THE PEZINOK ANTIMONY MINE MALE KARPATY MOUNTAINS, SLOVAKIA.
The Pezinok antimony mine in southwestern Slovakia is a relatively small ore deposit, but it is important for its unusually large and beautiful crystals of kermesite, a red antimony sulfoxide. Kermesite at other world localities usually forms pink to purple fine-grained powdery aggregates, and occurs only rarely in well-developed larger crystals, e.g., at Braunsdorf near Freiberg (Saxony, Germany) and Que-Que (Zimbabwe). The first large kermesite crystals to come from the Pezinok area were found in the Kriznica mine near Pernek between 1915-1922, but the crystals from the Pezinok mine are of better quality and are among the best specimens of the species in the world. Hundreds of top kermesite specimens are preserved in numerous private collections, mainly in Slovakia, the Czech Republic, Austria and Hungary, as well as museums in Bratislava and Prague. A variety of other primary and secondary minerals from the Pezinok antimony deposit are also very interesting for collectors. This article will examine the history, geology and especially the minerals of the Pezinok antimony deposit.
The Pezinok mine (also known as the Kolarsky Hill deposit) is situated about 4 km northwest of downtown Pezinok, a historical town in southwestern Slovakia, about 10 km northeast of the city limits of Bratislava, the capital of the Slovak Republic. Pezinok is a picturesque little town (population: ca. 25,000) with many medieval historical monuments. The town lies at the foot of the granite slopes of the Male Karpaty Mountains; the area is well-known for its many vineyards producing excellent white and red wines.
The Pezinok antimony mine is situated on the southeastern slope of the Male Karpaty Mountains, between 260 to 400 meters above sea level, in a forested area of the Hruba Valley. The mine can be reached by a car road from Pezinok or Pernek. The deposit has been exploited by a 50 x 300-meter open pit and several underground galleries. The New Alexander tunnel is the longest; it measures about 1 km. The Stare Mesto deposit, an old gold mine in Pezinok, is situated only 2 km northwest of the antimony deposit.
The long history of mining in the Pezinok area has been documented in a manuscript by Bergfest (1952). The first record of the mining activity in the area dates to 1339, when Hungarian king Carol Robert of Anjou claimed the gold mining rights for the family of Earls of St. Georg and Pezinok. The Earls owned the mines during the 14th to 16th centuries. Renewed mining activity began in the 18th century, when eight galleries were reported at the Stare Mesto (Old Town) gold deposit in 1779. Unfortunately, the production of gold from thin quartz veins was small (maximum 2 kg/year) and the uneconomical mining expired in 1861, when only 49 grams of Au and 6 grams of Ag(!) were produced.
The earliest record of the mining of antimony in the Pezinok deposit is much more recent, in 1790. Ignatz Lill, the Mayor of the Mining Court of Pezinok, visited the mine and reported that the Francisci stope and the Joseph pit were 10 meters deep. In 1810, 11,100 kg of stibnite were recovered. Stibnite occurrence in the Pezinok area near Kolarsky Hill (Wagnerberg) was also reported by Andrian and Paul (1864), but this first attempt at antimony mining ended during the 19th century. The exploitation of antimony was renewed around 1906, when a flotation plant, the first of its type in Austria-Hungary, was built. However, mining activity ended after World War I.
A modern operation for recovery of stibnite ore began in 1940, during World War II, when the demand for antimony as a "war metal" was high. During this year, the German company Antimon-Aktion-Gesellschaft built a new mine with a railway to the ore dressing plant. After a short break in 1947-1951, the exploitation of antimony ore at the Pezinok mine continued until 1991, when the mine was closed for economic reasons, and the technologically unfavorable composition of the ore.
The geology of the Pezinok antimony mine (the Kolarsky Hill deposit) has been dealt with by numerous authors; we will summarize here mainly from data of Cambel (1959), Polak and Rak (1980), Andras (1983), Chovan et al. (1992) and Grecula et al. (1996). The mine occurs in Lower Paleozoic (Silurian to early Carboniferous) metamorphosed black shales (with a basic pyroclastic volcanic admixture and pyrite [plus or minus] pyrrhotite bands), actinolite schists, amphibolites and phyllites to paragneisses, locally penetrated by two-mica granites of the Bratislava Massif.
The ore-bearing zone is about 3.5 km long and 50 to 100 meters thick; it has a folded anticlinal structure oriented northwest-southeast, and dips southwest 60-90 [degrees] (Fig. 10). The stibnite deposit has been worked over a length of 430 meters, to a depth of between 10 and 40 meters (Mrakava 1987). Vertical thickness of the central orebody reaches 65 meters (Andras 1983). The ore-bearing zone is associated with a large low-angle fault or thrust zone which tectonically amputated the deposit. A two-mica granite with numerous pegmatite veins from the Bratislava Massif (Rb-Sr isotope age 348 [plus or minus] 4 Ma, Cambel et al., 1990), which intruded into sillimanite-garnet-biotite paragneisses, lies in tectonic contact below the ore-bearing metamorphic zone. The Stare Mesto gold deposit occurs directly in these leucocratic granites.
The antimony ores form irregular nests, lenticular bodies, small veinlets and veins and impregnations. They are situated in subvertical (up to 20-meter-thick) stratabound structures, referred to as "veins" (due to their vein shape), composed of metamorphosed black shales with basic pyroclastic material, quartz, pyrite/pyrrhotite and arsenopyrite. From southwest to northeast, the Zlata (Gold), Karolina, Centralna (Central) and Plocha are the principal "veins" or structures.
Four mineralization stages of hydrothermal Sb-Au-As mineralization in the Pezinok mine have been distinguished (Andras 1983, Chovan et al., 1992, slightly modified by the authors):
(1) quartz-arsenopyrite, with gold incorporated in arsenopyrite and pyrite;
(3) quartz-carbonate-stibnite-(gudmundite-pyrrhotite-pyrite sphalerite-Pb, Sb-sulfosalts-berthierite);
The origin of the Pezinok antimony mine (Kolarsky Hill deposit) is suggested as hydrothermal epigenetic, and of Hercynian (Upper Paleozoic) in age. The Bratislava granite intrusion caused a contact thermal metamorphism of adjacent metalliferous black shales with pyrite bands, the generation and migration of ore-bearing hydrothermal solutions, and their precipitation in available subvertical tectonic zones. Negative sulfur isotopic composition in sulfides ([[delta].sup.34]S = -1 to -13.5 [%.sub.o]) indicates the important role of biogenic sulfur, and corroborates the leaching of sulfur and metals from metasedimentary black shales with synsedimentary pyrite, plus their interaction with endogenous granite-related fluids (Kantor 1974). Also the negative isotopic oxygen and carbon values ([[delta].sup.18]O = -17.5 to -13.6 [%.sub.o], [[delta].sup.13]C = -11.8 to 9.7 [%.sub.o]) indicate a mixing of meteoric and endogenous solutions and exchange reactions between the fluids and country rocks (Andras 1983). The estimated m etamorphic conditions: T = 350-450 [degrees]C and P = 3.5-5.5 kbar, were sufficiently intense for the mobilization of the ore compounds (Grecula et al., 1996). The study of gas-liquid inclusions in quartz gave homogenization temperatures between 320[degrees] and 150 [degrees]C for the (1) to (4) mineralization stage of the Pezinok antimony deposit (Chovan et al., 1992).
The Pezinok mine was the second largest antimony deposit in Slovakia, after the Dubrava mine in Central Slovakia. More than one million metric tons of antimony ore (with 1.3 to 2.5 weight % Sb) was recovered during the 1951-1991 period, which represented ca. 20,000 metric tons of pure antimony metal. The Pezinok mine flotation dressing plant produced an ore concentrate with 18-25 weight % Sb, 3-5 weight % As, 15-30 ppm Ag and 6-10 ppm Au (Andras 1983), but considered to be poor quality due to the admixture of 15 to 20 other minerals (mainly graphite, arsenopyrite and pyrite).
Numerous authors have studied the minerals of the Pezinok antimony deposit, from the first reports of Leonhard (1843), Zepharovich (1859) and Andrian and Paul (1864), through the special monograph of Cambel (1959) to the recent papers of Chovan et al. (1992) and Andras et al. (1993a, b). All of the mineralogical data through 1980 are reported in Topographic Mineralogy of Slovakia, Part 2 (Kodera et al., 1990); we have supplemented the data in this worth with citations of other authors and with notes on our own observations.
Primary Hydrothermal Minerals
Albite is a very rare mineral at the Pezinok mine; it occurs with carbonates in the Pyrite stope (Cambel and Bohmer, 1955).
Although pure ankerite has not been identified, a mixture of calcite, ferroan dolomite and ankerite is suggested by some chemical analyses of carbonates in the Pezinok mine (Cambel 1959). These carbonates form small veins, veinlets and irregular nests, and they cemented fissures in the country rocks. Ankerite and other carbonates form granular aggregates with quartz, stibnite and other sulfides; the maximum size of crystals is about 1 cm.
Native antimony is a relatively common mineral in some parts of mine. The mineral forms irregular, fine-grained aggregates with white color and metallic luster. The size of aggregates is commonly several millimeters but has been found locally in monomineralic aggregates up to 10 cm. Antimony occurs in association with stibnite, gudmundite, arsenopyrite, quartz and carbonates. Andras et al. (1993) described an interesting example of replacement of antimony and stibnite by secondary senarmontite along a contact. The electron microprobe analyses show practically pure antimony (99.8 weight % Sb, Andras et al., 1993b).
Arsenopyrite is among the most common hydrothermal minerals in the Pezinok antimony mine. It occurs in older and higher-temperature ores of the first and second hydrothermal stages. The mineral forms irregular aggregates, small veinlets and massive monomineralic aggregates in blackish gray quartz. The grain size is up to 5 mm; aggregates can reach from several cm to 50 cm. Prismatic, 1-2 mm crystals of quartz are associated rarely. Finegrained euhedral arsenopyrite from the first stage is a principal carrier of sub-microscopic gold in the Pezinok deposit. The gold content ranges up to 170 ppm, averaging 120 ppm (Andras et al., 1988). Mossbauer spectroscopy has confirmed the presence of gold in arsenopyrite (Andras et al., 1993c, Chovan et al., 1994). Locally, a stibian arsenopyrite with up to 9.2 weight % Sb was reported (Dadak 1983).
Although barite from the Pezinok mine is not reported in any of the published papers, it occurs locally as tiny white crystals on stibnite, together with kermesite, and as massive aggregates. The mineral probably formed during the most recent (4) mineralization stage.
Berthierite is a relatively widespread mineral at the Pezinok mine, associated mainly with stibnite and gudmundite. The mineral forms irregular nests, veinlets, and aggregates of small (up to 3 mm), columnar to acicular crystals. Fresh berthierite is a pale steel-gray color; a bluish iridescence forms on exposure to the air.
Stibian bismuth (with 8.6 to 15.6 weight % Sb) forms rare microscopic, 10 to 60-[micro]m separated grains and thin, short veins with bismuthinite and garavellite in gangue quartz. It also forms along the contacts of stibnite with sphalerite and pyrite (Andras et al., 1993a).
Sb-rich bismuthinite having an empirical formula close to [Bi.sub.1.5][Sb.sub.0.5][S.sub.3] was described from Pezinok as very rare microscopic ([less than or equal to]20 [micro]m) intergrowths with native bismuth and garavellite in stibnite (Andras et al., 1993).
Boulangerite (?) [Pb.sub.5][SB.sub.4][S.sub.11]
Boulangerite from the Pezinok mine has been identified only by ore microscopy (Cambel, 1959). The mineral forms rare microscopic fibrous intergrowths with jamesonite and berthierite in 3mm-thick veins.
Calcite occurs in intergrowths with ferroan dolomite and ankerite, veins and irregular masses with quartz and sulfide minerals. Calcite also forms rare rhombohedral crystals to 1 cm with stibnite.
Chalcopyrite occurs as scarce, small ([less than or equal to]0.5 mm), anhedral grains and aggregates in quartz.
Dolomite forms a mixture with calcite and ankerite in veins and irregular masses. Small veins of dolomite fill a tectonic fissure in the Kolarska adit (Cambel, 1959).
The Pezinok antimony mine is the second known locality for garavellite in the world. The mineral forms very rare, microscopic (only ca. 10 [micro]m) intergrowths with stibian bismuth in stibnite (Andras et al., 1993a).
Besides the gold from the nearby Stare Mesto gold deposit, and chemically bonded Au in the arsenopyrite structure, discrete gold grains are exceptionally rare at the Pezinok antimony mine. Only a few needle-shaped wires of native gold, 5 to 10 [micro]m in length have been described from a carbonate vein (Andraas 1983).
Graphite is a relatively widespread mineral in the Pezinok mine. It forms irregular nests, veins and lenses in and around hydrothermal minerals, and it is an important component of the older stratiform pyrite-pyrrhotite mineralization in the deposit. The mineral forms very fine-grained, poorly crystallized aggregates.
Gudmundite occurs commonly as isolated, anhedral, isometric grains to 2 mm and in aggregates to 5 mm, mainly in stibnite, berthierite, quartz and carbonates. Fin-shaped prismatic crystals up to 1.5 mm long in carbonates are less common (Cambel, 1959).
Jamesonite is among the rare minerals in the Pezinok mine. It forms typical acicular intergrowths ([less than or equal to]1 mm) with berthierite and boulangerite (?) in small veins (Cambel, 1959).
Kermesite is the most famous mineral from the Pezinok antimony deposit. The mine has produced some of the world's best specimens of this species. It forms excellent radial aggregates of acicular crystals, commonly 1 to 4 cm but rarely up to 14 cm long (Huber and Huber, 1985), with deep cherry-red to reddish violet color and strong metallic to adamantine luster. The kermesite crystals are up to 0.5 mm thick and are transparent under strong light. The radial aggregates of crystals are usually flat, because they form fracture fillings, however superb free-growing crystals have been collected. The best examples of kermesite were found in the New Alexander stope during the 1970's and 1980's. Kermesite occurs together with tiny stibnite crystals, and rarely also with valentinite. The paragenetic relations between these minerals indicate a primary hydrothermal origin for kermesite during stage-4 mineralization, through the mixing of ascending sulfur-rich and descendent oxygen-rich solutions.
Lollingite forms in metamorphosed black shales as independent, monomineralic, nest-shape aggregates to several cm, and rarely over 10 cm in size. Locally, lollingite occurs associated with arsenopyrite, pyrite and stibnite. The aggregates consists of fine-grained, 0.02-0.03 mm grains of lollingite, which form pseudomorphs after pyrite (Cambel, 1959).
Marcasite is a relatively rare mineral at the Pezinok mine; it occurs as concentric and colloform aggregates with calcite (Chovan et al. 1994).
Massive stratiform lenses of pyrite with pyrrhotite form the older metamorphosed deposit at the Pezinok antimony deposit. On the other hand, pyrite also occurs in Sb-As-Au mineralizations in several generations. The oldest pyrite of the stage-1 mineralized period contains about 40 ppm of Au on average (Andras, 1987). In the antimony mineralization, pyrite forms small 0.5 to 1-mm cubic or pyritohedral crystals and anhedral grains in quartz, carbonates and sulfide minerals (Cambel, 1959). In addition, we have found rare, unusual, stalactitic aggregates of pyrite, confirmed by X-ray diffraction.
In addition to the metamorphic (mainly hexagonal) pyrrhotite of the older stratiform pyrite-pyrrhotite deposit, the mineral also occurs as aggregates to 3 mm of microscopic ([greater than or equal to]0.1 mm) grains and columnar crystals or myrmekitic pyrrhotite-gudmundite intergrowths (Cambel, 1959). It is associated mainly with carbonates, gudmundite, pyrite and stibnite.
Although quartz is a very common mineral in the Pezinok mine, it is not an interesting mineral from a collector's point of view. Gray or white quartz forms an important part of hydrothermal veins, veinlets and irregular nests, commonly with carbonates, stibnite and other sulfide minerals. The mineral is usually massive, and anhedral; tiny crystals in vugs are rare.
Microscopic rutile inclusions in arsenopyrite have been reported by Andras (in Chovan et al., 1994).
Scheelite (?) Ca[WO.sub.4]
Although scheelite has been briefly noted by the earliest authors (Leonhard, 1843; Zepharovich, 1859), recent confirmation is lacking at the Pezinok mine.
Sphalerite is not a common mineral in the Pezinok deposit. It forms 0.05 to 1-mm grains with stibnite, arsenopyrite, pyrite and pyrrhotite (Cambel, 1959).
Stibnite is the most important economic mineral in the Pezinok mine. The stibnite-bearing ore masses reach thickness up to 40 meters, locally with 1 to 2-meter-thick nests of fine-grained stibnite-rich to monomineralic stibnite aggregate (Cambel, 1959; Mrakava, 1987). This economically important stibnite aggregate consists of anhedral grains to 0.5 mm.
A second type of stibnite is economically insignificant, but is interesting for collectors. It forms tiny hemispheric or flat radial aggregates of acicular stibnite crystals, usually 2 to 5 mm long. These crystals are commonly associated with kermesite and valentinite.
Tetrahedrite is very rare mineral at the Pezinok mine, where it forms 30-[micro]m inclusions in pyrite of stage 3 (Andras, 1983).
Hydrothermal valentinite is one of the most beautiful minerals in the Pezinok mine. It forms white radial aggregates of flat acicular crystals, commonly 0.5 to 1 cm, but rarely 2 cm long. Rich valentinite rosettes cover rock in areas of several tens of [cm.sup.2], locally with kermesite and stibnite crystals.
Allophane [Al.sub.2][O.sub.3] 1.3-2Si[O.sub.2]2.5-3[H.sub.2]O
Allophane forms fine, earthy and glassy white to yellow-brown masses in vugs with kaolinite, halloysite and limonite, covered by cervantite and stibiconite aggregates (Andras, 1983). It contains 1.8 weight % [Sb.sub.2][O.sub.3] and 2.75 weight % [Fe.sub.2][O.sub.3]. Spherical structure is visible under SEM; sphrerules are only a few [micro]m in size (Harman, 1969).
Cervantite occurs as white concretional aggregates after senarmontite (Ruzbacka, 1968) and as yellowish to brownish coatings on stibiconite (Andras and Chovanec, 1985).
The rare mineral chapmanite was first described from the Pezinok mine by Polak (1983, 1988) as pale, yellow-brown, powdery aggregates on metamorphosed black shale from the Sirkova stope and the Stanislav horizon. Under SEM, chapmanite forms irregular aggregates of columnar crystals measuring up to 0.5 x 4 [micro]m.
Destinezite [[Fe.sup.3+].sub.2][([PO.sub.4]).sub.4]([SO.sub.4])(OH) 5[H.sub.2]O
Destinezite occurs here as powdery pale yellow-brown concretions (Mitacek, 1980). Under BSE, diadochite shows well-shaped 5-15 [micro]m, pseudohexagonal (triclinic) tabular to columnar prismatic-pyramidal crystals which locally resemble feldspars.
Goethite [Fe.sup.3] O(OH)
Brown crusts and coatings of what is probably goethite "limonite" are very common on the stope walls, and on the dumps of the Pezinok mine.
Gypsum is a common alteration product of pyrite and other sulfides; it forms small, colorless to white crystals and crusts.
Halloysite occurs together with allophane in rock vugs (Ruzbacka, 1968; Harman, 1969).
Hematite forms compact, finely crystalline masses together with "limonite" (Ruzbacka, 1968).
Jarosite occurs as yellow-brown crystals on the walls of stopes, and on the dumps.
Kaolinite forms microscopic, pseudohexagonal tabular crystals, visible under SEM (Harman, 1969).
Secondary kermesite differs from hydrothermal material by its pink to cherry red powdery appearance in vugs of rocks (Ruzbacka, 1968; Andras and Chovanec, 1985).
Rare green coatings of malachite occur in the oxidation zone of the Pezinok antimony deposit.
Opal has been found as thin, white to white-blue films, and rarely as colorless hyalite on rocks.
Secondary senarmontite occurs with cervantite (Ruzbacka, 1968).
Schafarzikite (?) [Fe.sup.2+][[Sb.sup.3+].sub.2][O.sub.4]
Schafarzikite was described as a new mineral from the neighboring Pernek antimony deposit (Krenner, 1921). In the Pezinok deposit, schafarzikite is present as tiny, 0.1-0.3 mm crystals with valentinite. The electron microprobe did give only Fe and Sb peaks, but the amount of the material was insufficient for X-ray identification (Andras and Chovanec, 1985).
Scorodite forms pale white-green coatings on arsenopyrite and black quartz (Ruzbacka, 1968; Uher, 1990). SEM reveals rich, well-crystallized aggregates of dipyramidal, rarely prismatic scorodite crystals to 2 [micro]m.
Senarmontite is a product of hypergene alteration of stibnite and native antimony, occurring along the margins of these minerals (Andras et al., 1993b).
Unusual, secondary siderite forms veins to 3 cm thick and fillings in brecciated rocks (Polak 1988).
Slavikite Na[Mg.sub.2][[Fe.sup.3+].sub.5][([SO.sub.4]).sub.7][(OH).sub.6]*33[H. sub.2]O
Recently, slavikite has been identified by X-ray analysis in the dumps of the open pit in the Pezinok mine (Trtikova, personal communication, 1997).
Stibiconite forms white crystalline aggregates to 0.8 mm thick on stibnite from the Antimony adit (Andras and Chovanec, 1985).
Secondary valentinite occurs as relatively common white to yellowish coating and fan-shaped aggregates on stibnite and native antimony (Cambel, 1959; Andras and Chovanec, 1985).
The mine has been abandoned since 1991, and entrance into the old workings., open pit and dumps is still forbidden for common visitors. The area is fenced and watched by a guard. The mine is still a property of the Rudne Bane (Ore Mining) Co. and access to the dumps is possible only with special permission. Thus, collecting minerals in the Pezinok mine is today practically impossible; all high-quality specimens were found in the stopes, especially the New Alexander stope, during mining between 1940 and 1991, especially in the 1970's and 1980's. It is still possible, however, to find rare new species on the dumps.
The authors wish to thank Mr. L. Osvald for numerous specimen photographs, and Dr. I. Holicky for SEM photomicrographs. We also thank Dr. M. Chovan (Cormenius University, Bratislava) and Dr. P. Andras (Geological Institute of the Slovak Academy of Sciences, Banska Bystrica) for reviewing the manuscript and for their constructive criticisms which helped to improve the text.
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|Author:||Uher, Pavel; Michal, Silvio; Vitalos, Jiri|
|Publication:||The Mineralogical Record|
|Date:||Mar 1, 2000|
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