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BOOK OF ABSTRACTS 7 th International Congress on the Application of Raman Spectroscopy in Art

BOOK OF

ABSTRACTS

BOOK OF ABSTRACTS 7 th International Congress on the Application of Raman Spectroscopy in Art and
7 th
7
th

International Congress on the Application of Raman Spectroscopy in Art and Archaeology

2-6 September 2013

7 th International Congress on the Application of Raman Spectroscopy in Art and Archaeology

Book

of

A B str A cts

7th International Congress on the Application of Raman Spectroscopy in Art and Archaeology Ljubljana, Slovenia, 2th–6th September 2013

Book of Abstracts 7th International Congress on the Application of Raman Spectroscopy in Art and Archaeology (RAA 2013), Ljubljana (Slovenia), 2th–6th September 2013

Publisher: Institute for the Protection of Cultural Heritage of Slovenia Editors: Polonca Ropret, Nadja Ocepek Editorial Board: Klara Retko, Lea Legan, Tanja Špec, Črtomir Tavzes Print: Birografika BORI d.o.o. Copies: 400

Copyright © RAA 2013 and the Authors All Rights Reserved

Ljubljana 2013

No part of the material protected by this copyright may be reproduced or utilized in any form or by any means, electronic or mechanical, includ- ing photocopying, recording or by any storage or retrieval system, without written permission from the copyright owners.

The publication is published with the financial support of the Ministry of Culture, and is not payable.

REPUBLIC OF S LOVENIA MINISTRY OF CULTURE

CIP - Kataložni zapis o publikaciji Narodna in univerzitetna knjižnica, Ljubljana

543.424.3:7(082)

543.424.3:902(082)

INTERNATIONAL Congress on the Application of Raman Spectroscopy in Art and Archaeology (7 ; 2013 ; Ljubljana) Book of abstracts / 7th International Congress on the Application of Raman Spectroscopy in Art and Archaeology, Ljubljana (Slovenia), 2th-6th September 2013 ; [editors Polonca Ropret, Nadja Ocepek]. - Ljubljana : Institute for the Protection of Cultural Heritage of Slovenia, 2013

ISBN 978-961-6902-38-0

1. Ropret, Polonca, kemik

268489728

The use of Raman spectroscopy for identifying and studying the material component of the objects of art and antiquities has flourished in recent years. The increasing importance of the application of Raman spectroscopy in art and archaeology is illustrated by an increasing number of research papers published each year, and by the scientific conferences and sessions that have been dedicated to this research area in the past decade. The RAA conferences promote Raman spectroscopy and play an important role in the increasing field of its ap- plication in Art and Archaeology. The RAA is an established biennial international event. It brings together studies from diverse areas and represents dedicated work on the use of this technique in connection to the fields of art-history, history, archaeology, palaeontology, conservation and restoration, museology, etc. Furthermore, the development of new instrumentation, especially for non-invasive measurements, has received a great atten- tion in the past years. These prominent, international events have a long tradition. Previously they were held in London (2001), Ghent (2003), Paris (2005), Modena (2007), Bilbao (2009), Parma (2011), and this year (2013) in Ljubljana.

The RAA 2013 conference received over 100 high quality contributions from different research laboratories all over the world, and this book of abstracts presents their latest advancements. One of the important topics is studies of deterioration induced by different environmental factors, such as biodeterioration, pollution, light and humidity exposure. The outcomes of these studies can give important information for designing safe conserva- tion – restoration treatments and help in creating a better environment for cultural heritage objects, for their storage and display, all contributing to increasing of its sustainability. A great number of research contributions are presenting the latest achievements in the characterisation of traditional organic colorants by introducing new solutions for Surface enhanced Raman spectroscopic studies. This is an important topic that contributes to understanding not only the composition of the organic colorants, but also their production processes. The ad- vancements in metals characterisation give important information to understanding of their corrosion processes and/or deliberate patinations by artists, which can give important input in designing further corrosion inhibition processes. A special topic is dedicated to the archaeometry research, from characterisation of ancient artefacts, their degradation processes, to finding possible solutions for their preservation. New, presented knowledge on gemstones characterisation, provenance, authenticity research, and furthermore, forensics applications, all attest of the wide applicability of Raman spectroscopy. The latest innovations in Raman instrumentation is presented by well – known companies in the field of Raman instruments, with a special emphasis in the development of portable, non-invasive instruments. Many research laboratories are taking the advantage of non-invasive instru- ments in order to keep the full integrity of works of art. However, the interpretation of the results is often chal- lenging, which gives scientific contributions dealing with these questions a special, important place. Finally, the importance of a comprehensive Raman database is emphasised, and the latest work of the Infrared and Raman Users Group (IRUG) is presented, a database which we all help creating, and which can help in solving many questions that we all face.

We wish to thank all of the authors who submitted their latest research results and helped creating the scientific program of the RAA 2013 conference, as well as this Book of Abstracts.

On behalf of the organizing committee, Polonca Ropret,

Research Institute, Conservation Centre, Institute for the Protection of Cultural Heritage of Slovenia

Scientific Committee

Dr. Polonca Ropret Research institute, Conservation Centre, Institute for the Protection of Cultural Heritage of Slovenia

Dr. Danilo Bersani Dipartimento di Fisica e Scienze della Terra, Università degli Studi di Parma, Italy

Prof. Dr. Juan Manuel Madariaga Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country, Spain

Prof. Dr. Peter Vandenabeele Research group in Archaeometry, Department of Archaeology, Ghent University, Belgium

Prof. Dr. Howell G. M. Edwards Centre for Astrobiology and Extremophiles Research, School of Life Sciences, University of Bradford, UK

Prof. Dr. Pietro Baraldi Department of Chemical and Geological Sciences, University of Modena and Reggio Emilia, Italy

Dr. Sandrine Pagès-Camagna Centre de Recherche et de Restauration des Musées de France (C2RMF), France

Dr. Francesca Casadio The Art Institute of Chicago, USA

Organizing Committee

Janez Kromar Director of Conservation Centre, Institute for the Protection of Cultural Heritage of Slovenia

Jernej Hudolin Head of Restoration Centre, Conservation Centre, Institute for the Protection of Cultural Heritage of Slovenia

Dr. Polonca Ropret Head of Research Institute Conservation Centre, Institute for the Protection of Cultural Heritage of Slovenia

Dr. Črtomir Tavzes Research Institute, Conservation Centre, Institute for the Protection of Cultural Heritage of Slovenia

Tanja Špec Research Institute, Conservation Centre, Institute for the Protection of Cultural Heritage of Slovenia

Lea Legan Research Institute, Conservation Centre, Institute for the Protection of Cultural Heritage of Slovenia

Klara Retko Research Institute, Conservation Centre, Institute for the Protection of Cultural Heritage of Slovenia

Nadja Ocepek Research Institute, Conservation Centre, Institute for the Protection of Cultural Heritage of Slovenia

List of accepted works with corresponding authors

PL: Plenary Lecture OP: Oral Presentation P: Poster Presentation

Monday, September 2, 2013 ORAL SESSION 1

Deterioration studies and organic materials

Raman Spectroscopy of Extremophilic Biodeterioration: An Interface between Archaeology and the Preservation of Cultural Heritage

Howell G. M. Edwards

PL1

20

Identification of endolithic survival strategies on stone monuments

Annalaura Casanova Municchia

OP1

22

FT-Raman analysis of historical cellulosic fibres infected by fungi

Katja Kavkler

OP2

24

Combined FT-Raman and Fibre-Optic Reflectance Spectroscopic Characterisation of Simulated Medieval Paint Films: a Chemometric Study of the Effects of Natural and UV-Accelerated Ageing

Anuradha Pallipurath

OP3

26

Study of malachite degradation in easel (model) paintings by spectroscopic analysis

Tanja Špec

OP4

27

Portable and laboratory analysis to diagnose the formation of efflorescence on walls and wall paintings of Insula IX, 3 (Pompeii, Italy)

Juan Manuel Madariaga

OP5

29

Decorated plasterwork in the Alhambra investigated by Raman spectroscopy: field and laboratory comparative study

Ayora-Cañada María José

OP6

31

Multi-technical approach for the study of French Decorative Arts furniture and luxury objects

Céline Daher

OP7

33

POSTER SESSION 1

Deterioration of lead based pigments on a fresco: a micro-Raman investigation

Ilaria Costantini

P1

35

Investigation of colour layers in easel (model) paintings influenced by different ageing processes

Klara Retko

P2

36

Identification of copper azelate in 19th century Portuguese oil paintings: Characterisation of metal soaps by Raman Spectroscopy

Raman study of pigment degradation due to acetic acid vapours

Investigating the sources of degradation in corroded lead sculptures from Oratory Museum (Museu do Oratório), Brazil

Evora Cathedral: Pink! Why not?

Study of red biopatina composition on sandstone from a historical war Fort in La Galea (Biscay, north of Spain) by means of single point focusing Raman analysis and Raman Imaging combined with microscopic observation

Raman and non invasive IR analyses of natural organic coatings: application to historical violin varnishes

Characterization of green copper organometallic pigments and understanding of their degradation process in European easel paintings

Optical Microscopy and Micro-Raman studies of The Hans Memling’s Triptych “The Last Judgment”

Non-destructive micro-Raman and XRF investigation on parade saddles of italian renaissance

Phoenicians preferred red pigments: micro-Raman investigation on some cosmetics found in Sicily archaeological sites

Raman microscopy and X-ray fluorescence for the rediscovering of polychromy and gilding on classical statuary in the Galleria degli Uffizi

Raman spectroscopic investigation of black pigments

Raman Spectroscopy and SEM-EDS Studies Revealing Treatment History and Pigments of the Government Palace Tower Clock in Helsinki Empire Senate Square

Feasibility Study of Portable Raman Spectroscopy for Characterization of Ground Material of Easel Paintings (Case Study: Sradar As’ad-e Bakhtiary Painting of Kamal-al Molk)

Vanessa Otero

P3

38

Alessia Coccato

P4

40

Thiago Sevilhano Puglieri

P5

42

Ana Teresa Caldeira

P6

44

Juan Manuel Madariaga

P7

46

Céline Daher

P8

48

Carlotta Santoro

P9

50

Ewa Pięta

P10

51

Pietro Baraldi

P11

52

Cecilia Baraldi

P12

54

Pietro Baraldi

P13

56

Alessia Coccato

P14

58

Kepa Castro

P15

60

Mohsen Ghanooni

P16

62

The Sibyls from the church of San Pedro Telmo: a spectroscopic investigation

Pigment identification of illuminated medieval manuscripts by means of a new, portable Raman equipment

Micro-Raman identification of pigments on wall paintings: characterisation of Langus and Sternen’s palettes

ORAL SESSION 2

RENISHAW: New Methods in Raman Spectroscopy – Combining Other Microscopes for mineral and pigment analysis

HORIBA JOBIN YVON: Advances in Raman instrumentation: explore new boundaries in Art and Archaeology

NORDTEST: A portable 1064 nm Raman spectrometer for analysis of cultural heritage items

BAYSPEC: Novel 1064 nm Dispersive Raman Spectrometer and Raman Microscope for Non-invasive Pigment Analysis

Tuesday, September 3, 2013 ORAL SESSION 3

Surface Enhanced Raman Spectroscopy in Art and Archaeology

Surface-Enhanced Raman Spectroscopy in Art and Archaeology

TLC-SERS of mauve, the first synthetic dye

New photoreduced substrate for SERS analysis of organic colorants

Laser Ablation Surface-enhanced Raman Microspectroscopy

Marta S. Maier

P17

64

Debbie Lauwers

P18

66

Petra Bešlagić

P19

68

Josef Sedlmeier

OP8

70

Romain Bruder

OP9

72

Alessandro Crivelli

OP10

73

Lin Chandler

OP11

75

Marco Leona

PL2

78

Maria Vega Cañamares

OP12

80

Klara Retko

OP13

82

Pablo S. Londero

OP14

84

Silver colloidal pastes for the analysis via Surface Enhanced Raman Scattering of colored historical textile fibers: some morphological and spectroscopic considerations

Ambra Idone

OP15

86

Surface enhanced Raman spectroscopy for dyes and pigments – Can non-invasive investigations become a reality?

Brenda Doherty

OP16

88

Surface Enhanced Raman Scattering of organic dyes on gold substrates prepared by pulsed laser ablation

N. R. Agarwal

OP17

90

Combining SERS with chemometrics: a promising technique to assess historical samples with historically accurate reconstructions

Rita Castro

OP18

92

Characterization and Identification of Asphalts in Works of Art by SERS complemented by GC-MS, FTIR and XRF

María Lorena Roldan

OP19

94

Study of Raman scattering and luminescence properties of orchil dye for its nondestructive identification on artworks

Francesca Rosi

OP20

95

POSTER SESSION 2

Application to historical samples of in situ, extractionless SERS for dye analysis

Ambra Idone

P20

96

Application of surface-enhanced Raman spectroscopy (SERS) to the analysis of red lakes in French Impressionist and Post-Impressionist paintings

Federica Pozzi

P21

98

Surface-Enhanced Raman Spectroscopy (SERS) of historical dyes on textile fibers: evaluation of an extractionless treatment of samples

Chiara Zaffino

P22

100

Suitability of Ag-agar gel for the micro-extraction of organic dyes on different substrates: the case study of wool, silk, printed cotton and panel painting mock-ups

Elena Platania

P23

102

PB15 polymorphic distinction in paint samples by combining micro-Raman spectroscopy and chemometrical analysis

Jolien van Pevenage

P24

104

First identification of the painting technique in 18th Century Transylvanian oil paintings using micro- Raman and SERS

Oana-Mara Gui

P25

106

Organic materials in oil paintings and canvas revealed by SERS

Oana-Mara Gui

P26

108

Characterization of SOPs in acrylic and alkyd paints by means of µ-Raman spectroscopy

Marta Angehelone

P27

110

Synthetic Polymers and Cultural Heritage. Analytical approach by Raman spectroscopy

Margarita San Andrés

P28

112

Raman monitoring of the sol-gel process on OTES/ TEOS hybrid sols for the protection of historical glasses

L.

de Ferri

P29

114

Possible differentiation with Raman spectroscopy between synthetic and natural ultramarine blues. Comparative analysis with the blue pigment of a painting of R. Casas (1866–1932)

A.

R. De Torres

P30

116

Raman monitoring of the polymerization reaction of a hybrid protective for wood and paper

Laura Bergamonti

P31

118

Reference Raman data of the artist palette – tool for in- situ investigation of J. Matejko (1838–1893) paintings

Iwona Żmuda-Trzebiatowska

P32

119

Material analysis of the Manueline Foral Charters of Lousã and Marvão

António Candeias

P33

121

Materials and gilding techniques on plasterwork in the Alhambra (Granada, Spain)

Domínguez Vidal Ana

P34

123

Characterization of gypsum and anhydrite ground layers on 15th and 16th centuries Portuguese painting by Raman Spectroscopy, Micro X-ray diffraction and SEM-EDS

António Candeias

P35

125

Identification of deteriorated pigments on wall paintings from Lutrovska klet, Sevnica, Slovenia, using Raman spectroscopy and SEM-EDS

Katja Kavkler

P36

128

Characterization of middle age mural paintings: in situ Raman spectroscopy associated with different techniques

Julene Aramendia

P37

130

Raman microspectroscopic identification of pigments of newly discovered gothic wall paintings from the Dominican Monastery in Ptuj (Slovenia)

Maja Gutman

P38

132

Shot Noise Reduction through Principal Components Analysis

J. J. González-Vidal

P39

134

ORAL SESSION 4

Raman for characterization of metal artefacts

Raman investigation of artificial patinas on recent bronze, protected by different azole type inhibitors in outdoor environment

Tadeja Kosec

OP21

135

Micro-Raman Investigation on corrosion of Pb-Based Alloy Replicas

Giorgia Ghiara

OP22

136

Conservation diagnosis of weathering steel sculptures using a new Raman quantification imaging approach

Julene Aramendia

OP23

138

Raman study of the salts attack in archaeological metallic objects of the Middle Age: The case of Ereñozar castle (Bizkaia, Spain)

Kepa Castro

OP24

140

Thursday, September 5, 2013 ORAL SESSION 5

Raman Spectroscopy in Archaeometry

The Contribution of Archaeometry to Understanding of the Past Effects and Future Changes in the World Heritage Site of Pompeii (Italy)

Juan Manuel Madariaga

PL3

143

Raman spectroscopy applied to the study of Cretaceous fossils from Araripe Basin, Northeast of Brazil

Paulo T. C. Freire

OP25

145

Raman spectroscopic analyses of~75. 000 year old stone tools from Middle Stone Age deposits in Sibudu Cave, KZN, South Africa

Linda C. Prinsloo

OP26

147

Raman Spectroscopy in Archaeometry: multi-method approaches and in situ investigations: advantages and drawbacks

Peter Vandenabeele

OP27

149

Spectroscopic Analysis of Chinese Porcelain Excavated in Clairefontaine (Belgium): Pigment Identification and Dating

Jolien van Pevenage

OP28

150

Characterization of ancient ceramic using micro- Raman spectroscopy: the cases of Motya (Italy) and Khirbetal-Batrawy (Jordan)

Laura Medeghini

OP29

152

Hispano-Moresque architectural tiles from the Monastery of Santa Clara-a-Velha, in Coimbra, Portugal: a µ-Raman study

Vânia S. F. Muralha

OP30

154

The blue colour of glass and glazes in Swabian contexts (South of Italy): an open question

Maria Cristina Caggiani

OP31

155

Spectroscopic characterisation of crusts interstratified with prehistoric paintings preserved in open-air rock art shelters

Antonio Hernanz

OP32

157

POSTER SESSION 4

Micro-Raman on Roman glass mosaic tesserae

Claudia Invernizzi

P40

159

Raman and IR Spectroscopic Study of Vitreous Artefacts from the Mycenaean to Roman Period: Glassy Matrix & Crystalline Pigments

Doris Möncke

P41

160

The detection of Copper Resinate pigment in works of art: contribution from Raman spectroscopy

Irene Aliatis

P42

162

Micro-Raman and internal micro-stratigraphic analysis of the paintings materials in the rock- hewn church of the Forty Martyrs in Şahinefendi, Cappadocia (Turkey)

Clauda Pelosi

P43

164

Vibrational characterization of the new gemstone Pezzottaite

Erica Lambruschi

P44

166

FTIR-ATR and ESEM of wall paintings from the tomb of Amenemonet (TT277), Qurnet Murai necropolis, Luxor, Egypt

Mohamed Abd El Hady

P45

168

Physico-chemical characteristics of Predynastic pottery objects from Maadi – Egypt

Mohamed Abd El Hady

P46

170

Raman Database of Corrosion Products as a powerful tool in art and archaeology

Serena Campodonico

P47

171

MicroRaman as a powerful non-destructive technique to characterize ethonological objects from D’Albertis Castle Museum of World Cultures in Genova

Serena Campodonico

P48

173

Micro ATR-IR study of pollutions affecting radiocarbon dating of ancient Egyptian mummies

Ludovic Bellot-Gurlet

P49

175

Raman Scanning of Biblical Period Ostraca

Arie Shaus

P50

176

Analyses of pigments from 4th century B.C. the Shushmanets tombs in Bulgaria

Cristina Aibéo

P51

178

Raman Spectroscopic Study of the Formation of Fossil Resins Analogs

Margarita San Andrés

P52

179

Pigments from Templo Pintado (Pachacamac, Perú) investigated by Raman Microscopy

Dalva Lúcia Araújo de Faria

P53

181

Lithic tools raw materials recognition by Raman spectroscopy of Palaeolitihic artifacts

Sonia Murcia-Mascaros

P54

183

Raman characterization on historical mortar. Crossing data with XRD and Color Measurements

Dorotea Fontana

P55

184

Roman ceramics from Vicofertile (Parma, Italy):

Elisa Adorni

P56

185

micro-Raman study of the heat diffusion during the production process

Raman spectroscopic study on ancient glass beads found in Thailand archaeological sites

Pisutti Dararutana

P57

187

Identification of Neolithic jade found in Switzerland studied using Raman spectroscopy: Jadeite – vs. Omphacite – jade

Marie Wörle

P58

188

Raman Spectroscopy as useful tools for the gemmological certification and provenance determination of sapphires

Simona Raneri

P59

190

Authentication of ivory by means of 1064 nm Raman spectroscopy and X-ray fluorescence spectrometry

Alessandro Crivelli

P60

191

ORAL SESSION 6

Characterization of Gems and Forensic Applications

Characterization of emeralds by micro-Raman

Danilo Bersani

OP33

192

spectroscopy Raman micro spectroscopy of inclusions in gemstones from a chalice made in 1732

Miha Jeršek

OP34

194

Spectroscopic investigation: impurities in azurite as provenance markers

Lucia Burgio

OP35

196

Implementation of scientific methods of fine art authentication into forensics procedures: the case study of “Bolko II Świdnicki” by J.J Knechtel

Barbara Łydżba-Kopczyńska

OP36

198

Raman analysis of multilayer automotive paints in forensic science: measurement variability and depth profile

Danny Lambert

OP37

200

Friday, September 6, 2013

ORAL SESSION 7

Non-invasive Raman Investigation

The Art of non-invasive in situ Raman spectroscopy:

Costanza Miliani

PL4

203

identification of chromate pigments on Van Gogh paintings

Characterisation of a new mobile Raman spectrometer for in-situ analysis

Debbie Lauwers

OP38

205

On-site high-resolution Raman spectroscopy on minerals and pigments

Martin A. Ziemann

OP39

207

Molecular characterization and technical study of historic aircraft windows and head gear using portable Raman spectroscopy

Odile Madden

OP40

208

ROUND TABLE – Raman spectral database

The Infrared and Raman Users Group Web-based Raman Spectral Database

Marcello Picollo

PL5

210

Monday, September 2

PL1

Raman Spectroscopy of Extremophilic Biodeterioration: An Interface Between Archaeology and the Preservation of Cultural Heritage

Howell Gwynne M. Edwards 1*

1 Centre for Astrobiology and Extremophiles Research, School of Life Sciences, University of Bradford, West Yorkshire, UK, + 44 1274 233787, h.g.m.edwards@bradford.ac.uk

The identification of biological colonisation in archaeological artefacts and ancient art works represents major problems for the preservation of materials and objects of cultural heritage for conservation scientists and art restorers with the realisation that the deleterious effects of this colonisation can be ongoing even when the artworks have been prepared for storage. The conservation strategies and curation of biodegraded objects from archaeological sites are especially difficult to enforce when the incipient damage has yet to be made evident. Artefacts composed of biological materials are particularly susceptible to biological degradation especially by extremophilic organisms which have developed sophisticated chemical protection strategies for survival in extreme environments which prove to be toxic to other organisms. The application of analytical Raman spectroscopic techniques to the characterisation of the chemical composition of mineral and synthetic paint pigments, ceramics, resins, dyes, textiles and human skeletal remains is also now finding much interest in cultural heritage circles; during these studies it has become apparent that the spectral signatures of biological colonisations that are responsible for the serious deterioration or degradation of archaeological artefacts are closely similar to those which one might expect to find with remote robotic Raman spectroscopic instrumentation on planetary surface and subsurface exploration rover vehicles for the detection of extinct or extant life.

The miniaturisation of Raman spectrometers for the detection of life signatures on planets and their satellites in our Solar System is exemplified by the forthcoming ESA ExoMars mission to the planet

Mars which will specifically search for extant or extinct life in the Martian subsurface geological record through a powerful suite of instrumentation that includes a Raman laser spectrometer for the first time.

A database of key Raman spectral signatures of species such as carotenoids, chlorophyll, scytonemin

and other key protective biochemicals produced by terrestrial specimens of cyanobacterial and lichen extremophiles which exist in stressed hot and cold terrestrial environments such as the Atacama Desert,

Arctic meteorite impact craters, volcanic outcrops in Svalbard and the dry Valleys in Antarctica is being complied to identify the presence of biological colonisation in suitable rock matrices. The adaptation

of the mineralogy and the host geological matrices by the cyanobacterial colonies and their production

of protective biochemicals is a vital requirement for the survival strategy for biological growth and

evolution. This is also the case for the biological colonisation of archaeological relics excavated from

a depositional environment and a readily available spectral database can hence be assimilated for

the identification and characterisation of areas of biological degradation in ancient artefacts which may be used to alert conservators to the urgent need for restorative and preservative strategies to prevent further ongoing specimen deterioration subsequent to superficial cleaning procedures being undertaken.

The potential afforded by the reduction in size and increased portability of Raman spectrometers appeals to conservation scientists for the in situ analytical measurements that can be performed on

PL1

objects without the need for destructive sampling, often in inaccessible locations, and an awareness that the Raman spectral information can reveal the presence of biological agents that could cause the ongoing deterioration of a cultural object need to be recognised. Also, the unsightly growths of cyanobacteria and lichen communities on exposed works of art such as wall paintings, statues and frescoes can be very deleterious and damaging to artistic viewing; in this context, the ability of biological colonies to attach themselves to mineral pigments which are often very hazardous and highly toxic to humans, such as compounds of lead, copper, mercury, antimony and arsenic provides an example of extremophilic behaviour which equally matches the strategies they have adopted to overcome extremes of temperature, pH, radiation insolation and barometric pressure elsewhere terrestrially.

Hence, in this presentation we shall explore some examples of the occurrence of biological colonisation of art works and artefacts in which Raman spectroscopy has provided novel information about the onset of degenerative processes which are often apparent spectroscopically before they are observed visually; this affords the establishment of analytical Raman spectroscopy as an early warning monitor of biological degradation in an artefact which may therefore require urgent conservational treatment to prevent further damage occurring and which will lend support to the apparently unrelated scientific engagement between Raman spectroscopists working on space missions and in the field of cultural heritage preservation.

- The examples used to illustrate this approach will be taken from the following cultural heritage case-studies and scenarios;

- Lichen degradation of wall-paintings;

- Biological colonisation of badly damaged frescoes undergoing restoration;

- Degradation of human mummies from Egyptian Dynastic burials preserved in museum collections;

- Biological invasion of grave sites and contributions to the mineral degradation of human skeletal remains; - Definition of biological spectral signatures in archaeological excavations of human and mammoth remains;

The impact of space mission derived data for key biological signatures on the identification of similar signatures from biodegraded artefacts from archaeological excavations will inform future Raman spectrosopic applications for such instruments in archaeological and cultural heritage site work and the identification of biological and associated mineralogical materials which could advise and inform future conservation protocols and approaches.

OP1

Identification of endolithic survival strategies on stone monuments

Annalaura Casanova Municchia, 1* Giulia Caneva, 1 Maria Antonietta Ricci, 1 Armida Sodo 1

1 Department of Sciences, University of Roma Tre, Rome, Italy, +39 06 5757336374,

A relevant aspect of stone bio-deterioration is the colonization by endolithic microorganisms that

penetrate some millimetres or even centimetres into the rock. This phenomenon is mainly due to a strategy of protection from desiccation and high solar radiation. [13] In the literature there are only few studies about the impact of endolithic microorganisms on stone monuments, and on the ecological conditions favouring this kind of colonization. Additionally most

studies refer to colonization at extreme environmental conditions, such as cold and hot deserts. Nevertheless, the presence of endolithic microorganisms has been observed in stone monuments in Temperate and Mediterranean climates, especially in comparably dry environments (e.g. vertical surfaces of buildings exposed to sunlight). [46]

In recent years the study of endolithic organisms in extreme environments has been busted by several

astrobiological studies, aimed at finding a trace of life on Mars, where cold deserts, such as Antarctica

or the Arctic, have been proposed as the closest analogues to Martian on Earth. [79] Consequently, the interest for the development of techniques and protocols for the identification of endolithic microorganisms on stones is spread over a wide scientific field.

We have used Raman spectroscopy to identify rock alteration and pigments traces produced by endolithic microorganisms as survival and adaption strategies to adverse conditions on stones monuments. Notably this technique can easily be implemented (and already is) in space missions. Endolithic cyanobacteria can produce photo protective accessory pigments, such as scytonemin, parietin, calycin; they also mobilize some iron oxides to create a mineral screen layer on the rock surface. In both cases they leave biological or geological traces on rock due to their metabolic activity or indirect effects. We have performed the experiment on different rock samples, in order to investigate the impact of endolithic microorganisms on stone monuments from areas characterized by Temperate and Mediterranean climates. In detail, the aim is to detect key biomarkers and geomarker providing an indicator of different adaptation strategies used in adverse condition and identifying the alterations produced on the substrate.

and identifying the alterations produced on the substrate. Figure 1. Microphotographs of cross-section. a.) Sample

Figure 1. Microphotographs of cross-section. a.) Sample of Church of Martvili b.) Sample of Hebrew’s cemetery tombstone c.) Sample of cliff of the Amalfi Coast.

OP1

Three different case studies were investigated: Marly limestone samples from the outer wall of Church of the Virgin in Martvili in Georgia that showed a peculiar bio deterioration form, Istrian stone samples from Hebrew’s cemetery tombstone in Venice, and carbonate samples from calcareous cliff of the Amalfi Coast.

In this work we report the observations of cross-section by optical microscope (Figure 1) and scanning electron microscope (SEM) in order to identify the interaction between substrate and microorganisms. Spectra obtained by Raman spectroscopic investigations, carried out in cross-section, were useful to determine the organic and inorganic compounds used by microorganisms as protective mechanisms against stress conditions. The data obtained from the spectra gave rise to identification of molecular bio and geo-marker.

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C. K. Gehrmann, W. E. Krumbein, K. Peterson, International Journal of Mycololgy and Lichenology.

[2]

1992, 5, 37–48. O. Salvadori, Characterisation of endolithic communities of stone monuments and natural outcrops.

[3]

In: O. Ciferri, P. Tiano, G. Mastromei, Of Microbes and Art. The Role of Microbial Communities in the Degradation and Protection of Cultural Heritage. 2000, pp. 89–101. G. Caneva, M. P. Nugari, O. Salvadori, Plant Biology for Cultural Heritage. Biodeterioration and

[4]

Conservation. The Getty Conservation Institute, Los Angeles, 2009. A. Danin, G. Caneva, International Biodeterioration & Biodegradation. 1990, 26, 397–417.

[5]

V. Lombardozzi, T. Castrignanò, M. D’Antonio, A. Casanova Municchia, G. Caneva, International

[6]

Biodeterioration & Biodegradation. 2012, 73, 8–15. C. Ascaso, J. Wierzchos, J. Delgado Rodrigues, L. Aires-Barros, F. M. A. Henriques, A. E. Charola,

[7]

International Zeirschrift fur Bauinstandsetzen. 1998, 4, 627–640. H. G. M. Edwards, E. M. Newton, D. L. Dickensheets, D. D. Wynn-Williams, Spectrochimica Acta Part A.

[8]

2003, 59, 2277–2290. S. E. J. Villar, H. G. M. Edwards, C. S. Cockell, Analyst. 2005, 130, 156–162.

[9]

S. E. J. Villar, H. G. M. Edwards, Raman spectroscopy in astrobiology. Anal Bioanal Chem. 2006, 384(1),

100–113.

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FT-Raman analysis of historical cellulosic fibres infected by fungi

Katja Kavkler, 1* Andrej Demšar 2

1 Restoration Centre, Conservation Centre, Institute for the Protection of Cultural Heritage of Slovenia, Ljubljana, Slovenia, katja.kavkler@rescen.si 2 Department of Textiles, University of Ljubljana, Faculty of Natural Sciences and Engineering, Ljubljana, Slovenia, andrej.demsar@ntf.uni-lj.si

Introduction Historical textiles can be degraded by different internal and external factors. Fungi are one of the most severe textiles’ degraders [1] , which attack especially pre-degraded materials, since the depolymerisation and changes in inter- as well as intramolecular bonds facilitate access of fungal enzymes to molecules. Textile deterioration has been studied previously with different methods [2,3] . This time we decided to analyse bio-deteriorated as well as non-affected objects by FT-Raman spectroscopy.

Materials and methods Textile samples Historical samples were obtained from 14 different historical textile objects originating from different historical periods since 16th century. The samples were taken off in the form of pieces of fabrics or single threads, from objects, where stains were observed, for which we suspected to be of fungal origin, or where mycelium was observed on the surface of the objects.

FT-Raman The FT-Raman instrument is a Bruker multiRAM with cryo-cooled Ge detector and a Nd-YAG laser with a wavelength of 1064 nm with a line width of ~ 5-10 cm -1 and a resolution of 4 cm -1 . The software used is OPUS Beta version. The laser intensity has been between 30 and 150 mW. The number of scans has generally been between 100 and 5000. The surface area of analysis is ~ 20 µm in diameter.

Results and discussion Of all the 14 investigated objects, three were made of cotton, two of mixture of flax and hemp and all others of pure flax. Half of the investigated objects were infected by different fungal strains, among them one made of cotton and six made of flax. The infected cotton object was underwear, whereas all other infected objects were painting canvases.

We observed structural properties using FT-Raman spectroscopy, after the dispersive Raman spectroscopy proved to be long lasting and not always reliable method [2] . However, the FT-Raman spectroscopic method caused some problems with luminescent background as well. The spectra of non-infected cotton specimen, spectra of both samples with mixed fibres as well as two spectra of flax had strong background with non-visible or barely visible cellulose bands and their structure could not be interpreted.

To determine structural changes within cellulose fibres we compared spectra from investigated objects with those from contemporary fibres, processed in old fashioned manner, of natural colour and non- sized. Some differences in spectra can be attributed to different growth and processing conditions, but others are sings for different intensive structural changes.

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The inoculated object made of cotton gave spectra with only low background and clear bands. From the spectrum we concluded, that ageing as well as biodeterioration caused decreased crystallinity of cellulose and its degradation [4] , as seen from the decrease of the bands at 380 cm -1 , 437 cm -1 , 1096 cm -1 and 1120 cm -1 .

Of the investigated objects made of flax, six were inoculated and four not. In one of the non-inoculated spectra, obtained from the only object made of flax, which was not painting but an embroidered tablecloth, we could observe opposite changes than usually. The increased bands at 457 cm -1 , 520 cm -1 and 1120 cm -1 are signs of increased crystallinity or more ordered cellulose structure [4-6] .

In spectra of two of the inoculated samples no bands could be observed due to strong background emissions, which is probably the consequence of bio-deterioration [5] . In one spectrum only the strongest bands were visible. Due to deterioration the two bands around 1100 cm -1 joined into a broad band with peak at 1096 cm -1 . In three inoculated specimens bands were clearly visible despite the luminescent background, and the structural changes could be investigated. The decreased bands at 995 cm -1 and 1480 cm -1 are a sign of deterioration of cellulose in all three investigated spectra, [7] as well as the decrease of the bands at 1096 cm-1 and 1120 cm -1 [5] in two spectra.

From the results of the FT-Raman analysis of museum objects infected by fungi we can conclude that as does the dispersive Raman, also the FT-Raman can cause difficulties when analysing historical textiles, especially when the fibres are severely deteriorated. However, structural changes can be observed in most of the spectra already after a short acquisition times. In the investigated specimens we observed that not only biodeterioration, but also other ageing factors can cause changes in cellulose structure. As seen from our results, the fungi caused more severe decrease in crystallinity than environmental factors.

The authors would like to thank Ingalill Nystrom and Department for Conservation of the University of Gothenburg, Sweden, for giving the possibility to use the FT-Raman in their institution. We would also like to thank Slovene Museum of Christianity, Ptuj Regional Museum and Department for Easel Paintings of the Restoration Centre of the Institute for the Protection of Cultural Heritage of Slovenia for providing the sampling objects.

References

[1] A. Seves, M. Romanò, T. Maifreni, S. Sora, O. Ciferri, International Biodeterioration & Biodegradation. 1998, 42, 203.

[2]

K. Kavkler, A. Demšar, Spectrochimica Acta. Part A. 2011, 78(2), 740–746.

[3]

K. Kavkler, N. Gunde-Cimerman, P. Zalar, A. Demšar, Polymer degradation and stability. 2011, 96(4), 574.

[4]

M. Petrou, H. G. M. Edwards, R. C. Janaway, G. B. Thompson, A. S. Wilson, Analytical and Bioanalytical

[5]

Chemistry. 2009, 395, 2131. H. G. M. Edwards, J. M. Chalmers, Raman Spectroscopy in Archaeology and Art History, Royal Society of

[6]

Chemistry: Cambridge, Great Britain, 2006, p. 304. H. G. M. Edwards, N. F. Nikhassan, D. W. Farwell, P. Garside, P. Wyeth, J. of Raman spectrosc. 2006, 37,

1193.

[7]

H. G. M. Edwards, E. Ellis, D. W. Farwell, R. C. Janaway, J. of Raman Spectrosc. 1996, 27, 663.

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Combined FT-Raman and Fibre-Optic Reflectance Spectroscopic Characterisation of Simulated Medieval Paint Films: a Chemometric Study of the Effects of Natural and UV-Accelerated Ageing

Anuradha Pallipurath, 1 Jonathan Skelton, 1* Spike Bucklow, 2 Stephen R. Elliott 1

1 Department of Chemistry, University of Cambridge, UK, arp59@cam.ac.uk

2 The Hamilton Kerr Institute, Fitzwilliam Museum, Cambridge, UK

Non-invasive methods for analysing artwork are fast gaining interest due to their facilitating non- destructive and in-situ analyses, without the need for sampling. Raman spectroscopy is one such technique, and has been widely used for this purpose. Despite being a weak phenomenon, Raman scattering can give a wealth of information about the chemical functional groups that make up chromophores, as well as the crystal structures of pigment molecules, from their atomic-vibrational spectra. This information can not only be used to characterise the materials in, and hence date, artwork, but can also be used to detect forgeries.

However, during in-situ analyses of artwork, distinguishable Raman scattering from the pigment can often be reduced, or even completely masked, by fluorescence from the glazing materials or organic binders used. While a lot of importance has been given to the study of pigments, identifying the organic binding materials used has never been an easy task. In addition to fluorescing at visible wavelengths, most binders also have characteristic vibrational-spectroscopy peaks in the same spectral regions, e.g. corresponding to C-H and carbonyl stretches, making their differentiation challenging. Previously, we have shown that the use of multiple spectroscopic data sources, e.g. FT-Raman and fibre-optic reflectance spectra, together with multivariate analysis techniques, not only helps to indentify fat- based binders, but also proteinacious and polysaccharide-based binders, such as gum Arabic and egg, which are otherwise difficult to differentiate. [1]

In this work, we have extended these techniques to understand the nature of possible interactions between binders and bound pigments, and to estimate relative concentrations of components in paint films using FT-Raman spectroscopy. We have also studied naturally and artificially (UV) aged samples to understand how these interactions change with time. In addition, we have developed chemometric methods to enable computer-assisted analysis of such spectral data from simulated paint samples, with a view to working towards an automated identification of paint-binder materials from spectroscopic data.

Finally, we have also investigated how several different support materials, viz. glass, canvas and parchment, the latter two of which, like binding media, are organic materials, influence the paint film spectra and hence the results from our analysis techniques.

References

[1]

A. Pallipurath, J. Skelton, P. Ricciardi, S. Bucklow, S. Elliott, J. of Raman Spectrosc . 2013 , 44 (6), 866–874.

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Study of malachite degradation in easel (model) paintings by spectroscopic analysis

Tanja Špec, 1* Klara Retko, 1 Polonca Ropret, 1,2 Janez Bernard 3

1 Research Institute, Conservation Centre, Institute for the Protection of the Cultural heritage of Slovenia, +386 1 2343118, (tanja.spec, polona.ropret, klara retko)@rescen.si 2 Museum Conservation Institute, Smithsonian Institution, Suitland, MD, USA 3 Slovenian National Building and Civil Engineering Institute, +386 1 2804204, janez.bernard@zag.si

Malachite, copper(II) carbonate [Cu 2+ 2 (CO 3 )(OH) 2 ] is perhaps the oldest green pigment and has been intensively used in different works of art from Antiquity until late 1800. It has often been proved to be permanent in oil and tempera paintings, although sometimes brownish hue may appear due to the oil darkening. [1] The present study describes an interaction between pigment and different binders and an effect of accelerated aging in easel model paintings which were prepared according to the traditional Baroque recipes. [2] Before applied on white gesso ground, colour layers containing malachite, mixed with egg tempera and/or oil medium were prepared. As finishing protective layers, egg white and mastics were added on selected areas of the easel painting. The use of different combinations of binders and varnishes enabled an extended study of different influential factors on pigment degradation. One set of model samples

factors on pigment degradation. One set of model samples Figure 1. a.) A Photomicrograph of the

Figure 1. a.) A Photomicrograph of the polished cross-section and location of spot 2 for Raman analysis. b.) A Photomicrograph of the polished cross section and location of spot 3 for Raman analysis. c) Raman spectra of Malachite (1), Copper oxide (2) and Copper oxalate (3).

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were exposed to the effects of climate parameters variations, such as temperature, relative humidity and UV-VIS radiation. The other set was left non-aged and it served as the control. Exposure of model easel paintings to environmental parameters in climate chambers was completed after two months. On both model paintings, colorimetric measurements were made in order to determine the differences in colour before and after ageing. Utilizing Micro-Raman spectroscopy, different green areas of each sample’s cross-section were analyzed. Supporting analytical methods, such as SEM (Scanning electron microscopy), FT-IR (Fourier transform infrared spectroscopy) and XRD (X-ray Diffraction) were employed to obtain additional information on the degradation process of malachite colour layers. The Raman bands of malachite were determined on all control samples, where the bands are in a good agreement with literature data. [3] Beside the green particles of malachite, the black particles were also detected in all of the samples. Nevertheless, much higher proportion of the latter was observed in the aged samples. Obtained Raman spectra of those particles indicate the presence of a copper oxide. (Figure 1c, Graph 2). [4] In addition, the scanning electron microscopy (SEM) shows the increased relative amount of copper on dark particles in respect to green ones. Furthermore, where oil medium was used as the binder, Raman spectra offered additional results. Beside copper oxide, strong bands of another compound were recorded at 552, 588, 618 cm -1 (Figure 1b and Figure 1c, Graph 3), which suggests the presence of a copper oxalate. [5] The formation of oxalates on easel paintings is more likely to appear in the presence of biochemical activity of lichens, fungi or bacteria [6] , which in our study can be eliminated, due to the known preparation of the model samples and controlled environmental conditions in climatic chambers. However, some of the previous studies concluded that decomposition of organic materials, such as proteins, oil, waxes, etc., can also lead towards the formation of oxalic acid [7] , which is most likely the reason for the copper oxalate formation found in the present study. The presence of oxalate was confirmed also by FT-IR spectroscopy.

References

[1] A. Roy (Ed.), Artists’ Pigments. A handbook of their History and Characteristics, vol. 2 Oxford University Press: New York, 1993, p. 184.

[2]

R. Hudoklin, Tehnologije materialov, ki se uporabljajo v slikarstvu, vol. 2, Ljubljana, 1958, p. 121.

[3]

R. J. H. Clark, P. J. Gibbs, Spectrochim. Acta Part A. 1997, 53 , 2159.

[4]

L. Debibichi, M. C. Marco de Lucas, J. F. Pierson, P. Küger, J. Phys. Chem. 2012 , 116, 10232.

[5] K. Castro, A. Sarmiento, I. Martinez-Arkarazo, J. M. Madariaga, L. A. Fernandez, Anal. Chem, 2008, 80,

4103.

[6]

H. G. M Edwards. N. C. Russel, M. R. D Seaward, Spectrochimica Acta Part A. 1999, 53, 99.

[7]

N. Mendes, C. Lofrumento, A. Migliori, E. M. Castellucci, J. Raman Spectros. 2008, 39, 289.

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Portable and laboratory analysis to diagnose the formation of efflorescence on walls and wall paintings of Insula IX, 3 (Pompeii, Italy)

Juan Manuel Madariaga, 1* Maite Maguregui, 2 Silvia Fdez-Ortiz de Vallejuelo, 1 Africa Pitarch, 1 Ulla Knuutinen, 3 Kepa Castro, 1 Irantzu Martinez-Arkarazo, 1 Anastasia Giakoumaki 1

1 Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country UPV/EHU, Spain, +34946018298, juanmanuel.madariaga@ehu.es 2 Department of Analytical Chemistry, Faculty of Pharmacy, University of the Basque Country UPV EHU, Spain 3 Department of Art and Culture Studies, University of Jyväskylä, Finland

Since the time that any archaeological site is brought to light, it suffers deterioration due in part to rain- fall, humidity, water infiltrations, etc., but mainly to environmental stressors. Raman spectroscopy and other analytical techniques, both portable and laboratory, are increasingly used to identify the deteri- oration compounds promoted by the reactivity between stressors (acidic gases, microorganisms, etc.) and original materials that promotes the formation of new compounds (efflorescence or crystallized salts) like bicarbonates, sulphates and nitrates. In the particular case of the Pompeii site, the impacts due to the eruption must be added to the others. The APUV expeditions (2010, 2011 and 2012) were focused on the walls and wall paintings of two houses from Insula IX, 3 (Houses 1,2 and 5,24); some rooms of greater importance are covered with ceilings but the majority of rooms in both houses are exposed to the open air. During the expeditions, the nature of the efflorescence in the walls and wall paintings was evaluated using portable, non-destructive instrumentation. Raman spectroscopy, assist- ed by diffuse reflectance infrared spectroscopy (DRIFTS) was used to obtain the molecular composi- tion and energy-dispersive X-ray fluorescence (ED-XRF) for the elemental analysis. Some efflorescence samples were also taken to perform laboratory analysis using the same analytical techniques but also DRX and SEM/EDX, as well as some mortar samples, detached from the walls, were taken to perform the soluble salt quantification. Exposed and protected rooms were measured in spring (May 2010) and summer (September 2011 and 2012), considering different orientations and the walls affected (and not affected) in its back by rainfalls to observe possible variations in the salts crystallizations. The spring 2010 was with few rainfalls, and little amount of efflorescence were detected in the walls and practically nothing in the wall paintings of the protected rooms. The end of August 2011 was rainy and the walls in the protected rooms, especially those oriented in its back to the main rainfalls, were completely wet; some efflorescence like crystals were two to five millimeters long. The middle of summer 2012 was also rainy, the walls were not wet when we performed the measurements, but in this case a notable amount of efflorescence crystals were evident even in the wallpaintings of the covered rooms. The CO 2 attack on non-protected walls is the greatest decaying phenomena accompanied by rain wash of the highly soluble metal bicarbonate salts formed after the acid attack (decarbonation of wall paint- ings and plaster layers till observation of the arriccio mortar). Any bicarbonate salt was measured in-situ and only calcium, sodium and potassium carbonate (CaCO 3 , Na 2 CO 3 , K 2 CO 3 ) were identified by Raman spectroscopy. All of them can be considered original compounds in the mortars; the source for potassium was found in the own walls, probably coming from the original mortar manufacturing when using local potassium-bicarbonate type waters.

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In protected wall paintings and walls (rooms covered by roof) higher sulphur contents were observed (severe sulphation decaying) while a lower amount of sulphur was quantified in exposed walls (partial dissolution of metallic sulphate salts by rain-washing). Apart from gypsum (CaSO 4 .2H 2 O), thenardite (Na 2 SO 4 ), mirabillite (Na 2 SO 4 .10H 2 O), aphthitalite (K 3 Na(SO 4 ) 2 ) and syngenite (K 2 Ca(SO 4 ) 2 .H 2 O) were detected in areas far from the presence of modern mortars and cements used un past restoration pro- cesses; sulphates with higher water content were observed in protected rooms where the wall was wet (2011 expedition), i.e., those having its back in front of the main wind (and rain falls) and belonging to other rooms without any roofing protection. Additionally, nitrate salts like lime nitrate (Ca(NO 3 ) 2 ), niter (KNO 3 ) and nitrammite (NH 4 NO 3 ) were detected only in protected rooms due to its high solubility. Especially in the expedition of 2011, nearly pure Raman spectra of niter were collected with the portable instrument, indicating the high concen- tration of this nitrate in the analysed efflorescence. But the most surprising result was observed in the 2012 expedition, where niter was in-situ measured in the white efflorescence crystals appearing through the pigmented layers in wall paintings of several rooms, all of them having well setting roofs. Chemical modeling and chemometrics were used to explain the results of quantitative concentrations of ions dissolved from the samples taken to the laboratory. This has resulted in a model that explains the deterioration process in terms of chemical reactivity, taking into account the orientations of the walls as well as the covered and not covered situations of the rooms analysed in Insula IX, 3 of the archaeological city of Pompeii. This model will be presented and discussed.

Acknowledgements This work was financially supported by the projects DEMBUMIES (ref.BIA2011-28148), funded by the Spanish MINECO, and Global Change and Heritage (ref. UFI11-26), funded by the University of the Basque Country (UPV-EHU). The accompanying actions CTQ2010-10810-E (MINECO), AE11-27 (UPV- EHU) and AE12-32 (UPV-EHU) supported the expeditions APUV2010, APUV2011 and APUV2012 re- spectively.

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Decorated plasterwork in the Alhambra investigated by Raman spectroscopy: field and laboratory comparative study

María José Ayora-Cañada, 1* Ana Domínguez-Vidal, 1 María José de la Torre López, 2 María José Campos Suñol, 3 Ramón Rubio Domene 4

1 Department of Physical and Analytical Chemistry, University of Jaén, Spain, mjayora@ujaen.es, adovidal@ujaen.es

2 Department of Geology, University of Jaén, Linares, Spain, mjtorre@ujaen.es

3 OTRI, University of Jaén, Spain, mjcampos@ujaen.es

4 Conservation Department, Council of The Alhambra and Generalife, Granada, Spain, ramonf.rubio@juntadeandalucia.es

This work presents the results of the Raman micro-spectroscopic study of decorated plasterworks, situated on the vaults of the Hall of the Kings in the Lions Palace, at the Alhambra in Granada, Spain. The Alhambra was built and decorated during the Nasrid period in the XIII-XVth centuries and then adapted during the first period of Christian domination (XVIth cent). Throughout its history, it has experienced many transformations, with the most important and generalized restorations taking place in XIXth century. The decorated plasterwork under study are the mocarabes or stalactites vaults of the Hall of the Kings. These are self-supporting domes built up with gypsum. Vertical gypsum prisms applied one over an- other are joined in multiple different arrays resembling stalactites of a cave. These mocarabes are decorated with a wide range of colors mainly red, blue, green, golden and black. Our study has been initiated with a totally non-invasive investigation on the field using a fiber-optic portable Raman microspectrometer. The works were conducted on scaffolding platforms at a height of ca. 12 m above the ground level coinciding with conservation works. The portable Raman microspec- trometer (B&W Tek InnoRam) was equipped with a 785-nm laser and an optical probe head attached to a videomicroscope which was mounted on a tripod motorised in the X–Y–Z axes with remote control.

Good quality Raman spectra were obtained during this survey despite working under non-laboratory conditions (e.g. dust, scaffolding, vibrations, daylight, temperature differences). The main practical problems encountered had been related to lack of space for probe positioning due to the typical stalac- tite like disposition of the mocarabes and vibrations of the scaffolding.

The best results of the field investigations were obtained from red decorations where cinnabar and minium were clearly identified. The position of cinnabar could indicate that this pigment was originally used by Nasrid artists although it was also used in restorations. On the contrary, minium seems not to correspond to original decorations. In many areas red colors appeared altered due to degradation products some of which were identified in situ (like anglesite and calomel). Furthermore, black decorations showed always the Raman signature of carbon and natural Afghan lapis lazuli was identified in most of the blue decorated motifs. Synthetic ultramarine blue was detect- ed only in one of the vaults revealing a recent restoration. However, we did not succeed in obtaining good spectra from green and pale blue-greenish decorations. This is because the laser power had to be extremely low to prevent photodecomposition due to the strong absorption of the 785 nm laser light by green pigments and the scaffolding vibrations made difficult the use of measurement times longer than

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a few minutes. These field studies have been complemented with laboratory studies on microsamples. Microsamples were carefully taken with a scalped taking into account the information provided by the in situ mea- surements. They were studied directly by means of a Renishaw (in Via Reflex) Raman microspectrom- eter coupled to a Leika microscope. The best compacted samples were selected to prepare thin cross sections by embbeding with epoxy resin. With this approach the stratigraphy of the decorations can be also investigated. In this way, we could confirm our previous hypothesis: in several samples a first pictorial layer of cinnabar applied over the gypsum substrate appeared covered by a second pictorial layer of minium. Furthermore, using a 514 nm laser the pale-blue pigment was identified as azurite. Degradation products like calcium oxalates probably formed through microbial degradation of the or- ganic materials employed as binders. In conclusion, the complementary information provided by field measurements with the portable spec- trometer and laboratory measurements especially on thin cross sections has allowed a good under- standing of the pigments and other materials employed for the decoration of the plasterwork in this Hall of the Alhambra as well as the several degradation phenomena that are taking place.

as the several degradation phenomena that are taking place. Figure 1. Detail of the Raman probe

Figure 1. Detail of the Raman probe head with the microscope during measure

Acknowledgements This work was financed by the research project CTQ2009-09555 from the Ministry of Science and Innovation. The Council of the Alhambra and Generalife, PAIDI Research Groups FQM 363 and RMN 325 are also acknowledged for supporting this project.

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Multi-technical approach for the study of French Decorative Arts furniture and luxury objects

Céline Daher, 1 Ludovic Bellot-Gurlet, 2 Céline Paris, 2 Juliette Langlois, 1 Yannick Vandenberghe, 1 Jean Bleton, 3 Anne Forray-Carlier, 4 Anne-Solenn Le Hô 1 *

1 Centre de Recherche et de Restauration des Musées de France (C2RMF), Palais du Louvre – Porte des Lions, Paris, France, +33 1 40 20 24 22, anne-solenn.leho@culture.gouv.fr, cel.daher@gmail.com

2 Laboratoire de Dynamique, Interactions et Réactivité (LADIR), UMR7075, UPMC-CNRS, Paris, France

3 Laboratoire d'Études des Techniques et Instruments d'Analyse Moléculaire (LETIAM), IUT d'Orsay, Orsay, France

4 Musée des Arts Décoratifs, Les Arts Décoratifs, Paris, France

During the eighteenth century in Europe, a trend in the furniture field was to imitate the Asian lac- quers, [1] known as exceptional for their great aesthetic beauty and gloss (Figure 1), and the delicate and fine ornaments. Four brothers, “les frères Martin” were considered as the most famous painters, gilders and varnishes in Paris, and used to work, followed by their descendents, at the royal court of Louis XV. Their work was dedicated to different types of objects, such as household furniture, small boxes for perfumes or make-up, wooden wall paneling, or even sledges and coaches. Their art of imitating Japa- nese and Chinese lacquers required the development of different painting and varnishing techniques, based on European familiar material, and became famous for its high and fine quality.

The Martin’s particularity was to apply a specific varnish “Vernis Martin” [2] on multilayered painted background, on wooden, papier mâché or metallic artifacts. The composition of the varnishes and paints, the different used materials (resins, pigments, dyes, etc.), and in a larger point of view, the Martin’s painting and varnishing techniques, have not been studied yet. These varnishes, or to a larger extent, European lacquers are complex systems made of a colored background, covered with a number of transparent layers. [3,4] Then, colored or gilded ornaments are applied, representing different charac- ters, flowers, or landscapes. The aim of this project was to improve the varnishing techniques knowl- edge in the Decorative Arts field during the 18th century to enrich the history of art and techniques, and to have a better conservation strategy of such fancy objects.

have a better conservation strategy of such fancy objects. Figure 1. Photography of a French imitation

Figure 1. Photography of a French imitation of Japanese artwork. Inv57965, Musée des Arts Décoratifs, Paris.

In order to reveal this unfamiliar complex system and the Martin’s specific technique, and to charac- terize the employed materials, a combination of analytical techniques was set up. Among these tech- niques, some were non-destructive such as Raman, FT-Raman and infrared in reflectance mode, [5] used to identify the varnish composition and the dyes employed for the painted areas directly on the

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object, or on micro-samples taken from lacunar areas of the artifacts. Other methods were employed to complete the organic analyses (GC/MS, py-GC/MS) or to characterize the mineral compounds (SEM, micro-diffraction).

The presented results are mainly the vibrational analyses ones, on which specific spectral treatments [6] were applied in order to extract detailed information and a better molecular identification thanks to these vibrational signatures. A synthetic overview of the whole obtained data is given, showing the singularity of these complex European preparations not or poorly studied.

Acknowledgements The authors would like to thanks the different museums which collaborated to this project, giving access to all the studied objects: musée des Arts Décoratifs (Paris), musée du Louvre (Paris), and Le Château de Versailles. This work has been financially supported by the foundation “Sciences du Patri- moine” and Labex “Patrima”.

References

[1] A.-S. Le Hô, M. Regert, O. Marescot, O., C. Duhamel, J. Langlois, T. Miyakoshi, C. Genty, M. Sablier, Anal. Chim. Acta. 2012, 710, 9. [2] J. F. Watin, L’art de faire ou d’employer les vernis, ou l’art du vernisseur, Quillau, Paris, 1772. [3] A.-S. Le Hô, E. Ravaud, J. Langlois, A. Mathieu-Daudé, E. Laval, A. Jacquin, I. Chochod, M. Bégué, J. Mertens, M.-L. Deschamps, A. Forray-Carlier, ICOM Committe for Conservation: 16th Triennial Meeting, Lisbon, Portugal,19-23 September, 2011, Preprints, electronic format 2011 (CD-ROM). [4] A. Rizzo, Anal. Bioanal. Chem. 2011, 392, 47. [5] W. Vetter and M. Schreiner, e-Preservation Science. 2011, 8, 10. [6] C. Daher, PhD thesis, Université Pierre et Marie Curie (UPMC), 2012, available online: http://tel.ar-

chives-ouvertes.fr/tel-00742851/

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Deterioration of lead based pigments on a fresco: a micro-Raman investigation

Ilaria Costantini, 1 Antonella Casoli, 1 Daniele Pontiroli, 2 Danilo Bersani, 2 Pier Paolo Lottici 2*

1 Chemistry Department, University of Parma, Italy, +39 0521 905425, ilaria.costantini@studenti.unipr.it 2 Physics and Earth Sciences Department, University of Parma, Italy, +39 0521905238, lottici@fis.unipr.it

Micro-Raman spectroscopy analyses were carried out on some pictorial fragments taken from a portion of the fresco in the Chapel of St. Stephen, situated in Montani (BZ), Val Venosta, Italy, and painted around 1430. Within this building, especially on the apse and on the vault, an alteration of lead based pigments is clearly visible, as a dark coating. The lead pigment was presumably mainly white lead, used to create highlights and light and dark effects. Samples were taken from altered blackened areas and from areas cleaned according to the traditional method of conversion of white lead, using a solution of acetic acid and hydrogen peroxide in cellulose pulp. The “cleaned” samples appear in their original colors, yellow and green. The samples taken from cleaned areas show characteristic spectra of lead- tin yellow pigments, both type I and type II, identified predominantly from green samples. Goethite, hematite, celadonite green earth, and lapis lazuli have also been found. The Raman spectra have been taken at very low (< 0.1 mW) laser power due to the complex behaviour of lead oxides for photo- thermal effects induced by the laser excitation (here 632.8 nm). [1] The micro-Raman spectra from blackened degraded samples give no evidence of white lead but show always a structured wide band centered at about 515-520 cm -1 which can be attributed to the presence of plattnerite (PbO 2 ), well known alteration product of lead based pigments, especially in presence of moisture and in strongly alkaline environment. The Raman spectra are nearly insensitive of the laser power and very often show PbO (litharge/

massicot) features of varying intensities. Other features at about 230 cm -1 and 600 cm -1 cannot be attributed to lead oxide phases, litharge or massicot (Figure 1). On the other hand, starting from synthetic plattnerite, lead oxides (red lead Pb 3 O 4 , litharge and massicot) are obtained at increasing laser power (Figure 1). The nature of the dark degradation material is discussed on the basis of Raman and XRD results and on degradation tests on white lead, with different binders.

on degradation tests on white lead, with different binders. Figure 1. Raman spectrum of the black

Figure 1. Raman spectrum of the black degradation material a.) compared with that of plattnerite b.). c.) and d.) are Raman spectra (massicot and litharge, respectively) obtained by laser photo-degradation of plattnerite.

References

[1]

L. Burgio, R. J. H. Clark, S. Firth, Analyst, 2001, 126, 222–227.

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Investigation of colour layers in easel (model) paintings influenced by different ageing process

Klara Retko, 1* Tanja Špec, 1 Polonca Ropret, 2

1 Research Institute, Conservation Centre, Institute for the Protection of Cultural Heritage of Slovenia, Ljubljana, Slovenia, +386 1 2343118, klara.retko@rescen.si, polona.ropret@rescen.si 2 Museum Conservation Institute, Smithsonian Institution, Suitland, MD, USA

Investigation of deterioration and material degradation on works of art has a great impact in designing better conservation and preservation procedures. Colour layers stability depends to a great extent on the individual stability of a pigment and binder, and possible pigment-binder interactions. Influential factors such us UV-VIS radiation, pollutants exposure, and humidity and temperature oscillation may also accelerate degradation processes. In this study, changes of physical and chemical properties of different colour layers as a consequence of degradation are presented. For that purpose several easel (model paintings), containing different colour layers were prepared in which all materials selected for the preparation of model samples corre- sponded to the materials used in the Baroque period. [1] Therefore pigments such as lead white, lead tin yellow (type I), prussian blue, smalt, azurite and vermilion were employed. Each pigment was mixed with egg tempera or oil medium and applied on a gesso ground. Model samples were then exposed to artificial accelerated ageing process for a period of two months, using well-controlled climatic chambers. One set of model easel paintings was exposed in the climatic chamber where oscillations of temperature and relative humidity were performed, while the other set of samples was exposed to the UV-VIS radiation. The last set of model samples was left non-aged and served as control.

of model samples was left non-aged and served as control. Figure 1. Raman spectra of non-aged

Figure 1. Raman spectra of non-aged azurite colour layer (AZ_ B2_REF) and azurite colour layers after T,RH (AZ_B2_T,RH) and UV-VIS exposure (AZ_B2_UV-VIS). In all presented samples, linseed oil (B2) was selected as the binder.

Utilizing Micro-Raman spectroscopy all colour layers were examined. The main differences in Raman spectra of aged and non-aged samples that indicate possible degradation process were observed in azurite and lead white containing colour layers. After completed accelerated aging process of blue azurite colour layers, greenish hue has been observed. According to literature data, conversion of blue pigment azurite (Cu 3 (CO 3 ) 2 (OH) 2 ) to the green pigment malachite (Cu 2 (CO 3 ) 2 (OH) 2 ) is possible, although mechanism is not well understood. [2] The Raman bands at ~ 153, 180, 220, 269, 354, 432, 1055, 1091 and 1491 cm -1 revealed the presence of malachite [3] (Figure 1), interestingly, only in colour layers prepared in oil medium, and after both exposures (UV-VIS and T, RH). It is possible that the presence of malachite stems from azurite conver-

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sion, which appears to be less stable in the medium with higher amount of fatty acids. In cases, when azurite was mixed with lead tin yellow and lead white, it showed a lower stability in the egg tempera after exposed to UV-VIS radiation. To acquire additional knowledge on mechanism of reactions further research is necessary. In lead white colour layers, which were prepared with both binders and exposed to UV-VIS radiation changes in Raman spectra were observed The additional band at 967cm -1 (Figure 2) can be assigned to ν(SO 4 2- ). It is possible that the lead white interacted with a sulphate containing compound. [4]

While the easel painting have not been exposed to air pollutants, such as SOx, which could initiate the formation of sulphates, the source of sulphates is possibly contributed to gypsum (CaSO 4 ·2H 2 O), present in the ground layer. Interestingly, the effect was observed only after UV-VIS exposure and not under humid conditions. However, additional research needs to be carried out.

However, additional research needs to be carried out. References Figure 2. Raman spectra of non aged

References

Figure 2. Raman spectra of non aged lead white colour layers prepared with egg yolk (LW_B1_REF) and linseed oil (LW_B2_REF) and after UV-VIS exposure (LW_B1_UV-VIS,

LW_B2_UV-VIS).

[1]

R. Hudoklin, Tehnologije materialov, ki se uporabljajo v slikarstvu, vol. 2. Ljubljana, 1958, p. 121.

[2]

A. Lluveras, S. Boularand, A. Andreotti, M. Vendrell-Saz, Applied Physics A. 2010, 99, 363.

[3] R. J. H. Clark, P. J. Gibbs, Spectrochimica Acta Part A. 1997, 53 , 2159. [4] E. Kotulanová , P. Bezdička, D. Hradil, J. Hradilová, S. Švarcová, T. Grygar, J. Cult. Her. 2009 . 10, 367.

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Identification of copper azelate in 19 th century Portuguese oil paintings: Characterisation of metal soaps by Raman Spectroscopy

Vanessa Otero, 1,2 Diogo Sanches, 1, 2 Cristina Montagner, 1, 2 Márcia Vilarigues, 1, 3 Leslie Carlyle, 1, 2 Maria J. Melo 1, 2*

1 Departamento de Conservação e Restauro, Faculdade de Ciências e Tecnologia, Universidade Nova

de Lisboa, Portugal, van_otero@campus.fct.unl.pt

2 REQUIMTE-CQFB, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Portugal

3 VICARTE, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Portugal

Several 19 th century oil paintings by the artist Tomás da Anunciação (1821-1879) who is considered a prominent figure of Portuguese romanticism were studied. The identification of the green pigment used in the trees and foliage was not straightforward. The presence of copper in cross-sections was confirmed by micro-Energy Dispersive X-ray Fluorescence (µ-EDXRF) and Scanning Electron Micros- copy coupled with an Energy Dispersive X-ray Spectrometer (SEM-EDS). The green particles were then characterised by micro-Fourier Transform Infrared Spectroscopy (µ-FTIR) and Raman Microscopy

(µ-Raman). The infrared fingerprint does not match a copper resinate, but it was possible to detect a band at 1586 cm -1 attributed to the asymmetric COO - stretching of copper carboxylates [1,2] . The detec- tion of these compounds was also confirmed by µ-Raman through the identification of bands at 1440

cm -1 and 1296 cm -1 assigned to CH 2 bending. This indicates a reaction between the copper pigment with

the surrounding oil binding media [2,3] .

Based on these findings, it was decided to test a new set of metal soaps synthesised in the laboratory. The synthesis method was adapted from Robinet and Mazzeo [1, 4] . Metal salts of lead, zinc, calcium, cadmium, copper and manganese II were used and the carboxylic acids chosen were palmitic, stearic, azelaic and oleic acids. Characterisation was performed by µ-FTIR, µ-Raman and X-ray Diffraction (XRD) and it is anticipated that these results will be of great value for in situ detection of metal soaps by µ-Raman.

The distinction between the saturated carboxylates, copper palmitate and stearate, is not straightforward. The applica- tion of a chemometrics approach based on µ-Raman data, for the discrimination of the type of carboxylate, was tested and will be discussed. In contrast, copper azelate and oleate show distinct spectra by µ-Raman as well as by µ-FTIR. Copper azelate shows a dif- ferent Raman CH 2 bending profile and different characteris- tic bands for C-C stretching and bending. As may be seen in figure 2, the green degradation product detected on Tomás da Anunciação oil paintings matches the copper azelate µ-Raman spectrum. Its identification was also confirmed by µ-FTIR on a very small green micro-sample, free from lead white. It was possible to identify both the asymmetric and symmetric COO - stretching of copper azelate at 1586 cm -1 and

- stretching of copper azelate at 1586 cm - 1 and Figure 1. Oil painting on

Figure 1. Oil painting on canvas entitled Paisagem e Animais (1851) from Tomás da Anunciação.

1417 cm -1 , respectively.

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Acknowledgements This work has been financially supported by national funds through FCT- Fundação para a Ciência e a Tecnologia under the project PTDC/EAT-EAT/113612/2009. We also thank FCT-MCTES for Vanessa Otero’s PhD grant SFRH/BD/74574/2010, Cristina Montagner’s PhD grant SFRH/BD/66488/2009 and Diogo Sanches’s PhD grant, SFRH / BD / 65690 / 2009. We would also like to thank the curator of The Museu Nacional de Arte Contemporânea – Museu do Chiado, Maria de Aires, for her collaboration.

– Museu do Chiado, Maria de Aires, for her collaboration. Figure 2. Raman spectra of a.)

Figure 2. Raman spectra of a.) green area of a cross-section taken from Paisagem e Animais oil painting of Tomás da Anunciação, b.) copper azelate and c.) copper palmitate.

References

[1] L. Robinet, M. Corbeil, Sudies in Conservation. 2003, 48, 23–40. [2] M. Gunn, G. Chottard, E. Rivière, J. Girerd, J. Chottard, J. Studies in Conservation. 2002, 47, 12–23.

[3] J. J. Boon, F. Hoogland, K. Keune, AIC paintings specialty group postprints: papers presented at the 34th annual meeting of the AIC of Historic & Artistic Works providence, Rhode Island, 16–19 June, 2006. AIC:

H. M. Parkin, Washington, 2007, pp. 16–23. [4] R. Mazzeo, S. Prati, M. Quaranta, E. Joseph, E. Kendix, M. Galeotti, Anal. Bional. Chem. 2008, 392, 65–

76.

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Raman study of pigment degradation due to acetic acid vapours

Alessia Coccato, 1* Nathalie De Laet, 2 Sylvia Lycke, 1,2 Jolien Van Pevenage, 2 Luc Moens, 2 Peter Vandenabeele 1

1 Department of Archaeology, Ghent University, Belgium, Alessia.coccato@ugent.be, raman@ugent.be 2 Department of Analytical Chemistry, Ghent University, Belgium

The conservation of works of art that consist of different materials is complicated as the component materials are not equally sensitive to the same environmental conditions. Humidity, light exposure and temperature are known to be dangerous to cultural heritage objects, favouring their degradation through physical, chemical and biological processes. These factors can be easily controlled, especially when the work of art is placed at display in a museum, with limited air circulation, controlled humidity, and temperature. Nevertheless, display cases with wooden parts may cause further damage to their content, because of the release of acetic and formic acid. [1] This evidence has been highlighted by many studies, [2-4] and proved to be itself sensitive to humidity and temperature conditions. For conservative purposes, it is necessary to study also the contribution of acid organic pollutants to the degradation of the materials present in a work of art. Studies are currently performed on pigments, varnishes, leather, parchment, paper and textiles, in the frame of the European FP-7 project MEMORI. Our research is focused on pigment degradation and on the development of a passive air sampler coupled to a dosimeter reader, which is the MEMORI-dosimeter, to monitor the combined effects of all the conditions to which the art object is exposed (climate, organic and inorganic vapours). The pigment selected for this study are malachite (Cu 2 (CO 3 )(OH) 2 ), lead white (Pb 2 (CO 3 )(OH) 2 ), red lead (Pb 3 O 4 ), lead-tin yellow type I (Pb 2 SnO 4 ) and pigment orange 36 (C 17 H 13 ClN 6 O 5 ). Different acetic acid atmospheres were produced to simulate the release of organic pollutants from wood in closed cases. Five samples of each pigment were kept in the closed vessels and monitored over 5 weeks. The evaluation of the effects of acetic acid were checked both as a change in colour, and with Raman spectroscopy. Samples were analysed with a Kaiser Hololab 500R spectrometer (λ=785 nm) or a Bruker Senterra spectrometer (λ=532 nm). To take sample inhomogeneity into account, 100 spectra were recorded for each sample, and the results were averaged. Here we present some results for lead- tin yellow (type I). The spectrum of the original pigment is in good agreement with literature (top spectra in Figure 1 and Figure 2) is in good agreement with literature, [5] while it is possible to notice the appearance of new bands (652, 924, 1337, 1422, 2940 cm -1 ) and sometimes the decrease in intensity of some bands (452 cm -1 ) in relation with increasing dose (time x concentration), as can be seen in Figure 1. No shifts in the band positions were noticed. The newly formed bands can be ascribed to the formation of acetate salts of lead (II). It seems that acetic acid does not affect the ν(Sn-O) vibration at 194 cm -1 , while the ν(Pb-O) stretching band at 452 cm -1 decreases in intensity, suggesting the formation of lead acetate and tin dioxide. The white colour of lead acetate is responsible for the lightening of the yellow tint. The studied pigments showed a different sensitivity towards the aggressive acetic acid atmosphere, some of them being reactive but showing no change in colour (lead acetate is white, as well as basic lead carbonate [6] ), some showing strong colour changes (lead-tin yellow type I becomes paler, [7] malachite turns to a bluish-green shade because of the formation of verdigris, [7] red lead darkens probably in relation to the formation of the black lead(IV) oxide plattnerite [8] ), finally pigment orange 36 showed no changes in colour nor in the vibrational spectrum. Raman spectroscopy demonstrated once more its effectiveness in the characterization of pigments and their degradation products, in this case in combination with digital photography and RGB measurements.

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Acknowledgements The authors wish to acknowledge the MEMORI project for their financial support and for the interesting discussions with the colleagues. The MEMORI, ‘Measurement, Effect Assessment and Mitigation of Pollutant Impact on Movable Cultural Assets. Innovative Research for Market Transfer‘, project is supported through the 7 Framework Programme of the European Commission (http://www. memori-project.eu/memori.html).

Commission (http://www. memori-project.eu/memori.html). Figure 1. Left: Effect of time on lead tin yellow type I
Commission (http://www. memori-project.eu/memori.html). Figure 1. Left: Effect of time on lead tin yellow type I

Figure 1. Left: Effect of time on lead tin yellow type I exposed to 33% acetic acid vapours. From top to bottom: pure pigment, after one, three and five weeks of exposure. Right: Effect of increasing concentration of acetic acid on lead tin yellow type I, after four weeks of exposure. From top to bottom: pure pigment, 9%, 20% and 33% acetic acid atmosphere

References

[1]

W. Hopwood, T. Padfield, D. Erhardt, Science and Technology in the Service of Conservation. 1982, 24–

27.

[2]

T. Baird, N. H. Tennent, Studies in Conservation. 1985, 30, 73–85.

[3]

C. Laine, Structures of Hemicelluloses and Pectins in Wood and Pulp. University of Technology: Helsinki,

[4]

Espoo, Finland, 2005. L. T. Gibson, Corrosion Science. 2010, 52, 172–178.

[5]

I. M. Bell, R. J. H. Clark, P. J. Gibbs, Spectrochimica Acta Part A. 1997, 53(12), 2159–2179.

[6]

J. E. Svensson, A. Niklasson, L.G. Johansson, Corrosion Science. 2008, 50, 3031–3037.

[7]

G. Calvarin, N. Q. Dao, J. P. Vigouroux, E. Husson, Spectrochimica Acta Part A. 1982 , 38, 393–398.

[8]

D. A. Scott, T. D. Chaplin, R. J. H. Clark, J. of Raman Spectroscopy. 2006, 37, 223–229.

[9]

L. Burgio, R. J. H. Clark, S. Firth. The Analyst. 2001, 126, 222–227.

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Investigating the sources of degradation in corroded lead sculptures from Oratory Museum (Museu do Oratório), Brazil

Thiago Sevilhano Puglieri, 1 Dalva Lúcia Araújo de Faria, 1* Luiz Antônio Cruz Souza 2

1 Instituto de Química, Universidade de São Paulo, Brazil, +55 11 30913853, dlafaria@iq.usp.br 2 Lacicor – Laboratório de Ciência da Conservação Escola de Belas Artes, Universidade Federal de Minas Gerais, Belo Horizonte, MG, Brazil

The presence of acetic and formic acids and formaldehyde, combined with inadequate environmental conditions, as high relative humidity (RH) and temperature, constitute a very threatening scenario for the integrity of materials such as metals [1-3] . Wood is a common source of such volatile organic com- pounds and its use in showcases should be avoided. However, Pb sculptures from Oratory Museum (Museu do Oratório) at Ouro Preto, in the Brazilian state of Minas Gerais, exposed inside glass show- cases presented an increasing degradation (Figure 1) and the corrosion sources were to be identified to stop further damage.

Small fragments of the corrosion products, a whitish hair-like material, were collected and analyzed by Raman microscopy, stereomicroscopy, SEM-EDX, FTIR and XRD. Raman spectroscopy was also used to test possible sources of pollutants.

Stereomicroscopy confirmed the formation of crystals, excluding the possibility of a fungi attach, while SEM-EDX also revealed the presence of Pb, C and O. XRD detected basic lead carbonate and Raman microscopy showed the formation of Pb carbonates and formates (Figure 2).

The glass showcases were mounted on a painted steel baseplate and, thus, the considered formate sources were the paint used and glass cleaning products. Formaldehyde was widely used as preserva- tive in house-keeping products and, although in Brazil this practice is prohibited since 2008, its use in

in Brazil this practice is prohibited since 2008, its use in Figure 1. Corroded polychrome lead

Figure 1. Corroded polychrome lead sculptures of Museu do Oratório.

Corroded polychrome lead sculptures of Museu do Oratório. Figure 2. Raman spectra (632.8 nm) from different

Figure 2. Raman spectra (632.8 nm) from different areas of samples collected from the analyzed polychrome lead sculpture.

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informal market products is common. An investigation was then carried out on the effects of the paint and glass cleaning products used in the Museum on Pb coupons under controlled conditions (100% RH and 23 ± 2 ˚C). When Pb coupons were exposed to environments containing the fresh paint at 100% RH only carbon- ates were detected in the corrosion layer, while the coupons exposed together with the cured paint showed the presence of carbonates and formates. Only carbonates were found on the Pb coupons when commercial glass cleaning products were tested (Veja Vidrex® and Cif®) but with a street marketed cleaning product, formates were produced on the metal surface. The results here reported highlight the importance of a careful evaluation of commercial products, particularly cleaning products and paints, aimed to be used inside museums or other institutions that keep artworks or cultural heritage items, considering the potential risk of harmful volatile compounds release that can cause significant damage in the artworks and objects in general.

References

[1]

A. Niklasson, L. G. Johansson, J. E. Svensson, Journal of the Electrochemical Society. 2007, 154, C618.

[2]

J. Tetreault, E. Cano, B. M. Van, D. Scott, M. Dennis, M. G. Barthes-Labrousse, L. Minel, L. Robbiola, Stud-

[3]

ies in Conservation. 2003, 48, 237. D. L. A. de Faria, A. Cavicchioli, T. S. Puglieri, Vibrational Spectroscopy. 2010, 54, 159.

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Evora Cathedral: Pink! Why not?

Tânia Rosado, 1 Andreia Reis, 1 António Candeias, 1 José Mirão, 2 Peter Vandenabeele, 3 Ana Teresa Caldeira 1*

1 HERCULES Laboratory and Evora Chemistry Centre, Évora University, Portugal, +351 266745300, tanocasrosado@gmail.com, candeias@uevora.pt, atc@uevora.pt 2 HERCULES Laboratory and Evora Geophysics Centre, Évora University, Portugal, +351 266745300, jmirao@uevora.pt 3 Gent University, Department of Archaeology, Gent, Belgium, +09 264 47 17, Peter.Vandenabeele@UGent.be

Evora Cathedral or Santa Maria Church is one of the most emblematic monuments in Evora, a Southern Portugal monumental town classified by UNESCO as World Heritage. This monument is the biggest Portuguese Cathedral and has a Romanic-Gothic style, or Gothic with Cistercian and Medicant influences. Its construction dates back to the 13th century and was inspired in the model of Lisbon’s Cathedral and other foreign cathedrals. This monument has suffered several conservation and restoration interventions through the ages, without, however, any type of previous knowledge about the type of mortars and materials used. Recent works [1,2] focused on the material characterization of the renders, have shown that the inner walls of the Cathedral are composed of dolomitic aerial lime mortars with siliceous aggregates similar in composition to the granodiorites of Evora’s region with crushed ceramics as additives which can be dated back to a 16 th century documented rehabilitation intervention. These works, however, were unable to detect any pigment and hence to explain the pink colour that covers the majority of the inner walls surface. The present work reports our search to explain the pink colour of Evora Cathedral inner walls. An integrated approach was envisaged to explore the anthropic or natural sources of the walls pink colour by combining the material characterization of the surface layers with its microbiological study. Several micro-samples of the surface layer were collected with a small chisel for material characterization by scanning electron microscopy coupled with energy dispersive X-ray spectrometry (SEM-EDS), micro-Raman spectrometry and micro X-ray diffraction. For the microbiological assays, samples were aseptically collected in pink areas of the walls, followed inoculation in selective media for microorganisms development. The identification of the microbial isolates was performed based on the macroscopic and microscopic features. Microfragments of mortars were further analised by SEM-EDS and micro-Raman spectrometry [35] to understand the proliferation of the microorganisms and to characterise the chromatic and microstructural alterations observed in the walls. As expected, the material characterization showed no presence of inorganic chromophores and therefore the use of pigments in the mortars. The microbiological study, however, allowed the identification of several bacterial strains (eg Gram+ cocci/bacilli), 3 yeast strains in particular one of the genera Rhodotorula and filamentous fungi, 5 strains of the genera Penicillium, one strain of the genera Cladosporium, mycelium and sterile micelia were also isolated.

Particularly relevant was the fact that, the predominant isolated microrganism colonies, Rhodotorula sp yeast, exhibited a strong pink / dark orange colour that was further investigated to establish the

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effect of its growth on the mortars by different sets of experiments:

- Innoculation of Rhodotorula sp yeast on mortar test specimens for microorganisms proliferation evaluation,

- Insertion of original historical mortar on sterilized liquid culture media under controlled conditions for detection of metabolic compounds,

- Liquid cultures of isolated Rhodotorula sp yeast for production of metabolic compounds.

A) C) B)
A)
C)
B)

Figure 1. a.) Detail of the inner wall of the Évora Cathedral with the SEM micrograph of the mortar with the yeast b.) Isolated yeast culture c.) Raman spectrum of mortar microsample biological contaminated with carotenoids peaks evidenced (carbon-carbon single-bond stretch vibration (1159 cm1) and carbon- carbon double-bond stretch vibration (1525 cm1) of the molecule’s backbone).

The envisaged spectroscopic approach on historical and test specimens, and particularly the micro- Raman spectrometry, allowed evaluating the micro flora proliferation, the presence of oxalates in the mortars, due to the metabolic activity of the microorganisms and carotenoids detection that can be attributed to the development of the Rhodotorula sp yeast. Therefore, the perceived pink color of the Cathedral is due to nature’s process rather than to Human intention.

Acknowledgements This work has been financially supported by the Portuguese Science and Technology Foundation (FCT) through SFRH/BD/65747/2009 PhD grant and contract PEst-OE/QUI/UI0619/2011.

References

[1]

A. S. Silva, P. Adriano, A. Magalhães, J. Pires, A. Carvalho, A. J. Cruz, J. Mirão, A. Candeias, Int. J. Arch.

[2]

Heritage, 2010, 4, 1. P. Adriano, A. Santos Silva, R. Veiga, J. Mirão, A. E. Candeias, Materials Characterization , 2009 , 60, 610.

[3]

J. R. Goodwin, L. M. Hafner, P. M. Fredericks, J. Raman Spectrosc. 2006 , 37, 932.

[4]

S. E. J. Villar, H. G. M. Edwards, M. R. D. Seaward, Spectrochimica Acta Part A. 2004, 60, 1229.

[5]

H. G. M. Edwards, E. M. Newton, J. Russ, J. Molec. Struct. 2000, 245, 550.

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Study of red biopatina composition on sandstone from a historical War Fort in La Galea (Biscay, north of Spain) by means of single point focusing Raman analysis and Raman Imaging combined with microscopic observations

Héctor Morillas, 1 Maite Maguregui, 2 Josu Trebolazabala, 1 Isabel Salcedo, 3 Juan Manuel Madariaga 1*

1 Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country UPV/EHU, Bilbao, Basque Country, Spain, +349 46018298, juanmanuel.madariaga@ehu.es 2 Department of Analytical Chemistry, Faculty of Pharmacy, University of the Basque Country UPV/ EHU, Vitoria-Gasteiz, Basque Country, Spain 3 Department of Vegetable Biology and Ecology, Faculty of Science and Technology, University of the Basque Country UPV/EHU, Bilbao, Basque Country, Spain

For many years, historical buildings have suffered the aesthetical and structural changes caused by cyanobacteria, algae, etc. colonization. Among building materials used in historical buildings sandstone is one of the most used materials together with stone, bricks and mortars. This material can suffer biological colonization and consequently colored biofilms can be formed on its surface, giving as a result the pathology called biodeterioration. In the literature many authors pointed out that the biodeterioration process can promote physical and mechanical stress, chemical changes in the composition of porous building materials, etc. To understand this deterioration process it is important to study the composition of the newly formed biopatina. In this work, the characterization of the nature of main carotenoids and their distribution on red biopatinas formed over the sandstones that constitute the tower in the Fort of Galea, located in Getxo (Basque Country, North of Spain) was carried out. For that purpose, single point focusing Raman analysis and Raman imaging was carried out. This spectroscopic technique was also useful to perform the mineralogical characterization of the sandstone. In order to obtain preliminary results, a portable Raman instrument was also moved to the place where the fort is located, in order to obtain on site Raman spectra of the colonized areas. In the laboratory, and additionally to the Raman analysis, the nature of the main colonizer of the sandstone in the Fort of Galea (see Figure 1-A) was approached using scanning electron microscopy and phase contrast microscopy. On site analysis performed over red biopatinas (see Figure 1-B) with the portable Raman instrument showed the main bands of carotenoids (1526, 1158 and 1006 cm -1 ). This observation indicate that the main colonizer of the sandstone is able to excrete carotenoids or it is an organic pigment constituent of its structure. Raman analysis performed on the laboratory showed that the main components of the sandstone, which acts as the support for the colonization, are quartz, iron (III) oxides or oxihydroxides such as hematite, limonite and lepidocrocite, aluminosilicates such as adularia, ortoclasa, carbon etc. In order to extract more information about the nature of the main colonizer, samples were observed under phase contrast optical microscopy and scanning electron microscopy (see Figure 1-C and D). According to the SEM and optical microphotographs, it can be concluded that an algae is the main colonizer of the red biopatina that belongs to a genus of filamentous green chlorophyte algae, specifically in the family of Trentepohliaceae. Trentepohlia algae can provide a very efficient biological system for harvesting solar energy for the production of organic compounds through the photosynthetic process. Concretely, the identification

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of β-carotene crystals (see Figure 1-C, D and E) in the pigment globules suggests that the algae have developed a defense system against photooxidative and oxidative damages. Apart from β-carotene, scytonemin (see Figure 1-F) was also identified in some areas of the red biopatina. This yellow-brown pigment is usually present in the extracellular sheaths of cyanobacteria. The presence of this organic pigment could suggest a combined presence of Trentepohlia and cyanobacteria. To understand better the distribution of β-carotene and scytonemin over the Trentepohlia, Raman imaging on β-carotene crystals and scytonemin was carried out.

on β-carotene crystals and scytonemin was carried out. Figure 1. a.) The Tower of Fort of

Figure 1. a.) The Tower of Fort of Galea. b.) A detail of the red colonization on the sandstone of the fort. c.) Microphotography obtained with the phase contrast microscope showing Trentepohlia alga and its β-carotene crystals in the pigment globules. d.) SEM microphography showing β-carotene crystal. e.) Raman spectrum of β-carotene and f.) Raman spectrum of Scytonemin.

Acknowledgements This work was financially supported by DEMBUMIES (ref.BIA2011-28148) funded by (MINECO). H.Morillas is grateful to the University of the Basque Country (UPV-EHU) and mainly to the action UFI 11-26 Global Change and Heritage, who funded his pre-doctoral fellowship.

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Raman and non invasive IR analyses of natural organic coatings:

application to historical violin varnishes

Céline Daher, 1,3 * Ludovic Bellot-Gurlet, 1 Stéphane Vaiedelich, 2 Jean-Philippe Echard 2

1 Laboratoire de Dynamique, Interactions et Réactivité (LADIR), UMR7075, UPMC-CNRS, Paris, France

2 Laboratoire de Recherche et de Restauration, Musée de la Musique, Cité de la Musique, Paris, France

3 Centre de Rechercheet de Restauration des Musées de France (C2RMF), Palais du Louvre, Paris, France, +33 1 40 20 24 22, cel.daher@gmail.com

During the eighteenth century in Europe, musical instruments’ varnishes have been essentially made with an oil base (linseed oil, in most cases) to which terpenic resins have been added, such as colophony, Venice turpentine, mastic, etc [1] . Moreover, these varnishes were sometimes slightly pigmented for a light red color. The most used approaches determining the composition of ancient varnishes were based on destructive analyses of micro samples, mainly gas chromatography methods coupled to mass spectrometry. [2,3] Other analytical approaches, non-destructive and even non-invasive ones, have been investigated. Indeed, previous studies [46] show that Raman and Infrared spectroscopies can identify and discriminate between natural organic media. The pigments inclusions can also be identify using vibrational spectroscopies whether for mineral pigments or organic ones.

A first aspect of this study is to characterize historical varnishes by using a totally non-invasive

technique, IR spectroscopy in a specular reflection mode for the varnish analyses. [7] However, using this unusual mode can present difficulties for the spectra interpretation; the bands have often a derivative shape, [8] and no databases of such spectra are available yet. In order to get a better understanding

of the obtained spectra and to be able to characterize the vibrational features, the Kramers Kronig

transformation (KKT) has to be applied. In order to validate this new approach, model experimental varnishes were analyzed both in specular reflection mode then KKT-corrected, and in conventional absorbance mode, showing that the spectral features were similar.

The studied stringed instruments, kept in the Musée de la Musique in Paris, are from the 18 th and early 19 th centuries and from different European violin makers: Antonio Stradivari and Giuseppe Guarneri ‘del Gesù’ (Italy), Gabriel Buchstetter and Leopold Widhalm (Germany) and Nicolas Lupot (France). In situ IR spectroscopy in reflectance mode appeared to be the most suitable non-invasive and non- destructive technique to date to allow the characterization of their organic coatings. The presented results show the influence of the instrument’s surface aspect (conservation state) on the reflectance spectra: The more smooth and reflective the object surface is, the better is the signal, which is however difficult to meet on ancient objects. Nevertheless, it has been possible to positively characterize the nature of the upper varnish layer, but also the chemical nature of the underlayer, visible on lacunar or erosion areas.

The second aspect is to characterize the colored red grains by Raman spectroscopy. Tests by portable 785 nm Raman were unfortunately not successful; the fluorescence of the varnish hampered the Raman signal. Therefore, micro-samples were taken from three instruments by A. Stradivary were analyzed using a bench top instrument working at 458 nm [9] . The red particles appeared to be a mix between an anthraquinonic organic pigment (possibly carminic acid) and inorganic iron oxide (hematite).This

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study is a first example of non-invasive analyses of natural organic compounds using IR spectroscopy. Moreover, post treatments could be applied on the resulting spectra such as spectral decomposition, in order to get more detailed information of the varnish composition, for instance the different compounds present in mixtures. On the other hand, we attested the presence of a fine dispersion of various pigments by Raman spectroscopy, documenting the varnishes coloring techniques. Finally, the next step of this study would be to try in situ Raman analyses under a micro-spectrometer of the varnish instrument knowing that the difficulty is actually the moving of these prestigious historical instruments out of the museum.

References

[1]

J.-P. Echard and B. Lavedrine, J. Cult. Herit. 2008, 9, 420.

[2]

J.-P. Echard, C. Benoit, J. Peris-Vicente, V. Malecki, J. V. Gimeno-Adelanto, S. Vaiedelich, Anal. Chim. Acta.

[3]

2007, 584, 172. G. Chiavari, S. Montalbani and V. Otero, Rapid Commun. Mass Sp. 2008, 22, 3711.

[4]

P. Vandenabeele, B. Wheling, L. Moens, H. Edwards, M. De Reu, G. Van Hooydonk, Anal. Chim. Acta

[5]

2001, 407, 261. C. Daher, C. Paris, A.-S. Le Hô, L. Bellot-Gurlet, J.-P. Echard, J. Raman Spectrosc. 2010, 41, 1204.

[6]

L. Bertrand, L. Robinet, S. X. Cohen, C. Sandt, A.-S. Le Hô, B. Soulier, A. Lattuati-Derieux and J.-P.

[7]

Echard, Anal. Bioanal. Chem. 2011, 399, 3025. W. Vetter and M. Schreiner, e-Preservation Science. 2011, 8, 10.

[8]

C. Miliani, F. Rosi, A. Daveri, B. G. Brunetti, Applied Physics A. 2012, 106, 295.

[9]

J.-P. Echard, L. Bertrand, A. von Bohlen, A.-S. Le Hô, C. Paris, L. Bellot-Gurlet, B. Soulier, A. Lattuati- Derieux, S. Thao, L. Robinet, B. Lavédrine, S. Vaiedelich, Angew. Chem. Int. Edit., 2010, 49, 197.

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Optical Microscopy and Micro-Raman studies of The Hans Memling’s Triptych “The Last Judgment

Ewa Pięta, 1* Justyna Olszewska-Świetlik, 2 Edyta Proniewicz 3

1 Faculty of Chemistry, Jagiellonian University, Kraków, Poland, +48 12 663 22 55, pieta@chemia.uj.edu.pl 2 Department of Painting Technologies and Techniques, The Institute for the Study, Restoration and Conservation of Cultural Heritage, Nicolaus Copernicus University in Toruń, Poland, +48 056 611 38 22, justol@op.pl 3 Faculty of Chemistry, Jagiellonian University, Kraków, Poland, +48 012-663 2077, podstawk@chemia.uj.edu.pl

The general aim of this work, that combines chemical and historical knowledge, was Optical Microscopy and Raman analysis of four multilayered samples taken from four different painting’s parts (three from the central panel and one from the right wing) of the Hans Memling’s Triptych “The Last Judgment” (Figure 1). “The Last Judgment” (1467–1471) by Hans Memling is one of the most precious works of Polish art collections. This outstanding masterpiece belongs to the collection of National Museum in Gdańsk and has been classified as the netherlandish painting.

The Raman spectra of the painting’s cross-sections taken from these samples possess a unique set of bands corresponding to the individual layers [1] . Therefore, these spectra allowed us to determine the chemical composition of each layer in the cross- section of samples. The following pigments were detected: lead white, lead tin yellow type I, cinnabar, red ochre, and carbon black. In all of the cases chalk was used as a ground layer. These results are precious source of information about main features of school of painting presented by Hans Memling. Additionally, our results allow art historians to characterize the influence of different cultures on the Memling’s artistic work and to plan conservation, restoration, and preservation procedures of his paintings.

References

and preservation procedures of his paintings. References Figure 1. Hans Memling, “ The Last Judgment ”,

Figure 1. Hans Memling, “The Last Judgment ”, Netherlands school, National Museum in Gdańsk (photo A. Skowroński).

[1]

E. Pięta, E. Proniewicz, J. Olszewska-Świetlik, Raman spectroscopy for the identification of pigments, dyes, and binding media from the Hans Memling Triptych The Last Judgment, in: On the border of Chemistry and Biology, vol. 29, UAM Press: Poznań, 2012, p. 343.

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Characterization of green copper organometallic pigments and understanding of their degradation process in European easel paintings

Carlotta Santoro, 1,2* Anne-Solenn Le Hô, 2 Sigrid Mirabaud, 3 François Mirambet, 2 Sandrine Pagès-Camagna, 2 Pascal Griesmar, 4 Nadège Lubin-Germain, 1 Michel Menu 2

1 Le laboratoire de Synthèse Organique Sélective et de Chimie bioOrganique (SOSCO, EA 4505), CNRS, Université de Cergy-Pontoise, France, +33134257384, carlotta.santoro@u-cergy.fr

2 Centre de Recherche et Restauration des Musées de France (C2RMF), Paris, France

3 Institut National du Patrimoine (INP), France

4 Laboratoire Système de l’Application des Technologies de l’Information et de l’Energie (SATIE), UMR 8029 CNRS, ENS, Université de Cergy-Pontoise, France

Verdigris and copper resinate are organometallic complexes of Cu(II). They were widely use as pigments in XV th and XVI th centuries for their transparency in glazes. These compounds are often subject to changes with time. There are numerous cases of ageing and darkening, which have caused chromatic alterations in the appearance and tonality of the paintings. [1] The understanding of the alteration mechanism, indispensable to orientate the conservation protocols, is not yet fully elucidate despite several studies. [2,3] In order to clarify the discoloration process it is necessary to get information on the geometry of the copper cluster and the nature of the copper-ligand bonds. The observed discoloration of these pigments has led to the research into the effect of environmental conditions surrounding works of art (light exposure, T) thanks to natural and accelerated ageing. With this aim, a multi analytical methodology has been developed coupling the characterization of real ancient painting samples and model systems (made by various proportion of different pigments and binding media). Model samples were investigated by a set of analytical techniques before and after thermic and light ageing: SEM-EDS, IRTF, Raman, UV-Visible, GC-MS, XAS, EPR. The data collected were compared with those obtained from real samples. Preliminary results show that copper concentration is constant between alterated and non alterated zone, and that the darkening seems not influenced by others metals and elements (like calcium, chloride or sulfur). The darkening is related to reaction between copper and bi/tri unsaturated fatty acids, while saturated and monounsaturated compounds are stable. The alteration is not correlated with hydration of the organometallic complexes but is possibly related to reorganization of the metallic cluster.

References

[1]

C. Altavilla, E. Ciliberto. Appl. Phys. A. 2006, 83, 699-703.

[2]

M. Gunn, G. Chottard, E. Rivière, J. J. Girerd, J.C. Chottard, Studies in Conservation. 2002, 47(1), 12-23.

[3]

L. Cartechini, C. Miliani, B. G. Brunetti, A. Sgamellotti, C. Altavilla, F. Ciliberto, F. D’Acapito, Appl. Phys. A. 2008, 92, 243-250.

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Non-destructive micro-Raman and XRF investigation on parade saddles of the Italian renaissance

Pietro Baraldi, 1 Davide Gasparotto, 2 Claudia Pelosi, 3 Paolo Zannini 1

1 Department of Chemical and Geological Sciences, University of Modena and Reggio Emilia, Italy, +390592055087, pietro.baraldi@unimore.it

2 Galleria Estense, Superintendence BSAE Modena and Reggio Emilia, Modena, Italy

3 Department of Cultural Heritage Sciences, University of Tuscia, Viterbo, Italy

Some parade saddles are preserved in Italian Museums and Institutions with typological and structural differences on their decorations. Two saddles are observable in the Museum of the Bargello in Florence and preserve pigments and gildings on their ivory plaques, but enough obscured by the time patina. One of them is similar to the one in the Estense Gallery: it is one of these special saddles that is chronologically placed in the time of Hercules’ Dukedom in Ferrara (1471-1505). The aim of this research was to identify the materials and techniques used in the Renaissance times to prepare the structure of this kind of saddle, to work the tusks for obtaining the plaques to be carved, to place the plaques on the structure and to decorate them with pigments, dyes and metal sheets. For the time elapsed and the exposition in a case in the Estense Gallery, some parts of these aerodynamic structure may have undergone degradation and alterations and the pigments may have changed they hues as a consequence of their molecular changes. Therefore, all the structure was examined and an analytical procedure was prepared so as to take into consideration many materials on the wooden structure.

The surface of the ivory plaques, covering all the surface of the saddle, is almost all well preserved, as can be observed by carefully inspecting all the details and covered areas, where polychrome survivals could be present. This visual inspection with a digital microscope led to the identification of small pigmented areas with bright colours: red, yellow, green blue and black. Some gilding on Hercules’ hair and on the lion mane can be appreciated. XRF measurements (Bruker instrument) were taken on all the colours ascertained and on the wood structure, the parchment intermediate leaves, the white ivory and each coloured small fragments. Infrared spectra were obtained using a Jasco 4200 Fourier transform spectrometer. The spectral range was 4000 to 400 cm -1 in ATR mode with 16 scans and a resolution of 4 cm -1 .

The micro-Raman spectrometer used in this case was a HE633 transportable from the Jobin Yvon- Horiba with a spatial resolution of 5 µm and with quick detection ability as a result of the CCD detector 1024x256 pixels cooled to -70 °C by the Peltier effect. The spectral resolution was 10 cm -1 . The exciting wavelength was the 632.8 nm red line of a He-Ne laser. A long distance 50x objective was used.

The different ivory plaques of the Hercules of Este saddle exhibit traces of pigments underlining the particular detail. The vegetable parts of the carvings are described by a green composed of a copper salt and an organic part rarely found in artworks. Red is frequently obtained with vermilion, black in the gothic-like writings is in carbon, but in some points there was also indigotine. Both the mane of the lion and of Hercules’s hair are obtained with a gold foil perhaps obtained with the usual gold of the florins of that time. Microscopic details showed the deposition of the gold foil on a whitish preparation with white lead [2] . Blue areas are obtained with a lightly ground azurite, mainly abraded or fallen from those surfaces. In the emblem of the Este that contained blue and yellow, only microscopic areas can still be

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seen. Lead white in many small areas was partly transformed into grey plattnerite. The nails were realized with a copper alloy covered with silver. The ensemble of techniques applied enabled the series of materials and particularly pigments of the Hercules’ saddle to be identified. The most difficult one to be identified was the green jelly pigments, an elaboration of verdigris. This kind of artifact is very attractive and other items should be investigated in order to find similarities and differences and supposing, also on the basis of artistic and historical sources, their possible origin.

Acknowledgements The research could not have been carried out without the permission by the Superintendant BSAE of the Provinces of Modena and Reggio Emilia, dr. Stefano Casciu.

References

[1]

T. Tuohy, Herculean Ferrara, Cambridge University Press: Cambridge, 2009, pp. 187-200.

[2]

P. A. Andreuccetti, The polychromy of stone sculptures in Tuscany between the XIII and XV century, Polistampa Ed., 2008.

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Phoenicians preferred red pigments: micro-Raman investigation on some cosmetics found in Sicily archaeological sites

Cecilia Baraldi, 1,* Giada Freguglia, 1 Elsa Van Elslande, 2 Pamela Toti, 3 Pietro Baraldi, 4 Maria Cristina Gamberini, 1 Claudia Pelosi 5

1 Department of Life Sciences, University of Modena and Reggio Emilia, Modena, Italy, +390592055157, cecilia.baraldi@unimore.it

2 UPMC - Laboratoire d’Archéologie Moléculaire et Structurale UMR 8220, Paris, France, elsa.van_elslande@upmc.fr

3 “Giuseppe Whitaker” Foundation, Palermo, Italy, museo.g.whitaker@tiscali.it

4 Department of Chemical and Geological Sciences, University of Modena and Reggio Emilia, Modena, Italy, +390592055087, pietro.baraldi@unimore.it

5 Department of Cultural Heritage Sciences, University of Tuscia, Viterbo, Italy, +390761357684, pelosi@unitus.it

This research was undertaken in the aim of identifying and getting deeper knoowledge into materials and pigments used in cosmestics concerning the contest of the phoenician settlements in Sicilian territory. In fact, about the typologies of cosmetics in use among the Phoenicians, little is known. On this subject, generally references come from bibliographic latin sources: in antiquity, women preferred to paint white their face, red lips and cheeks, yellowish eyes and black to sorround their look (Pliny the Elder, Naturalis Historia; Ovidius, De medicamine faciei feminae). An interesting aspect of this research is that just one paper is known on Punic cosmetics. [1] In the Museo Archeologico Regionale “Antonino Salinas” (Palermo, Sicily) an important collection of unguentaries coming from the town of Selinunte is preserved. Some of them, finely crafted, come from the sanctuary of Demetra Malophoros, some unguentaries come from the acropolis and some more from the necropolis (dating from the 6th to the 5th century b. C). The sacred area, excavated by Cavallari (1818) and Salinas (1903-1905), have provided a great amount of archaeological materials. In the area where once the acropolis rose, the remains show a mixed village, Phoenician and Greek. In this study, the findings from Salinas were considered, as well as some others from the Museum Conte Agostino Pepoli (Trapani), from the Museum Baglio Anselmi (Marsala) and from the museum of Mozia. The number of glass and fictile unguentaries, pyxis and alabastra examined were large: 142 items from Salinas, 210 from Mozia, 14 from Pepoli and 117 from Baglio Anselmi. This research has completed the one carried out on 210 samples from the Museum of Whitaker Foundation from Mozia, a merely phoenician –punic settlement. [2,3] The samples were analyzed by spectroscopic techniques. The IR spectra were acquired with a spectrophotometer VERTEX 70 (Bruker) FT-IR, equipped with a detector deuterium triglycine sulphate (DTGS). The setting parameters were: resolution 4 cm -1 , spectral range 4000-600 cm -1 , number of scans 32. ATR spectra were recorded using an Elmer Golden-Gate accessory. The micro-Raman spectrometer used in this case was a Labram Model from the Jobin Yvon-Horiba with a spatial resolution of 1 µm and with quick detection ability as a result of the CCD detector 1024x256 pixels cooled to -70°C by the Peltier effect. The spectral resolution was 1 cm -1 . The exciting wavelength was the 632.8 nm red line of a He-Ne laser. Generally the samples were presented as inorganic powders of different colors: white, black, blue and

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red. Though the samples came from different museums, they were considered togheter, since they belonged all to the Phoenician culture and coming from Trapani archaeological sites. The white samples were of two types. The first one was mainly composed of gypsum and anhydrite

mixtures (e.g. Inv No 1680, 1663, 1753); the other type (e.g. pyxes Inv N° 1393, 1451) was composed of fully carbonated cerussite, gypsum and litharge. The second kind of cosmetic corresponded to the most famous Greek cosmetic, called psymition, used by women to white the skin. The first type suggested that, for the same use, alternative materials, cheaper and most readily available, could be employed in the past. The black powders, usually used to outline the eyes, were mostly given by carbon obtained from vegetable combustion (e.g. Inv. N° 1566, 2314, 4313) or, sometimes, from bone combustion (animal charcoal) as for the samples Inv. N° 3140, 1761.

A single blue powder (Inv N° 42259) was consisted by the famous Egyptian blue (CaCuSi4O10).

The love for the red color by Phoenician is evident from the great number of powders of this color, probably used to give color to the cheeks or lips. A wide variety of red minerals was found. In many cases the presence of hematite (e.g. Inv N° 2309, 2689, 4269) was detected.

A large number of pink and red powders containing cinnabar (unguentaries Inv N° 1393, 6480-1,

34396) was observed. No frequent and very interesting is in fact the HgS finding powder into alabastra (e.g. Inv. N° 7317/7, 1255), a holder typically used to contain ointments. Another red pigment was identified as red lead (e.g. Inv N° 1606). Finally, a singular discovery was the presence of red lead chromates chrocoite and phoenicochroite, two very rare minerals (e.g. sample Inv. N° 805, 1-98-2, 4386). In fact, they have never been previously attested for cosmetic use, and also rarely attested in paintings before the end of the 18 th century when it began to be produced industrially.

[4]

The high number of Phoenicians samples taken into examination has allowed to understand the typology of raw materials used by the Phoenicians settled in Sicilian contexts. In this study affects the materials heterogeneity used for the make-up, even for example in comparison to the Roman culture, for which there has come a greater number of samples (sites such as Pompeii, Herculaneum and Oplontis were analyzed by our research group), [5-7] but which revealed a palette less extensive and less refined. In particular, this study identified the use of many kind of red pigments, also very rareof mineral origin.

Acknowledgement. The project couldn’t have been carried out without the kind permission granted by the Superintendence

of Cultural Heritage (Palermo), Museo Archeologico Regionale “Antonino Salinas” (Palermo), Museo

Regionale Pepoli (Trapani), Museo Archeologico Regionale Baglio Anselmi (Marsala).

References

[1] Huqet al., Combined, Appl. Phys. A, 2006, 83, 253–256. [2] G. Freguglia, C. Baraldi, M. C. Gamberini, P. Toti, P. Baraldi, PRIN07- Colors and balms in antiquity:

from the chemical study to the knowledge of technologies in cosmetics, painting and medicine. Aboca, Sansepolcro (Arezzo, Italy), 2-3th December 2010, p. 50-51.

[3] Baraldi, G. Freguglia, M.C. Gamberini, P. Baraldi, 5-8th September 2011, RAA2011, Parma, 2011 , p. 103-

104.

[4] R. J. H. Clark. Chimie, 2002, 5, 7–20. [5] P. Baraldi, C. Fagnano, C. Baraldi, M.C. Gamberini, Automata. 2006 , 1, 49. [6] M. C. Gamberini, C. Baraldi, F. Palazzoli, E. Ribechini, P. Baraldi , Vib. Spectrosc. 2008, 47/2, 82. [7] E. Van Elslande, M. C. Gamberini, C. Baraldi and P. Walter, An overview of the Raman studies on cosmetic powders from Pompeii, 14-18th September 2009. RAA2009, Bilbao, 2009.

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Raman microscopy and X-ray fluorescence for the rediscovering of polychromy and gilding on classical statuary in the Galleria degli Uffizi

Pietro Baraldi, 1 Paolo Bensi, 2 Alessandro Muscillo, 3 Fabrizio Paolucci, 3 Andrea Rossi, 4 Paolo Zannini 1

1 Department of Chemical and Geological Sciences, University of Modena and Reggio Emilia, Italy, +39 0592055087, pietro.baraldi@unimore.it.

2 Department of Sciences for Architecture, University of Genua, Italy

3 Ministry for Cultural Heritage, Uffizi Gallery, Florence, Italy

4 Center for Multispectral Analyses, Modena, Italy

The Uffizi Gallery in Florence is mainly known for its patrimony of Gothic and Renaissance painting, but it has also a considerable collection of Greek and Roman statues. The collection is one of the oldest in Europe and derives from the Medici personal collection and from acquirements during the centuries and donation from noble families. Great part of the statuary is not exposed in the Gallery, and in the aim of showing to the public a greater number of them, the new Museum of Villa Corsini on the hills of Florence was open last year. All the statue have a long stay in the Gallery and/or in the depositories, so that many need a control for their present conservation state. Therefore, a research program was set up in order to control the statues that in turn will be reconsidered for an exhibition or a re-proposal. The items will be studied firstly as they are, nextly as they will be under cleaning and after cleaning, in such a way to follow every detail of the surface and to put in evidence the survivals of polychromy, of metal laminas, the encrustations, the corrosion signs and the biological trace of attack by vegetables. This program is now in progress and till present the procedure has been applied to some famous masterpieces placed in the Tribuna. Some of them showed survival of interesting materials that offer new points for discussion of chronology of art materials and techniques. Research of this kind is now applied in European Museums and devoted to Greek and Roman statuary.

[1-7]

Museums and devoted to Greek and Roman statuary. [1-7] Figure 1. XRF (left) of the preparation