Provenance study of the Early Iron Age Knobbed ware in Troia, NW Turkey and the Balkans. Petrographic and geochemical evidence Dissertation zur Erlangung des Grades eines Doktors der Naturwissenschaften der Geowissenschaftlichen Fakultät der Eberhard-Karls-Universität Tübingen vorgelegt von Farkas Pintér aus Budapest 2005 Tag der mündlichen Prüfung: 20. 07. 2005 Dekan: Prof. Klaus G. Nickel, Ph.D. 1. Berichterstatter: Prof. Dr. Muharrem Satır 2. Berichterstatter: Prof. Dr. Ernst Pernicka 3 TABLE OF CONTENTS Summary 7 Zusammenfassung 9 Összefoglalás 11 Acknowledgements 13 1. ARCHAEOLOGICAL EVIDENCE 16 2. IMPORTANCE AND AIM OF THE STUDY 21 3. OVERVIEW OF THE PREVIOUS RESEARCH IN POTTERY ANALYSES 22 3.1. Archaeometrical ceramic studies in Troia 25 4. SAMPLING AND ANALYTICAL METHODS 26 4.1. Sampling 26 4.2. Analytical methods 30 4.2.1. Mineral separation 31 4.2.2. Petrographic analyses and cathodoluminescence investigation (CL) 32 4.2.3. X-ray diffractometry (XRD) 36 4.2.4. X-ray fluorescence spectroscopy (XRF) 38 4.2.5. Radiogenic isotopes (87Sr/86Sr, 143Nd/144Nd) 42 4.2.6. Electron microprobe analysis (EMPA) 45 4.2.7. Neutron Activation Analysis (NAA) 46 5. MAIN GEOLOGICAL FEATURES OF THE STUDY AREAS 47 5.1. Introduction 47 5.2. The Troad 48 5.3. The Avşa Island and surrounding areas 51 5.4. The Thrace basin and its southern coast at the Sea of Marmara 51 (Menekşe Çataği) 5.5. The south-western Strandja Massive (north Turkish Thrace and 53 Ovcarovo) 5.6. The south-eastern Rhodope Mts. (Chal) 55 5.7. The southern Balkanides (Diadovo, Pshenitsevo, and Kirilovo) 57 5.8. The north-eastern Moesian platform (Sborianovo) 59 6. RESULTS 62 6.1. Petrography, mineralogy and phase analysis 62 6.1.1. Petrographic analysis of the sherds and comparative materials 62 6.1.1.1. Troia 65 6.1.1.1.1. Petrography of the comparative materials 65 6.1.1.1.2. Petrography of the sherds; Petrographic group 1 68 6.1.1.2. The Avşa Island 77 6.1.1.2.1. Petrography of the sherd; Petrographic group 2 77 6.1.1.3. Menekşe Çataği East (MCE) and West (MCW) 78 6.1.1.3.1. Petrography of the sherds; Petrographic group 3 78 6.1.1.4. North Turkish Thrace 83 6.1.1.4.1. Petrography of the comparative material 83 6.1.1.4.2. Petrography of the sherds; Petrographic group 4 83 6.1.1.5. Ovcarovo 88 6.1.1.5.1. Petrography of the sherds; Petrographic group 5 88 4 6.1.1.6. Chal 90 6.1.1.6.1. Petrography of the comparative material 90 6.1.1.6.2. Petrography of the sherds; Petrographic group 6 90 6.1.1.7. Diadovo, Pshenitsevo, and Kirilovo 92 6.1.1.7.1. Petrography of the comparative materials 92 6.1.1.7.2. Petrography of the sherds; Petrographic group 7 92 6.1.1.8. Sborianovo 96 6.1.1.8.1. Petrography of the sherds; Petrographic group 8 96 6.1.2. Cathodoluminescence investigation 97 6.1.3. X-ray diffractometry 98 6.1.3.1. Sherds from Troia (TR-7, 12, 19, and 25) 99 6.1.3.2. Sherds from the Avşa Island and Menekşe Çataği (A-1, MCW-6, and MCE-1) 100 6.1.3.3. Sherds from north Turkish Thrace (AT-2, DH-2, HM, and YK-3) 100 6.1.3.4. Sherds from Chal (CH-1 and 3) 101 6.1.3.5. Sherds from Ovcarovo and Sborianovo (OVC-1, 4, and SBO-3) 102 6.1.3.6. Sherds from Diadovo, Pshenitsevo and Kirilovo 103 (DIA-6, 13, PSH-2, and KIR-2) 6.2. Geochemical analyses 104 6.2.1. Geochemical composition of comparative sediments and the sherds 104 6.2.1.1. Comparative sediments and the sherds from Troia 106 6.2.1.2. Comparative sediments and the sherds from Menekşe Çataği 113 6.2.1.3. Comparative sediments and the sherds from north Turkish Thrace 116 6.2.1.4. Comparative sediments and the sherds from Ovcarovo 119 6.2.1.5. Comparative sediments and the sherds from Chal 121 6.2.1.6. Comparative sediments and the sherds from Diadovo-Pshenitsevo, and Kirilovo 123 6.2.1.7. Comparative sediments and the sherds from Sborianovo 126 6.2.2. Radiogenic isotopes 128 6.2.2.1. Troia 128 6.2.2.2. Menekşe Çataği 129 6.2.2.3. North Turkish Thrace 129 6.2.2.4. Chal 129 6.2.2.5. Diadovo-Pshenitsevo 130 6.2.2.6. Sborianovo 131 6.2.3. Electron microprobe analysis (EMPA) 132 6.2.3.1. Sample MCE-1 (Menekşe Çataği) 132 6.2.3.2. Sample AT-2 (north Turkish Thrace) 134 6.2.4. Neutron activation analysis (NAA) 139 6.2.4.1. The sherd from Troia (Tr-20) 139 6.2.4.2. Intermediate volcanite fragments from the sherd MCE-1 and the rock sample Mc-8 (Menekşe Çataği) 140 7. SUMMARY AND INTERPRETATION OF THE RESULTS 142 7.1. The origin of the Knobbed ware 143 7.1.1. Summary and interpretation of the petrographic and cathodoluminescence results 143 7.1.1.1. Troia 143 7.1.1.2. The Avşa Island 146 7.1.1.3. Menekşe Çataği 147 7.1.1.4. North Turkish Thrace 148 7.1.1.5. Ovcarovo 148 5 7.1.1.6. Chal 149 7.1.1.7. Diadovo-Pshenitsevo, Kirilovo 149 7.1.1.8. Sborianovo 150 7.1.2. Summary and interpretation of the chemical data of comparative sediments and the sherds 151 7.1.2.1. Troia 151 7.1.2.2. Menekşe Çataği 155 7.1.2.3. North Turkish Thrace 156 7.1.2.4. Ovcarovo 158 7.1.2.5. Chal 159 7.1.2.6. Diadovo-Pshenitsevo, Kirilovo 160 7.1.2.7. Sborianovo 161 7.1.3. Summary and interpretation of the radiogenic isotope results 163 7.1.4. Summary and interpretation of the EMPA results 166 7.1.5. Summary and interpretation of the NAA results 168 7.1.6. The grouping of the sherds on the basis of their origin 169 7.2. The production technology of the Knobbed ware 170 7.2.1. Possible raw materials used for the pottery production 170 7.2.2. Firing atmosphere of the sherds 172 7.2.3. Maximum firing temperatures of the sherds 173 8. CONCLUSION AND DISCUSSION 176 8.1. General conclusions 176 8.2. Archaeological discussion of the results 178 8.3. General observations concerning the provenance analysis of coarse wares 179 8.4. Open questions resulting from this study 180 LITERATURE 182 APPENDICES Appendix 1. Archaeological description and photographs of the sherds from Troia, Chal, Diadovo, Pshenitsevo, and Kirilovo. 192 Appendix 2. Geological samples analysed in this study. 200 Appendix 3. Petrographic modal composition of the Knobbed ware sherds analysed in this study 202 Appendix 4. Textural features of the Knobbed ware sherds analysed in this study 205 Appendix 5. Measured elements, number of the standards applied, standard deviation (3σ), detection limit, and standard concentrations of the X-ray fluorescence (XRF) analysis 211 Appendix 6. X-ray fluorescence (XRF) data of geological samples 212 Appendix 7. X-ray fluorescence (XRF) data of the sherds 214 Appendix 8. Radiogenic isotope data of geological samples and the sherds analysed in this study 217 Appendix 9. Data of the electron microprobe analysis (EMPA) of the sherds MCE-1 and AT-2 218 Appendix 10. Data of the neutron activation analysis (NAA) of the sherd TR-20, the volcanite fragments in the sherd MCE-1, and the basalt sample Mc-8 220 Curriculum vitae 221 6 7 Summary At the beginning of the Early Iron Age in Troia, in the settlement phase VIIb2 (ca. 1100-1000 B.C.), new vessel forms (Knobbed ware or in German Buckelkeramik) of hand-made pottery appeared. The same vessel forms, with similar decoration can be found in several archaeological localities in Turkish Thrace and the Balkans (Bulgaria, SE-Romania). In this geoarchaeological work the primary question is whether there is a possible common origin of the pottery from different regions? Was the Knobbed ware in Troia transported from the Balkans, or do we have to do it with transfer of technological solutions, and the vessels were made on the spot from local material? Moreover, which raw materials and technique (firing temperatures, etc.) were used in producing the ceramics? In order to answer these questions samples of 90 ceramic fragments and 69 comparative geological materials (clayey, silty, sandy sediments, rock fragments, etc.) have been collected from the most important archaeological sites and survey areas of the occurrence of the Knobbed ware: Troia, the Avşa Island, Menekşe Cataği, north Turkish Thrace (near Edirne) in Turkey, and Chal, Ovcarovo, Diadovo, Pshenitsevo, Kirilovo, and Sborianovo in Bulgaria. A complex analytical procedure employed in this study included optical microscopy (petrographic modal and cathodoluminescence), chemical (XRF, NAA, EMPA) radiogenic isotopes of 87Sr/86Sr and 143Nd/144Nd, and XRD (X-ray diffractometry) analyses. In the first step the sherds have been grouped into eight petrographic groups and several subgroups based on their non-plastic inclusion (temper) composition. Using the major and trace elements Mg, K, Rb, Ba, Sr, Nb, Ti, Y, Zr, Fe, V, Cr and Ni, bivariate plots and PAAS-normalised (post-Archaean average Australian Shale) multi-element diagrams were edited in order to determine the local sediment patterns of the different areas based on clayey and sandy sediments (local reference materials), sampled near the archaeological sites.