEMICAL AND SURFACE TREATMENT OF 251 MATERIALS IN THE APPLIED ARTS L. Petkov

P35 ANTIOXIDANT PROTECTION OF PAPER-BASED 255 HERITAGE OBJECTS K. Vizrov, S. Kirschnerov, M. Rehkov, J. Kazkov, K. ov

P37 PREPARATION OF DIFFERENT DISPERSIONS FORMULATION 260 FOR CONSOLIDATION OF JORDANIAN BASALTIC ARTIFACTS A. Al Bawab, H. M. Z. Al Hamaty, R. Abd-Allah

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P39 METAL FOIL COATINGS IN ALTARPIECES: A 264 MICROANALYTICAL STUDY OF THE MATERIALS AND THEIR ALTERATIONS N. Salvad, S. But, G. Cinque, J. Juanhuix, C. Clemente, V. Beltran, T. Pradell

P41 PLATINUM PRINTS EXAMINED USING VARIABLE PRESSURE 269 HIGH RESOLUTION SCANNING ELECTRON MICROSCOPY P. Ravines, N. Erdman, R. McElroy

P43 CONSOLIDATING ADHESIVES: A STUDY OF BEVA 371 274 R. Ploeger, Ch. McGlinchey, E. R. De La Rie

P45 TECHNICAL EXAMINATION OF VIRGIN SURROUNDED BY 278 FLOWERS, BY JAN VAN KESSEL I C. Barbosa, A. Calvo, J. C. Frade

P47 CARAVAGAGGISTI PAINTINGS IN POLISH COLLECTION 283 TECHNOLOGICAL RESEARCH M. Jasiski

P49 NANO-GRAPHENE FOR THE RESTORATION & PRESERVATION 288 OF DAMAGED PAPERS & MANUSCRIPTS: CASES OF STUDY F. Valentini, I. Ficorella, C. Coletti, A. Rubechini

P51 MATERIAL CHARACTERIZATION OF THE 15th- 20th CENTURY 293 WALL PAINTINGS FROM SINOP BALATLAR CHURCH COMPLEX IN THE BLACK SEA REGION OF TURKEY B. Krmz, U. Alanyurt, S. ngin, E. zgl, G. Krolu, M. Bakiler

P53 OLD NUBIAN WALL PAINTINGS ELEMENTAL ANALYSIS BY 298 MEANS OF PORTABLE XRF SPECTROMETRY O. Syta, K. Rozum, B. Wagner, D. Zieliska

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P55 A MULTI-SPECTROSCOPIC CHARACTERIZATION OF NUDE 303 PAINTINGS (LATE 19TH CENTURY) BY JOSE VELOSO SALGADO A. M. Cardeira, St. Longelin, S. Costa, A. Candeias, M. L. Carvalho, M. Manso

P57 UNRAVELING GRO VASCO WORKSHOP TECHNIQUE 308 B. Campos-Maia, J. C. Frade, A. Calvo, L. Dias, J. Miro, A. Cardoso, C. Dias, A. Claro, A. Candeias

P59 STUDY OF GANSU WOODEN GRAVE GOODS 313 CHEMICAL AND BIOLOGICAL INVESTIGATIONS A. Favaretto, E. Diana, F. Ruffinatto, A. Agostino, M. Aceto

P61 CHARACTERIZATION OF 19th CENTURY 318 PHOTOGRAPHIC PRINTS BY NON-DESTRUCTIVE MULTI-ANALYTICAL TECHNIQUES M. Peres, T. Ferreira, L. Dias, J. Miro, M. L. Carvalho, A. Gomes, E. Jardim, F. Costa

P63 STUDY OF THE IMPACT OF CHLORINE IN THE 324 DEGRADATION OF A MEDIEVAL GILDED SPUR M. Veneranda, J. Aramendia, S. Fdez-Ortiz de Vallejuelo, L. Garca, I. Garca, K. Castro, M. Maguregui, J. M. Madariaga

P65 STUDY OF THERMOOXIDATIVE STABILITY OF 328 HERITAGE MATERIALS A. Peller, M. Rehkov, K. Vizrov, P. imon

P67 METHODOLOGY FOR NON-INVASIVE RESEARCH 333 D. Stepien

P69 A SCIENTIFIC STUDY OF THE PIGMENTS IN THE WALL 338 PAINTINGS AT JOKHANG MONASTERY IN LHASA, TIBET, CHINA Z. Li, L. Wang, Q. Ma, J. Mei

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P71 ENVIROMENTAL IMPACT ON THE DEGRADATION 344 PROCESSES OF BRICKS AND MORTARS: CASE STUDY OF THE BAC FORTRESS Sneana Vueti, Jonjaua Ranogajec, Eva Lonar, Ognjen Rudi, Sinia Markov, Ana Vidakovi

12.40 Lunch Break

Session 5: Degradation / Corrosion: Study of Chemical Processes and Interaction of Environment with Different Materials II Chair: Bruno Brunetti

14.00 DEGRADATION OF NATURAL RUBBER IN WORKS OF 92 ART STUDIED BY UNILATERAL NMR AND HIGH FIELD NMR SPECTROSCOPY C. Kehlet, A. Catalano, E. Del Federico, J. Dittmer

14.20 THE DEGRADATION OF DAMMAR VARNISHES AS 94 EFFECT OF ACETIC AND FORMIC ACIDS IN MUSEUM ENVIRONMENTS I. Bonaduce, M. P. Colombini, F. Di Girolamo, M. Odlyha, S. Rutkowska, M. Scharff, T. Grntoft

14.40 FOURIER TRANSFORM IR SPECTROSCOPY A NON- 98 INVASIVE TOOL TO MONITOR CHEMICAL DEGRADATION AND MECHANICAL STRENGTH IN WOOD G. Almkvist, S. Norbakhsh, I. Bjurhager

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15.00 Poster Session II Chair: Jana Sanyova, Kim Simonson

P02 ATR-RAS: AN INNOVATIVE METHOD FOR THE ANALYSES 171 OF COLORANTS IN MICRO EXTRACTS S. Prati, G. Sciutto, I. Bonacini, R. Mazzeo

P04 MICRO-DESTRUCTIVE ELEMENTAL ANALYSIS OF CULTURAL 176 HERITAGE OBJECTS BY LA-ICPMS B. Wagner, K. Malinowska, M. Donten, I. Fuks, B. Szelegejd

P06 MEASUREMENT OF pH IN IRON-BASED INKS BY MEANS 181 OF MICRO-RAMAN SPECTROSCOPY G. Piantanida, E. Menart, M. Bicchieri, M. Strli

P08 TESTING ACID DIGESTION METHOD FOR THE ANALYSIS 186 OF LIME MORTARS: A CASE STUDY R. evk, P. aek, M. Neuwirthov, R. Fabe, M. Prez-Estbanez, A. Viani

P10 MACRO-XRF SCANNING AND OPTICAL COHERENCE 190 TOMOGRAPHY (OCT) TECHNIQUES FOR THE AUTHENTIFICATION OF SELECTED ARTWORKS B. ydba-Kopczyska, P. Targowski, M. Iwanicka

P12 THE USE OF NON-DESTRUCTIVE METHODS AS A TOOL FOR 196 THE IDENTIFICATION OF HIDDEN DEFECTS OF SANDSTONE BLOCKS FROM PRAGUES CHARLES BRIDGE, CZECH REPUBLIC K. Bayer, J. Havln

P14 EXAMINATION OF HISTORIC PARCHMENT MANUSCRIPTS 201 BY NON-INVASIVE REFLECTION-FTIR POSSIBILITIES AND LIMITATIONS W. Vetter, G. Pllnitz, M. Schreiner

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P16 USE OF PORTABLE XRF FOR QUANTITATIVE ANALYSIS ON 207 CORRODED METALLIC ARTEFACTS D. atovi, V. Desnica, S. Fazini

P18 A TIME-LAPSE SYNCHROTRON X-RAY DIFFRACTION 211 (SR-XRD) STUDY OF THE CORROSION OF SILVER BY H2S AND O3 R. Grayburn, R. Wiesinger, M. Dowsett, P. Thompson, A. Adriaens

P20 DIFFERENTIAL SCANNING CALORIMETRY FOR 216 QUANTIFYING DAMAGE IN ARTIFICIAL AGED LEATHER C. Carsote, E. Badea, L. Miu, G. Della Gatta, P. Budrugeac

P22 ANALYTICAL RESEARCH ON ILLUMINATED FORAL 221 CHARTER OF MURA (1512-PORTUGAL): PARCHMENT, INKS AND MATERIALS S. Pessanha, C. Mortari, M. Manso, St. Longelin, M. Guerra, A. Le Gac, S. P-Leve Santos, M. L. Carvalho

P24 FTIR ANALYSIS OF BINDING MEDIA DEGRADATION AND 225 PIGMENT-BINDER INTERACTION OF AGED PAINT (REVEALING HIDDEN INFORMATION ON THE IR SPECTRA) A. Ceriotti, M. Pinto, A. Poliszuk

P26 NON-INVASIVE IDENTIFICATION OF PIGMENTS 229 TECHNOLOGY AND PAINTING TECHNIQUE USED BY MAKSYMILIAN GIERYMSKI, THE REPRESENTATIVE OF THE MUNICH ARTISTIC CENTER IN THE SECOND HALF OF THE NINETEENTH CENTURY A. Klisiska-Kopacz, P. Frczek, E. Zygier, A. Krypczyk

P28 SELF-HEALING NANOSTRUCTURED COATINGS FOR 235 CORROSION INHIBITION OF COPPER-BASED ARTIFACTS M. P. Casaletto, A. Mazzaglia, A. Scala, G. Lazzara, R. Schimmenti

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P30 MIXTURES OF SILICIC ACID ESTERS WITH NANOPARTICLES 241 THE POSSIBILITIES OF THEIR BEHAVIOR MONITORING P. Kotlik, M. Slavikova, B. Benetkova

P32 STUDY OF ACCELERATED AGING OF ARTISTIC MATERIALS 248 BY INFRARED SPECTROSCOPY A. Ceriotti, M. Pinto, A. Poliszuk, G. Ybarra

P34 MICROEMULSIONS AS A NEW STRATEGY FOR CORROSION 253 INHIBITION COATINGS FOR LEAD AND IRON V. Flexer, E. Ahmed, M. G. Dowsett, A. Adriaens

P36 MICRO-EMULSIONS FOR REMOVAL OF WAXES AND OILS 258 FROM ARTEFACT SURFACES M. Skrdlantova, K. Drabkova, P. Kotlik

P38 FROM ANALYSIS TO A SUITABLE RECIPE RECONSTRUCTION 261 OF THE AUTHENTIC MATERIAL AND TECHNOLOGY OF HISTORIC RENAISSANCE STUCCO DECORATIONS IN CASTLE OF TELC, CZECH REPUBLIC J. Havlin, R. Tislova, K. Bayer

P40 CHARACTERIZATION OF ARCHAEOLOGICAL IRON SLAGS 266 OF 12TH, 13TH, 16TH AND 19TH CENTURY BY RAMAN AND X-RAY FLUORESCENCE SPECTROSCOPY FROM DIFFERENT SETTLEMENTS OF NORTHERN SPAIN L. Gomez-Nubla, J. Aramendia, S. Fdez-Ortiz De Vallejuelo, K. Castro, L. Garca, J. . G. Carvajal, I. Garca, J. F. Ruiz, J. M. Madariaga

P42 A MULTI-ANALYTICAL APPROACH FOR THE STUDY OF 272 NEOLITHIC POTTERY FROM THE GREAT DOLMEN OF ZAMBUJEIRO, VORA, PORTUGAL A. Manhita, S. Martins, J. Costa, L. Rocha, C. Dias, J. Miro, D. Teixeira

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P44 THE WIENER NEUSTADT HOARD MATERIAL ANALYSIS AND 276 CLARIFICATION OF THE EXCAVATION SITE I. Martina, R. Wiesinger, K. Hradil, M. Melcher, M. Mehofer, N. Hofer, M. Schreiner

P46 IDENTIFICATION OF BINDERS FROM MURAL PAINTING 280 OF GEORGE RADU MELIDON PUBLIC LIBRARY, ROMAN CITY, NEAMT COUNTY, ROMANIA A. M. Baciu, Z. Moldovan, C. Marutoiu, I. Bratu, O. F. Marutoiu

P48 ANALYSIS OF THE CONSERVATION STATE OF A PANEL 286 PAINTING ICON FROM THE 19TH CENTURY R. A. Cristache, V. Vasilache, I. Sandu, A. Budu

P50 SCIENTIFIC INVESTIGATIONS OF HISTORIC ASIAN 290 LACQUER WORKS OF ART V. Pitthard, S. Stanek, M. Griesser, S. Miklin-Kniefacz

P52 DISCLOSING THE TECHNOLOGIES OF THE QING DINASTY 296 PAINTERS IN CIVIL BUILDINGS: THE MURAL PAINTINGS IN THE FIVE NORTHERN PROVINCES ASSEMBLY HALL, ZIYANG, CHINA A. Lluveras-Tenorio, I. Bonaduce, F. Sabatini, I. Degano, C. Blaensdorf, E. Pouyet, M. Cotte, M. Linyan, B. Chongbin, H. Kejia, M. P. Colombini

P54 THE NON-INVASIVE APPROACH TO THE ANALYSIS OF DYES 300 AND PIGMENTS IN MEDIEVAL PERSIAN MANUSCRIPTS M. Mahmoudi-Khorandia, M. Gulmini, A. Idone, A. Agostino, G. Fenoglio, A. Benotto, M. Aceto

P56 CHARACTERIZATION OF THE ARTIFICIAL ORPIMENT IN THE 305 INTERIOR DECORATIONS OF THE JAPANESE TOWER IN LAEKEN, BRUSSELS M. Vermeulen, C. Poleunis, F. Vanmeert, K. Janssens, J. Sanyova

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P58 THE MATERIALITY IN THE ALTAR SCREENS OF PEDRO 311 ALEXANDRINO DE CARVALHO C. Tavares, J. C. Frade, A. Calvo, A. F. Pimentel, A. J. Candeias

P60 FOXING ON PAPER: ANALYTICAL AND 316 MICROBIOLOGICAL EVALUATION M. Nunes, C. Relvas, F. Figueira, J. Campelo, A. Candeias, A. T. Caldeira, T. Ferreira

P62 IN-SITU CHARACTERIZATION OF POST-PALEOLITHIC 321 BLACKISH PICTOGRAPHS EXPOSED TO THE OPEN AIR IN LOS CHAPARROS SHELTER, TERUEL, SPAIN . Pitarch, J. F. Ruiz, S. Fdez-Ortiz de Vallejuelo, A. Hernanz, M. Maguregui, J. M. Madariaga

P64 CHARACTERIZATION OF THE MATERIALS IN GILDED AND 327 PAINTED BUDDHA SCULPTURES FROM QINGZHOU, SHANDONG PROVINCE OF CHINA S. Wei, L. Zhou, Q. Ma

P66 STUDY OF STABILITY OF BROWN-GREY INKS ON 330 PAPER SUPPORT M. Rehkov, M. eppan, K. Vizrov

P68 A STUDY ON A CULT OBJECT FROM THE 336 12th 13th CENTURY V. Vasilache, I. Sandu, O. Mircea, A. V. Sandu

P70 THE CHURCH IN NAQ ES-SHEIMA RECONSIDERED. 342 IT`S PAINTED DECORATION IN THE CONTEXT OF THE CHEMICAL ANALYSIS OF SOME FRAGMENTS OF PLASTER AND THE NUBIAN WALL-PAINTING TRADITION D. Zieliska, K. Uhlir, M. Griesser, B. Wagner

16.00 Coffee Break

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Session 6: Chemometrics in Cultural Heritage Chair: Matija Strli

16.30 Plenary Lecture 101 CHEMOMETRICS A USEFUL TOOL BUT NOT A MAGIC FLUTE Kurt Varmuza

17.00 ATMOSPHERIC CORROSION OF WEATHERING STEEL 103 A CHEMOMETRIC APPROACH S. Raffo, I. Vassura, C. Chiavari, C. Martini, M. Ch. Bignozzi, E. Bernardi

17.20 TECHNICAL STUDIES AND AUTHENTICITY OF A MEDIEVAL 107 ILLUMINATED MANUSCRIPT A CHEMOMETRIC APPROACH C. Miguel, C. Barrocas-Dias, A. Claro, T. Ferreira, A. Conde

Session 7: Chemo-/Nanotechnology Chair: Matija Strli

17.40 THE USE OF TiO2 NANOPARTICLES FOR THE PROTECTION 109 AND CONSERVATION OF PAINTING AND STONE SURFACES A. Colombo, F. Gherardi, S. Goidanich, C. Beccaria, R. Simonutti, L. Toniolo

18.00 NANOLIME SUSPENSION FOR THE CONSOLIDATION OF 112 HISTORIC PLASTER L. Machacko, R. Tislova

18.20 Introduction Heritage Science Journal Conference Proceedings

18.30 Poster Discussion & Reception by ChemCH 2014

27


Friday, July 4th, 2014

Session 8: New Materials and Methods for Chemical Heritage I Chair: Koen Janssens

9.00 Plenary Lecture BIOTECHNOLOGY APPROACHES FOR CULTURAL HERITAGE 115 Antnio Candeias

9.30 THE PROTECTIVE BEHAVIOUR OF ORGANIC COATINGS 118 CONTAINING CARBOXYLIC FUNCTIONAL GROUPS ON LEAD METAL SUBSTRATES M. De Keersmaecker, O. Van Den Berg, T. Hauffman, D. Depla, K. Verbeken, F. Du Prez, A. Hubin, A. Adriaens

9.50 THE EFFECTS OF LIGHT BLEACHING ON OPTICAL 121 BRIGHTENING AGENTS IN CONTEMPORARY PRINTMAKING PAPERS Ch. Taylor, R. Ploeger

10.10 A NEW CONSERVATION TREATMENT FOR STRENGTHENING 124 AND DEACIDIFICATION OF PAPER USING POLYSILOXANE NETWORKS C. Piovesan, A.-L. Dupont, I. FabreFrancke, O. Fichet, B. Lavdrine, H. Chradame

10.30 Coffee Break

Session 9: New Materials and Methods for Cultural HeritageII Chair: Yvonne Fors

11.00 XRF ANALYSIS OF METALLIC CULTURAL HERITAGE OBJECTS 127 FROM THE NATIONAL MUSEUM IN KRAKOW J. M. Del Hoyo-Melndez, M. Matosz, . Bratasz

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11.20 THE APPLICATION OF LOCALISED ELECTROLYTIC CLEANING 130 FOR THE RESTORATION OF MASTERPIECES OF THE TREASURY OF SAINT-MAURICE ABBEY, VALAIS, SWITZERLAND Ch. Degrigny, R. Jeanneret, D. Witschard, C. Baudin, G. Bussy, H. Carrel

11.40 ORGANIC RESIDUE ANALYSES BY GC/MS AND HPLC/CAD 134 SHED LIGHT ON HUMAN CHIEF MEANS OF SUBSISTENCE IN ANCIENT TIMES - CASE STUDIES ABOUT POTSHERDS COMING FROM EPHESOS (TURKEY) AND PUNTA DI ZAMBRONE (SOUTH ITALY) L. Puchinger, R. Paltram, J. Schrattenecker, S. Feichtinger, J. Schaub

12.00 ASSESSMENT OF CONSOLIDATION EFFECTIVENESS OF 137 NEW TEOS-BASED FORMULATIONS BY A MULTITECHNIQUE APPROACH C. Maurich, F. Rosi, F. Presciutti, L. Skrlep, A. Sever-Skapin, C. Miliani

12.20 DEVELOPMENT OF A NEW POLYMER GLASS USING 139 INTERPENETRATING POLYMER NETWORKS FOR CULTURAL HERITAGE WITH ENHANCED RESISTANCE TOWARDS SCRATCHES AND SOLVENT M. Berrebi, I. Fabre-Francke, B. Lavdrine, O. Fichet

12.40 Lunch Break

Session 10: Technical Studies and Authenticity (Case Studies) I Chair: Leopold Puchinger

14.00 Plenary Lecture 141 NON-INVASIVE IN-SITU STUDY OF PAINTINGS Bruno G. Brunetti

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14.30 SCIENTIFIC ANALYSES OF METAL ARTEFACTS FROM SAN 143 PEDRO DE ATACAMA: APPROACHES TO ANCIENT METALLURGY IN NORTHERN CHILE B. Maldonado, T. Rehren

14.50 GOLDEN PAINTINGS FOR THE GOLDEN ROOM OF THE 147 MAURITSHUIS? THE USE OF SEM-EDX ELEMENTAL MAPPING TO CHARACTERISE THE USE OF METAL LEAF AND ITS DEGRADATION IN SIX FLOWER TONDOS FROM THE GOLDEN ROOM OF THE MAURITSHUIS S. Meloni, M. Salazar-Walsh, R. Haswell, C. Toussat

15.10 SPECTROSCOPIC CHARACTERIZATION OF NATURAL DYES 150 FOR THEIR NON-INVASIVE IDENTIFICATION ON PRE-COLUMBIAN CODICES: THE MAYA YELLOW P. Nabais, D. Buti, Ch. Grazia, A. Romani, A. Sgamellotti, C. Miliani

15.30 Coffee Break

Session 11: Technical Studies and Authenticity (Case Studies) II Chair: David Hradil

16.00 NEW INSIGHT ON THE MAKING OF PURPLE CODICES 153 M. Aceto, A. Arraisa, F. Marsanoa, A. Agostinoc, G. Fenoglio, M. Gulmini, A. Idone, P. Baraldi, Ch. Porter

16.20 AN INVESTIGATION OF THE LEAD-TIN YELLOWS TYPE I 156 AND II AND THEIR USE IN BOHEMIAN PANEL PAINTINGS FROM THE GOTHIC PERIOD R. efc, . Chlumsk, A. Otmarov

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16.40 NON-INVASIVE PORTABLE METHODOLOGY APPLIED TO 160 THE CHARACTERIZATION OF JAPANESE INR, SUZURIBAKO, CHESTS, AND BOXES FROM THE BILBAO FINE ARTS MUSEUM COLECCIN PALACIO M. Maguregui, S. Fdez-Ortiz de Vallejuelo, H. Morillas, A. Giakoumaki, . Pitarch, I. Martinez-Arkarazo, G. Arana, J. L. Merino and J. M. Madariaga

17.00 BROWNISH ALTERATIONS ON THE MARBLE STATUES 164 IN THE CHURCH OF ORSANMICHELE IN FLORENCE: WHAT IS THEIR ORIGIN? D. Pinna, M. Galeotti, A. Rizzo

17.20 Poster Awards & Final Remarks

18.00 Guided Tour Gemldegalerie of the Academy of Fine Arts Vienna

20.00 Reception by the Rector of the Academy of Fine Arts Vienna, Mag. Eva Blimlinger

Saturday, July 5th, 2014

10.0012.00 Excursions to Museums in Vienna:

Kunsthistorisches Museum, Kunstkammer

The Kunstkammer Wien is the most important collection of its kind in the world. Since March 1, 2013 this unique collection is now again open to the public. From the late Middle Ages to the Baroque, Habsburg emperors and archdukes collected exotic and uncommon materials, to which they often ascribed magical powers, such as precious stones, ostrich eggs, coral, and sharks teeth, which were considered to be dragons tongues. From these natural products, artists created virtuoso works of art. Among its highlights are examples of fabulous goldsmith

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work such as the celebrated Saliera by Benvenuto Cellini, magnificent bronze statuettes, delicate and bizarre ivories, precious stone vessels, and much, much more.

Liechtenstein Museum Palais Liechtenstein, Frstengasse 1

The Liechtenstein GARDEN PALACE is home to one of the world s largest and most important private art collections, owned by the Prince von und zu Liechtenstein. Set in an extensive park, the Princely Collections contain some 1,600 paintings with masterpieces from the early Renaissance to the Biedermeier era, including works by Lucas Cranach the Elder, Raphael, Peter Paul Rubens, Anthony van Dyck, Frans Hals, and Rembrandt. Of equal art-historical importance is the collection of Italian bronzes, the focus of which lies in masterpieces of the 16th and 17th centuries. In addition to these outstanding paintings and sculptures, the Princely Collections also contain important holdings pietra dura objects, enamelwork, porcelain, tapestries, and furniture.

Upper Belvedere (Oberes Belvedere) Prinz Eugen-Str. 27

The Upper Belvedere houses the impressive collection of Austrian art dating from the Middle Ages to the present day. At the heart of the displays of art around 1900 is the world s largest Gustav Klimt collection. The glittering highlights are Klimt s golden pictures The Kiss and Judith, and masterpieces by Egon Schiele and Oskar Kokoschka. Prominent works by the French Impressionists and the outstanding collection of the Viennese Biedermeier paintings are further attractions at the Upper Belvedere.

Oral Presentations

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ChemCH 2014, Vienna / AustriaOral Presentations

Organic Analysis in Art and Archeology: From the Past to the Future

M. P. Colombini

University of Pisa and Institute of Conservation and Valorization of Cultural Heritage - National

Research Council (ICVBC - CNR), Italy

email: [email protected]

Since ancient times, a wide variety of natural organic materials have been used as adhesives, sealants, painting and coating materials. Proteins, oils, gums, natural resins and resinous materials played a prominent role, since their intrinsic properties meant that they could be used not only as painting materials, adhesives, hydro-repellents, coating and sealing agents, but also as flavours, incense, ingredients for cosmetics, medicines and mummification balms. Looking at paintings, modern paint media used by artists in the 20th century have expanded far beyond the traditional binders, by the introduction of industrially processed drying and semidrying oils, of synthetic materials and newly processed traditional natural binders. The range of phenomena and compositional features able to influence ageing processes and degradations is thus more complex than traditional binders.

The chemical characterization of such organic materials when properly integrated with related information from historical sources and archaeological data, has in the last few years considerably improved our knowledge of painting techniques, the crafts and technologies of the past, and has provided art historians and archaeologists with vital information. In fact, identifying specific materials from molecular patterns can assist in assessing the role that these substances played and in determining the use of artefacts on which these residues survive.

The study of organic materials in art and archaeology is a challenge due to the complexity of the chemical composition of the original materials, to changes in the chemical composition as a consequence of human activities and to

mailto:[email protected]

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ChemCH 2014, Vienna / Austria Oral Presentations

ageing under the influence of different environmental circumstances. Further transformations may also occur after the discovery caused by improper storage or by the museum environment itself.

This lecture will review the most significant results obtained worldwide by the application of analytical procedures mainly based on mass spectrometric techniques, to paintings and archaeological objects and will focus on the update chemical description of oily paint binders and their behavior under ageing by using analytical procedures based on Py-GC/MS, DE-MS, GC/MS and HPLC-ESI-Q-TOF. Specifically, it will be shown the development of an integrated methodology for the diagnosis of degradation phenomena in art and archeology, for an in depth, reliable understanding of typical conservation issues.

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ALMA: From Materials to the Painting Technique Investigation

D. Hradil 1,2,*, J. Hradilov 2

1 Institute of Inorganic Chemistry of the AS CR, v.v.i., ALMA laboratory, Husinec-e 1001, 250 68 e, Czech Republic

2 Academy of Fine Arts in Prague, ALMA laboratory, U Akademie 4, 170 22 Prague 7, Czech Republic

*email: [email protected]

ALMA (Academic Materials Research Laboratory of Painted Artworks) has been established in 2004 as a joint workplace of the Institute of Inorganic Chemistry, Czech Academy of Sciences, and the Academy of Fine Arts in Prague with the aim to share infrastructures, combine the material sciences, art conservation and the history of art, and thus deepen the knowledge of painting materials and techniques. In a close interaction with practical restoration/conservation ALMA focuses the methodological research (i.e. testing of novel methodological approaches to the analysis of painting materials) and, on the other hand, integrates the interdisciplinary knowledge for to better evaluate paintings with respect to their origin, age, and authenticity.

As a part of methodological research, laboratory powder X-ray micro-diffraction (micro-XRD) has been adopted as a very effective non-destructive technique for direct phase analysis of samples smaller than 1mm containing crystal constituents and applied in fields of fine arts and forensic science. We evaluated basic limits of micro-XRD, such as the size of irradiated area, the appropriate grain size and detection limits allowing identification of given phases, particularly pigments. The main benefit of micro-XRD can be seen in the field of mineralogical analysis, e.g. in differentiation of structural varieties of clay minerals in earthy pigments, detection on unstable crystalline products of salt corrosion etc.

Detailed mineralogical analysis leads to finding of specific characteristics, which are, in the second step, intentionally used as technological or provenance

mailto:[email protected], [email protected]

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fingerprints. In ALMA they are included to more profound and interdisciplinary research of art objects. In last decades, for example, the microanalysis of clays resulted in classification of ground layers of paintings to well defined types. Within comparative research on paintings of 17th to 18th century from the Czech collections we were able to distinguish those of Italian and Central-European provenance, respectively.

The issue truly crucial when combining scientific and art-historic views is the problem of specificity. Is the finding relevant for the attribution of a painting to certain period, or certain region, workshop, or even author? Comparative studies are, therefore, much needed. The two-layer ground with bottom grey-brown layer intentionally coloured with ash, carbon black and earths is not a local peculiarity of certain Gothic workshops (e.g. the workshop of Magister Theodoricus at the imperial court of the Charles IV. in Prague) as originally suggested, but represents much earlier West-European technological tradition originating already in polychrome Romanesque art as confirmed by comparative research, which, unfortunately, takes quite a long time and needs systematic archiving of samples and of relevant analytical data as well.

Within the overview lecture we will present selected findings of the methodological research, interdisciplinary case studies and background experimental research carried out in ALMA laboratory. The laboratory experiments include namely the processes of chemical degradation of pigments (e.g. lead and copper-based) leading to the colour change, studied extensively in last years.

References:

Hradil D., Hradilov J., Ko E., varcov S., Makov-Kubkov J.: Painting technique and

causes of damage of unique Pre-Romanesque murals in Kostoany pod Trbeom, Slovakia.

Archaeometry 55/4 (2013), 691-706.

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Koaov V., Hradil D., Nmec I., Bezdika P., Kanick V.: Microanalysis of clay-based pigments

in painted artworks by the means of Raman spectroscopy. Journal of Raman Spectroscopy 44

(2013), 1570-1577.

Serendan C., Hradil D., Hradilov J., Cannataci J.: Early Renaissance altarpieces in Transylvania:

materials and technological characteristics. In.: D. Saunders, M. Spring, A. Meek (Eds.): The

Renaissance Workshop, Archetype Publications Ltd., London, 2013, 60-71 (ISBN: 978-1-904982-

93-7).

Hradilov J., Hradil D. Foga I, Zmydlen M.: Newly found Romanesque Madonna of Sedes

sapientiae type coming from a Czech private collection with elements of West European fine

arts tradition. Acta Artis Academica 2012 Proceedings of the 4th interdisciplinary conference of

ALMA, Prague, 2012, 105-126 (ISBN: 978-80-87108-33-8).

varcov S., Bezdika P., Hradil D., Hradilov J., iak I.: Clay pigment structure characterisation

as a guide for provenance determination a comparison between laboratory powder micro-XRD

and synchrotron radiation XRD. Analytical and Bioanalytical Chemistry 399 (2011), 331-336.

varcov S., Ko E., Bezdika P., Hradil D., Hradilov J.: Evaluation of laboratory powder X-ray

micro-diffraction for applications in the field of cultural heritage and forensic science. Analytical

and Bioanalytical Chemistry 398 (2010), 1061 1076.

Hradil D., Hradilov J., Bezdika P. (2010): New criteria for classification of and differentiation

between clay and iron oxide pigments of various origins. Acta Artis Academica 2010 Proceedings

of the 3rd interdisciplinary conference of ALMA, Prague, 107-136 (ISBN: 978-80-87108-14-7).

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The Combination of FTIR and X-Ray Micro-Spectroscopy for the Analysis of Thin Sections of Artistic Materials at the ID21 Beamline, European Synchrotron Radiation Facility

E. Pouyet 1,*, M. Cotte 1,2, B. Fayard 3, A. Lluveras-Tenorio 4, F. Meirer 5, A. Nevin 6, D. Saviello 7, Ph. Sciau 8, M. Salom 1

1 European Synchrotron Radiation Facility, 6, rue Jules Horowitz, 38000 Grenoble, France 2 LAMS (Laboratoire dArchologie Molculaire et Structurale) UMR-8220, 3 rue Galile,

94200 Ivry-sur-Seine, France 3 Laboratoire de Physique des Solides, UMR 8502 Universit Paris Sud, 91405 Orsay cedex,

France 4 Dipartimento di Chimica e Chimica Industriale, Via Risorgimento 35, 56100, Pisa, Italy5 Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht

University, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands 6 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 7 Politecnico di Milano Dipartimento di Chimica Materiali e Ingegneria Chimica, Piazza

Leonardo da Vinci, 26, 20133 Milano, Italy 8 CEMES, CNRS, Universit de Toulouse, 29 rue J. Marvig, 31055 Toulouse, France


The chemical characterization of artistic materials, in particular paintings is complicated by their complex, layered, and heterogeneous structure. Chemical-imaging techniques, combining microscopy and spectroscopy, are well-suited to obtain full 2D analysis of paint fragments. Both the composition and the spatial organization of the multilayered complex mixtures constitutive of paintings are probed.

Over the last decades, synchrotron radiation (SR)-based analysis of paintings has been used to an increasing extent. With a highly bright and collimated source, they offer high spatial resolution combined with very low detection limits. Furthermore, the energy tunability of the SR source allows spectroscopy in the entire electromagnetic spectrum.


40


At the European Synchrotron Radiation Facility (ESRF), Grenoble, France, the beamline ID21 is primarily designed for scanning X-ray microscopy, and also hosts a Fourier Transform Infrared (FTIR) end-station. The X-ray microscope is devoted to micro X-ray fluorescence and micro X-ray Absorption Near-Edge Spectroscopy (XANES) in the tender X-ray domain (2 - 9 keV). Therefore, it is perfectly suited to reveal the chemical state of pigments with a very high lateral resolution (~ 0.3 0.7 m2) and detection limits at the ppm level. Additionally, the FTIR spectro-microscope gives essential molecular information, in particular regarding the organic binders and polyoxoanion pigments (chemical characterization, 2D mapping).

Whereas the combined access on a multi-modal and non invasive platform to both X-ray and FTIR micro spectroscopies has become a main asset in the characterization of paint samples, user communities push for an improved and easier combination of these spectroscopic techniques [1]. In this context, the full exploitation of both -FTIR and -X-ray techniques through transmission measurements can open new ways to hyper-spectral characterization of paint samples from works of art.

The development of new micro-spectroscopy tools for improving and diversifying the capabilities of analysis at ID21 will be discussed. These include the new XANES full-field imaging end-station which will be illustrated using the analysis of roman ceramics performed to study the firing technology used in the manufacturing process [2]. Compared with scanning techniques the full-field set-up allows reducing the acquisition time, limiting possible effects of radiation damage and improving statistical data significance.

In addition to these technical developments, several efforts are made in the improvement of sample preparation for micro analyses in transmission mode. While the instrumentation and the data treatment have been greatly improved, the collection and the preparation of the samples remains a critical step [3]. The most standard sample preparation approaches will be discussed and the

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related possible analytical and chemical interferences will be illustrated using two examples: i) Asiatic historical leanly bound gilded sculpture fragments, and ii) samples from design objects made of polymeric materials from the 1960s. The first set of samples shows complex multi-step gilding techniques based on the use of saponified oil as a mordant. The polymer samples present a degraded surface due to photo-oxidation processes, which could be reproduced artificially on model polymers. These results on materials distribution and ageing could not have been obtained without the development of the newly developed specific sample preparation presented here. Future trends and applications will be discussed.

References:

[1] M. Cotte et al., Journal of Analytical Atomic Spectrometry, 23 (2008), p. 820-828.

[2] F. Meirer et al., (2013), Journal of Analytical Atomic Spectrometry 28, p.1870 - 1883.

[3] E. Pouyet et al., Analytica Chimica Acta, (2014), submitted.

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Modelling of Indoor Particulate Matter Deposition and of Its Degradative Effects

J. Grau-Bov 1,*, L. Mazzei 2, B. Budi 3, D. Thickett 4, M. Strli 1

1 Centre for Sustainable Heritage, The Bartlett School of Graduate Studies, University College London, London, UK

2 Department of Chemical Engineering, UCL, London, UK3 Kemijski Intitut, Ljubljana, Slovenia4 English Heritage, London, UK

* email: [email protected]

In this work we demonstrate how the effects of particulate matter (PM) on paper can be predicted in specific heritage buildings. We achieve this by combining a mathematical model of air movement and particulate matter deposition with experimentally determined damage functions that relate deposition rates with paper degradation. Our research aims to understand the effects of PM on paper, which are currently largely unknown [1], and to offer heritage managers a tool which produces useful predictions that can enable risk assessment. Paper is used as a case study material to allow us to estimate the effect of PM on organic materials more generally.

In order to investigate the chemical effects of PM on paper we exposed model paper samples to the environment in different locations in central London, outdoors (in sheltered conditions) and indoors, for a period of 6 months (20/2/2013 to 20/7/2013), during which PM deposition was monitored. We exposed 5 sample sets in 5 different locations. Four of these were in Apsley House, located near a busy roundabout in Hyde Park Corner, while one was in the Wellcome Collection building, in Euston Road, one of the most polluted roads in London.

In order to isolate the effects of particulate matter and gaseous pollutants, we covered part of the samples using a permeable polymer membrane. This membrane protected the sample from particulate matter and light, but allowed


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gases to penetrate. We used an UV Logger (Hanwell) to ensure that it blocked 99.1 % 0.2 % of the incident UV light, and we used diffusion tubes to ascertain that the membrane allowed 77% of the O3 and 94% of the NO2 present in the environment to reach paper samples. On the other hand, SEM analysis of the protected paper samples did not reveal the presence of a measurable amount of particulate matter larger than 0.1 m.

With the purpose of accelerating the effects of the deposited particles on the paper substrate, we additionally degraded the samples for 2 and 3 weeks at 80C and 65% RH. We then used viscometry to measure the change in the degree of polymerisation, which is proportional to the decrease in the average molecular weight of cellulose. We also measured colour change and analysed elemental composition of the deposited particles using inductively coupled plasma mass spectrometry (ICP-MS). The experimental results relate PM deposition rates and elemental composition with colour change of paper and acceleration of paper degradation due to particulate matter.

We monitored particulate matter deposition by counting the particles deposited every month with an SEM microscope. Our method can count particles with diameters above 0.1 m, and based on this data, deposition rates were calculated, using the time of exposure and the dimensions of the analysed area. In two of the locations (outdoors and indoors in Apsley house), we also monitored the concentration of suspended particulate matter in different size modes (0.5-1 m, 1-2.5 m, 2.5-5 m and 5-20 m) every minute using several laser particle counters.

We simulate indoor air using a Computational Fluid Dynamics (CFD) model that we have developed and tested in the laboratory as well as in indoor heritage spaces [2]. This model requires several inputs, the most important of which are the geometry of the building, the velocities and temperatures of the ventilation and heating systems, and the outdoors PM concentration. It delivers predictions of the deposition flux of particulates between 0.1 and 10 m in every surface of

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the indoor environment, with a resolution between 10 cm for small spaces and approximately 1 m for large buildings. We use this data in conjunction with the damage functions to predict in which areas PM is more likely to cause damage to paper.

In this work we demonstrate the utility of this approach using several case studies. Our results allow the identification of suitable spaces for display or storage as well as allowing the choice of representative locations for particle sampling and monitoring. The predictions also allow to fine-tune cleaning schedules. The model can be used as a powerful exploratory tool to identify which are the main causes of deposition and to test alternative scenarios.

The model can be easily extended to larger geometries and to include any new damage functions that relate PM deposition rates with the chemical degradation of other materials.

References:

[1] J. Grau-Bov, M. Strlic, Fine particulate matter in indoor cultural heritage: a literature review,

Heritage Science, 2013, 1:8.

[2] J. Grau-Bov, L. Mazzei, M. Strlic, Implementation and validation of the drift-flux model for

particle deposition using environmental aerosols in a test tunnel, Submitted to: Journal of

Aerosol Science, 2014.

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Direct On-Target MALDI-TOF MS Analysis: A Fast Protocol for Lipid/Peptide Identification in Paint Samples

C. D. Calvano 1, I. D. Van Der Werf 1, F. Palmisano 1,2, L. Sabbatini 1,3,*

1 Department of Chemistry, University of Bari Aldo Moro, via Orabona 4, 70126 Bari, Italy2 Interdepartmental Center SMART3 Interdepartmental Center Laboratorio di ricerca per la diagnostica dei Beni Culturali,

University of Bari Aldo Moro, via Orabona 4, 70126 Bari, Italy


Since about a decade mass spectrometric (MS) techniques that make use of soft ionization sources like Matrix Assisted Laser Desorption Ionization (MALDI) and Electrospray Ionization (ESI) have been more and more applied for investigation of organic binders in paint samples. In general, these techniques are addressed to proteomics studies and, in fact, in the field of cultural heritage they are mostly employed for protein determination. The first studies report on investigation of paintings, whereas more recent ones mainly deal with archaeological findings.

For protein identification two techniques are commonly applied: Peptide Mass Fingerprinting (PMF) and tandem mass spectrometry (MS/MS). PMF is usually performed with MALDI - Time of Flight (TOF) - MS[1-5], whereas MS/MS analysis of peptide mixtures can be carried out either using MALDI(MALDI-MS/MS) [6-8] or High Performance Liquid Chromatography (HPLC) (LCMS/MS)[9-13].

Most frequently, proteins are extracted from paint samples making use of appropriate alkaline or acidic media and are then submitted to processes such as denaturation/reduction/alkylation and finally enzymatic (usually tryptic) digestion. Otherwise, digestion is directly performed on the paint fragments followed by MALDI-TOF-MS for PMF [1,2]. Recently, the latter method has been applied for peptide analysis on cross sections; if used in combination with suitable staining techniques, localization of proteins in multilayered structures can be achieved [14,15].


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Although MALDI-TOF-MS has been widely used in the field of cultural heritage for protein analysis, its use for lipid binders characterization is more limited. For instance, some papers report on the use of MALDI for studying the effects of processing (heating, etc.) and different pigments on the oxidative ageing of drying oil[16,17],egg-based paint specimens [18] and laser cleaned samples[19], or for the determination ofcholesterol oxidation products[20].

In previous studies, the authors proposed a combined protocol for MALDI-TOF-MS analysis of both lipids - in particular degradation products of triacylglycerols (TAGs) and phospholipids (PLs) - and proteins as contained in paint binders [21-23].

The purpose of the current study is to propose an innovative fast protocol applied directlyon solid paint samples without recurring to any preliminary extraction of the analytes. To this aim, paint fragments were sticked and processed directly on target both for peptide and lipid MALDI TOF MS analysis.

Paint specimens composed of egg yolk and different pigments were prepared and naturally aged for eighteen months. Moreover, small samples from historical paintings were analyzed in order to verify the potential of the analytical approach.

Different materials were tested for fixing the paint fragment on the spot of the target plate. In fact, these materials should not only assure the adhesion of the sample, but also enhance charge conduction. Once fixed on the target plate, lipid analysis was carried out just applying the matrix solution on the top, while protein identification was accomplished on in situ tryptic digests. Also, analysis of lipids and proteins was also performed in sequence on the same sample fragment.

Good quality mass spectra of lipids and peptides were obtained for both standard and historical paint samples.

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The main point of strength of this approach is that it would allow to easily manage paint fragments, usually very small (< 100 mg) without sample processing thus avoiding the risk of material loss or contamination. Moreover, direct on-target MALDI analysis is non-destructive since samples may be reused for other purposes such as examination with other analytical techniques.

Acknowledgement:

This work was performed in the framework of the PRIN 2010-11 funded by the Italian Ministry of

Education, University and Research (Project No. 2010329WPF_001).

References:

[1] R. Hynek, et al., Rapid Commun. Mass Spectrom.18(2004) 18961900.

[2] S. Kuckova, et al., Anal.Bioanal. Chem. 382 (2005) 275282.

[3] W. Fremout, et al., Rapid Commun. Mass Spectrom. 25(2011) 16311640.

[4] D.P. Kirby, et al., Analyst 138 (2013) 4849-4858.

[5] M. Buckley, N.D. Melton, J.Montgomery,RapidCommun. Mass Spectrom. 27 (2013) 531538.

[6] M. Buckley, et al., J. Archaeol. Sci. 37 (2010) 1320.

[7] T.Tripkovi, et al., Talanta 113 (2013) 4961.

[8] C. Hong, et al., PloS one 7 (2012) e37053.

[9] C. Tokarski, et al., Anal. Chem. 78 (2006) 14941502.

[10] A. Chambery, et al., Anal. Bioanal.Chem. 395 (2009) 22812291.

[11] G. Leo, et al., Anal. Chem. 83 (2011) 20562064.

[12] W.Fremout, et al., AnalyticaChim. Acta 728 (2012) 39 48.

[13] S. Dallongeville, et al., Anal.Bioanal. Chem. 399 (2011) 30533063.

[14] S.Kuckova,et al., J. Cul. Herit. 14 (2013) 31-37.

[15] S. Kuckova, et al., Microchem.J. 110 (2013) 538-544.

[16] J.D.J Van den Berg, N.D. Vermist, J.J. Boon, Adv.MassSpectrom.15 (2001) 823-824.

[17] J.D.J. Van den Berg, et al., J. Sep. Sci. 27 (2004) 181-199.

[18] O.F. Van den Brink, et al., J. Mass Spectrom.36 (2001) 479-492.

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[19] M. Castillejo, et al., J. Cul.Herit. 4 (2003) 257s263s.

[20] O. Van den Brink, et al., Int. J. Mass Spectrom. 284 (2009) 1221

[21] C.D. Calvano, et al., Anal.Bioanal. Chem. 400(2011) 2229-2240.

[22] I.D. van der Werf, et al., AnalyticaChim. Acta 718 (2012) 1-10.

[23] I.D. van der Werf, et al., Microchem. J. 106 (2013) 87-94.

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Surface Enhanced Raman Spectroscopy: A Robust New Technique for the Identification of Organic Colorants in Textiles and Paints

F. Casadio 1,*, F. Pozzi 1, L. Chang 1, R. P. Van Duyne 2, N. C. Shah 2

1 The Art Institute of Chicago, 111 S. Michigan Ave., Chicago, Il 60603-61102, USA2 Department of Chemistry, Northwestern University, 2145 Sheridan Road Evanston, Illinois

60208-3113, USA


In the past few years Surface Enhanced Raman Spectroscopy (SERS) has emerged as a powerful technique for the minimally invasive, ultra-high sensitive detection of both natural and synthetic organic colorants in severely mass-limited samples embedded in complex matrices. The ability to successfully identify dyes in works of art from samples as small as a few grains (i.e. a few mg) of pigmented material or 25 m of fiber has opened the path for systematic studies of colorants using SERS across entire collections of objects, thus significantly impacting our understanding of artists practices, artists intention, and alerting conservators to the sensitivity to light of specific artworks.

This talk will present an overview of the efforts of an interdisciplinary group of scientists at Northwestern University and the Art Institute of Chicago to develop tailored nanostructured substrates, experimental protocols, and most recently, theoretical approaches for dye identification, with a special focus on artistic production of the late 19th and early 20th centuries. This particular time period poses interesting challenges as it corresponds with an exuberant introduction on the market of the first synthetic dyes and pigments, to enhance the traditional palette of natural organic dyes derived from plant and insect sources, thereby exponentially increasing the types of materials available to artists.

The case studies discussed in this paper will include a survey of natural and synthetic colorants found in 19th century Navajo blankets from the Art Institute


50


of Chicago (AIC) collection, which, combined with a comprehensive technical study of the physical attributes of the Chicago weavings, allowed to reassess the interpretation and dating of some of these pieces. Furthermore, several examples from the study of the AIC collection of 19th century French Impressionist and Post-Impressionist paintings and works on paper, one of the largest and most prestigious in the world, will also be discussed. SERS analytical protocols that are substrate independent have allowed to expand on the current knowledge of the materials of the Impressionists, especially on the less studied red organic lakes - widely employed for their vibrant intensity and color saturation. For the first time, the identification of two different dyes in a single oil paint layer with SERS will be presented, as well as insights on how the information uncovered by SERS can assist in the digital color reconstruction of works that have experienced color changes due to the fading of red lake components.

References:

[1] Francesca Casadio, Marco Leona John R. Lombardi and Richard P. Van Duyne, Identification

of Organic Colorants in Fibers, Paints and Glazes by Surface Enhanced Raman Spectroscopy

Accounts of Chemical Research, 43, 6 (2010)782-791.

[2] Nathan G. Greeneltch, Amber S. Davis, Nicholas A. Valley, Francesca Casadio, George C.

Schatz, Richard P. Van Duyne, and Nilam C. Shah Near-Infrared Surface-Enhanced Raman

Spectroscopy (NIR-SERS) for the Identification of Eosin Y: Theoretical Calculations and

Evaluation of Two Different Nanoplasmonic Substrates The Journal of Physical Chemistry

A 2012;116(48):11863-11869.

[3] Christa L. Brosseau, Francesca Casadio, and Richard P. Van Duyne Revealing the Invisible

Using Surface-Enhanced Raman Spectroscopy to Identify Minute Remnants of Color in

Winslow Homers Colorless Skies J. Raman Spectrosc. 42, 6 (2011) 1305-1310.

[4] Kristin L. Wustholz, Christa L. Brosseau, , F. Casadio, Richard P. Van Duyne, Surface-

Enhanced Raman Spectroscopy of Dyes: from Single Molecules to the Artists Canvas,

Physical Chemistry Chemical Physics, Physical Chemistry Chemical Physics 11, 34 (2009)

7350-7359.

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MeV SIMS Versus Py-GC/MS: Analysis of Modern Paint Materials

D. Jembrih-Simbrger 1,*, I. Bogdanovic-Radovic 2, M. Anghelone 1,3, N. Markovic 2, Z. Siketic 2, M. Schreiner 1,3, T. Tadic 2

1 Institute of Science and Technology in Art, Academy of Fine Arts Vienna, Schillerplatz 3, 1010 Vienna, Austria

2 Laboratory for Ion Beam Interactions, Rudjer Boskovic Institute, Bijenicka 54, 10000 Zagreb, Croatia

3 Institute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/161, 1060 Vienna, Austria


MeV Secondary Ion Mass Spectrometry (MeV SIMS) was first developed in 1970 s as Plasma desorption Mass Spectrometry (PDMS) using fission fragments from a radioactive source. Due to development of a large number of promising techniques as MALDI, ESI etc., PDMS studies decreased continuously. Nowadays MeV SIMS with soft MeV Cu4+ and ToF detection is successfully applied for analysis of intact bio-molecules of 45,000 Da.

Within the scope of the project [1] MeV SIMS application in the field of cultural heritage is systematically tested. During this 2 year project,results of MeV SIMS measurements will be compared with those of (keV) ToF-SIMS, Py-GC/MS, FTIR-ATR, and -Raman spectroscopy with emphasis on modern paint materials and their ageing properties under outdoor conditions.

The main benefits of the MeV SIMS method are:

i. Desorption of larger intact organic molecules from the sample surface due to the electronic sputtering effect leads to molecular ion yields three orders of magnitude higher compared to keV SIMS. Thus molecular imaging in submicron scale can be easily performed.


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ii. Due to the less fragmentation of organic molecules, MeV SIMS spectra are simpler for interpretation in comparison to other MS techniques. Furthermore both, synthetic organic pigments as well as binders in paint materials can be detected simultaneously.

iii. Direct analysis of the sample surface without sample preparation which is usually necessary for a number of other mass spectrometric analytical techniques.

iv. Due to the facts that MeV SIMS is highly surface sensitive method and material degradation causes often changes in the uppermost surface layers the degradation products can be localised. Different Gas Chromatography (GC) or Liquid Chromatography (LC) methods coupled with MS-detection allow only average information about degradation products without any depth information e.g. in paint layers. Apart of them these methods require a certain amount of sample material which would not be enough if taken only of outermost layers of the sample.

v. As -beam is available, MeV SIMS measurements can be combined with PIXE and RBS, techniques already widely used in analysis of art works.

In the work presented here the results of systematic study using MeV SIMS with MeV primary ion beam and Py-GC/MS carried out on self-prepared mock-ups will be discussed. These samples consist of paint layers containing acrylic or alkyd binders mixed with synthetic organic pigments (SOPs) PB15:1, PB 15:3, PB15:6, PB16, PG7, PG36, PY3, and PY74 without any further additives. Those mock-ups were prepared in order to get most simple paint samples for the first systematic MeV SIMS measurements in order to get reference spectra. Those spectra could be used later on for identification of paint materials. For comparison, mock-ups made with commercial tube paints containing acrylics and alkyd binders with pigments mentioned above were processed in parallel. The focus of the first step in this research lies in the identification of different SOPs with very small differences in their chemical structures (e.g. blue and green phthalocyanine and yellow azo pigments in different shades) in paint layers as well as in the identification of different synthetic binders. Furthermore, fragmentation patterns

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of binding media (acrylic and alkyd) will be compared and discussed due to their MeV SIMS and Py-GC/MS mass spectra.

Acknowledgement:

This study is part of the project Study of modern paint materials and their stability using MeV

SIMS and other analytical techniques, supported by UKF, Ministry of Science, Education and

Sports, Croatia.

54


Oriental Lacquers Hardening Process Characterization by FTIR Microspectroscopy and Py-GC/MS

J. C. Frade 1,*, J. C. Rodrigues 2, A. J. Candeias 3,4

1 CITAR - Centro de Investigao em Cincia e Tecnologia das Artes | Escola das Artes, Universidade Catlica Portuguesa, Rua Diogo Botelho 1327, 4169-005 Porto, Portugal

2 Tropical Research Institute of Portugal, Forestry and Forest Products Group, Tapada da Ajuda, 1349-017 Lisboa, Portugal

3 Laboratrio HERCULES, Universidade de vora, Palcio do Vimioso, Largo Marqus de Marialva 8, 7000-809 vora, Portugal

4 Laboratrio Jos de Figueiredo, Direco-Geral do Patrimnio Cultural, Rua das Janelas Verdes 37, 1249-018 Lisboa, Portugal


Oriental lacquers are coating materials that are applied in furniture and decorative objects since centuries ago, in different regions of Asia. When the first lacquered objects came to Europe in the 16th century they were considered as exotic decorative pieces, and became highly appreciated by the Europeans due to their unique lustrous and elegant finishing. Soon an active trade was established between Asia and Europe, with the intense participation of the Portuguese, who gave an important contribution for the dissemination of lacquerware and influenced the artistic styles produced in many regions of Asia. The most well-known example is that of Namban style where Japanese techniques and materials are brought together with European decorative influences.

Lacquers are produced by three species of trees in different regions of Asia, and are collected in a similar way as latex from rubber trees. Liquid lacquer hardens by an enzyme catalysed oxidation mechanism, in which the polymerization of catechol derivatives takes place leading to the formation of lacquer films. An aerobic oxidation mechanism also occurs during lacquer films formation, competing with that of enzyme catalysed oxidation.


55


In this work, the characterisation of the curing process of Asian lacquers is presented. Films of lacquer were prepared and their hardening process was monitored in diverse moments of lacquer curing by Fourier transform infrared microspectroscopy (micro-FTIR) and by pyrolysis - gas chromatography / mass spectrometry (Py-GC/MS) . IR absorption bands in liquid lacquer and lacquer films were assigned, and pyrolysis products of lacquer films were identified.

IR spectra differ in some modifications of the absorption bands which resulted by means of their comparison in a better knowledge of the mechanisms involved in Asian lacquers polymerization. The two oxidation mechanisms proposed in literature were confirmed by the alterations observed in IR spectra, and it was possible to understand the dynamics of these two competing mechanisms. The enzyme catalysed oxidation mechanism is very fast and occurs mainly in the beginning of lacquer films formation, and with time the aerobic mechanism becomes predominant. Py-GC/MS analyses complete these observations and allowed to verify that C-C bond formation between phenyl groups and the lateral chains of lacquer catechols is preferential in the initial steps of lacquers polymerization.

References:

Honda T, Lu R, Sakai R, Ishimura T, Miyakoshi T (2008) Progress in Organic Coatings 61:68-75.

Impey O, Jrg C (2005) Japanese Export Lacquer 1580-1850. Hotei Publishing, Amsterdam.

Kumanotani J (1995) Progress in Organic Coatings 26:163-195.

Kumanotani J (1998) Progress in Organic Coatings 34:135-146.

Niimura N, Miyakoshi T, Onodera J, Higuchi T (1996) J Anal Appl Pyrol 37:199-209.

Niimura N, Miyakoshi T, Onodera J, Higuchi T (1996) Rapid Commun Mass Sp 10:1719-1724.

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Discriminating Bone, Antlers, Ivories, Horn and Tortoiseshell Using Quantitative FTIR

G. Turner-Walker *, B.-Y. Xu

Graduate School of Cultural Heritage Conservation National Yunlin University of Science &

Technology, Douliou, Taiwan


The foundation of all care and conservation of mu-seum collections rests on correct identification of the items being curat-ed. Correct identification is important not solely so that the objects and specimens in a museum collection can be prop-erly registered and docu-mented, but also so that appropriate security, en-vironment, conservation and pest management

regimes may be specified for their storage, display or loan. Both cultural history museums and museums of natural history may hold collections containing an-imal hard tissues. Hard tissues may be characterised as those body parts that are resistant to the autolysis, putrefaction and microbial degradation commonly taking place within days or weeks of the death of an animal. Typically, the hard tis-sues are composed of structural proteins (or carbohydrates in the case of insects and arthropods) rather than functional proteins and have both a high density and low water content, even during life. The animal hard tissues fall into two broad groups: the mineralised tissues such as bone, antler, dentine, enamel and shell

Figure 1: Plot of amide:phosphate ratio versus infra-red splitting

factor for various ivories. This is principally a measure of the relative

proportions of collagen and mineral, and the degree of crystallinity in

the bioapatite


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which each have different proportions of mineral to protein; and the un-miner-alised tissues such as horn, tortoiseshell and baleen.

The identification of an-imal hard tissues in mu-seum collections is com-monly achieved visually from gross morphology or using low power mi-croscopy to recognise key characteristic features of porosity, microstructure or texture, together with an appreciation of a spec-imens hardness, density and colour. This approach is not without its limita-tions. In carved cultural artefacts and fragmentary

specimens, part or all, of the telltale morphology may have been removed or con-founded by working. Furthermore, in the case of elephant ivory the characteristic Schreger pattern may only be readily seen in cross sections. The recent rapid economic development of China has provided an additional pressure on certain endangered species do to an unprecedented rise in demand for exotic animal parts as wealthy Chinese seek to acquire elephant ivory, rhinoceros horn and ti-ger parts for prestige artworks or for medical purposes. Thus there is a pressing need for rapid and accurate identification of animal hard tissues seized by police and customs officials.

Here, a method is described for a rapid throughput and economical analysis of animal hard tissues for museum curatorial and conservation purposes, and for the forensic investigation of illegally trafficked body parts of endangered species.

Figure 2: Plot of amide: (CH2,CH3) ratio versus infra-red splitting

factor for all the keratins. Numbers in open circles indicate raw

(unprocessed) specimens whereas the numbers in black circles

represent those that have undergone some kind of thermal or

chemical treatment

58


The technique employs a simple FTIR spectrometric approach using KBr pellets and is suitable for any well-equipped analytical- or conservation laboratory. A novel approach is the comparison of the intensities of key absorption bands to differentiate between different tissues. The method readily distinguishes bones from antler and between different kinds of ivory. It also shows great promise in differentiating between different kinds of animal horn more especially distinguishing rhino horn form some of its common substitutes, e.g. water buffalo horn that has been boiled to alter its colour and translucency. Although the method currently requires 2 mg of powdered sample it is envisaged that in future the method can be adapted for non-destructive analyses.

References:

Edwards, H.G.M., Farwell, D.W., Holder, J.M. and Lawson, E.E. 1998. Fourier transform-Raman

spectroscopy of ivory: A non-destructive diagnostic technique. Studies in Conservation 43: 9-16.

Edwards, H.G.M. and Farwell, D.W. 1995. Ivory and simulated ivory artefacts: an FT Raman

diagnostic study, Spectrochimica Acta, Part A 51: 2073-2082.

Espinoza, E.O., Baker, B.W., Moores, T.D and Voin, D. 2008. Forensic identification of elephant

and giraffe hair artifacts using HATR FTIR spectroscopy and discriminant analysis. Endangered

Species Research 9(3): 239-246.

Yan, D., Luo, J.Y., Han, Y.M. Peng, C. Dong, X.P., Chen, S.L., Sun, L.G. and Xiao, X.H. 2013.

Forensic DNA barcoding and bio-response studies of animal horn products used in traditional

medicine. PLoS ONE 8(2): e55854. doi:10.1371/journal.pone.0055854.

59


Identification of Microbial Volatile Organic Compounds Emitted by Moulds Infesting Objects Made of Cellulose

T. Sawoszczuk *, J. Sygua Cholewiska

Cracow University of Economics, Faculty of Commodity Science, Department of Microbiology,

Cracow, Poland


A real risk for historical objects is biodeterioration caused by various microorganisms, especially by moulds. Spores of various mould species are a typical form of contamination inside buildings. Moreover it has been proven that moulds are able to grow even when small amount of organic compounds are available, for example on the dust layer that cover historical objects [1]. The growth of moulds on historical objects made of wood, paper and others containing cellulose, causes mechanical destruction of their structure and also chemical degradation, which is a consequence of moulds metabolic activity [2]. Two processes are involved in these phenomena biodeterioration and microbial corrosion. Hence, infestation by moulds is obviously risky for historical objects but it can be also large hazard for health and life of museum visitors and museum staff due to contact with fragments of moulds hyphae, spores, mycotoxins [3] presented in indoor air, and volatile organic compounds emitted by moulds to the ambient air. These are named Microbial Volatile Organic Compounds MVOCs.

Moulds emit MVOCs into the ambient air at each stage of their growth [4]. Hence applying the MVOCs investigation for detection of moulds infestation on historical objects made of cellulose can be a unique tool for rapid warning of microbial biodeterioration of priceless historical objects. Moreover detection of moulds based on MVOCs analysis is faster and more convenient in comparison with standard microbial analysis. One more advantage of MVOCs analysis is possibility of mould detection in hidden spaces (on the backs of objects or inside them) even if they do not produce spores or growth. In this case, the results of classical microbial analysis does not confirm that objects are attacked by


60


moulds. Thus, measurement of MVOCs allow to detect mould infestation.These statements were a base for undertaking the investigations.

The main goal of the measurements has been quantitative and qualitative analysis of MVOCs emitted by moulds that could infest historical objects containing cellulose. The researches were carried out for ten selected strains of moulds that were proofed to produce cellulolytic enzymes. The moulds were inoculated on two kinds of microbial broth (Czapek Dox agar) prepared in hybridization tubes: first - that did not contain source of coal (only microelements, blank sample), second - as the first one but with sterile sample of Whatman paper placed on surface (cellulose was source of coal). After incubation of moulds for seven days at 25oC the samples of MVOCs were gathered. The sampling technique that was used for MVOCs collecting was Solid Phase Microextraction (SPME) [5]. The crucial advantage of this technique was small dimension of sorbent bed mounted at the end of SPME fibre needle. It allow to gather the sample of volatile organic compound directly from over the surface of moulds. MVOCs adsorbed on SPME fibre during 24h period of sampling (at 25C) were analysed in gas chromatography mass - spectrometry system (GC-MS).

The quantitative analysis of chromatograms gained for MVOCs emitted by various moulds inoculated on cellulose based samples gave the evidence that these compounds are emitted with various concentrations but usually it is up to few g/m3. Only some of detected MVOCs are release by moulds in amounts reaching tens of g/m3. This was measured mostly for alcohols and aldehydes.

At the last step the list of so called indicatory MVOCs has been established. They were supposed to be a fingerprint each of investigated cellulolytic moulds. Thus, it would be possible to apply the analysis of indicatory MVOCs for discovering the presence of definite mould strain on historical objects made of cellulose.

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Acknowledgement:

The research was financed by National Science Centre Poland based on decision

DEC 2012/05/B/HS2/04094.

References:

[1] Korpi A., Pasanen A. L., Pasanen P. & Kalliokoski P., Microbial growth and metabolism in

house dust, , International Biodeterioration & Biodegradation, Vol. 40, No. 1 (1997), 19 27.

[2] Wady L., Bunte A., Pehrson Ch., Larsson L., Use of gas chromatography mass spectrometry/

solid phase microextraction for the identification of MVOCs from moldy building materials,

Journal of Microbiological Methods 52 (2003) 325-332.

[3] Nielsen K.-F., Mycotoxin production by indoor molds, Fungal Genetics and Biology 39 (2003)

103 117.

[4] Sunesson A.-L., Nilsson C.-A., Andersson B., Bolmquist G., Volatile metabolites produced

by two fungal species cultivated on building materials, Ann. Occup. Hyg. Vol. 40, No. 4,

397 410.

[5] Pawliszyn, J., 1997. Solid Phase MicroextractionTheory and Practice. Wiley-VCH,

Chichester.

[6] Kuske M., Romain A.-C., Nicolas J., Microbial volatile organic compounds as indicators of

fungi. Can an electronic nose detect fungi in indoor environments?, 40 (2005) 824 831.

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X-Ray Based Imaging and Spectroscopy of Paintings by V. Van Gogh from the dm to the nm Level

K. Janssens 1,*, L. Monico 1,2 C. Miliani 2, G. Van Der Snickt 1, S. Legrand 1, F. Vanmeert 1, M. Alfeld 1,3, B. G. Brunetti 2, M. Cotte 4, G. Falkenberg 3, E. Hendriks 5

1 AXES Research group, Department of Chemistry, University of Antwerp, Belgium2 Centro SMAART, University of Perugia/ISTM, CNR, Perugia, Italy3 X-ray microprobe beamline P06, PETRA-III at DESY, Hamburg, Germany4 X-ray microscopy beamline ID21, ESRF, Grenoble, France5 Conservation Department, Van Gogh Museum, Amsterdam, The Netherlands


The later works of the 19th C. painter Vincent Van Gogh are well known for their vibrant colours and striking contrasts. We have recently examined several of his works in which the pigment chromium yellow is (abundantly) present: it concerns Sunflowers, Sunflowers gone to seed, Bank of the Seine and Portrait of Gauguin. In some cases, this pigment is suspected to slowly turn brown. Next to examination of a few of these paintings by macroscopic X-ray fluorescence scanning (MA-XRF) in order to document the distribution of the pigments at the scale of the entire painting, also mobile equipment for performing different forms of vibrational spectroscopy such as mid-FTIR and Raman analysis were employed to characterize the pigmented materials at a number of pre-selected points. The latter information was collected as part of a MOLAB/CHARISMA intervention. Bench-top FTIR and Raman microscopy as well as synchrotron-radiation based X-ray near edge absorption spectroscopy (XANES), X-ray diffraction (XRD) and XRF mapping of paint samples at the microscopic scale were employed to better understand the above-mentioned degradation phenomenon.

Whereas the MAXRF data suggests that the elemental Pb:Cr ratio in some of the yellow areas is subject to significant variations, both Raman and XRD measurements indicated that next to regular (monoclinic) PbCrO4, other types


63


of chrome yellow having lighter hues, richer in sulfur and poorer in chromium, are present. Artificial ageing experiments conducted on these different types of chrome yellow showed that the S-rich compounds are unstable during UV irradiation. Both in artificially aged model samples as well as in a number of original paint micro samples, a significant reduction of the Cr6+ originally present in the chrome yellow is observed, leading to superficial formation of Cr3+ compounds such as Cr2O3, causing the original bright yellow color to change to olive-brown.

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Portable Biosensors for On-site Detection of Proteins in Artworks by Chemiluminescent Immunochemical Contact Imaging

G. Sciutto 1,*, M. Zangheri 2, M. Guardigli 2, M. Mirasoli 2, S. Prati 1, R. Mazzeo 1, A. Roda 2

1 Microchemistry and Microscopy Art Diagnostic Laboratory, University of Bologna, Via Guaccimanni 42, 48121 Ravenna, Italy

2 Department of Chemistry G. Ciamician, University of Bologna, Via Selmi 2, 40126 Bologna, Italy


The reliable identification of organic substances still represents a challenging issue in analytical studies on Cultural Heritage materials. Immunological methods represent a powerful approach to protein identification, as alternative method to conventional chromatographic- and proteomic-based techniques [1]. Moreover, immunoassays require simple instrumentation and can be performed using portable analytical devices, thus enabling on-site analyses [2]. The present research work was aimed at developing an ultrasensitive device (biosensor) for the on site characterization of proteins in artworks by CL immunochemical contact imaging. By using this device, the immunochemical detection of chicken ovalbumin - a protein found in egg tempera and in egg-based protective varnishes was performed. The assay exploited a simple extraction of the target protein from paint samples followed by a non-competitive immunoassay with chemiluminescent (CL) detection and employing ready-to-use analytical cartridges. In more detail, the target protein was captured by specific primary antibodies immobilized on a glass surface, then revealed by a CCD camera modified for lensless CL imaging (contact imaging) using enzyme-labelled secondary antibodies and a suitable enzyme CL substrate. Such an approach requires simple instrumentation and can be performed using the portable system, enabling analyses accomplished directly where the sample is collected by unskilled personnel (e.g. restorers). Besides laboratory-based analytical methods, on site investigations play a crucial


65


role for a prompt and efficient diagnosis on the artworks materials and state of conservation, addressing urgent restoration issues and allowing the selection of proper conservation strategies during restoration campaigns. Moreover, on site analyses are required for a preliminary screening and documentation of chemical heterogeneity of paintings, providing the identification of areas to be submitted to further analyses (e.g. stratigraphic analyses). In addition, such investigations could be performed without any movement of artworks (when it is possible: e.g., easel paintings) avoiding risks or possible damages related to their transportation. The assay was successfully applied and tested for the detection of ovalbumin in fresh and aged paint samples collected from standard mock-ups.

References:

[1] G. Sciutto, L.S. Dolci, M. Guardigli, M. Zangheri, S. Prati, R. Mazzeo, A. Roda, Anal Bioanal

Chem, 45 (2013) 933-940.

[2] A. Roda, M. Mirasoli,LS Dolci, A. Buragina, F. Bonvicini, P. Simoni, M. Guardigli, Anal Chem

(2011) 83:3178-185.

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XEOM 1 a Novel Microscopy System for the Chemical Imaging of Heritage Metal Surfaces

M. G. Dowsett 1,*, M. Hand 1, P.-J. Sabbe 2, A. Adriaens 2

1 Department

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