UDC 542.907:902/904

V. V. Zaikov, E. V. Zaikova, V. A. Kotlyarov

Institute of Mineralogy of the Ural Branch of the Russian Academy of Sciences

Ilmensky Nature Reserve, Miass, Chelyabinsk region, 456317, Russia

E-mail: zaykov@mineralogy.ru; zaykova@mineralogy.ru; kotlyarov@mineralogy.ru

Microinclusions of osmium group minerals in gold, from which Ural products dating back to the 15th century BC - 9th century AD are made, have been established. All of them are included in the high-temperature iridium subgroup. The diversity of composition and morphology indicates the placer nature of the inclusions. Mineral sources are placers associated with ultrabasites of large faults in the Ural Fold belt. The possibility of identifying osmium minerals in the gold of ancient products that are attracted to the cultural base zones of Southern Siberia, the Caucasus, Asia Minor and other regions is determined. After receiving additional analyses of platinoids from placers and indigenous localities, it will be possible to outline the "osmium paths" of distribution of gold products.

Keywords: microinclusions, osmium, microprobe analysis, burial mounds, Urals, osmium trace, Bronze Age, Scythians, ultrabasites, gold products, placers.

Introduction

In archaeological research, a special place is occupied by determining the connections of ancient societies, figuratively referred to as" paths " of contacts and exchange: lapis lazuli, amber, obsidian, etc. The analysis is based on products made from rare minerals and rocks whose deposits are well known. The use of the results of mineralogical and geochemical studies of such finds in archeology makes it possible to trace not only the named "paths", but also the geography of ancient products, to determine their sources and distribution paths by the composition of metal products (Chernykh, 1970). Thus, it was possible to identify an "osmium trace" based on mineral inclusions in gold products, which can indicate the sources of gold.

The group of native osmium according to the accepted mineralogical nomenclature (Harris and Cabri, 1991) includes minerals from the family of platinoids. They are solid solutions of Os, Ir, and Ru and are characterized by a variable composition, but have a single structure that differs from that of other minerals in this family. Further, all the minerals included in the group of native osmium will be called native osmium or simply osmium.

One of the first people to mention the presence of native osmium inclusions in ancient gold products was D. Williams and J. Smith. Ogden [1995]: in the description of the products of Greek craftsmen, they noted the presence of osmium grains, which made it difficult to produce a thin gold sheet and small-diameter wire. However, additional data on the presence of such inclusions in the metal of ancient products are not yet available.

The purpose of the article is to identify ways of distribution of ancient gold by inclusions of native osmium in the metal of precious products on materials of the Urals. Objects discovered by A.D. Tairov, D. G. Zdanovich, V. V. Tkachev, and A. N. Sultanova at Ural archaeological sites were studied (Fig. 1). Samples of 1 - 5 mm in size were analyzed,

The research was supported by the Russian Foundation for Basic Research (project 08.06.00136; 10 - 06 - 96009-r_ural_a), interdisciplinary and integration projects of the Ural Branch of the Russian Academy of Sciences.

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Figure 1. Layout of the studied archaeological sites in the Southern Urals.

1, 2 - monuments where gold products with osmium inclusions were found (7-burial grounds and mounds; 2-ancient settlements); 3-mounds with no osmium inclusions in their materials; 4-deep faults with hyperbasic bodies; 5-areas of the main gold-bearing placers (Gold of the Urals..., 1993). Arrows show the direction of the "osmium paths" of ancient gold.

carved from gold pieces. After washing the gold in alkalis and acids, it was pasted on an electrically conductive adhesive tape or incorporated into an epoxy resin, followed by polishing and carbon deposition. When shooting unpolished foil, more prominent images of inclusions in secondary electrons were obtained. After studying the metal by optical methods, sites for microprobe analysis with a beam diameter of 1-3 microns were selected. The metal composition was determined using SEMMA-202M, JEOL-733, and JSM-6460LV electron microscopes (operators V. A. Kotlyarov, E. I. Churin, and O. V. Samoilova).

Distribution, morphology, and composition of inclusions and host gold

To date, inclusions of native osmium in gold products have been identified in 5 out of 14 mounds and hillforts surveyed from the middle course of the Ural River to the upper reaches of the Tobol River. Archaeological sites, according to the authors of the excavations, belong to the XV century BC-IX century AD.

Gold containing osmium has significant differences in composition (Table 1). 1), which indicate different sources and different technologies for obtaining metal. The gold of the Filippovsky burial ground is characterized by high penetration: it has a minimal content of silver and copper. Perhaps this metal was refined. In gold objects from the Steppe Mound, the ratios of gold and silver are close to those in the minerals of gold-pyrite-polymetallic ores (Zaikov et al., 2001, p. 198). Samples from items found in the Kichiginsky burial mound and the Ufa II ancient settlement show rather high concentrations of copper (3-6 %), which go beyond the content of natural gold. The silver content varies from 22 to 32 %. The data obtained suggest that this metal may belong to artificial Au+Ag+Cu alloys.

The most significant inclusions of native osmium were found in the inlay of an iron sword from mound No. 4 of the Filippovsky burial ground. In recent years, the object has been studied by L. T. Yablonsky [2008]. Inlays are installed and analyzed

Table 1.

Composition of gold containing osmium inclusions in finds from archaeological sites of the Urals and Siberia, %

N n/a

Subject

Monument

N samples

Number of tests

Au

Hell

Si

The amount

Date

1

Sword Inlay

Filippovsky N 4

7 - 1

11

97,52

0,82

1,29

99,63

V-IV centuries BC

2

Spiral

Ufa II

UGO-12 - 3

6

63,10

31,18

5,41

99,69

VII-IX centuries AD

3

Foil

Kichiginsky N 3

MIA5-br

6

72,68

23,23

3,95

99,86

IV century BC

4

"

Kichiginsky N 5

7 k

4

71,52

24,37

3,79

99,68

IV century BC

5

Pendant

Steppe

1637ab

5

86,28

12,13

0,89

99,30

XIV-XV centuries BC

6

"

Ushkattynsky

Uk7

3

77,24

18,26

5,39

100,89

XIII-XV centuries BC

Notes. The analyses were performed at the Institute of Mineralogy of the Ural Branch of the Russian Academy of Sciences on a JEOL-733 microanalyzer, operator E. I. Churin. Item No. 1-from the collection of L. T. Yablonsky, No. 2-A. N. Sultanova, No. 3, 4-A.D. Tairov, No. 5-D. G. Zdanovich, No. 6-V. V. Tkachev.

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2. Osmium inclusions in a polished section (sample N 7). Filippovsky burial ground, mound No. 4. Reflected light, image width 0,6 mm. You can see the split of the rounded grain at the edge of the image.

16 osmium grains of rounded, elongated and triangular shape with a long axis size of 40-200 microns. Rounded grains are fragmented or split by cleavage (Figs. 2, 3).

The golden spiral from the Ufa II ancient settlement (Mazhitov, Sungatov, and Sultanova, 2007) contains a rounded grain. It shows cleavage cracks separating the grain into two individuals, which are slightly different in composition (Table 2). It is assumed that this is a fragment of the joint.

Gold products from the mounds of the Kichiginsky burial ground (Tairov, Botalov, and Pleshanov, 2008) contain four rounded grains. Three of them (one measuring 45x20 mk, two adjacent to it, smaller ones) are installed in gold foil covering the bracelet from mound No. 3 (Fig. 4), the composition of individuals is different (Table 2). The fourth grain, measuring 5x20 mk, is found in foil superimposed on a wooden vessel from mound No. 7.

A lamellar osmium grain was found in gold foil from a Steppe mound covering a spiral suspension with a diameter of 0.7-1.5 cm (Zaykov et al., 2008). It consists of three contiguous individuals and is divided into two parts. The inclusions are 6 - 7 thick and 25 - 40 microns long (Fig. 5).

In the Ushkattyn mound studied by V. V. Tkachev, an osmium grain of a shape close to prismatic, measuring 4x9 mm, was found. It is located across the flattening of the gold foil containing small copper inclusions.

3. Osmium inclusions in secondary electrons (sample N 7, unpolished foil). Filippovsky burial ground, mound No. 4.

A - N 10 (assays a-g), 11 (assays i-m); B-N 12 (assays a - e); C-N 13 (assays a - k); D-N 14 (assays a-f).

4. Osmium inclusions in secondary electrons (sample N 5, polished section). Kichiginsky burial ground, mound No. 3.

A-N 20 (assays a-e); 21 (assays 5-3); 22 (assays 5, 4); B-N 23 (assays a-f).

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Table 2.

Composition of inclusions of osmium minerals in ancient gold products

N Enabling options

Number of tests

Average content, wt. %

Formula

Os

lr

Ru

Pt

The amount

1

6

45,76

36,10

17,45

-

99,31

Os0,40Ir0,31Ru0,29< /SUB>

2

10

34,54

29,30

27,66

8,06

99,56

Ru0,42Os0,28Ir0,24< /SUB>Pt0,06

3

7

35,28

29,20

27,63

7,36

99,47

Ru0,42OS0,29lr0,23< /SUB>Pt0,06

4

1

57,58

14,82

27,02

-

99,42

Os0,47Ru0,41lr0,12< /SUB>

5

8

56,88

17,04

25,57

-

99,49

Os0,47Ru0,39lr0,14< /SUB>

6

7

55,07

8,97

35,42

-

99,46

Ru0,51Os0,42lr0,07< /SUB>

7

5

32,67

53,85

3,43

9,50

99,45

lr0,53Os0,32Pt0,09< /SUB>Ru0,06

8

6

45,03

20,56

33,93

-

99,52

Ru0,49Os0,35lr0,16< /SUB>

9

7

37,23

29,91

26,88

5,58

99,60

Ru0,41Os0,30lr0,24< /SUB>Pt0,05

10

5

35,12

58,52

2,26

3,63

99,53

lr0,57Os0,35Ru0,04< /SUB>Pt0,04

11

5

56,53

10,16

32,78

-

99,47

Ru0,48Os0,44lr0,08< /SUB>

12

5

37,74

56,05

5,87

-

99,66

lr0,53Os0,36Ru0,11< /SUB>

13

11

77,44

14,23

8,00

-

99,67

Os0,73Ru0,14lr0,13< /SUB>

14

6

40,32

38,13

17,28

3,80

99,53

Os0,35lr0,33Ru0,29< /SUB>Pt0,03

15

5

35,83

53,34

2,85

7,59

99,61

Ir0,52Os0,36Ru0,05Pt0,07

16

8

38,99

42,80

17,71

-

99,50

lr0,37Os0,34Ru0,29< /SUB>

17

4

44,25

41,83

13,40

-

99,48

Os0,40lr0,37Ru0,23< /SUB>

18

2

47,85

37,34

14,92

-

100,00

Os0,42lr0,33Ru0,25< /SUB>

19

4

49,62

36,82

14,02

-

100,46

Os0,44lr0,32Ru0,24< /SUB>

20

1

1,48

78,43

12,47

-

100,00

lr0,76Ru0,23Os0,01< /SUB>

21

1

13,79

22,06

36,15

-

99,99

Ru0,66lr0,21Os0,131

22

4

46,23

11,82

41,53

-

99,58

Ru0,57Os0,34lr0,09< /SUB>

23

6

40,78

40,56

18,38

-

99,72

Os0,35lr0,35Ru0,30< /SUB>

24

5

39,43

41,74

18,28

-

99,45

lr0,36Os0,34Ru0,30< /SUB>

25

3

64,82

34,11

0,47

-

99,40

Os0,65lr0,34

Notes. Inclusions 1-16 from sample N 7 (Filippovsky burial ground, mound N 4, collection of L. T. Yablonsky); 17, 18 - from sample N UP-G012-3 (Ufa II settlement, collection of A. N. Sultanova); 19-21 - from sample N 5 (Kichiginsky burial ground, mound No. 3, collection of A.D. Tairov); 22 - from sample No. 7 (Kichiginsky burial ground, Kurgan. No. 5, collection of A.D. Tairov); 23, 24-from sample No. 1637 (Kurgan. Steppe, collection of D. G. Zdanovich); 25 - from the UK-7 sample (Ushkattynsky mound, collection of V. V. Tkachev).

Analyses N 1 - 19, 23 - 25 were performed by operator V. A. Kotlyarov, microprobe REMMA-202M; N 20, 21-O. V. Samoilova, microprobe JSM-64601 LV; N 26-E. I. Churin, microprobe JEOL-733.

Dash - less than the sensitivity limit (0.5 %).

A large variation in the values of osmium content is established (Table 1). 6, 7). We use the nomenclature [Harris and Cabri, 1991] with the addition of a definition consisting of the names of related elements (ruthenium, iridescent, osmaceous). This method was used by Yu. S. Kobyashev and S. N. Nikandrov [2007] to characterize the corresponding minerals of the Urals.

According to the atomic ratio of Os, Ru, and Ir in crystal-chemical formulas, grains of three types are distinguished (Table 2):

1st - with a predominance of Os

1a-osmium: a sharp predominance of Os with a low content of Ru and Ir (N 13, 24); 1b-ruthenium osmium with iridium: Os content of approx. 50 at.%, the predominance of Ru over Ir is approximately 2.8-3.4 times (N 4, 5); 1b-ruthenium-iridescent osmium: 35-50% osmium, a slight predominance of Ir over Ru, sometimes the values are approximately equal (N 1, 14, 17 - 19, 23, 26, 281g-iridescent osmium: Os predominates over Ir, ruthenium is low (N 25, 27, 28).

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5. Osmium grains in polished section 1637. Mound of the Steppe burial ground. Reflected light, image width 0.2 mm. The lamellar structure of two grains is visible.

2nd - with a predominance of Ru 2a - ruthenium iridisto-osmisty: predominance of Ru, close values of Os and Ir (N 2, 3, 9); 2b - osmium with iridium: predominance of Ru, significant predominance of Os over Ir (N 6, 8, 11, 22); 2b - osmium with osmium: predominance of Ru, significant content of Ir and low Os (N 21).

3rd - with a predominance of Ir (A) - ruthenium iridium with a negligible admixture of osmium (N 20); 3b-osmous iridium with ruthenium: a predominance of Ir, a significant content of Os and a small Ru (N 7, 10, 12, 15); 3b-ruthenium-osmous iridium: a predominance of Ir, a significant content of and Os, and Ru, osmium is slightly larger (N 16, 24).

Platinum is present in three samples with a predominance of ruthenium (N 2, 3, 9) and three samples with a predominance of iridium (N 7, 10, 15). Platinum was found only in one sample with a predominance of osmium (N 14).

The position of mineral varieties and selected fields of osmium compositions is shown in Figures 7 and 8. Most of the figurative points of osmium analysis from ancient gold jewelry of the Urals fall in field IV, located in the center of the area where the points of osmium analysis from local placers fell. This field includes data on the Filippovsky and Kichiginsky burial grounds, the Steppe and Ushkattynsky mounds, as well as the Ufa settlement of P. The connection between osmium from gold products and local placer material is obvious. Three groups of analysis results were also identified for items from the Filippovsky burial ground (fields I-III), for which placer analogues have not yet been identified.

6. Triple diagram of the composition of osmium minerals in gold products from the mounds of the Southern Pre-Urals and Eastern Trans-Urals. The numbers indicate the inclusion numbers shown in Table 2.

7. Triple diagram of the fields of osmium mineral compositions in gold products from mounds and settlements of the Southern Urals and in metal sources.

1 - in gold products from monuments of the Southern Urals; 2-in indigenous manifestations of the Middle Urals; 3-in placers of the Urals. Mineral composition fields in archaeological sites: I - III-Filippovsky burial ground, mound No. 4; IV-Filippovsky, Kichiginsky burial grounds and Ufa settlement II.

Fields of grain composition from gold placers: V-Southern Urals (Uchalinsky district, V. A. Kadikov collection); VI - Polar Urals; VII-Middle Urals (Mineralogy of the Urals..., 1990; Ivanov, 1944).

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Discussion of the results

We will evaluate the probable sources of gold from which the studied products were made. To understand the general situation, it is advisable to give a brief summary of the region's precious metal deposits.

Co-occurrence of native gold and osmium has been established in placer deposits located along the outcrops of deep faults on all continents (Gold of the Urals..., 1993; Sazonov et al., 2001). This connection is due to the fact that these structures are associated with the introduction of deep igneous rocks - hyperbasites containing platinoids.

Information on osmium mineralization in Ural hyperbasites is most thoroughly reviewed in the monographs [Ivanov, 1944; Platinometalnoe mineralization..., 2001]. Basic occurrences of iridium osmide in chromite-bearing peridotites of the Vostochno-Tagil and Verkhny Neuvinsky massifs are identified. The chromite ores of the Nuralinsky massif in the Southern Urals show sulfide-osmium mineralization. When the main outcrops of osmium-containing rocks are destroyed, osmium gets into loose deposits and is concentrated in placers.

The history of the ancient gold mining industry in the Urals is considered in a number of works (Iessen, 1948; Marfunin, 1987; Shumikhin and Volgin, 2008). Typical deposits of indigenous gold in the Urals have reserves of 5-20 tons, and the largest - up to 300 tons. The reserves of placer deposits, from which part of the gold was received for the manufacture of jewelry, are an order of magnitude smaller, but the total number of deposits is approx. 1 thousand rubles. According to A. S. Marfunin (1987), the total amount of alluvial gold produced and accounted for in tsarist times was about 650 tons. In the Soviet period, this figure was approximately 300 tons. With a certain reservation, it can be assumed that in the Urals, approx. 1 thousand tons of placer metal.

Osmium minerals from placer gold deposits are extracted in the Urals, Siberia, Turkey, Bulgaria, California, Canada, and Tasmania (Ivanov, 1944; Craddok, 2000; Tsintsov, 2001). The presence of osmium grains in gold products made from placer material is natural. They are not affected by melting, but have only experienced deformation and splitting during gold processing, for example, when forging foil (see Figure 5).

In the Southern Urals, there are two major faults - the Main Ural and East Ural. Hyperbasite bodies localized in the first fault formed placers in the valleys of the Miass, Kizil, Tanalyk, and Sakmara Rivers and their tributaries, draining the Main Ural Fault for 600 km, and associated gold-bearing structures (Zolotoe Urala..., 1993; Sazonov et al., 2001). This segment includes the Karabash, Miass, Mindyak, and Baymak ore and placer regions, where osmium group minerals are found. Numerous gold nuggets are found in placers, including the largest in Russia "Big Triangle" (Godovikov, 1975). Nuggets are quite impressive in size, weighing up to 36 kg; they lie in placers in nests with a total weight of tens and hundreds of kilograms. It is not surprising that bright golden stones attracted the attention of our ancestors. The main Ural fault, a gold-bearing structure, is located closest to the Filippovsky burial ground and the Ufa settlement.

In the Trans-Urals, indigenous and placer deposits are known in the Kochkarsky, Dzhetygarinsky, and Kumak ore districts (Zolotonosnost ' Urala..., 2005, p. 78, appendix 1). The presence of osmic iridium, which forms light silvery grains, is also found in placers of the Kochkarsky district (Kolisnichenko and Popov, 2008). In addition, the placers contain iridium ruthenium-osmium with a content of (wt. %): Ir 80, Os 15, Ru 5. This suggests that the source of native osmium in products from the Kichiginsky and Steppe mounds was hyperbasites of the East Ural fault.

The available data allow us to outline the" path " of gold distribution for jewelry making from the Southern Urals in the south-western direction to Ufa and the Filippovsky mounds (Southern Urals). The length of this section is approximately 200-300 km, but the "path" could have continued to the Volga basin. The source of raw materials for gold products from the Don and Dnieper mounds, as well as arsenic bronze products (Selimkhanov, 1970), was probably located in the Caucasus.

In the mountains of Southern Siberia, hyperbasics are found in the Kaakhem, Kurtushibinsky, Borussky, and North Sayan faults. Within the latter, osmium was found (Agafonov et al., 2005, p. 115), which is similar in composition to the mineral identified, according to A. M. Yuminov, in the gold products of the Arzhan II mound (Chugunov, Parzinger, Nagler, 2004). Similar ore-bearing hyperbasites are known in the Caucasus, Asia Minor and Bulgaria, where numerous placers are also noted. The study of the composition of gold products from monuments found near them should help identify new osmium inclusions. Each piece of information of this kind will expand the knowledge about the areas of contact of ancient societies.

Conclusion

A wide distribution of inclusions of osmium group minerals in gold products of the Urals has been established,

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Dating from the 15th century BC to the 9th century AD, the diversity of composition and morphology indicate the detrital nature of these inclusions. The metal sources are placers associated with hyperbasites of large faults in the Ural fold belt. To determine specific sources of metal, it is necessary to obtain platinoids from placers and indigenous localities and conduct detailed mineralogical, geochemical and isotopic studies of minerals. After completing this work, it will be possible to more confidently establish the "osmium paths" for the distribution of gold products.

Gratitude

The authors are grateful to A. M. Yuminov, E. I. Churin, G. G. Mikhailov, O. V. Samoilova, E. V. Belogub, I. G. Mikhailov, L. T. Yablonsky, M. S. Shemakhanskaya, A.D. Tairov, D. G. Zdanovich, V. V. Tkachev, V. K. Chugunov, and V. I. Gulyaev for their help and advice.

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Zaykov V.V., Yuminov A.M., Tairov A.D., Zdanovich D.G., Churin Eu.I., Kotlyarov V.A., Zaykova E.V. The composition of gold and silver objects from the South Urals burial mounds // Geoarchaeology and Archaeomineralogy. -Sofia: Publishing House "St. Ivan Rilski", 2008. - P. 239 - 243.

The article was submitted to the Editorial Board on 06.08.09.

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