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

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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

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 Tenfel-de (), Bochum; Prof. Dr. Wolfhard Weber, Bochum

Layout: Karina Schwunk

ISSN 0003-5238

Anschrift der Geschftsfhrung und der Schriftleitung:Deutsches Bergbau-Museum BochumAm Bergbaumuseum 28, D-44791 BochumTelefon (02 34) 58 77 112/124Telefax (02 34) 58 77 111http://www.bergbaumuseum.de

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Alacahyk gehrt zu den wichtigsten prhistorischen Stdten in

Anatolien. Besonders berhmt sind die frhbronzezeitlichen Fr-

stengrber mit ihren zahlreichen Grabbeigaben aus Gold, Silber

und Bronze, darunter die frhesten Eisenfunde Anatoliens. Zum

Grabinventar zhlten auch zahlreiche bronzene Sonnenstandar-

ten und Tierguren. Im Vordergrund ist eine dieser Sonnenstan-darten zu sehen. Sie dient heute als Symbol des Kultur- und Tou-

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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.

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Inhaltsverzeichnis

Vorwort 9

Gruwort 11

Rainer Slotta & Andreas Hauptmann

Robert Maddin and the Deutsches Bergbau-Museum Bochum 13

James D. Muhly

Robert Maddin: An Appreciation 17

Mehmet zdoan

The Dynamics of Cultural Change in Anatolia 21

H. Gnl Yaln

Die Karaz-Kultur in Ostanatolien 31

Ulf-Dietrich Schoopamlbel Tarlas, ein metallverarbeitender Fundplatz des vierten Jahrtausends v. Chr.

im nrdlichen Zentralanatolien 53

Horst Klengel

Handel mit Lapislazuli, Trkis und Karneol im

alten Vorderen Orient 69

Metin Alparslan & Meltem Doan-Alparslan

Symbol der ewigen Herrschaft: Metall als Grundlage des hethitischen Reiches 79

nsal Yaln & Hseyin CevizoluEine Archaische Schmiedewerkstatt in Klazomenai 85

Martin Bartelheim, Sonja Behrendt, Blent Kzlduman, Uwe Mller & Ernst Pernicka

Der Schatz auf dem Knigshgel, Kaleburnu/Galinoporni, Zypern 91

Hristo Popov, Albrecht Jockenhvel & Christian Groer

Ada Tepe (Ost-Rhodopen, Bulgarien):

Sptbronzezeitlicher ltereisenzeitlicher Goldbergbau 111

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


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Svend Hansen

Mal sou-ea ad cal euop

bw 4500 ad 2900 Bce 137

Evgeny N. Chernykh

euaa spp Bl: radoabo coology ad Mallugal Pov 151

Andreas Hauptmann

Gold Goga i: s ivgao o compoo of Gold 173

Thomas Stllner & Irina Gambashidze

Gold Goga ii: t Old Gold M Wold 187

Khachatur Meliksetian,Steffen Kraus, Ernst Pernicka

Pavel Avetissyan,

Seda Devejian & Levron Petrosyan

Mallugy of Po Ama 201

Nima Nezafati, Ernst Pernicka & Morteza Momenzadeh

ealy t-copp O fom ia, a Pobl clu fo egma of Boz Ag t 211

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

t fom Kazaka spp t fo W? 231

Auol 253


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Andreas Hauptmann

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middle of the 4thmillennium (Gopher et al.1990). Theywere found in the cave in the Nahal Qana. As in Geor-

gia, gold is more common in the 3rdmillennium BC, asproved by finds from the Royal tombs of Alacahyk,central Anatolia (Koay 1951), from Majkop, North of theGreat Caucasus (Munchaev 1975), from Troy (Tolstikow& Treister 1996/97), Ebla (Matthiae et al. 1995), andfrom Ur, Mesopotamia (Woolley 1934). All these wereprestige objects, and were offerings. In opposite, golddid not play any economic role in the Early Bronze Age.

In the presented study, we report on the investigation ofgold artefacts from various periods in Georgia and onsamples 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 ofSakdrisi, ca. 50 km Southwest of Tbilisi, close to thecentral area of the Middle Bronze Age Trialeti-Culture(see Gold in Georgia II). Analytical studies and excava-tions are performed in an ongoing Georgian-Germanresearch project.

We aim at answering several questions in this project.What sort of gold and how much gold was extracted fromSakdrisi and its vicinity? Are there any characteristic in-clusions in the gold such as those of the platinum-group

elements, which otherwise could serve as important trac-ers? Is it possible to collate the composition of the Geor-gian gold, especially the one from Sakdrisi with artefactsfrom 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 in-vestigations performed at the laboratories of the Deut-sches Bergbau-Museum Bochum and at the Institute ofGeoscience, Dept. of Mineralogy, at the Goethe-Univer-sity Frankfurt/Main. Results obtained so far incl. chemi-cal and lead isotope analyses are published in greaterdetail 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 golddistricts in Georgia which are located in the Greater Cau-casus and in the Transcaucasus (Fig. 1). Both primarygold occurrences and (paleo-) placer gold from variousgeological epochs were found in these districts. In be-tween, north of the capital of Tbilisi, there are some small-er (paleo-) placers in the Aragvi river. Placer gold of sub-ordinated importance was also observed in the lowerChorokhi river near Batumi in Adjaria. All these occur-rences 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 numer-ous single manifestations are those of Svaneti / Racha

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).


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in the Greater Caucasus (Fig. 2) and of Bolnisi / Sak-drisi in the Transcaucasus, close to the border of Arme-nia (Fig. 3). These should be discussed in more detail.

Svaneti and Racha

Numerous (sub-)recent and (paleo-) placers occur in therivers of Enguri, Khrami and Rioni and in their tributesin the Greater Caucasus. In Svaneti in 1850 gold waswashed from placers near the village of Ieli in the upperEnguri (Godabrelidze 1933). Other placers were ex-ploited in the tributes Zchumari and Charach near Tet-nashera (formerly Teshnieri) and in the river Dolra whichflows from the north into the Enguri near Becho, in theMestia district. This placer is related to a gold-silver bear-

ing quartz veins in lower Jurassic clay shale (Okrosts-varidze & Bluashvili 2010). Placer gold was exploited inconsiderable quantities at Jvari, and in several rivers inRacha and in Imereti such as the Kvirila, Gubis-Tskali

und Tkibuli. Godabrelidze (1933) notes that basically allthose rivers in Georgia are bearing gold which are with-in the drainage area of these rocks in Svaneti and Racha.

Fig. 2 shows some of these localities, and it provides agood overview on the gold district in Svaneti. The mapclearly shows that many of the placers mentioned notonly originate from gold bearing quartz veins embeddedin the huge complex of clay shales of Cretaceous toJurassic age. Much gold originates from primary sourc-es (quartz-gold-silver-antimony veins) located in Pre-

Alpine crystalline rocks (granitic rocks, gneisses andother metamorphic rocks of the Makera series) whichdate from the Proterozoic (Precambrian) up to the upperPalaeozoic periods (Adamia 2004). The largest prospect

of gold in Svaneti is the Sakeni ore field, where lowsulphide quartz-gold-antimony hydrothermal veins areembedded in this crystalline basement. Much of the goldfrom Svaneti therefore was built in a geological time

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 PaleozoicTriassic volcanogenic-sedimentary and sedimentary rocks (Dizi series; 5 Middle Jurassic diorites and granodiorites; 6 Upper paleo-zoic quartz diorites and granodiorites; 7 Upper Paleozoic plagiogneisses and plagiogranites; 8 Upper Paleozoic granitoids; 9Paleozoic granite-migmatite complex; 10 Geological borders; 11 Thrusts; 12 Tectonic faults; 13 Gold mineralizations; 14 Goldplacers. 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).


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chai originate from wolframite-molybdenite-scheelite-veins embedded in the intrusion of granodiorites. Cas-siterite (SnO2) was observed here as an accessory

constituent. Of the same origin is placer gold close tothe villages of Mamulo and Grakhevi. Note that the pri-mary gold mineralisations are accompanied by weakmineralisations of mercury (Moon et al. 2001).

There is a possibility that there are also prehistoric minesamong the countless ancient mines that were observedby modern geologists in this gold district during prospec-tion work at the surface. The gold district of Bolnisi con-tinues further to the south in Jurassic volcanic rocks inthe Alaverdi-Kafan metallogenic province in Armenia(Moon et al. 2001), where copper and polymetallic ore

deposits of Agvi, Alaverdi, Shamlug and Akhtala are lo-cated.

Geological Context of the

Prehistoric Mine of Sakdrisi

Next to placer gold this noble metal occurs in the Boln-isi-district in VMS-deposits and in porphyry copper de-posits (Tvalchrelidze 2001). VMS are of major impor-tance. They were formed during the early phase (Jurassicto Cretaceous) of the Alpine metallogenesis. They are

parts of the Tethyan Eurasian Metallogenetic Belt(TEMB, Jankovic 1997; Moon et al. 2001) which ex-tends from the Alps in the west over the Balkan Moun-tains, Anatolia, Armenia, Iran to the Himalayas.

The Madneuli polymetallic ore deposit is part of the Artvin-Bolnisi unit of the TEMB. It is a hybride between VMSand an epithermal (subvolcanic) gold-silver deposit (Mig-

ineishvili 2002). Also the prehistoric copper district ofMurgul and at Cerattepe, northeastern Anatolia, belongto this unit (Moon et al. 2001). The ore body of Mad-neuli is bound to a rhyolithic dome above an intrusion ofgranodiorite. Kalium-argon-dating of the mineralisationprovide 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 thegossan near the surface, where ancient galleries werefound (Stllner et al. 2010). Copper is associated in smallamount with gold, but economic valuable amounts occur

in a depth of ca. 60 m. Sulfobismuthide and tellurideoccur occasionally. Copper is exploited in the open castmine of Madneuli by Joint Stock Co. GeoProMining andgold is mined from secondary quarzite by the Georgian-Russian Quartzite Co..

Madneuli and the close by located former open castmine of David Garedji are in a distance of only a fewkilometers from the prehistoric gold mine of Sakdrisi(Fig. 3). The area around Sakdrisi itself consists of sev-eral prospects (Fig. 4). The Kalium-Argon age of thisore deposit is 77,6 - 83,5 millionen years (Gugushvili et

al. 2002). The prehistoric mine Sakdrisi-Kachagiani ex-ploited a swarm of vertical to irregularly formed hydro-thermal quartz veins with a thickness of only 10 30cm. Gangue is barite and hematite (in parts like a stock-

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


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work mineralisations) (Fig. 5). Hostrocks are ignimbrites

and other (pyroclastic) volcanic rocks (tuffs) often inten-sively affected by tectonic activities and metasomatism.

The ore deposit of Sakdrisi (Fig. 6) was explored andprospected in the 1980ies. The closer context of theprehistoric mine was studied by Omiadze (2007). Downthe hill where the ancient mine is located severalprospection galleries were opened which cut parts ofthe ancient mine at a depth of down to 27 m. Channelsamples taken by Georgian geologists gave 23 mt ofgold bearing rocks with an average of 1.03 g/t gold (Gu-gushvili et al. 2002). However gold enrichments up to

50 g/t and even 500 g/t were also analysed from bore-holes (personal communication Malkhaz Natsvishvili).Such enrichments were much more reasonable loadsfor ancient exploitation. We do not exclude that such

bonanzas of gold could have been available at the orig-inally untouched Pleistocene surface of the Sakrdisi hilland attracted the prehistoric miners.

The gold bearing quartz veins accessible today provideonly extremely fine grained flower gold hardly visiblewith the naked eye. It is questionable if the Bronze Agemining was focussed to extract such fine grained gold.No evidence for the application of metallurgical proc-esses such as amalgamation or cupellation exists whichcould have been used during this time period at Sak-drisi to enhance the yield of gold hidden in the rocks.

Analytical Investigation of Native

Gold and of Gold Objects from

Georgia

Sampling and Measurements

During the excavation and survey seasons in Georgiawe washed numerous gold samples from placers in thedistricts of Svaneti, Bolnisi and of Tbilisi. Between 500and 1000 kg of gold bearing gravels were washed usingvarious sized sluice boxes. In addition several hundredof kilograms of channel samples from ore veins and fromthe backfillings of the prehistoric mine of Sakdrisi weretaken. All concentrates obtained were further panned toextract 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 materialfrom 70 Late Bronze Age gold artefacts (Hauptmann etal. 2010). From these samples, and from those of nativegold grains collected, mounted samples were preparedfor further analytical investigation. They were studied byscanning electron microscopy (SEM), microprobe anal-yses (EMPA) and mass spectrometry.

Fig. 5: Section through the gold deposit of Sakdrisi, sites 3 und4 (Gugushvili et al. 2002). Basically, this section can be transferredto the prehistoric mine of Sakdrisi, however there the veins areexposed to surface. 1 Ignimbrite; 2 Limestone, dolomite; 3 Ar-

gillaceous tuff and tuffite; 4 Oxidized and silicified tuff; 5 Silicifiedand pyritizised tuff; 6 Fault; 7 Goldmineralisation.

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

Fig. 7: Gold extracted from c. 50 kg of backfillings in the mine of

Sakdrisi by panning (white material). The gold left by the ancientminers is extremely fine-grained. Foto: Alexandre Omiadze, Tbilisi.


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Other gold objects from various time periods from the

Early Bronze Age Kura-Araxes-culture to the Hellenisticperiod in the middle of the 1st millennium BC. storedin the vaults of the National Museum of Georgia wereanalysed non-destructively.

Non-destructive Analyses: Portable X-ray

Spectrometry

A series of non-destructive chemical analyses on goldobjects from the National Museum of Georgia, Tbilisiwere performed using a handheld X-ray fluorescencespectrometer (Niton XL.3t, Thermo Scientific) (Fig. 8).Because of its portable character the device could eas-ily be transported to the National Museum so that theobjects could be analysed while staying in their museumvaults location. The XRF is applicable to the determina-tion of main and minor element composition of inorgan-ic materials. In our case this means the (semi-) quanti-tative analysis of the elements gold, silver, copper,iridium, osmium, ruthenium, arsenic, tin. The method isbased on the analysis of small spots (diameter of 3 and8 mm) rather than of large areas, which gives the chanceto detect even small inclusions or heterogeneities. As aconsequence, in many cases several analyses were

performed on one and the same object to characterizeits specific compositions.

Fire Assaying

To provide evidence if Sakdrisi actually was a gold mine,and to determine gold concentrations in the ore veinsexploited and the gold concentrations left by the ancientswe applied one of the oldest analytical processes wasapplied: fire assaying. This method is still applied eventoday in a modern version to determine noble metals inlarge quantities of noble metal containing ores. Fire as-saying 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 con-centrations of ores.

Fig. 8: Valuable gold artefacts from the National Museum of Geor-gia were analysed by permission of Prof. Dr. David Lordkipanidzeand Dr. Irina Gambachidze non-destructively for their main andminor elements using a portable X-ray spectrometer. Foto: MoritzJansen, Deutsches Bergbau-Museum Bochum.

Fig. 9: Results of fire assaying of several hundred kilograms sample taken from a gold bearing vein in the prehistoric mine of Sak-drisi: A Gold bearing lead ingot ready for cupellation to extract the gold-content. B After cupellation in a porous MgO-crucible thelead 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 SergoNadareishvili (Homann et al., in prep.). Foto: Sergo Nadareishvili, Tbilisi.


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3. Smelting of a concentrate together with lead or leadcontaining chemical agents and by adding borax(Na2B4O710H2O). Noble metals will be collected inthe lead ingot formed during the smelt (Fig. 9A).

4. The lead ingot will be oxidised by cupellation to leadoxide while the noble metal remains in the metallicstate and separates from lead oxide. This will be ab-sorbed by the porous cupel in the liquid state (Fig. 9B).

5. Weighing the noble metal prill. Calculate metal con-tent of the original sample.

We took a channel sample of 175 kg from the gold bear-ing hydrothermal vein in side the mine of Sakdrisi, andwe treated more than 600 kg of backfillings and samplesfrom the nearby Kura-Araxes settlement of Dzedzwebifor fire assaying to get an idea about the yield of theancient 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 ResearchLaboratories at the Deutsches Bergbau-Museum Bo-chum using a SEM/EDS (JEOL 6400/Noran Vantage) tocheck the gold for possible inclusions of, e. g., platinumgroup 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 sys-tem (JEOL 8900 Superprobe) for the quantification of themain and a selection of trace elements to characterisethe bulk chemical composition of the material. This pre-ceeding step is necessary to find the appropriate dissolu-tion factor for solution based ICP-MS and also as a basefor 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-Spectrom-eter (Finnigan MAT eNeptun). Generally, due to the highcultural value of gold objects destructive sampling as itwas permitted here is an exception. We therefore uti-lised, for comparison, Laser Ablation ICP-Mass-Spec-trometry analysis as a non-destructive method, too. Thismethod is most suitable for analysing objects from whichonly very few material or even none is available foranalysis. In Frankfurt, a UP-213 Laser Ablation system(New Wave) was used coupled with an Finnigan Ele-ment2 Mass Spectrometer. A measurement method wasdeveloped to combine extern standard solutions. Its

reproducibility could be verified by multiple measure-ments (Bendall 2003). In order to check the precisionof the method, the copper standard SRM C1252 wasused.

Details of these measurements are discussed in Haupt-mann & Klein (2010). A handicap of LA-ICP-MS is theunexact analysis of the isotope 204Pb due to the ex-tremely low concentrations of lead in gold, and due topossible contents of mercury. In our evaluation this iso-tope, therefore, was neglected.

Results and Discussion

Provenance studies of metals are one of the major ob-jectives in archaeology. So far, mainly copper and cop-per based alloys as well as lead and silver objects wereanalysed using emission spectrometry. Hartmann(1970, 1982) analysed a large number of gold objectsall over Europe. He measured the concentrations of themost important minor elements such silver and copper,

but also tin, platinum, nickel, arsenic and bismuth wereanalysed. It was assumed that the geochemical finger-print of gold would be largely kept on its way from nativegold to the final artefact because no smelting processwith major partitioning of chemical elements would oc-cur. It was therefore the opinion that provenance stud-ies to trace the sources of gold would be more success-ful than those of copper. However provenance studieson gold have been much less significant so far, becauseapart from silver and copper most of the trace elementsin gold exist only in very low concentrations very difficultfor analysing. Silver and copper are not suitable as trac-

ers. As a rule, only very small samples were available

In comparison between the native gold collected fromvarious localities in Georgia and the analysed gold arte-facts it becomes clear that the latter are generally high-er in trace elements and in copper than the native gold.The native gold samples, are, except of their silver con-centrations remarkably pure. Neither inclusions of plati-num-group elements (PGE), Ag-Au tellurides, nor Agsulfides were detected, although tellurides from nearbyMadneuli were described earlier by Migineishvili (2002).

We suggest that the higher trace element content of theartefacts is due to an incomplete separation of gold fromassociated heavy mineral fractions by the Bronze Agegold washers. Such impurifying elements could be part-ly incorporated from the heavy minerals into the goldduring the (s)melting process.

Silver in Gold

Both Bronze Age gold artefacts and native gold show alarge range of silver concentrations from 1 up to almost40 wt.%. Traditionally gold with up to c. 25 wt.% silver is

described as gold. If it is a gold-silver alloy with morethan c. 25 % silver, then it is named electrum. Hence, afew 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 mayoccur in nature, or caused by anthropogenic treatmentssuch as gilding techniques. Ag concentrations of thisrange are not anomalous for native gold, and the matchwith silver contents of the artefacts points out that silverwas not intentionally added to the gold. If intentionallyadded, the alloy would be expected to be remarkablycontaminated by lead. Due to the rare occurrence ofnative silver, this noble metal was mostly extracted sincethe 4thmillennium BC (Hess et al. 1998; Pernicka et al.1998) by the cupellation process from Ag-bearing leadores. Because the lead concentrations range within thelower level of parts per million (or gram per ton) (Fig.10), we exclude an intentional adding of silver to thegold. Obviously, no parting was performed during theMiddle and Late Bronze Age periods in Georgia to in-crease the gold concentrations of artefacts. However,the remarkable increase of gold-rich compositions in the

middle of the 1stmillennium BC in gold artefacts fromBrili, and from Vani could reasonably be explained bysuch a process. This is in accord with Babylonian cu-neiform tablets from the second millennium BC. Herewe find written evidence that gold-silver partitioning waspractised during this time period (Reiter 1997). How-ever, there are indications from the 4 thand 3rdmillen-nium BC for surface enrichment of gold (or gold-silveralloys, respectively) following the principles of depletiongilding. This was proven for Ur, Mesopotamia by Bach-mann (1999), La Niece (1995) and Hauptmann & Klein(in prep.).

Copper in Gold

Alluvial gold from Georgia contains far below 1 wt.% ofcopper while almost all gold artefacts contain between1 and 7.7 wt.% ( c. 3 %). This exceeds the averagelevel of Cu-concentrations in natural gold which other-wise 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 separa-

tion of gold from the placer or from primary gold depos-its. In gold deposits, copper minerals use to be associ-ated with the noble metal. The minerals are reducedduring the (s)melting process and are taken up easilyby gold. 2.) Copper was deliberately added to gold tomanipulate the colour of the gold to a reddish tint, or toenhance its physical properties. While noticeable chang-es in colour do not occur by only 5 wt.% of copper, themelting temperature is considerably lowered combinedwith an increase of the hardness (Serner-Rainer, ref. inBepohl 2003). 3.) Copper was incorporated into the goldby re-melting of gold objects originally decorated e.g.

with granulation, i.e., granules soldered with copper. Wedo not believe that this was the major reason for thecopper contents in gold artefacts. As shown by only afew artefacts, granulation was known in Georgia since

the 20th century BC, but is was not very common(Dchaparidze 2001).

We suggest that copper was relatively enriched in goldartefacts, because native gold grains were insufficientlyseparated from copper mineral grains while washing theplacer material and subsequently introduced into thegold metal during the smelting or melting process.

The Ternary System Gold-Silver-CopperThe diachronic variations of silver and copper concentra-tions in gold, non-destructive analyses using a portableX-ray spectrometer were made from a number of goldartefacts from the National Museum of Georgia. Theresults are shown in Fig. 11. As an example for thecomposition of gold from the middle of the 3rdmillen-nium BC the famous golden lion from Znori Kurgan 2 ispresented. The lion is made by lost wax-casting. It con-tains 70 wt.% gold, 29 wt.% silver, and 1 % copper. Thecomposition of gold from the middle of the 1sthalf of the2rdmillennium BC is represented by a golden bowl from

Trialeti. It is ornamented by twisted wire and inlays ofagate. The bowl is higher in gold than the lion from Znori:it contains c. 83 %, 11-12 % silver and 4-7 % copperwhich is obviously deliberately added. The compositionsof the golden artefacts from the acropolis of Vani showa conspicuous increase of gold. 23 bracelets with ramsheads at the end with 97 % gold, 2.5 % silver and < 1% copper. The explanation for this tendency to high fine-ness gold may have two reasons. Either the source ofthe gold utilized to make these artefacts has changedduring this time period of Greek colonisation. Or thesilver rich gold used in earlier periods was treated by

parting to get rid of the silver. Clear evidence for a de-liberate large scaled parting comes from excavations atSardis (West Anatolia) from the 6thcentury BC, the reignof the king Croesus: Furnace fragments, crucibles and

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


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gold grains point to the extraction of silver from the leg-endary placer gold of the river Paktalos (Ramage &Craddock 2000). The extraction of silver from a gold-silver alloy is a based upon the treatment with salt underhigh temperatures. The metal would be hammered to asheet and then heated up covered by NaCl. Silver wouldslowly react with the chloride-ions to form AgCl whilegold remains in the metallic state.

Mercury a Trappy Element

Among the gold grains that were washed in some rivers

near Sakdrisi, Bolnisi and Dambludka, gold-silver-amal-gams were identified by EDS-analyses in a scanningelectron microscope. Fig. 12 provides the distinct poroustexture in a gold grain which is typical for amalgamatedgold. It results from the evaporation of mercury by heat-ing gold amalgam. There are two possible explanationsfor the mercury concentrations in the gold: 1. The amal-gams are native and occur in the ore deposits. 2. Theamalgams are anthropogenic products and result asdebris from historical gold washers activities.

Aspects in the favour of explanation point 1 are: gold-

mercury-compounds occurs in the deposits of the Sak-drisi-Bolnisi district (Moon et al. 2001). This is not un-common, natural gold may contain up to 6 wt.%mercury, as shown by the paleo-placer deposits of Wit-

watersrand (Oberthr & Saager 1986). Placer-gold ofScotland contained up to 8 % mercury (Leake et al.1998). The metal was found to be a more common mi-nor component in gold than copper.

Arguments in favour of an explanation of point 2 arethat historical sources from Georgia report on multiplegold extraction in the 19thcentury by amalgamation. Thisseems to have been a widespread technique, and Dila-bio et al.(1988) reports about world wide anthropogen-ic pollution by mercury in gold placer deposits.

As we could not exclude anthropogenic input of mer-cury rich in gold grains from Sakdrisi suspicious grainswere sorted out in advance to the lead isotope analysisto avoid contaminations of the natural gold. Hg-contain-ing grains make the analysis of 204Pb impossible, be-cause the isotopes 204Hg and202Hg interfere with 204Pb.

We did not find any traces of mercury in Bronze Age ar-tefacts. They all were obviously smelted from Hg-free gold.

Trace Element Concentrations

Trace element concentrations in the gold artefacts fromGeorgia as analysed by LA-ICP-MS are very low. Of inter-est may be platinum and osmium contents which reachup to several ppm each. They are positively correlated.

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


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

We did not find any inclusions in the gold of platinumgroup elements which might host these elements. Wetherefore believe that they are dissolved in gold.

Tin reaches the highest concentrations (3-50 ppm). How-ever, these values much below those reported by Hart-mann (1970, 1982) for gold artefacts from all over Eu-

rope. At the moment, it is open whether or not tin aswell as platinum and osmium - can be used as a tracerto find the origin of the Georgian gold.

Lead concentrations are about 2 ppm and are at thedetection limit necessary for lead isotope analyses.

Lead Isotopy

208Pb/206Pb vs. 207Pb/206Pb-ratios of gold artefacts andof native gold and gold bearing concentrates are shownin a two-dimensional diagram in Fig. 13. Most of theartefacts lie on a virtual line which cut the compositionsof ore deposits in the Aegean, Anatolia and Armenia.

Although ore deposits from there are designated as cop-per deposits and the dotted ellipses comprise lead iso-tope data of copper ores, we have inserted these com-positions into the diagram because they are very often

gold bearing (Lutz 1990; Yiit 2006). An example is Mad-neuli (Dsaparidze, in prep.) which is genetically con-nected with Sakdrisi, and where prehistoric gold miningwas 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 fallinto this range of compositions (Meliksetyan & Pernicka2010).

From the geological point of view this means that mostof the gold artefacts from Georgia could originate fromores located in the Mesozoic Alpine folded mountain

range of the Pontides and the Transcaucasia. We con-clude that the (copper) ore districts in this area arepromising candidates to search for at least a part of theGeorgian gold artefacts.

Fig. 13: 208Pb/206Pb vs. 207Pb/206Pb-abundance ratios of gold artefacts and native gold from Georgia. For comparison isotope ratiosof copper- and lead ores and artefacts from the Aegean, Anatolia and Armenia are shown (after Seeliger et al. 1985; Hauptmann etal. 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 ratiosmay be caused by the time duration of the Alpine oro-genesis over several hundred million of years, and bythe occurrence of geologically very old lithological unitsfrom the Proterozoic period. High 208Pb/206Pb vs.207Pb/206Pb-ratios in the upper right corner of Fig. 13such as analysed in samples of native gold from Ma-mulo, Pinezauri and Dambludka. They all are located inthe Bolnisi district and originate from geologically veryold mineralisations, i.e., from proterozoic (younger Cam-brian) paleozoic magmatic rocks (granites and grano-diorites) and shists. Only two samples of gold sheetsfrom the Kurgan of Mrawalskali, in Kacheti (GEO-27/1and -8) were analysed. In general, such old gold fromplacers may be intermingled by the precipitation of (sub)recent of gold and, hence, shifted to lower 208Pb/206Pbvs. 207Pb/206Pb-ratios of younger geological ages in thelower left of the diagram.

We note a pronounced cluster of gold artefacts at208Pb/206Pb 2,077 to 2,087 which match the compositionsof the gold-bearing copper deposit of Murgul. These areartefacts from Kurgans of Tavkvetili in Meskheti in south-ern Georgia, from Gantiadi (Dmanisi) and from Mrawalz-kali in Kacheti. Some of these artefacts also match theisotopic compositions of the Georgian VMS deposit ofMadneuli, and the Armenian ore deposits of Alaverdi,

Aghvi and Shamlug in the northern part of the Transcau-casian Mountain Belt (Meliksetyan & Pernicka 2010).

A gold ring from Kurgan 18 in Irgantschai (GEO-24/1)shows an isotopic composition comparable to lithargefound at the 4thmillennium BC settlement of Fatmali-Kalecik, southeast Anatolia (unpublished data Bochum).Here, silver was extracted (HESS et al. 1998) from poly-metallic and gold bearing ores (Bayburtolu & Yldrm2008). Ample evidence for lead-silver mining was re-ported by Wagner & ztunal (2000), but a possible goldproduction was not explored.

Summary and Conclusions

This pilot study presents first results of investigations toreconstruct the technology and origin of archaeologicalgold artefacts from Georgia. We used various chemicaland physical methods to determine main componentsof artefacts in a non-destructive way, we analysed goldconcentrations form soil and rock samples by fire assay.Trace elements were determined using modern ICP-Mass-spectrometry. Recent developments in mass-spectrometry during the last ten years or so enabled theanalysis of lead isotope (Bendall 2003) and osmium iso-tope ratios (Junk & Pernicka 2003) to trace back the

provenance of gold from raw sources.

However, to provide sufficient and convincing answersfor archaeological questions we are in need for larger

databanks in order to argue on a safe statistical basis.This in turn needs ample sampling and/or analysis of goldartefacts and gold from natural deposits. It is of majorimportance that even valuable gold objects may be ana-lysed in a quasi-non-destructive way as long as theyare permitted to be brought to the laboratory. In total wecan conclude that during the late 4thmillennium gold highin silver was mined in the area of Sakdrisi. Copper con-centrations of several weight percent in Bronze Age goldartefacts indicate incomplete separations of copper min-erals from gold during the beneficiation. The potential ofosmium-, platinum- and other trace element concentra-tions will be evaluated in further studies.

Acknowledgement

This Georgian German research project is based

upon a long term cooperation which began in 1996, andwhich is proposed to continue. The analytical work asoutlined in this paper is part of the entire project. Wegreatly acknowledge the generous support of Prof. Dr.David Lordkipanidze, Dr. Irina Gambashidze, Dr. Wolf-gang Homann und Hildegund Kordon,Dr. Darejan Kach-arava, David Melaschvili,Dr. Malkhaz Natsvlishvili, Ser-go Nadareischwili, Alex Omiadze, Schota Oniani, Prof.Dr. Michael Tschochonelidze. Special thanks go to PDDr. Sabine Klein who contributed much of the analyticalpart of the project. This projekt is supported by theVolkswagenStiftung, Hanover, within the program Im

Fokus der Wissenschaft: Lnder Mittelasiens und desKaukasus.

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Documents

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