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Recent developments in atomic/nuclear methodologies used for the studyof cultural heritage objectsCarlos Roberto Appoloni Citation: AIP Conf. Proc. 1529, 30 (2013); doi: 10.1063/1.4804077 View online: http://dx.doi.org/10.1063/1.4804077 View Table of Contents: http://proceedings.aip.org/dbt/dbt.jsp?KEY=APCPCS&Volume=1529&Issue=1 Published by the American Institute of Physics. Additional information on AIP Conf. Proc.Journal Homepage: http://proceedings.aip.org/ Journal Information: http://proceedings.aip.org/about/about_the_proceedings Top downloads: http://proceedings.aip.org/dbt/most_downloaded.jsp?KEY=APCPCS Information for Authors: http://proceedings.aip.org/authors/information_for_authors

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Recent Developments In Atomic/Nuclear Methodologies Used For The Study Of Cultural

Heritage Objects

Carlos Roberto Appoloni

Departamento de Física, CCE, Universidade Estadual de Londrina – UEL, P.O.Box 6001, CEP 86055-990, Londrina, PR – Brazil; [email protected]

Abstract. Archaeometry is an area established in the international community since the 60s, with extensive use of atomic-nuclear methods in the characterization of art, archaeological and cultural heritage objects in general. In Brazil, however, until the early '90s, employing methods of physics, only the area of archaeological dating was implemented. It was only after this period that Brazilian groups became involved in the characterization of archaeological and art objects with these methodologies. The Laboratory of Applied Nuclear Physics, State University of Londrina (LFNA/UEL) introduced, pioneered in 1994, Archaeometry and related issues among its priority lines of research, after a member of LFNA has been involved in 1992 with the possibilities of tomography in archaeometry, as well as the analysis of ancient bronzes by EDXRF. Since then, LFNA has been working with PXRF and Portable Raman in several museums in Brazil, in field studies of cave paintings and in the laboratory with material sent by archaeologists, as well as carrying out collaborative work with new groups that followed in this area. From 2003/2004 LAMFI/DFN/IFUSP and LIN/COPPE/UFRJ began to engage in the area, respectively with methodologies using ion beams and PXRF, then over time incorporating other techniques, followed later by other groups. Due to the growing number of laboratories and institutions / archaeologists / conservators interested in these applications, in may 2012 was created a network of available laboratories, based at http://www.dfn.if.usp.br/lapac. It will be presented a panel of recent developments and applications of these methodologies by national groups, as well as a sampling of what has been done by leading groups abroad.

Keywords: Archaeometry; Atomic/Nuclear Methodologies; Brazilian Groups; Cultural Heritage PACS: 29.90.+r; 34.90.+q; 89.90.+n; 89.20.Mn

INTRODUCTION

Archaeometry is an established area since the 60's, with extensive use of atomic-nuclear methods in the characterization of art objects, archaeological and cultural heritage in general. In Brazil, until the early '90s, employing methods of physics, it was implemented only the area of archaeological dating, especially those involving the technique of thermoluminescence.

Only in some punctual cases, very few brazilian works employed “non conventional” methodologies for the characterization of archaeological objects (in almost of them the measurements were done abroad). No brazilian group worked systematically employing atomic-nuclear methodologies before '90s, besides dating methodologies.

XXXV Brazilian Workshop on Nuclear PhysicsAIP Conf. Proc. 1529, 30-39 (2013); doi: 10.1063/1.4804077

© 2013 AIP Publishing LLC 978-0-7354-1154-8/$30.00

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In 1992 a member of the Laboratory of Applied Nuclear Physics, State University of Londrina (LFNA / UEL) studied the possibilities of CT in archaeometry [1], as well as the technique of EDXRF analysis of ancient bronzes (Figure 1), working with Prof. Roberto Cesareo, Italy. LFNA measurements in Brazil initiated in 1993 at LIN/CENA/USP and IFUSP/Pelletron. It led in 1994 to formalize Archaeometry (and related issues) among the research lines of LFNA.

The first LFNA research on cultural heritage was the study of a selection of fragments of the archaeological pottery collection of the Historical Museum of Londrina / UEL by Energy Dispersive X-Ray Fluorescence (EDXRF), Rutherford backscattering (RBS ) and Gamma-ray transmission (GRT ) [2,3].

Since then, other brazilian research groups began to get involved with archaeometry.

Due to the growing number of laboratories and institutions / archaeologists / conservators interested in these applications, in may 2010 a network of 11 available laboratories was created, based at http://www.dfn.if.usp.br/lapac.

FIGURE 1. Scanning of a page of the 1992 notebook, which shows the EDXRF data analysis of a

bronze Etruscan bracelet (VIII BC, tomb in the region of Genova).

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BRAZILIAN GROUPS INVOLVED WITH THE CHARACTERIZATION OF CULTURAL HERITAGE OBJECTS

This list will never be completed, as new groups are being formed in Brazil and it is possible that some information could be missing. Only groups which are continuously working on characterization of Cultural Heritage with atomic/nuclear techniques will be nominated. Groups or individuals with works scattered over time, without continuity, will not be mentioned, which doesn’t means that they are not important. Data were taken from CV Lattes / CNPq database (http://lattes.cnpq.br) at august, 2012.

Table 1 shows data about the groups which began to work on this issue in the 1990s. In the table are cited the first publication and the first article about Cultural Heritage, respectively. Similarly, Tables 2 and 3 present data about the groups which began to work on this issue in the 2000s and 2010s, respectively.

TABLE 1. List of the groups which began to work on characterization of Cultural Heritage in the 1990s. For each group are cited the first publication and the first article about Cultural Heritage, respectively.

GROUP

University City/State

First Published work performed in Brazil on Cultural Heritage

objects employing atomic/nuclear methodologies

Applied Nuclear Physics LFNA

Physics Department

UEL

Londrina

PR

1994 (EDXRF, RBS, GRT)

[2 - 4]

Physical and Nuclear Chemistry Group

Chemistry Institute

UFF

Niterói

ES

1995 (NAA)

[5,6]

Group of Meteoritic, Mineralogy and Archaeometry

CBPF

Rio de Janeiro RJ

1996 (Mossbauer)

[7,8]

Nuclear Analytical Techniques Applied to

Environmental and Archeological Studies

IPEN

CNEN

São Paulo

SP

1997 (NAA)

[9,10]

The articles cited in these tables give a good picture of how each brazilian group

begin in the field of characterization of Cultural Heritage objects and the range of methodologies employed at that time.

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Group

University

City/State



Laboratory of Cultural Heritage Characterization

Labens / Chemistry

Engineering Department POLI

USP

São Paulo SP

2003 (XRD, MEV, EIE) [11,12]

Applied Physics with Accelerators

GFAA/DFN/IF/USP +P.R.

Pascholati/DFE/IF/USP

Physics Institute

USP

São Paulo SP

2004 (PIXE) [13, 12]

Nuclear Instrumentation Laboratory

LIN/COPPE

UFRJ

Rio de Janeiro

RJ

2004 (EDXRF)

[14,15]


Group

University

City/State



Archaeological and Heritage Metrology Group

UFPE

Recife

PE

2010 (EDXRF)

[16,17]

LACICOR/EBA Laboratory of Conservations

Sciences

UFMG

Belo

Horizonte MG

2011 (PXRF; other techniques)

[18]

LFNA RECENT WORKS ON CULTURAL HERITAGE

LFNA / UEL has been involved since 1994 with a large variety of Cultural Heritage objects and questions to be answered, with different geometries and matrix, implying in a large range of experimental difficulties to face and solve [19]. Archaeological ceramics has been one of the more frequent object of study since the beginning [2 – 4]

33


1

3

5 67

2

4

1189

1013

12

0

10

20

30

40

50

60

70

80

90

100

0 10 20 30 40 50 60 70 80 90 100Cu content (%)

Ag

cont

ent (

%)

1 - Real with FR 8 - 1/2 Real Cruzado (1st emission)2 - Real with FR 9 - 1/2 Real Cruzado (2nd emission)3 - Real with FR 10 - Real de 3 1/2 Libras4 - Real with FR 11 - Real de 3 1/2 Libras5 - Real with FR 12 - 1/2 Real of 10 Soldos6-1/2 Forte 13 - 1/4 of Real Cruzado7-1/2 Real with F

Reign of King João I

Reign of King Fernando I

and until the present [20], but other materials from polychromatic wood statues to mural paintings, from metal objects to art rock, among many other different kind of objects, have been studied.

Recent study cases performed by LFNA are briefly presented as follows. Analysis of 179 coins from Portugal, Colonial Brazil and Imperial Brazil,

belonging to the Historical National Museum (RJ) were performed in situ by PXRF at the museum, coins of Ag, Au and Cu were measured. One of the interesting results was the verification of currency devaluation in Portugal during the reigns of kings Fernando I (1367-1383) and João I (1385-1433) of Portugal, as depicted in Figure 2 [21].

FIGURE 2. Ag and Cu content in percent for coins minted during the reigns of kings Fernando I (1367-1383) and João I (1385-1433) of Portugal [20].

Another example is the non-destructive study of obsidians sourcing by PXRF. This

study was performed employing obsidians from Ecuador, in collaboration with R. B. Scorzelli (CBPF / RJ) and G. Poupeau (Université Bordeaux 3, Pessac, France). Measurements were performed with two X-rays tubes, one with Ag anode and another with W anode. Twenty samples from three regions were studied: “Mullumica-Callejones” type (obsidians from the Mullumica and Callejones lava flows, Oyacachi samples, and from their related Rio Guambi secondary sources), “Quiscatola-Yanaurcu” type (obsidians from various sub-primary sources of the Quiscatola area) and samples collected among various volcanoclastic deposits of the Cotopaxi volcano (south of Quito). Grouping results obtained by PXRF are as good as PIXE and ICP, as presented at Figures 3A, B and C, respectively [22, 23].

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FIGURE 3A. Two-dimensional plot of the ratios between the concentrations Rb / Rb and Fe / Sr for the Ecuadorian samples measured by PXRF.

FIGURE 3B. Two-dimensional plot of the ratios between the concentrations Rb / Rb and Fe / Sr for the Ecuadorian samples measured by ICP.

0,0 0,5 1,0 1,5

0,014

0,021

MullumicaCotopaxiRio GuambiOyacachiQuiscatola

Rb/F

e

Rb/Sr

0,3 0,6 0,9 1,2 1,5 1,8 2,140

80

120

160

200

240

280

320

CMCSMCTXOYAQSC

Rb/F

e 2O3

Rb/Sr

35


FIGURE 3C. Two-dimensional plot of the ratios between the concentrations Rb / Rb and Fe / Sr for the Ecuadorian samples measured by PIXE.

Rock art is another interesting and important object of study, due to the large

amount of archeological sites in Brazil which presents these kind of paintings. Portable systems allow analysis in the field. The first study was carried out at Jaguariaíva Shelter 1 (Paraná State), by PXRF [24]. More recently, both portable Raman spectroscopy and PXRF have been used to study paintings at Morro Azul Caves 1, 2 and 3, also in Paraná State, employing PCA analysis of the data [25]. As an example of the results, Figure 4 presents the PCA analysis of Raman spectra of different figures and pigment colours.

MORE DATA ABOUT OTHER TWO BRAZILIAN GROUPS ON CULTURAL HERITAGE

Two Brazilian groups which entered in the Cultural Heritage area during the 2000´s (Table 2) also evolved to use many complementary methodologies in order to enhance the quality and confidence of the results, as well as to solve more complex problems presented by conservators and archaeologists.

GFAA/DFN/IF/USP group nowadays employs, besides PIXE, also UV and IR examination, Digital Radiography and Portable XRF. Among the last published papers on Cultural Heritage of this group, it is interesting to cite a work about Pre-Hispanic ceramics analyzed using PIXE and radiographic techniques [26].

LIN/COPPE group, besides EDXRF, employs PXRF, Tomography, Digital Radiography, XRD and Raman spectroscopy. Among the last published papers on Cultural Heritage of this group, it is important to cite a systematic work about the characterization of Brazilian artists palette from the XIX century using PXRF [27].

0,0 0,3 0,6 0,9 1,2 1,5 1,8 2,1 2,480

120

160

200

240

280

320

360

CMCSMCTXGMBOYAQSC

Rb/F

e 2O3

Rb/Sr

36


FIGURE 4. PCA analysis of Raman spectra of different figures and pigment colours at Morro Azul Caves [25].

SOME LEADING RESEARCHERS ABROAD

It is very difficult to choose among so many important researches which have been devoted to the study of Cultural Heritage objects, some of them to talk about. There is also my personal bias. So, taken this into account, I’ll present some information about the work of three leading researches abroad.

René Van Grieken, from the Environmental Analysis Group, Micro and Trace Analysis Centre, University of Antwerp, Antwerp, Belgium has published his first paper on Cultural Heritage in 1997. It was about the evaluation of environmental effects on stone decay phenomena at the cathedral of Bari, Italy [28]. More recently he has performed many works about the characterization of indoor atmospheric particles in museums and their sources, employing many complementary techniques. Two recent papers are representative of these researches [29,30].

Roberto Cesareo, now retired from the Dipartimento di Matematica e Fisica, Università di Sassari, Sassari, Italy, has published his first paper on Cultural Heritage in 1973. It was about nondestructive analysis of early Etruscan gold objects by XRF [31]. Since then he has published hundreds of papers about his researches on Cultural Heritage and also develop scientific collaborations with many Brazilian groups. A representative work is a research which has been taken more than a decade and involved collaborations with many researches in Peru, Italia and Brazil is about the evolution of Pre-Columbian metallurgy from the North of Peru, studied mainly with PXRF and some complementary techniques. The last publication about it was published in 2011 in a 34 pages article [32]. Among the co-authors of this paper are

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members of three Brazilians groups, LFNA – UEL (Table 1), GFAA – USP and LIN – COPPE (Table 2).

Maria Luisa Carvalho, from Atomic Physics Centre, Lisbon University Lisbon, Portugal, has published his first paper on Cultural Heritage in 2002. It was about Arsenic detection in nineteenth century Portuguese King post mortem tissues by energy-dispersive X-ray fluorescence spectrometry [33]. A representative work among her recent research employing many complementary techniques is the study of mural paintings using In Situ XRF, Confocal Synchrotron μXRF, μXRD, Optical Microscopy and SEM-EDS of the Frescoes from Misericordia Church of Odemira, Portugal [34].

As final remarks, for who wants to work in the field of archaeometry, or wants to follow what is going on in this area, among dozens of international congresses about Cultural Heritage (or with sessions on Cultural Heritage), pay attention specially to: (a) International Symposium on Archaeometry (ISA), the 39th International Symposium on Archaeometry - “50 years of ISA” took place in Leuven, Belgium, 28 May – 1 June 2012, web site is http://ees.kuleuven.be/isa2012, where the abstracts can be downloaded - the next meeting will be in 2014; (b) Non-destructive and Microanalytical Techniques in Art and Cultural Heritage (TECHNART) Congress, the TECHNART 2011 took place in Berlin, April 26 - 29, 2011, web site is http://www.technart2011.bam.de, where the abstracts can be downloaded - next meeting will be in 2013.

REFERENCES

1. R. Cesareo, C. R. Appoloni and M. Marabelli, “The impact of X and Gamma Ray Tomography in the field of Archaeometry”, in Proceedings of the III Conferenza Internazionale Sulle Prove Non Distrutive Per Lo Studio Delle Opere D´Arte, 1992, V.01, pp. 262-263.

2. C. R. Appoloni et al., “ A gamma ray study of indian ceramics from southern Brazil”, in Conference Records of the 4th International Conference on Non-Destructive Testing of Works of Art, 1994, V. 01, pp. 135-149.

3. C. R. Appoloni, “Non-destrutive analysis of brazilian archaeological pottery from the region of Londrina city”, in 5th International Conference on Non-Destructive Testing and Environmental Evaluation for Study of Works of Art, 1996, V. 01, pp. 75-88.

4. C. R. Appoloni et al., Revista do Museu de Arqueologia e Etnologia, 1997, v. 2, pg. 135-149. 5. R. M. Latini and A. V. B. Bellido, “Técnicas Nucleares Aplicadas em Arqueologia no Estado do

Acre, Através da Análise por Ativação”, in V Congresso Brasileiro de Geoquímica e III Congresso de Geoquímica dos Países de Língua Portuguesa, 1995.

6. R. M. Latini and A. V. B. Bellido, Química Nova, v. 24, n.6, p. 724-729, 2001. 7. S. Petrick, R. B. Scorzelli, A. M. Rossi, G. Poupeau and A. Seelenfreund, “Mossbauer

spectroscopy: one clue for the deciphering of obsidian aechaeological artefacts provenience”, in Book of Abstracts of Latin American Conference on the Applications of the Mössbauer Effect, 1996.

8. G. Poupeau and R. B. Scorzelli, Revista do Museu de Arqueologia e Etnologia, v. 2, p. 191-215, 1997.

9. C. J. A. S.Munita, M. Alves and R. P. Paiva, “Characterization of Brazilian prehistoric ceramics. Part I”, in First Research Co-Ordinations Meeting of the Co-Ordinated Research Programme on Nuclear Analytical Techniques in Archaeological Investigations, 1997, Washington, USA. June 23 - 26, 1997. v. 1. p. 20-40.

10. C. J. A. S.Munita, R. P. Paiva, M. A. Alves and E. F. Momose, Journal of Radioanalytical and Nuclear Chemistry , v. 244, n.3, p. 575-578, 2000.

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11. A. C. Neiva, R.D. P. B. Hernández, S. C. Lima, V. Costa and H. G. de Melo, “Caracterização Visual, Espectrocópica e por Difração de Produtos de Corrosão de Peças Metálicas do MAE-USP”, in Conservação e Preservação do Patrimônio Histórico - Rede de Materiais e Estruturas do CNPq, 2003, Tiradentes. Conservação e Preservação do Patrimônio Histórico - Rede de Materiais e Estruturas do CNPq, 2003.

12. M. A. Rizzutto at al., Nuclear Instruments & Methods in Physics Research. Section B. Beam Interactions with Materials and Atoms, v. 240, n.1-2, p. 549-553, 2005.

13. M. A. Rizzutto at al., “The external beam facility used to characterize corrosion products in metallic statuettes”, in 8th European Conference on accelerators in applied research and technology, 2004, Paris, France, Program and Resums v. 1. p. 131-131.

14. C. Calza, M. J. Anjos and R. T. Lopes, “X-Ray Fluorescence analysis in pigments from sarcophagus cartonage of an Egyptian mummy”, in Activity Report of Laboratório Nacional de Luz Síncrotron, v. 1, p. 1, 2004.

15. C. Calza, M. J. Anjos, S. M. F. M. de Souza, A. Bracaglion Jr. and R. T. Lopes, Journal of Biological Research, v. LXXX, p. 136-138, 2005.

16. V. K. Asfora at al., “Characterization of pigments of faiences of Brazilian colonial period”, in European Conference on X-Ray Spectrometry, 2010, Abstracts, p. PS2-47.

17. F. Borba et al., Journal of the Brazilian Chemical Society (Impresso), v. 23, p. 958-965, 2012. 18. A. Rosado et al., “Candido Portinari: materials and techniques of a Brazilian modern painter part I”,

in ICOM - CC, 201, Lisboa, Anais do 16th Triennial Conference. 19. C. R. Appoloni, P. S. Parreira and F. Lopes, “Thirteen years of activities on Art, Archaeometry and

Cultural Heritage Conservation at the State University of Londrina Applied Nuclear Physics Laboratory”, in Anais do 1o Simpósio LatinoAmericano sobre Métodos Físicos e Químicos em Arqueologia, Arte e Conservação de Patrimônio Cultural, São Paulo, TecArt, 2007. v. CD-ROM. p. 34-43.

20. R. A. Ikeoka, C. R. Appoloni, P. S. Parreira, F. Lopes and A. M. Bandeira, X-Ray Spectrometry, v. 41, p. 12-15, 2012.

21. P. S. Parreira, C. R. Appoloni, R. M. L Vieira, R. B. Scorzelli, L. Le Corre and M. F. Guerra, ArcheoSciences, v.33, p.313 - 318, 2009.

22. T. D. Galvão, F. Lopes and C. R. Appoloni, “Exame da sensibilidade analítica em sistemas PXRF para análises de obsidianas”, La arqueometría en Argentina y Latinoamérica, 1.a ed. Córdoba-Argentina, Universidad Nacional de Córdoba - Editorial de la Facultad de Filosofía y Humanidades, 2011, pp. 183-188.

23. T. D. Galvão. Elemental chemical characterization and identification of obsidian sources using portable X-ray fluorescence. 2010. Dissertation (MSc in Physics) – State University of Londrina, Coordination of Improvement of Higher Education Personnel (CAPES). Advisor: C. R. Appoloni.

24. C. R. Appoloni, F. Lopes , F. L. Melquiades and C. I. Parellada, FUMDHAMentos, v. 09, p. 555-562, 2010.

25. C. R. Appoloni, C. I. Parellada, F. L. Melquiades, E. I. Jussiani, F. C. Pereira and F. Lopes, “The first in situ portable Raman and XRF study of rock art in South America: paintings from Morro Azul caves in Paraná State, Brazil”, in 6th International Congress on the Application of Raman Spectroscopy in Art and Archaeology, 2011, Parma, Italia. RAA 2011, Book of Abstracts, TIMEO Editore, 2011. p. 98.

26. S. C. Lima, M. A. Rizzutto, N. Added, M. D. L. Barbosa, G. F. Trindade and M. I. D. A. Fleming, Nuclear Instruments & Methods in Physics Research. Section B, Beam Interactions with Materials and Atoms, v. B269, p. 3025-3031, 2011.

27. C. Calza, M. O. Pereira, A. Pedreira and R. T. Lopes, Applied Radiation and Isotopes, v. 68, p. 866-870, 2009.

28. K. Torfs, R. Van Grieken, F. Zezza and N. Garcia, Studies in Conservation , v. 42(4) p. 193-206, 1997.

29. R. Van Grieken and A. Worobiec, Pramana, v.76, No. 2, 2011, p.191–200. 30. B. Krupińska et al., Microchemical Journal,102, 2012, p. 49–53. 31. R. Cesareo and F. W. V. Hase, Kerntechnik, v.15 (2), 1973, p. 565-569. 32. R. Cesareo et al., Journal of Materials Science and Engineering B, v. 1, 2011, p. 48-81. 33. M. L. Carvalho et al., X-ray Spectrometry, v. 31(4), pp. 305-309, 2002. 34. S. Valadas et al., Microscopy and Microanalysis, v. 17 (05), 2011, p. 702 709.

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