Roman lead and copper mining in Germany their origin and development through time, deduced from lead and copper isotope provenance studies Dissertation zur Erlangen des Doktorgrades Der Naturwissenschaften Vorgelegt beim Fachbereich Geowissenschaften der Johann Wolfgang Goethe-Universität in Frankfurt am Main von Soodabeh Durali-Müller aus Tehran/Iran Frankfurt (2005) Von Fachbereich .............................................................................................. der Johann Wolfgang Goethe – Universität als Dissertation angenommen. Dekan: ................................................................................................ Gutachter: ........................................................................................... Datum der Disputation: ....................................................................... ACKNOWLEDGEMENTS I would like to express my gratitude to Prof. G. Brey for his support and guidance. I profited much from discussions with Prof. S. Weyer, Prof. W. Püttmann and Prof. H.M. von Kaenel. Dr. D. Wigg-Wolf is specially thanked for his valuable comments and for finding me very useful contacts and I thank Dr. Y. Lahaye, Dr. H. Höfer, Dr. Ch. Bendall and A. K. Neumann for helping me in the laboratory and with measurements. I like to thank Dr. H.M. Seitz and Dr. Ch. Bendall for reviewing the German and English text respectively. I would also like to thank those people and institutions, which provided artifacts and ore samples for analysis: For artifacts: Dr. D. Wigg-Wolf: Akademie der Wissenschaften und der Literatur Mainz Prof. G. Fingerlin: Archäologische Denkmalpflege, Freiburg Dr. G. Rasbach and Dr. K.-F. Rittershofer: Römisch-Germanische Kommision, Frankfurt Dr. A. Heising: Archäologie und Geschichte der römischen Provinzen, Johann Wolfgang Goethe Universität Frankfurt Dr. G. Rupprecht and Dr. J. Dolata: Landesamt für Denkmalpflege, Mainz Dr. S. Faust and Dr. L. Schwinden: Landesmuseum, Trier Dr. H. Merten: Bischofliches Museum, Trier Dr. C. Nickel and Dr. M. Thoma: Landesamt für Denkmalpflege, Außenstelle Koblenz Dr. D. Krausse: University of Kiel For ores: Dr. L. Krahn: Fraunhofer IZM, Paderborn Dr. A. Hauptmann and Dr. M. Ganzelewski: Bergbau Museum, Bochum Dr. A. Wiechowski: Institut für Mineralogie und Lagerstättenlehre RWTH, Aachen Dr. K. Schürmann: Mineralogisches Museum der Philipps Universität, Marburg Dr. R. Schumacher: Rheinische Friedrich Wilhelms Universität, Bonn Dr. R.T. Schmitt: Museum für Naturkunde, Universität zu Berlin Dr. Dr. H. Lutz and C. Poser: Naturhistorisches Museum, Mainz Dr. M. Günter: Senckenberg Museum, Frankfurt Dr. U. Neumann: Institut für Geowissenschaften, Universität Tübingen Prof. W. Püttmann: Institut für Atmosphäre und Umwelt, Universität Frankfurt Dr. A. Bechtel: Montanuniversität Leoben, Österreich Above all I wish to thank my parents and my husband, Thomas, for their love, patience and encouragement. ACKNOWLEDGEMENTS ABSTRACT KURZFASSUNG GERMAN SUMMARY INTRODUCTION CHAPTER 1 GEOLOGY AND METALLURGY OF LEAD .....................1 1.1 GEOLOGICAL SETTING........................................................................1 1.2 ORE MINERALIZATION............................................................................1 1.2.1 VARISCAN VEIN-TYPE MINERALIZATION ................................................1 1.2.2 POST-VARISCAN VEIN-TYPE MINERALIZATION IN PALEOZOIC SEDIMENTS...........................................................................................................2 1.2.3 POST-VARISCAN CARBONATE-HOSTED LEAD-ZINC MINERALIZATION OF AACHEN-STOLBERG AND EASTERN BELGIUM .........4 1.2.4 TRIASSIC SANDSTONE-HOSTED ORE IMPREGNATIONS OF MAUBACH-MECHERNICH ...................................................................................4 1.3 METAL OCCURRENCE AND METALLURGY OF LEAD IN ROMAN PERIOD...........................................................................................................6 1.3.1 THE SOURCES OF LEAD IN ROMAN PERIOD ...........................................6 1.3.2 METAL REFINING PROCESSES ...............................................................10 1.4 USE OF LEAD IN ROMAN PERIOD ........................................................12 CHAPTER 2 ANALYTICAL METHODS...............................................14 2.1 ELEMENTAL ANALYSIS ........................................................................14 2.1.1 INSTRUMENTATION ..................................................................................14 2.1.2 SAMPLE PREPARATION...........................................................................14 2.2 LEAD ISOTOPE ANALYSIS....................................................................14 2.2.1 INSTRUMENTATION ..................................................................................14 2.2.2 SAMPLE PREPARATION...........................................................................15 2.2.3 STANDARD.................................................................................................15 2.3.4 COMPARING THE RESULTS OF THE MEASUREMENTS WITH TIMS AND MC-ICP-MS ..........................................................................................................16 2.3.5 COMPARING THE LASER MC-ICP-MS AND SOLUTION MC-ICP-MS RESULTS OF LEAD ISOTOPE ANALYSIS.........................................................19 2.4 COPPER ISOTOPE ANAYLSIS ..............................................................20 2.4.1 SAMPLE SELECTION AND ANALYSIS.....................................................20 2.4.2 MEASUREMENT AND STANDARDIZATION ............................................21 2.5 ZINC ISOTOPE ANAYLSIS.....................................................................22 2.5.1 INTRODUCTION .........................................................................................22 2.5.1 SAMPLE PREPARATION AND ANALYSIS ...............................................23 CHAPTER 3 ELEMENTAL ANALYSIS................................................24 3.1 ELEMENTAL ANALYSIS OF GALENA FROM THE RHEINISCHE SCHIEFERGEBIRGE ....................................................................................24 3.1.1 INTRODUCTION .........................................................................................24 3.1.2 RESULTS AND DISCUSSION ....................................................................25 3.2 ELEMENTAL ANALYSIS OF LEAD OBJECTS FROM MAINZ WORKSHOP AND WALDGIRMES ...............................................................29 3.2.1 RESULTS ....................................................................................................29 3.2.2 DISCUSSION ..............................................................................................30 CHAPTER 4 LEAD ISOTOPE ANALYSIS...........................................31 4.1 LEAD ISOTOPE ANALYSIS OF GERMAN ORES ..................................31 4.1.1 INTRODUCTION .........................................................................................31 4.1.2 RESULTS AND DISCUSSION ....................................................................32 4.2 LEAD ISOTOPE ANALYSIS OF LEAD OBJECTS.................................. 35 4.2.1 INTRODUCTION .........................................................................................35 4.2.2 RESULTS ....................................................................................................38 DANGSTETTEN .............................................................................................38 WALDGIRMES ...............................................................................................39 MAINZ.............................................................................................................41 MARTBERG ...................................................................................................44 TRIER..............................................................................................................48 WALLENDORF...............................................................................................54 DÜNSBERG....................................................................................................55 4.2.3 DISCUSSION ..............................................................................................57 4.2.4 CONCLUSION.............................................................................................59 CHAPTER 5 ELEMENTAL AND ISOTOPIC ANALYSIS OF COPPER ORES AND ALLOYS............................................................................62 5.1 METALLURGY OF COPPER ..................................................................62 5.1.1 INTRODUCTION .........................................................................................62 5.1.2 MINING AND MINERALS............................................................................62 5.1.3 COPPER ALLOYS ......................................................................................64 5.2 ELEMENTAL ANALYSIS ........................................................................67 5.2.1 INTRODUCTION .........................................................................................67 5.2.2 RESULTS ....................................................................................................68 5.2.3 DISCUSSION ..............................................................................................70 5.3 COPPER ISOTOPE ANALYSIS ..............................................................71 5.3.1 INTRODUCTION .........................................................................................71