University of Bradford eThesis This thesis is hosted in Bradford Scholars – The University of Bradford Open Access repository. Visit the repository for full metadata or to contact the repository team © University of Bradford. This work is licenced for reuse under a Creative Commons Licence. THE PROVENANCE OF BRONZE AGE POTTERY FROM CENTRAL AND EASTERN GREECE The analysis of Bronze Age pottery from Eastern Thessaly, Boeotia and Euboea by optical emission and atomic absorption spectroscopy, and considerations of its place of manufacture. i Thesis submitted for the degree of Doctor of Philosophy by Selina WHITE, B. A., Dip. Arch. Sci. University of Bradford Postgraduate School of Studies in Physics .r September, 1981 Selina White. ABSTRACT The Provenance of Bronze Age Pottery from Central and Eastern Greece. Samples from nearly 800 Bronze Age pottery sherds from Euboea, Eastern Boeotia and Eastern Thessaly were analysed together with 9 raw clays from the same areas. The-analysis was carried out in an attempt to identify areas of pottery manufacture, to discover the origin of spec- ific groups of pottery, to relate pottery to, raw clays and to see how far pottery compositions can be associated with, and predicted by, geo- logy. The work was done on the same lines as earlier studies at the Oxford Laboratory and at the British School at Athens. The main anal- ytical technique used was therefore optical emission spectroscopy. Some 25% of the total number of sherds were also analysed by atomic absorption spectrophotometry so that the results obtained by the two techniques could be compared. The interpretation of the results was facilitated by the use of, computer program packages for cluster and discriminant analysis. Both optical emission and atomic absorption analysis resulted in broadly similar groupings although the absolute concentrations were not directly comparable. The groupings obtained after atomic absorption analysis had the narrower concentration ranges. Nine elements were measured by both techniques but in atomic absorption potassium was added and proved; usefulas an additional discriminant. 777 Six composition groups were distinguished from the data. " One of identified them was as Euboean, 2 as Boeotian and 3 as coming from diff- erent regions of Thessaly. The greatest movement of pottery within these areas was from Euboea to Thessaly. No composition group which originated from outside these regions was identified. Six of the 9 raw clays were associated with the prevailing composition group in the from area which they came. It was not possible to predict trends in pottery composition by examination of the local geology. -i- ACKNOWLEDGMENTS I would like to thank my supervisor, Mr. S. E. Warren for his help, advice and support over the'last three years and Dr. R. E. Jones, Dir- ector of the Fitch Research Laboratory of the British School at Athens, who introduced me to composition and provenance work and to optical emission analysis, and who answered my incessant questions. I would also like to thank the Director of the British School at Athens, Dr. H. W. Catling and all his staff for their help and for making the facilities of the School available to me. I am grateful to the Greek Archaeological Service for permission to take and to analyse samples and to Mr. and Mrs. Kakavoyannis and Mr. in Hourmouziades Volos, Mr. Gallis in Larissa and Dr. K. Kilian-. -, and Dr. Hagg in Athens R. for making the samples available to me. Joseph Maran, Elmar Christman and Robert Avila of Heidelberg selected the Pevkakia samples and provided me with background information; Robert Avila also sampled the sherds from Iolkos, and I would like to thank them for their help. Dr. 0. T. P. K. Dickinson kindly discussed the archaeology and my interpretation of the results and Professor K. Branigan read the Chapter on the archaeological background. I am grateful to both of them for their comments and criticisms. Dr. M. Hughes of the Research Laboratory of the British Museum provided essential advice on atomic absorption spectrophotometry, and Mr. J. Pocock provided me with considerable technical assistance. -ii- I would particularly like to thank Glynis Jones and Paul Halstead for their hospitality, discussions and encouragement, which were more help than they realise. I am especially grateful to my parents and to my brother and sister for their constant support and for their faith in me. My sister also helped with the maps and my mother. with proof-reading. Last, but by no means least, I would like to thank my typist, Mrs. Lilian Carberry, very much indeed for her typing marathon. Fý -iii- PREFACE This thesis describes the analysis by the author of nearly 800 sherds of Bronze Age pottery and 9 raw clays from Central and Eastern Greece with a view to establishing their place of manufacture according to their chemical composition and to answering specific archaeological questions. The analysis was done using optical emission and atomic absorption spect- roscopy. The optical emission analysis was carried out in the Fitch Research Laboratory of the British School at Athens under the supervision of the Director of the laboratory, Dr. R. E. Jones, who also helped to obtain the samples for analysis. The technique used throughout the ana- lysis was that established at the Oxford laboratory in the early 1960s and followed both there and subsequently at the Fitch Laboratory. The Fitch Laboratory's data bank of previous analyses was also used. Nearly a quarter of the samples were also analysed by atomic absorption at the University of Bradford using the method of sample preparation recommended by Dr. M. Hughes of the British Museum Research Laboratory. All of the data was submitted to multivariate analysis using the CLUSTAN and SPSS computer packages at the University of Bradford Computer Centre and with a link to the computer of the University of Manchester. The sherds from the Euboean sites, from five of the Boeotian sites and from 5 of the Thessalian sites are housed in the sherd collection of the British School at Athens and were selected for analysis by the Dir- ector of the School, Dr. H. W. Catling. Dr. Catling also advised on the scope of the project and arranged for the necessary permission to be given for sherds housed in Volos and Larissa Museums to be sampled. The sherds from Thebes in Boeotia are housed in the Swedish Institute in Athens and they were sampled by courtesy of the Director, Dr. R. HUgg. -iv- The remainder of the Thessalian material is housed in the museums of Volos and Larissa. Permission to sample these sherds was given by the Greek Archaeological Service and by the Ephors, Mr. Hourmouziades and Mr. Gallis. Mr. and Mrs. Kakavoyannis of Volos Museum selected the sherds from Velestino which were analysed and provided information about them. The sherds from Argissa and Pevkakia were made available by Dr. K. Ki11dr of the German Institute in Athens. The material from Iolkos was sampled for the author by Mr. Robert Avila. The rest of the sherds were sampled by the author. The discussion and the opinions expressed in the text are the responsibility of the author, /, -V- Abbreviations used in the text (other than those in common usage). OES Optical emission spectroscopy AAS Atomic Absorption Spectrophotometry NAA Neutron Activation analysis XRF X-Ray Fluorescence, analysis BSA Annual of the British School at Athens EBA Early Bronze Age MBA/MH Middle Bronze Age/Middle Helladic LBA/LH Late Bronze Age/Late Helladic USGS United States Geological Survey GAMS Gazetteer and Atlas of Mycenaean Sites. R. Hope Simpson, 1965 GAC Gazetteer of Aegean Civilisation in the Bronze Age. R. Hope Simpson and O. T. P. K. Dickinson, 1979 EUB Prehistoric Euboea: Contributions towards a survey. L. H. Sackett et al., 1966 DF Dr. D. H. French's unpublished survey of Thessaly Hunter The Bronze Age in Thessaly and its environs with Special Reference to Mycenaean Culture. B. Litt. Thesis, oxford, 1954 Oxford Research Laboratory for Archaeology and the History of Art. University of Oxford Athens/Fitch Laboratory. Fitch Research Laboratory of. the British School at Athens A Wavelength v Frequency Y The the for Seidel density log maximum slope of graph over 10 exposure, or the contrast factor for the emulsion of the photographic plate -V1- ml Millilitre P1 Microlitre mg Milligramme ppm Parts per million nm Nanometre = 10-9 metre s. d. Standard deviation x Mean I Intensity D Density S Seidel density Exp Exposure d. c. Direct Current P Percentage absorption A Absorbance -vii- CONTENTS Page No. ACKNOWLEDGMENTS PREFACE iii ABBREVIATIONS v LIST OF PLATES xi LIST OF FIGURES xii CHAPTER 1. INTRODUCTION 1 1.1 Introduction to Composition and Provenance Studies 1 of Aegean Pottery by Spectrochemical Analysis. 1.2. Aims. 15 CHAPTER 2. ARCHAEOLOGY 16 2.1 General Comments. 16 2.2 Late Bronze Age Euboea. 30 2.3. Late Bronze Age Boeotia and Locris. 32 2.4. Bronze Age Thessaly. 34 CHAPTER 3. GEOLOGYAND GEOGRAPHY 38 3.1 Euboea: Geology and Geography. 33 3.2 Boeotia and Locris: Geology and Geography. 42 3.3 Eastern Thessaly: Geology and Geography. 45 CHAPTER 4. SAMPLE CHOICE 50 4.1 General Comments 50 4.2 Euboea. 58 4.3 Boeotia and Locris 69 4.4 Thessaly 69 -V111- Page No. CHAPTER 5. ANALYTICAL TECHNIQUES 80 80 5.1 Choice of Techniques 5.2 Quantitative Optical Emission Spectroscopy 81 5.2.1 Theory 81 5.2.2 Internal Standard 88 5.2.3 Location Standard 90 5.2.4 Choice of Elements 90 5.2.5 Equipment 92 5.2.6 Sample Preparation 97 5.2.7 Analytical Procedure 98 5.2.8 Reading the Photographic Plate 100 5.2.9 Calibration of the Technique 101 5.2.10 Reliability of the Technique 114 5.2.10.1 Precision 114 5.2.10.