Comptes rendus de lAcad emie bulgare des Sciences Tome 65, No 11, 2012

GEOLOGIE
Min eralogie

FEATURES OF AuAg ALLOYS IN THE EPITHERMAL LOW-SULFIDATION AuAg KHAN KRUM DEPOSIT, EASTERN RHODOPES
Zdravko L. Tsintsov, Ivan P. Ivanov
(Submitted by Academician T. Nikolov on June 4, 2012 )

Abstract The paper presents the results from the study of AuAg alloys and bluegreen (amazonite type) adularia observed as surface nds in a veinlet with bonanza AuAg mineralization (Au content of up to 7.899 kg/t) in the socalled upper zone of Ada Tepe district of Khan Krum deposit. Separate grains of the natural series of AuAg solid solutions are represented by native silver, native gold, and electrum. Most of them are characterized by homogeneous distribution of the compositional elements, but rarely representatives with chemical inhomogeneity are also observed. Most often the grains are combined in aggregates with dierent morphology and sizes reaching up to 15 mm along the longest axis, which makes them observable with a naked eye. A coloured low-temperature variety of orthoclase was found, which was provisionally dened as blue-green (amazonite type) adularia. It is proposed that supergene processes have played an important role during the formation of the present outlook of the studied mineralizations. Key words: electrum, low-suldation, epithermal, Ada Tepe, Khan Krum deposit, Eastern Rhodopes

Introduction. Khan Krum deposit (Ada Tepe district) is considered as epithermal to low-sulde (adularia-sericite) type of gold deposit intruded in sedimentary rocks [1, 2 ]. All tectonic ruptures in the sediments are represented by normal slip faults and separation faults grouped in two main systems with comparatively steep slopes. These systems have controlled the hydrothermal activity in the area [3 ]. The latter author has pointed out that within the range of the
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separate knots low-temperature metasomatites with gold-bearing mineralization have been formed. Due to the great variation in the morphology of the mineralization zones and the lack of precise criteria for marking the ore bodies, the massif around Ada Tepe peak is looked upon as one big ore body in which, according to morphological features, two types of ore zones have been separated [3 ]: Lower zone (The Wall) is a sloping, layer-like ore zone dipping to north. The gold mineralization is incorporated in massive quartz body with a lenslike morphology and approximate sizes of 150 350 m with a mean thickness of 17 m and 7.3 g/t content of gold. Upper zone represents a series of a high-angle vein bundles with predominating E-W orientation, incorporated in breccia, breccia-conglomerates, and sandstones. Their thickness varies in the range from 0.10 to 0.80 m and the content of Au reaches 638 g/t. Four overlapping stages of mineral formation have been separated based on the cross-cutting specicity, variations in the mineral composition, the structures, and the content of Au [2 ]. The second stage has been considered as most important from economic point of view. The ore mineralization in Ada Tepe section is not much variable. It is represented mainly by electrum and subordinate quantities of pyrite and rare nds of AuAg tellurides (hessite and petzite), greenockite, gersdorte, marcasite, galena, and sphalerite [2, 3 ]. According to these authors, the gangue minerals are also reduced with respect to phase variation in the deposit and are restricted to quartz, adularia, carbonates (calcite, dolomite, ankerite, siderite), chlorite, sericite, and clay minerals (kaolinite, illite). Only electrum is of economic value and it is represented mainly by microscopic grains (according to [4 ]) in quartz and adularia and rarely in goethite. The mineralogical studies have proved that about 90% of the electrum grains in Ada Tepe section are with dimensions from 312 m to 6575 m, rarely in the range 50180 m (or represent chains with length up to 650 m) [3 ]. The electrum grains form impregnations, micro-clusters, colloform stripes, aggregates in interstices of quartz and adularia, or are spread among them in the form of single individuals [3, 5 ]. The SEM studies have showed that the aggregates have grape-like, globular, dendrite, or wire-like morphology and the grains that build these aggregates are characterized by an irregular lens-like form, which is often broken by plenty of small caverns [5 ]. Sometimes electrum is deposited in nests and ne veinlets with very high concentrations and forms rich in gold ore, forming the so-called bonanzas. All samples with content of Au higher than 1 g/t have almost constant Au/Ag ratios ( 3), reecting the composition of the electrum 7673 Au wt % and because of that the ore from Ada Tepe section has been
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named in the same way [2 ]. The separate AuAg individuals have neness from 637 to 828 with a tendency for lowering its values from the low towards the high parts, where the element admixtures (Ag Cu, Fe, Te, Sb, etc.) are in greater quantities [3 ]. The purpose of the present paper is to give additional data about the mineralogy of the high-angle gold-bearing veins of the so-called upper zone of Ada Tepe section. The terrain studies were realized during an archaeometallurgical experiment in the frame of the BulgarianGerman project Iron and gold. In the wake of the metallurgy of Ancient Thrace. This project was rstly nanced by Alexander von Humboldt Fund, Germany, and since the autumn of 2010 by Balkan Mineral and Mining AD. Materials and methods. The studied samples were isolated from a veinlet being a part of a high-angle vein bundle with E-W orientation from the so-called upper zone, which crops out on the surface in the highest part of Ada Tepe peak. The samples were collected from a chamber part of the veinlet and those a with signicant concentration of AuAg alloys (bonanza) on the surface were separated for analysis. The optical investigations were realized under binocular magnier (Olympus) and polarizing microscope Amplival. The composition of the separate grains was analyzed on a Philips SEM515 apparatus equipped with energy-dispersive electron-probe micro-analyzer EDAX PV 9100 under the following conditions: U = 2025 kV, I = 0.5 mA, beam diameter is 5 m, time of spectrum scanning is 5080 s. The powder XRD studies were performed on D2 Phaser (Bruker AXS) diractometer using Ni-ltered Cu radiation (30 kV and 10 mA) and step scanning in the interval 1080 2-theta. The powder XRD patterns were used for phase analyses by checking the data with the PDF database (ICDD). The chemical analyses were performed by use of the apparatuses SPECTRO Analytical instruments (Germany) and VISTAMPX (Australia). Results. The studied vein bundle is composed mainly of minerals from the rst stage of hydrothermal mineralization, which are represented principally by microcrystalline to ne-crystalline, white, massive and strong quartz. Later, products from the second stage have partially lled the free parts, thus forming veinlets with dierent morphology and sizes. Bonanza AuAg mineralization was in one of these veinlets, which is the subject of the present study. The veinlet is with lens-like form and with a length of 0.9 m and maximal thickness of 0.12 m. Its contacts with the host sediments are sharp and clear. It is built up mainly by quartz (represented by druses nets, etc.). In its central part, alternating thin quartz-adularia stripes are seen. A small chamber is formed among them coated by several very thin ne-grained quartz-adularia layers. The latter form many bubble-like swellings resembling foam with oval form (spherical and ellipsoid) and with dimensions up to 10 mm (Fig. 1a, b). The layers are most often deposited upon thin crusts (up to 1 mm thick) of quartz
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from the second stage and rarely upon the quartz from the rst stage. The layers are characterized by plenty of pores in the inner parts and reach a maximal total thickness of 4 mm. They have pale beige, pale red, pale brown, pale yellow to dirty white colour on the surface. Rare depositions of goethite give dark brown to black colour to some surface parts. The bubble-like swellings are very often fully or partially demolished, revealing in depth other similar bubble-like quartz-adularia layers. The bonanza AuAg mineralization has been deposited upon the surface of the quartz-adularia layers (Figs 2, 3). The data from the chemical analyses show that the mean contents of Au in the high-angle vein bundle are very high and usually display values is greater than 0.5 kg/t. The quantity of Au in the veinlet with bonanza AuAg mineralization in some cases reaches 7.899 kg/t. The aggregates of AuAg alloys built by many small grains have varying morphology (globular, dendrite, grape-like, band-shaped, etc.) and display a large range of sizes often reaching 15 mm along the longest axis (Figs 2, 3). In the latter case, the aggregates are observed with a naked eye. The noble metal mineralization additionally includes silver-white to darkgrey aggregate with a plastic form and approximate size of 25 60 m. This aggregate has a grape-like structure formed by plenty of small (from 3 to 10 m), isometric or slightly elongated grains, which are densely stuck to each other. The same aggregate has been deposited partially upon the surface of an aggregate of AuAg alloys with usual colouring (Fig. 4a). When separating it from its basis, the aggregate disintegrates in many small particles, which, conrmed by the analyses, are composed mainly of Ag. Very often the AuAg aggregates are covered by a thin layer of Fe-oxides/hydroxides. This layer lowers the diraction of the separate grains and during the optical observations gives a mat lustre of the aggregates, thus making them almost unobservable (Fig. 3a). In a regime of secondary electron emission, such aggregates are hardly observed and practically in these cases only their periphery contours can be followed. Having in mind the fact that the depth of penetration of the X-rays in this case is about 10 m, it can be assumed that the thickness of this covering is close to this size. The layer of Fe-oxides/hydroxides is the reason for the rich colouring of the surface of the quartz-adularia layers. Sometimes upon these aggregates single crystals and sponge groups of later deposited AuAg alloys diering with their surfaces glittering and non-polluted with Fe-oxides/hydroxides are observed(Fig. 5a). The grains of AuAg alloys from the ner fractions (< 50 m) have homogeneous distribution of the elements composing them. However, a part of the largest grains (those > 80 m) possess chemical heterogeneity, which is expressed in a considerable uctuation in the quantity of the separate compositional elements across dierent parts. In these cases, the content of Au varies in the range 65.6299.12 wt% and the admixtures are entirely from Ag. Upon polished sur1588
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Fig. 1. Features of surfaces formed by bubble-like swellings of quartz-adularia layers with distinctly observable aggregates of AuAg alloys, partially covered by: a) Fe-oxides/hydroxides; b) goethite. Natural surfaces

Fig. 2. Bonanza AuAg mineralization deposited upon destroyed quartz-adularia layers. Natural surfaces

Fig. 3. Aggregates of AuAg alloys deposited upon destroyed quartz-adularia layers: a) partially covered by Fe-oxides/hydroxides; b) with clear surfaces of the grains. Natural surfaces

Fig. 4. Formations of: a) aggregate of native silver; b) ellipsoid lamella of blue-green (amazonite type) adularia, partially covered by AuAg alloys. Natural surfaces

Fig. 5. SEM images of AuAg alloys with: a) clean surfaces deposited on earlier formed aggregates of AuAg alloys, covered by Fe-oxides/hydroxides; b)irregular distribution of the compositional elements (the dark regions rich in Ag). Natural surfaces (a), polished surfaces (b)

faces, these uctuations well mark the heterogeneous regions. The latter are with irregular character, sharp contours, varying form and are clearly dierentiated (the Ag rich parts are darker than the rest) both by optical microscopy and SEM observations in secondary electron emission (Fig. 5b). In a surface indentation partially lled with goethite, we found a thin (< 1 mm) blue-green formation with ellipsoid form and approximate dimensions 2 4 mm (Fig. 4b). About 2/3 of its observable surface is covered by single crystals, spongy aggregates or dense masses of AuAg alloys. The optical studies and analytical data showed that this is adularia (a low-temperature variety of orthoclase) and therefore we name it conditionally as blue-green (amazonitetype) adularia.
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Discussion. The specic conditions of mineral formation of Au deposits in epithermal systems of low sulde (adularia-sericite) class are reected in the form of the ore bodies, the mineralogy and variety of ore textures, etc. [6 ]. Characteristic features of the ore mineralogy of bonanza AuAg ores in similar epithermal vein deposits of volcanites in the western part of USA gave basis to mark them as Sleeper-type gold-dominant adularia-sericite deposits [7 ]. The latter authors have concluded that Au colloids exert inuence on the genesis of the Audominated epithermal deposits. According to the same authors, Au colloids also ensure an acceptable mechanism for generation of local parts with content of Au > 1 kg/t. Irrespective of the many studies on dierent geological-mineralogical aspects of Ada Tepe section, a series of genetic questions connected with the AuAg mineralization still remain not well explained. The genetic model, which may explain all available geological data, is connected with hydrothermal convection in the metamorphic basement during which the uids coming from depth to the surface form low-temperature hydrothermal solutions [2 ]. The latter authors have concluded that the magmatism in the nearby Kessebir dome may be looked upon as a possible source of the metal-bearing uids. According to them, the rich Au stripes have been formed by colloids and part of the rest mineralization has resulted from the boiling of the solutions. The surface textural features of the quartz-adularia layers observed by us have been formed as a result of boiling of ore-bearing solutions. The bonanza Au Ag ore formation is with colloidal origin and has been favoured by this boiling. This conclusion corresponds with the statements of other authors [2, 5, 7 ]. Our observations gave reason to accept that supergene processes have played main role during the formation of the contemporary outlook of the discussed mineralization. They have favoured both the surface deposition of Fe-oxides/hydroxides upon the grains of a considerable part of the earlier-formed AuAg alloys as well as the formation of supergene ones. The coverings of Fe-oxides/hydroxides upon AuAg alloys could exert unfavourable eect in the process of their dressing [4 ]. In this sense it is recommendable to take into account these features of the useful component during the processing of the deposit. In supergene conditions, the circulation of the chloride-sulfate waters favours the liberation of Au and Ag atoms and their transformation in cationic form, which form complex compounds (chlorides) weakly dissolvable in water, which allow transportation to great distances. In suitable medium, they can be reduced to elementary metals and the reducers can be Fe2+ , Mn2+ , etc. Through the mechanisms of cumulative crystallization, the metals Au and Ag are in condition to form metal phases new in composition and particle sizes, which in our case are represented by the grains and aggregates of Au and Ag and AuAg alloys with sparkling surfaces. The supergene processes have also caused the chemical inhomogeneities of the grains from the coarser fractions of the AuAg alloys.
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The chemical compositions of the grains are represented by a wide spectrum of AuAg series of solid solutions from pure end member Au and Ag representatives to such with dierent intermediate composition. According to the mineralogical classications, the quantity of these elements determines their mineral naming. In this sense it is recommendable to use during mineralogical studies the concrete mineral names. For the purposes of the metallogenic classications, comparisons, etc. as well as in case of missing data for the composition of the separate grains, one may use the generalized designations electrum and electrum ore. The colour of amazonite is formed during late metasomatic processes taking place at elevated activity of Na and the intrusion of Pb and Rb [8 ]. Later, it has been established that centres of [Pb-Pb]3+ couples have caused the typical blue-green colour of the amazonite microcline [9 ]. According to the latter authors, other feldspars with such colouration with chromophores of the type [Pb-Pb]3+ couples are not known. In regard to these conclusions, the above authors propose the name amazonite to be preserved only for the blue-green microcline, regardless of the proposal of other authors [10 ] to expand this designation over all feldspars similar in colour. In accordance with the above opinions, we accept the designation blue-green (amazonite) adularia for our blue-green nd. It has been formed at late metasomatic processes in a crystallization medium with exceptionally low fugasity of S and restricted income of Pb. Acknowledgements. Thanks are due to Dr Chr. Popov for his agreement to publish these data, to Dr V. Arnaudov for the helpful discussions on adularia, and to Dr B. Banushev for assisting us in the preparation of the manuscript.

REFERENCES
[1 ] Kunov A., V. Stamatova, P. Petrova. Mining and Geology, 2001, No 4, 1620 (in Bulgarian). [2 ] Marchev P., B. Singer, D. Jelev, S. Hasson, R. Moritz, N. Bonev. Schweiz. Mineral. und Petrogr. Mitt., 84, 2004, 5978. [3 ] Jelev D. In: Gold deposits in Bulgaria (eds V. Milev, N. Obretenov, V. Georgiev, A. Arizanov, D. Jelev, I. Bonev, I. Baltov, V. Ivanov), Soa, 2007, 104115 (in Bulgarian). [4 ] Harris D. C. Miner. Deposita, 25 (Suppl), 1990, S3S7. [5 ] Marinova I. Geologica Macedonica, Special issue, 2008, No 2, 111120. [6 ] Hedenquist J., E. Izava, A. Arribas, N. C. With. Resource Geology Special Publication, Published by the Society of Resource Geology, No 1, 1996. [7 ] Saunders J. A., P. A. Schoenly. Miner. Deposita, 30, 1995, 199210.
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[8 ] Arnaudov V., M. Pavlova, S. Petrussenko. Bulletin of the Geological Institute (Geochemistry, Mineralogy and Petrography), Bulgarian Academy of Sciences, 16, 1967, 4144 (in Bulgarian). [9 ] Petrov I., R. M. Mineeva, L. V. Bershov, A. Agel. American Mineralogist, 78, Nos 78, 1993, 500510. [10 ] Hofmeister A. M., G. R. Rossman. American Mineralogist, 70, 1985, Nos 56, 794804. Institute of Mineralogy and Crystallography Bulgarian Academy of Sciences Acad. G. Bonchev Str., Bl. 107 1113 Soa, Bulgaria e-mail : ztsintsov@mail.bg

GORUBSO Kurdjali AD 83, Republikanska Str. 6600 Kurdjali, Bulgaria e-mail : iv1960@abv.bg

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