Anatolian Metal V

Herausgeber: nsal Yaln

Bochum 2011

Montanhistorische Zeitschrift Der ANSCHNITT. Beiheft 24 = Verffentlichungen aus dem Deutschen Bergbau-Museum Bochum, Nr. 180

Titelbild Alacahyk gehrt zu den wichtigsten prhistorischen Stdten in Anatolien. Besonders berhmt sind die frhbronzezeitlichen Frstengrber mit ihren zahlreichen Grabbeigaben aus Gold, Silber und Bronze, darunter die frhesten Eisenfunde Anatoliens. Zum Grabinventar zhlten auch zahlreiche bronzene Sonnenstandarten und Tierfiguren. Im Vordergrund ist eine dieser Sonnenstandarten zu sehen. Sie dient heute als Symbol des Kultur- und Tourismusministeriums der Trkei. Im Hintergrund ist eine schroffe Landschaft bei Derekutuun, Kreis Bayat, Provinz orum zu sehen. In Derekutuun wurde seit dem 5. Jt. v. Chr. gediegenes Kupfer bergmnnisch gewonnen. Im Vordergrund ist eine der prhistorischen Strecken abgebildet. Fotos stammen von Herausgeber.

Diese Publikation entstand mit freundlicher Untersttzung der

Der Anschnitt Herausgeber: Vereinigung der Freunde von Kunst und Kultur im Bergbau e.V. Vorsitzender des Vorstandes: Dipl.-Ing. Bernd Tnjes Vorsitzender des Beirats: Bergassessor Dipl.-Kfm. Dr.-Ing. E.h. Achim Middelschulte Bibliografische Informationen der Deutschen Bibliothek Die Deutschen Bibliothek verzeichnet diese Publikation in der Deutschen Nationalbibliografie; detaillierte bibliografische Daten sind im Internet ber http/dnd.ddb.de abrufbar. Geschftsfhrer: Museumsdirektor Prof. Dr. phil. Rainer Slotta Schriftleitung (verantwortlich): Dr. phil. Andreas Bingener M.A. Editorial Board: Dr.-Ing. Siegfried Mller, Prof. Dr. phil. Rainer Slotta; Dr. phil. Michael Farrenkopf Wissenschaftlicher Beirat: Prof. Dr. Jana Gerlov, Ostrava; Prof. Dr. Karl-Heinz Ludwig, Bremen; Prof. Dr. Thilo Rehren, London; Prof. Dr. Klaus Tenfelde (), Bochum; Prof. Dr. Wolfhard Weber, Bochum Layout: Karina Schwunk ISSN 0003-5238 Anschrift der Geschftsfhrung und der Schriftleitung: Deutsches Bergbau-Museum Bochum Am Bergbaumuseum 28, D-44791 Bochum Telefon (02 34) 58 77 112/124 Telefax (02 34) 58 77 111 http://www.bergbaumuseum.de Einzelheft 9,- Euro, Doppelheft 18,- Euro; Jahresabonnement (6 Hefte) 54,- Euro; kostenloser Bezug fr die Mitglieder der Vereinigung (Jahres-Mitgliedsbeitrag 50,- Euro)

Redaktion nsal Yaln Christian Wirth Layout, Titelgestaltung Angelika Wiebe-Friedrich Druck WAZ-Druck GmbH & Co. KG, Duisburg

ISBN 3-937203-54-0 ISBN 978-3-937203-54-6

Dieser Band ist Robert Maddin gewidmet

Inhaltsverzeichnis

Vorwort Gruwort

9 11

Rainer Slotta & Andreas Hauptmann Robert Maddin and the Deutsches Bergbau-Museum Bochum James D. Muhly Robert Maddin: An Appreciation Mehmet zdoan The Dynamics of Cultural Change in Anatolia H. Gnl Yaln Die Karaz-Kultur in Ostanatolien Ulf-Dietrich Schoop amlbel Tarlas, ein metallverarbeitender Fundplatz des vierten Jahrtausends v. Chr. im nrdlichen Zentralanatolien Horst Klengel Handel mit Lapislazuli, Trkis und Karneol im alten Vorderen Orient Metin Alparslan & Meltem Doan-Alparslan Symbol der ewigen Herrschaft: Metall als Grundlage des hethitischen Reiches nsal Yaln & Hseyin Cevizolu Eine Archaische Schmiedewerkstatt in Klazomenai Martin Bartelheim, Sonja Behrendt, Blent Kzlduman, Uwe Mller & Ernst Pernicka Der Schatz auf dem Knigshgel, Kaleburnu/Galinoporni, Zypern Hristo Popov, Albrecht Jockenhvel & Christian Groer Ada Tepe (Ost-Rhodopen, Bulgarien): Sptbronzezeitlicher ltereisenzeitlicher Goldbergbau Tobias L. Kienlin Aspects of the Development of Casting and Forging Techniques from the Copper Age to the Early Bronze Age of Eastern Central Europe and the Carpathian Basin 127 111 91 85 79 69 53 31 21 17 13

Svend Hansen Metal in South-Eastern and Central Europe between 4500 and 2900 BCE Evgeny N. Chernykh Eurasian Steppe Belt: Radiocarbon Chronology and Metallurgical Provinces Andreas Hauptmann Gold in Georgia I: Scientific Investigations into the Composition of Gold Thomas Stllner & Irina Gambashidze Gold in Georgia II: The Oldest Gold Mine in the World Khachatur Meliksetian, Steffen Kraus, Ernst Pernicka Pavel Avetissyan, Seda Devejian & Levron Petrosyan Metallurgy of Prehistoric Armenia Nima Nezafati, Ernst Pernicka & Morteza Momenzadeh Early Tin-Copper Ore from Iran, a Posssible Clue for the Enigma of Bronze Age Tin Thomas Stllner, Zeinolla Samaschev, Sergej Berdenov , Jan Cierny , Monika Doll, Jennifer Garner, Anton Gontscharov, Alexander Gorelik, Andreas Hauptmann, Rainer Herd, Galina A. Kusch, Viktor Merz, Torsten Riese, Beate Sikorski & Benno Zickgraf Tin from Kazakhstan Steppe Tin for the West? Autorenliste 231 253 211 201 187 173 151 137

Andreas Hauptmann

Gold in Georgia I: Scientific Investigations into the Composition of Gold

The articles Gold in Georgia I, II are dedicated to our friend, colleague and mentor Robert Maddin on the occasion of the award of the Medal of Merit of the Deutsches Bergbau-Museum Bochum

Abstract
This is a joint pilot study between archaeological and natural sciences to explore the technology and provenance of gold artefacts from Georgia. It is focussed on the prehistoric gold mine of Sakdrisi, and of gold artefacts from the 3rd to the 1st millennium BC in Georgia. The study includes the investigation by chemical and lead isotope analyses using ICP-mass-spectrometry. The analyses of the artefacts indicate that the gold which was used to manufacture the artefacts was alloyed with variable amounts of silver. Beside silver, the gold is low in platinum, osmium, and other trace elements. In addition to the analysis of the chemical composition, lead isotope analyses were applied and provided insight into the provenance of gold from the region Georgia-Anatolia-Armenia. No sophisticated treatment of gold could be detected during the Bronze Age but parting was probably applied in the middle of the 1st millennium BC.

Iason). The Roman writer Appian (second century AD) later describes in his book The Mithridatic Wars ( 103, see White 1899) the old and simple technique of washing gold from placers: Many streams in the Caucasus are bearing gold-dust so fine as to be invisible. The inhabitants put sheepskins with shaggy fleece into the stream and thus collect the floating particles . Gold exploitation from placers using skins of sheeps or oxen or other comparable objects is a worldwide artisanal technique used up until the recent past, as shown by activities in Rosia Montana, Rumania (Slotta et al. 2001) or in West Africa (Werthmann 2009). The skin of an ox or a sheep is placed into a gold bearing river. In the flowing water, gold grains due to their high specific weight will be captured in the skin, while light constituents such as sand or clay will be washed away. The fleece with the captured gold grains is taken off the water after a while. Gold is then washed out of the skin, and further processing of the gold follows. The wealth of the Colchis is verified in an extraordinary way by the excavations of 5th to 3rd century BC royal graves of the acropolis at Vani, the capital of the kingdom of Colchis. The amount and the beauty of gold artefacts excavated are outstanding. This finally lead to the designation The golden Colchis (Lordkipanidze 1991). The graves, which are contemporaneous with the Greek colonisation of the eastern coast of the Black Sea, are still under excavation by Katcharava & Kvirkvelia (2008). There is however also gold from earlier periods in Georgia. Earrings were found in the tombs of the Kura-Araxes-Culture, and the manufacture of gold is also known from the Trialeti-Culture in the middle of the 3rd millennium BC (Lordkipanidze 1991). In comparison, these finds are somewhat younger than gold from elsewhere, e.g., from Varna, Bulgaria, where tomb offerings from the late 5th millennium BC, with a total weight of 6 kg were excavated (Higham et al. 2007). In the Southern Levant, gold is known by eight rings or ingots from the

Introduction
The region south of the Great Caucasus, the today state of Georgia, is known by the Greece myth of the Golden Fleece: Iason, a Mycenean hero of royal origin, sailed with his companions, the Argonauts, from Iolkos to the Colchis to demand from king Aietes the Golden Fleece of the ram Chrysomallos. Iason successfully looted the fleece with the help of the kings daughter Medea, the sorceress, who put the guard of the fleece, a dragon, to sleep. The Golden Fleece is a symbol for the recovery of gold from placer deposits. It seems to have its (mythological) origin in the Caucausus. The ancient Greek writer Strabo (first century AD; Geography I, 2, 39, see Jones 1917) sees the Golden Fleece in a wider sense. He states the wealth of the regions about Colchis, which is derived from the mines of gold, silver, iron, and copper, suggests a reasonable motive for the expedition(of

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Fig. 1: Ore deposits and ore occurrences in Georgia and surrounding countries. Note the stars which mark primary gold deposits and placers as well. From: Tvalchrelidze (2001).

middle of the 4th millennium (Gopher et al. 1990). They were found in the cave in the Nahal Qana. As in Georgia, gold is more common in the 3rd millennium BC, as proved by finds from the Royal tombs of Alacahyk, central Anatolia (Koay 1951), from Majkop, North of the Great Caucasus (Munchaev 1975), from Troy (Tolstikow & Treister 1996/97), Ebla (Matthiae et al. 1995), and from Ur, Mesopotamia (Woolley 1934). All these were prestige objects, and were offerings. In opposite, gold did not play any economic role in the Early Bronze Age. In the presented study, we report on the investigation of gold artefacts from various periods in Georgia and on samples of native gold from the two major gold districts in the Greater Caucasus and in Transcaucasia as well. Special attention is paid to the prehistoric gold mine of Sakdrisi, ca. 50 km Southwest of Tbilisi, close to the central area of the Middle Bronze Age Trialeti-Culture (see Gold in Georgia II). Analytical studies and excavations are performed in an ongoing Georgian-German research project. We aim at answering several questions in this project. What sort of gold and how much gold was extracted from Sakdrisi and its vicinity? Are there any characteristic inclusions in the gold such as those of the platinum-group elements, which otherwise could serve as important tracers? Is it possible to collate the composition of the Georgian gold, especially the one from Sakdrisi with artefacts from the Bronze Age Georgia? What did the ancient gold-

smiths know about the treatment of gold, its alloying? When was parting of gold and silver performed? Here, we present results of fieldwork and analytical investigations performed at the laboratories of the Deutsches Bergbau-Museum Bochum and at the Institute of Geoscience, Dept. of Mineralogy, at the Goethe-University Frankfurt/Main. Results obtained so far incl. chemical and lead isotope analyses are published in greater detail in Hauptmann et al. (2010), Hauptmann & Klein (2009), and Stllner et al. (2010).

Gold Districts in Georgia

Among the large number of ore deposits of copper, iron, lead, zinc and of other base metals, there are several gold districts in Georgia which are located in the Greater Caucasus and in the Transcaucasus (Fig. 1). Both primary gold occurrences and (paleo-) placer gold from various geological epochs were found in these districts. In between, north of the capital of Tbilisi, there are some smaller (paleo-) placers in the Aragvi river. Placer gold of subordinated importance was also observed in the lower Chorokhi river near Batumi in Adjaria. All these occurrences were exploited in the recent past (Godabrelidze 1933; see also Hauptmann et al. 2010; Stllner et al. 2010). The by far largest gold districts of Georgia with numerous single manifestations are those of Svaneti / Racha

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Fig. 2: Simplified geological map of Svaneti with primary gold occurrences and of placer gold. Legend: 1 Middle-Upper Cretaceous sediments; 2 Middle Jurassic porphyrite suite; 3 Lower Jurassic schists; 4 Upper Paleozoic Triassic volcanogenic-sedimentary and sedimentary rocks (Dizi series; 5 Middle Jurassic diorites and granodiorites; 6 Upper paleozoic quartz diorites and granodiorites; 7 Upper Paleozoic plagiogneisses and plagiogranites; 8 Upper Paleozoic granitoids; 9 Paleozoic granite-migmatite complex; 10 Geological borders; 11 Thrusts; 12 Tectonic faults; 13 Gold mineralizations; 14 Gold placers. Gold ore mineralizations (black ellipses): 1 Sakeni; 2 Tetnashera; 3 Shkenari; 4 Lukhra; 5 Guli; 6 Khishi; 7 Sgimazuki; 8 Tviberi; 9 Khalde; 10 Arshira; 11 Lasili. Placer gold (yellow ellipses): I Jvari; II Khudoni; III Khaishi; IV Chuberi; V Kharami; VI Lakhamula; VIII Becho; IX Arshira; X Lasili. Slightly revised version by Sergo Nadareishvili after Okrostsvaridze & Bluashvili (2010).

in the Greater Caucasus (Fig. 2) and of Bolnisi / Sakdrisi in the Transcaucasus, close to the border of Armenia (Fig. 3). These should be discussed in more detail.

und Tkibuli. Godabrelidze (1933) notes that basically all those rivers in Georgia are bearing gold which are within the drainage area of these rocks in Svaneti and Racha. Fig. 2 shows some of these localities, and it provides a good overview on the gold district in Svaneti. The map clearly shows that many of the placers mentioned not only originate from gold bearing quartz veins embedded in the huge complex of clay shales of Cretaceous to Jurassic age. Much gold originates from primary sources (quartz-gold-silver-antimony veins) located in PreAlpine crystalline rocks (granitic rocks, gneisses and other metamorphic rocks of the Makera series) which date from the Proterozoic (Precambrian) up to the upper Palaeozoic periods (Adamia 2004). The largest prospect of gold in Svaneti is the Sakeni ore field, where low sulphide quartz-gold-antimony hydrothermal veins are embedded in this crystalline basement. Much of the gold from Svaneti therefore was built in a geological time

Svaneti and Racha

Numerous (sub-)recent and (paleo-) placers occur in the rivers of Enguri, Khrami and Rioni and in their tributes in the Greater Caucasus. In Svaneti in 1850 gold was washed from placers near the village of Ieli in the upper Enguri (Godabrelidze 1933). Other placers were exploited in the tributes Zchumari and Charach near Tetnashera (formerly Teshnieri) and in the river Dolra which flows from the north into the Enguri near Becho, in the Mestia district. This placer is related to a gold-silver bearing quartz veins in lower Jurassic clay shale (Okrostsvaridze & Bluashvili 2010). Placer gold was exploited in considerable quantities at Jvari, and in several rivers in Racha and in Imereti such as the Kvirila, Gubis-Tskali

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Fig. 3: Simplified geological map of the copper-gold-district of Sakdrisi-Bolnisi. A number of primary gold deposits and occurrences are shown along with associated placers. Sakdrisi itself is located in close context to the massive sulfide deposits of Madneuli and David Garedji. The district is built up of basic to intermediate volcanic rocks of Cretaceous to Tertiary age, and of acidic magmatic rocks (Dambludka, Mamulo). Modified after the geologic-tectonic map of the Bolnisi-district, Georgia. Internal version, courtesy Prof. Dr. M. Tschochonelidze, Tbilisi.

period between c. 570 60 million years. As the geology is distinctly different from the gold district of the Bolnisi-Sakdrisi-area in the Transcaucasus, also the gold is expected to be of younger origin. According to modern estimations (Tvalchrelidze 2001), 8000 kg of gold were washed from placers in the Enguri and Khrami rivers since the beginnings. Today reserves of gold in Georgia are estimated to be at c. 100 tons of gold.

oritic composition and some metamorphic rocks occur. They date from the Paleozoic / Proterozoic period. Already in the first half of the last century the gold district of Bolnisi was intensively explored (Godabrelidze 1933). Gold mineralisations can be found at Mamulo, Dambludka, Bneli Khevi, Tetri Tskaro, Lokchai as well as in the modern open cast mines of the volcanogenic massive sulphide deposits (VMS) of David Garedji, Madneuli, Tsiteli Sopeli and at Sakdrisi. Numerous of the rivers in the drainage systems of this area are bearing placer gold, e.g., in the Mashavera and its tributes Dambludka, Karasu und Moshevani in the area of Pinazauri. Here, the prehistoric gold mine of Sakdrisi is located. It is reported (Godabrelidze 1933) that the sediments of the river Dambludka contain up to 2.5 g/t gold but nuggets of several grams were found in the 19th century AD. Here, gold was also mined in the 18th century from hydrothermal quartz-gold/silver veins with pyrite and galena in upper Cretaceous / Jurassic tuff and porphy. Gold from the upper Dambludka, Karasu, Pinazauri and Lok-

Bolnisi
The geological background of the gold bearing prospects and gold placers in the Bolnisi district can be described as follows. The largest part consists of a series of young volcanic rocks of basaltic and andesitic composition (Fig.3). In addition, consolidated pyroclastic sediments (ignimbrites) as well as quartzite and greywacke occur. These rocks are also forming large parts of the Trans caucasian Mountain range, of northeastern Anatolia and of Armenia. Close to the village of Mamulo, and at Dambludka as well intrusions of magmatic rocks of granodi-

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Fig. 4: Simplified geologic-tectonic map of the gold deposit of Sakdrisi-Kachagiani. The prehistoric mine of Sakdrisi which is investigated by the Georgian-German team is located in the Kachagiani site in the upper right corner of the map (see Fig. 5). The extent of the entire gold deposit is several kilometres to the southeast (Mamulisi, Postiskedi, Kviratskhoveli). Scale of the map 1 : 10.000 (from Omiadze 2007).

chai originate from wolframite-molybdenite-scheeliteveins embedded in the intrusion of granodiorites. Cassiterite (SnO2) was observed here as an accessory constituent. Of the same origin is placer gold close to the villages of Mamulo and Grakhevi. Note that the primary gold mineralisations are accompanied by weak mineralisations of mercury (Moon et al. 2001). There is a possibility that there are also prehistoric mines among the countless ancient mines that were observed by modern geologists in this gold district during prospection work at the surface. The gold district of Bolnisi continues further to the south in Jurassic volcanic rocks in the Alaverdi-Kafan metallogenic province in Armenia (Moon et al. 2001), where copper and polymetallic ore deposits of Agvi, Alaverdi, Shamlug and Akhtala are located.

Geological Context of the Prehistoric Mine of Sakdrisi

Next to placer gold this noble metal occurs in the Bolnisi-district in VMS-deposits and in porphyry copper deposits (Tvalchrelidze 2001). VMS are of major importance. They were formed during the early phase (Jurassic to Cretaceous) of the Alpine metallogenesis. They are parts of the Tethyan Eurasian Metallogenetic Belt (TEMB, Jankovic 1997; Moon et al. 2001) which extends from the Alps in the west over the Balkan Mountains, Anatolia, Armenia, Iran to the Himalayas.

The Madneuli polymetallic ore deposit is part of the ArtvinBolnisi unit of the TEMB. It is a hybride between VMS and an epithermal (subvolcanic) gold-silver deposit (Migineishvili 2002). Also the prehistoric copper district of Murgul and at Cerattepe, northeastern Anatolia, belong to this unit (Moon et al. 2001). The ore body of Madneuli is bound to a rhyolithic dome above an intrusion of granodiorite. Kalium-argon-dating of the mineralisation provide an age of 85-93 million years (Moon et al. 2001). Madneuli shows vertical telescoping of a copper-lead/ zinc-baryte-gold mineralisation (Gogishvili et al. 1976). Due to its geochemical stability gold is enriched in the gossan near the surface, where ancient galleries were found (Stllner et al. 2010). Copper is associated in small amount with gold, but economic valuable amounts occur in a depth of ca. 60 m. Sulfobismuthide and telluride occur occasionally. Copper is exploited in the open cast mine of Madneuli by Joint Stock Co. GeoProMining and gold is mined from secondary quarzite by the GeorgianRussian Quartzite Co.. Madneuli and the close by located former open cast mine of David Garedji are in a distance of only a few kilometers from the prehistoric gold mine of Sakdrisi (Fig.3). The area around Sakdrisi itself consists of several prospects (Fig. 4). The Kalium-Argon age of this ore deposit is 77,6 - 83,5 millionen years (Gugushvili et al. 2002). The prehistoric mine Sakdrisi-Kachagiani exploited a swarm of vertical to irregularly formed hydrothermal quartz veins with a thickness of only 10 30 cm. Gangue is barite and hematite (in parts like a stock-

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bonanzas of gold could have been available at the originally untouched Pleistocene surface of the Sakrdisi hill and attracted the prehistoric miners. The gold bearing quartz veins accessible today provide only extremely fine grained flower gold hardly visible with the naked eye. It is questionable if the Bronze Age mining was focussed to extract such fine grained gold. No evidence for the application of metallurgical processes such as amalgamation or cupellation exists which could have been used during this time period at Sakdrisi to enhance the yield of gold hidden in the rocks.

Fig. 5: Section through the gold deposit of Sakdrisi, sites 3 und 4 (Gugushvili et al. 2002). Basically, this section can be transferred to the prehistoric mine of Sakdrisi, however there the veins are exposed to surface. 1 Ignimbrite; 2 Limestone, dolomite; 3 Argillaceous tuff and tuffite; 4 Oxidized and silicified tuff; 5 Silicified and pyritizised tuff; 6 Fault; 7 Goldmineralisation.

Analytical Investigation of Native Gold and of Gold Objects from Georgia

Sampling and Measurements
During the excavation and survey seasons in Georgia we washed numerous gold samples from placers in the districts of Svaneti, Bolnisi and of Tbilisi. Between 500 and 1000 kg of gold bearing gravels were washed using various sized sluice boxes. In addition several hundred of kilograms of channel samples from ore veins and from the backfillings of the prehistoric mine of Sakdrisi were taken. All concentrates obtained were further panned to extract gold grains. In all cases we obtained very fine grained ( 0,1 to 1 mm) flower gold (Fig. 7). We were permitted to take some milligrams of material from 70 Late Bronze Age gold artefacts (Hauptmann et al. 2010). From these samples, and from those of native gold grains collected, mounted samples were prepared for further analytical investigation. They were studied by scanning electron microscopy (SEM), microprobe analyses (EMPA) and mass spectrometry.

Fig. 6: Aerial view of the prehistoric mine of Sakdrisi. Note the exploitation of the criss-cross vertically running gold veins (see Fig. 5). The mine reaches a depth of 27 m. Foto: A. Hauptmann, Deutsches Bergbau-Museum Bochum.

work mineralisations) (Fig. 5). Hostrocks are ignimbrites and other (pyroclastic) volcanic rocks (tuffs) often intensively affected by tectonic activities and metasomatism. The ore deposit of Sakdrisi (Fig. 6) was explored and prospected in the 1980ies. The closer context of the prehistoric mine was studied by Omiadze (2007). Down the hill where the ancient mine is located several prospection galleries were opened which cut parts of the ancient mine at a depth of down to 27 m. Channel samples taken by Georgian geologists gave 23 mt of gold bearing rocks with an average of 1.03 g/t gold (Gugushvili et al. 2002). However gold enrichments up to 50 g/t and even 500 g/t were also analysed from boreholes (personal communication Malkhaz Natsvishvili). Such enrichments were much more reasonable loads for ancient exploitation. We do not exclude that such

Fig. 7: Gold extracted from c. 50 kg of backfillings in the mine of Sakdrisi by panning (white material). The gold left by the ancient miners is extremely fine-grained. Foto: Alexandre Omiadze, Tbilisi.

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Gold in Georgia I: Scientific Investigations into the Composition of Gold

Non-destructive Analyses: Portable X-ray Spectrometry A series of non-destructive chemical analyses on gold objects from the National Museum of Georgia, Tbilisi were performed using a handheld X-ray fluorescence spectrometer (Niton XL.3t, Thermo Scientific) (Fig. 8). Because of its portable character the device could easily be transported to the National Museum so that the objects could be analysed while staying in their museum vaults location. The XRF is applicable to the determination of main and minor element composition of inorganic materials. In our case this means the (semi-) quantitative analysis of the elements gold, silver, copper, iridium, osmium, ruthenium, arsenic, tin. The method is based on the analysis of small spots (diameter of 3 and 8 mm) rather than of large areas, which gives the chance to detect even small inclusions or heterogeneities. As a consequence, in many cases several analyses were performed on one and the same object to characterize its specific compositions.
Fig. 8: Valuable gold artefacts from the National Museum of Georgia were analysed by permission of Prof. Dr. David Lordkipanidze and Dr. Irina Gambachidze non-destructively for their main and minor elements using a portable X-ray spectrometer. Foto: Moritz Jansen, Deutsches Bergbau-Museum Bochum.

Other gold objects from various time periods from the Early Bronze Age Kura-Araxes-culture to the Hellenistic period in the middle of the 1st millennium BC. stored in the vaults of the National Museum of Georgia were analysed non-destructively.

Fire Assaying To provide evidence if Sakdrisi actually was a gold mine, and to determine gold concentrations in the ore veins exploited and the gold concentrations left by the ancients we applied one of the oldest analytical processes was applied: fire assaying. This method is still applied even today in a modern version to determine noble metals in large quantities of noble metal containing ores. Fire assaying comprises several steps: 1. Weighing of the original gold or silver bearing sample. Grinding the material, washing a representative aliquot. 2.Roasting of the concentrate to remove sulphide concentrations of ores.

Fig. 9: Results of fire assaying of several hundred kilograms sample taken from a gold bearing vein in the prehistoric mine of Sakdrisi: A Gold bearing lead ingot ready for cupellation to extract the gold-content. B After cupellation in a porous MgO-crucible the lead oxide is absorbed by the crucible (which is now of yellowish colour), and a gold prill is left. The gold veins contain 6-7 g/t gold, and the backfillings of Sakdrisi 4-6 g/t, in one case 22 g/t. The fire assay was performed by Dr. W. Homann, Dortmund and Sergo Nadareishvili (Homann et al., in prep.). Foto: Sergo Nadareishvili, Tbilisi.

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3. Smelting of a concentrate together with lead or lead containing chemical agents and by adding borax (Na2B4O710H2O). Noble metals will be collected in the lead ingot formed during the smelt (Fig. 9A). 4. The lead ingot will be oxidised by cupellation to lead oxide while the noble metal remains in the metallic state and separates from lead oxide. This will be absorbed by the porous cupel in the liquid state (Fig. 9B). 5. Weighing the noble metal prill. Calculate metal content of the original sample. We took a channel sample of 175 kg from the gold bearing hydrothermal vein in side the mine of Sakdrisi, and we treated more than 600 kg of backfillings and samples from the nearby Kura-Araxes settlement of Dzedzwebi for fire assaying to get an idea about the yield of the ancient miners. The fire assaying was performed by Dr. Wolfgang Homann, Dortmund (Homann et al., in prep., Gambaschidze et al. 2010). Scanning Electron Microscopy (SEM) A selection of 15 samples was studied at the Research Laboratories at the Deutsches Bergbau-Museum Bochum using a SEM/EDS (JEOL 6400/Noran Vantage) to check the gold for possible inclusions of, e. g., platinum group elements or of tellurides, and to analyse (semi-) quantitatively) the main concentrations of gold, silver, copper (and mercury). Electron Microprobe Analysis (EPMA) We applied Electron microscopy with a wavelength system (JEOL 8900 Superprobe) for the quantification of the main and a selection of trace elements to characterise the bulk chemical composition of the material. This preceeding step is necessary to find the appropriate dissolution factor for solution based ICP-MS and also as a base for the Laser Ablation calculation of the trace elements. Laser Ablation Mass Spectrometry with Inductively Coupled Plasma (LA-ICP-MS) for Major, Minor and Trace Element Analysis Trace element and lead isotope analyses were analysed in Frankfurt using a Multi-Collector ICP-Mass-Spectrometer (Finnigan MAT eNeptun). Generally, due to the high cultural value of gold objects destructive sampling as it was permitted here is an exception. We therefore utilised, for comparison, Laser Ablation ICP-Mass-Spectrometry analysis as a non-destructive method, too. This method is most suitable for analysing objects from which only very few material or even none is available for analysis. In Frankfurt, a UP-213 Laser Ablation system (New Wave) was used coupled with an Finnigan Element2 Mass Spectrometer. A measurement method was developed to combine extern standard solutions. Its reproducibility could be verified by multiple measurements (Bendall 2003). In order to check the precision of the method, the copper standard SRM C1252 was used.

Details of these measurements are discussed in Hauptmann & Klein (2010). A handicap of LA-ICP-MS is the unexact analysis of the isotope 204Pb due to the extremely low concentrations of lead in gold, and due to possible contents of mercury. In our evaluation this isotope, therefore, was neglected.

Results and Discussion

Provenance studies of metals are one of the major objectives in archaeology. So far, mainly copper and copper based alloys as well as lead and silver objects were analysed using emission spectrometry. Hartmann (1970, 1982) analysed a large number of gold objects all over Europe. He measured the concentrations of the most important minor elements such silver and copper, but also tin, platinum, nickel, arsenic and bismuth were analysed. It was assumed that the geochemical fingerprint of gold would be largely kept on its way from native gold to the final artefact because no smelting process with major partitioning of chemical elements would occur. It was therefore the opinion that provenance studies to trace the sources of gold would be more successful than those of copper. However provenance studies on gold have been much less significant so far, because apart from silver and copper most of the trace elements in gold exist only in very low concentrations very difficult for analysing. Silver and copper are not suitable as tracers. As a rule, only very small samples were available In comparison between the native gold collected from various localities in Georgia and the analysed gold artefacts it becomes clear that the latter are generally higher in trace elements and in copper than the native gold. The native gold samples, are, except of their silver concentrations remarkably pure. Neither inclusions of platinum-group elements (PGE), Ag-Au tellurides, nor Ag sulfides were detected, although tellurides from nearby Madneuli were described earlier by Migineishvili (2002). We suggest that the higher trace element content of the artefacts is due to an incomplete separation of gold from associated heavy mineral fractions by the Bronze Age gold washers. Such impurifying elements could be partly incorporated from the heavy minerals into the gold during the (s)melting process.

Silver in Gold
Both Bronze Age gold artefacts and native gold show a large range of silver concentrations from 1 up to almost 40 wt.%. Traditionally gold with up to c. 25 wt.% silver is described as gold. If it is a gold-silver alloy with more than c. 25 % silver, then it is named electrum. Hence, a few of the Georgian gold artefacts are made of electrum. Silver is homogeneously distributed within the gold, and

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no particular enrichment of gold was observed as it may occur in nature, or caused by anthropogenic treatments such as gilding techniques. Ag concentrations of this range are not anomalous for native gold, and the match with silver contents of the artefacts points out that silver was not intentionally added to the gold. If intentionally added, the alloy would be expected to be remarkably contaminated by lead. Due to the rare occurrence of native silver, this noble metal was mostly extracted since the 4th millennium BC (Hess et al. 1998; Pernicka et al. 1998) by the cupellation process from Ag-bearing lead ores. Because the lead concentrations range within the lower level of parts per million (or gram per ton) (Fig. 10), we exclude an intentional adding of silver to the gold. Obviously, no parting was performed during the Middle and Late Bronze Age periods in Georgia to increase the gold concentrations of artefacts. However, the remarkable increase of gold-rich compositions in the middle of the 1st millennium BC in gold artefacts from Brili, and from Vani could reasonably be explained by such a process. This is in accord with Babylonian cuneiform tablets from the second millennium BC. Here we find written evidence that gold-silver partitioning was practised during this time period (Reiter 1997). However, there are indications from the 4th and 3rd millennium BC for surface enrichment of gold (or gold-silver alloys, respectively) following the principles of depletion gilding. This was proven for Ur, Mesopotamia by Bachmann (1999), La Niece (1995) and Hauptmann & Klein (in prep.).

Fig. 10: Pb/Ag-diagramm of some gold artefacts from Georgia. Very low lead concentrations and non-correlation between the two elements indicate that silver was not added deliberately to the gold to manipulate the gold, but that it originates primarily from the gold deposits. From Hauptmann et al. (2010).

the 20th century BC, but is was not very common (Dchaparidze 2001). We suggest that copper was relatively enriched in gold artefacts, because native gold grains were insufficiently separated from copper mineral grains while washing the placer material and subsequently introduced into the gold metal during the smelting or melting process.

The Ternary System Gold-Silver-Copper

The diachronic variations of silver and copper concentrations in gold, non-destructive analyses using a portable X-ray spectrometer were made from a number of gold artefacts from the National Museum of Georgia. The results are shown in Fig. 11. As an example for the composition of gold from the middle of the 3rd millennium BC the famous golden lion from Znori Kurgan 2 is presented. The lion is made by lost wax-casting. It contains 70 wt.% gold, 29 wt.% silver, and 1 % copper. The composition of gold from the middle of the 1st half of the 2rd millennium BC is represented by a golden bowl from Trialeti. It is ornamented by twisted wire and inlays of agate. The bowl is higher in gold than the lion from Znori: it contains c. 83 %, 11-12 % silver and 4-7 % copper which is obviously deliberately added. The compositions of the golden artefacts from the acropolis of Vani show a conspicuous increase of gold. 23 bracelets with rams heads at the end with 97 % gold, 2.5 % silver and < 1 % copper. The explanation for this tendency to high fineness gold may have two reasons. Either the source of the gold utilized to make these artefacts has changed during this time period of Greek colonisation. Or the silver rich gold used in earlier periods was treated by parting to get rid of the silver. Clear evidence for a deliberate large scaled parting comes from excavations at Sardis (West Anatolia) from the 6th century BC, the reign of the king Croesus: Furnace fragments, crucibles and

Copper in Gold
Alluvial gold from Georgia contains far below 1 wt.% of copper while almost all gold artefacts contain between 1 and 7.7 wt.% ( c. 3 %). This exceeds the average level of Cu-concentrations in natural gold which otherwise is set at a level of 1-2 % (Hartmann (1982), Tylecote (1987), Pingel (1995). There are three possibilities to explain this phenomenon: 1.) Copper was incorporated by an incomplete separation of gold from the placer or from primary gold deposits. In gold deposits, copper minerals use to be associated with the noble metal. The minerals are reduced during the (s)melting process and are taken up easily by gold. 2.) Copper was deliberately added to gold to manipulate the colour of the gold to a reddish tint, or to enhance its physical properties. While noticeable changes in colour do not occur by only 5 wt.% of copper, the melting temperature is considerably lowered combined with an increase of the hardness (Serner-Rainer, ref. in Bepohl 2003). 3.) Copper was incorporated into the gold by re-melting of gold objects originally decorated e.g. with granulation, i.e., granules soldered with copper. We do not believe that this was the major reason for the copper contents in gold artefacts. As shown by only a few artefacts, granulation was known in Georgia since

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Fig. 11: Composition of gold artefacts from Georgia plotted in the ternary system gold-silver-copper. Note the striking decrease of silver in gold artefacts from the middle of the third to the first millennium BC (above dotted line) which is due to the introduction of the parting process to the Colchis. Exemplified by the lion from Znori, Kurgan 2 (mid 3rd mill. BC), a golden bowl from Trialeti (1st half of the 2nd mill. BC) and a bracelet with two rams from Vani, grave 6 (4th century BC). Modified after Gambaschidze et al. (2010).

gold grains point to the extraction of silver from the legendary placer gold of the river Paktalos (Ramage & Craddock 2000). The extraction of silver from a goldsilver alloy is a based upon the treatment with salt under high temperatures. The metal would be hammered to a sheet and then heated up covered by NaCl. Silver would slowly react with the chloride-ions to form AgCl while gold remains in the metallic state.

watersrand (Oberthr & Saager 1986). Placer-gold of Scotland contained up to 8 % mercury (Leake et al. 1998). The metal was found to be a more common minor component in gold than copper. Arguments in favour of an explanation of point 2 are that historical sources from Georgia report on multiple gold extraction in the 19th century by amalgamation. This seems to have been a widespread technique, and Dilabio et al. (1988) reports about world wide anthropogenic pollution by mercury in gold placer deposits. As we could not exclude anthropogenic input of mercury rich in gold grains from Sakdrisi suspicious grains were sorted out in advance to the lead isotope analysis to avoid contaminations of the natural gold. Hg-containing grains make the analysis of 204Pb impossible, because the isotopes 204 Hg and 202Hg interfere with 204Pb. We did not find any traces of mercury in Bronze Age artefacts. They all were obviously smelted from Hg-free gold.

Mercury a Trappy Element

Among the gold grains that were washed in some rivers near Sakdrisi, Bolnisi and Dambludka, gold-silver-amalgams were identified by EDS-analyses in a scanning electron microscope. Fig. 12 provides the distinct porous texture in a gold grain which is typical for amalgamated gold. It results from the evaporation of mercury by heating gold amalgam. There are two possible explanations for the mercury concentrations in the gold: 1. The amalgams are native and occur in the ore deposits. 2. The amalgams are anthropogenic products and result as debris from historical gold washers activities. Aspects in the favour of explanation point 1 are: goldmercury-compounds occurs in the deposits of the Sakdrisi-Bolnisi district (Moon et al. 2001). This is not uncommon, natural gold may contain up to 6 wt.% mercury, as shown by the paleo-placer deposits of Wit-

Trace Element Concentrations

Trace element concentrations in the gold artefacts from Georgia as analysed by LA-ICP-MS are very low. Of interest may be platinum and osmium contents which reach up to several ppm each. They are positively correlated.

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rope. At the moment, it is open whether or not tin as well as platinum and osmium - can be used as a tracer to find the origin of the Georgian gold. Lead concentrations are about 2 ppm and are at the detection limit necessary for lead isotope analyses.

Lead Isotopy
208Pb/206Pb vs. 207Pb/206Pb-ratios of gold artefacts and of native gold and gold bearing concentrates are shown in a two-dimensional diagram in Fig. 13. Most of the artefacts lie on a virtual line which cut the compositions of ore deposits in the Aegean, Anatolia and Armenia. Although ore deposits from there are designated as copper deposits and the dotted ellipses comprise lead isotope data of copper ores, we have inserted these compositions into the diagram because they are very often gold bearing (Lutz 1990; Yiit 2006). An example is Madneuli (Dsaparidze, in prep.) which is genetically connected with Sakdrisi, and where prehistoric gold mining was found in the surface at the rim of the open mine (see above and Sllner et al. 2010). Also copper ores (and copper and bronze artefacts) from Armenia fall into this range of compositions (Meliksetyan & Pernicka 2010).

Fig. 12: Gold-amalgam grain from a small river in the Bolnisi district. The amalgam alloy consists of 80 82 % Au, 3,5 5,5% Ag und 14-15 % Hg. The porous texture suggests a gold extraction by amalgamation rather than natural amalgam (which is suggested to occur in this region, too). SEM-image, secondary electron mode. From Hauptmann et al. (2010).

We did not find any inclusions in the gold of platinum group elements which might host these elements. We therefore believe that they are dissolved in gold. Tin reaches the highest concentrations (3-50 ppm). However, these values much below those reported by Hartmann (1970, 1982) for gold artefacts from all over Eu-

From the geological point of view this means that most of the gold artefacts from Georgia could originate from ores located in the Mesozoic Alpine folded mountain range of the Pontides and the Transcaucasia. We conclude that the (copper) ore districts in this area are promising candidates to search for at least a part of the Georgian gold artefacts.

Fig. 13: 208Pb/206Pb vs. 207Pb/206Pb-abundance ratios of gold artefacts and native gold from Georgia. For comparison isotope ratios of copper- and lead ores and artefacts from the Aegean, Anatolia and Armenia are shown (after Seeliger et al. 1985; Hauptmann et al. 2002; Meliksetian & Pernicka 2010). Data of the copper deposits of Madneuli from Dchaparidze (in prep.), Murgul from Litz (1990)). Abbrevations: VMS = volcanogenic massive sulfide-deposits; MBA = Middle Bronze Age; LBA = Late Bronze Age.

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The large range of compositions of the isotope ratios may be caused by the time duration of the Alpine orogenesis over several hundred million of years, and by the occurrence of geologically very old lithological units from the Proterozoic period. High 208Pb/206Pb vs. 207Pb/206Pb-ratios in the upper right corner of Fig. 13 such as analysed in samples of native gold from Mamulo, Pinezauri and Dambludka. They all are located in the Bolnisi district and originate from geologically very old mineralisations, i.e., from proterozoic (younger Cambrian) paleozoic magmatic rocks (granites and granodiorites) and shists. Only two samples of gold sheets from the Kurgan of Mrawalskali, in Kacheti (GEO-27/1 and -8) were analysed. In general, such old gold from placers may be intermingled by the precipitation of (sub) recent of gold and, hence, shifted to lower 208Pb/206Pb vs. 207Pb/206Pb-ratios of younger geological ages in the lower left of the diagram. We note a pronounced cluster of gold artefacts at 208Pb/206Pb 2,077 to 2,087 which match the compositions of the gold-bearing copper deposit of Murgul. These are artefacts from Kurgans of Tavkvetili in Meskheti in southern Georgia, from Gantiadi (Dmanisi) and from Mrawalzkali in Kacheti. Some of these artefacts also match the isotopic compositions of the Georgian VMS deposit of Madneuli, and the Armenian ore deposits of Alaverdi, Aghvi and Shamlug in the northern part of the Transcaucasian Mountain Belt (Meliksetyan & Pernicka 2010). A gold ring from Kurgan 18 in Irgantschai (GEO-24/1) shows an isotopic composition comparable to litharge found at the 4th millennium BC settlement of FatmaliKalecik, southeast Anatolia (unpublished data Bochum). Here, silver was extracted (HESS et al. 1998) from polymetallic and gold bearing ores (Bayburtolu & Yldrm 2008). Ample evidence for lead-silver mining was reported by Wagner & ztunal (2000), but a possible gold production was not explored.

databanks in order to argue on a safe statistical basis. This in turn needs ample sampling and/or analysis of gold artefacts and gold from natural deposits. It is of major importance that even valuable gold objects may be analysed in a quasi-non-destructive way as long as they are permitted to be brought to the laboratory. In total we can conclude that during the late 4th millennium gold high in silver was mined in the area of Sakdrisi. Copper concentrations of several weight percent in Bronze Age gold artefacts indicate incomplete separations of copper minerals from gold during the beneficiation. The potential of osmium-, platinum- and other trace element concentrations will be evaluated in further studies.

Acknowledgement
This Georgian German research project is based upon a long term cooperation which began in 1996, and which is proposed to continue. The analytical work as outlined in this paper is part of the entire project. We greatly acknowledge the generous support of Prof. Dr. David Lordkipanidze, Dr. Irina Gambashidze, Dr. Wolfgang Homann und Hildegund Kordon,Dr. Darejan Kacharava, David Melaschvili,Dr. Malkhaz Natsvlishvili, Sergo Nadareischwili, Alex Omiadze, Schota Oniani, Prof. Dr. Michael Tschochonelidze. Special thanks go to PD Dr. Sabine Klein who contributed much of the analytical part of the project. This projekt is supported by the VolkswagenStiftung, Hanover, within the program Im Fokus der Wissenschaft: Lnder Mittelasiens und des Kaukasus.

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Summary and Conclusions

This pilot study presents first results of investigations to reconstruct the technology and origin of archaeological gold artefacts from Georgia. We used various chemical and physical methods to determine main components of artefacts in a non-destructive way, we analysed gold concentrations form soil and rock samples by fire assay. Trace elements were determined using modern ICPMass-spectrometry. Recent developments in massspectrometry during the last ten years or so enabled the analysis of lead isotope (Bendall 2003) and osmium isotope ratios (Junk & Pernicka 2003) to trace back the provenance of gold from raw sources. However, to provide sufficient and convincing answers for archaeological questions we are in need for larger

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