Geologica Macedonica, Vol. 15-16, p. 1-23 (2001-2002) Suppl. GEOME2 SSN 0352 - 1206 Manuscript received: December 15, 200 1 UDC: 553.08 (497 .7) Accepted: March 3, 2002 Original scientific paper ~•

ALLCHAR l\1INERAL ASSEMBLAGE

l 3 l 4 Blazo Boev , Vladimir Bermanec , Todor Serafimovski\ Sonja Lepitkova , Snezana Mikulcic , 5 5 5 Marin ~oufek\ Gligor Jovanovski , Trajce Stafilov , Metodija Najdoski IDepartment ofPetrology, and Geochemistry, Faculty ofMining and Geology, "Sv. Kiril i Metodij" University, Goce Delcev 89, MK-2000 Stip, Republic ofMacedonia 2Department ofMineral Deposits, Faculty ofMining and Geology, "Sv. Kiril i Metodij" University, Goce Delcev 89, MK-2000 Stip, Republic of Macedonia 3Institute ofMineralogy and Petrology, Department ofGeology, Faculty ofScience, University ofZagreb, Horvatovac bb, HR-JOOOO Zagreb, Croatia 4Department ofMineralogy and Petrology, Croatian Natural History Museum, Demetrova I, HR-JOOOO Zagreb, Croatia 5Institute of Chemistry, Faculty ofScience, "Sv. Kiril i Metodij" University, P.o. Box 162, MK-JOOI Skopje, Republic ofMacedonia

Abstract. The paper is a summary of investigatioris carried out on of the . It discusses the TI-As-Sb-Au ill emblage after detailed and intense research work. Four types of mineralization have been distinguished based on the mineral assemblage present: I. The first ly pe is characterised by high c ment of and sulphur, but lower and thalli um contenl. The - mineral assemblage is characterized by the presence of some quantities of arsenic-pyrite. 2. The second type is characterized by the high and low iron and content. is the most common mineral in the group. 3. The third type is characterized by the high arsenic and sulphur and relatively low thallium content. is the most common mineral in this group. 4. The fourth type of minerals is characterized by the high content of arsenic, sulphur. iron and thallium. This type of minerals is accompanied by the high content of and .

Key words: Allchar; Macedonia; mineral assemblage

INTRODUCTION

The Allchar complex Sb-As-TI-Au deposit is outcrops of the deposit. There are no data about the one of the unique deposits in the world not because amount of arsenic mined out at that time. of its size, but mineral composition. It contains The mineral potential of arsenic in the deposit significant thallium concentrations that classify it is estimated at some 15,000 tons (Ivanov, 1965). as a unique deposit containing that . Besides According to today's crileria arsenic is a harmful economically significant antimony and arsenic component that results from antimony processing. concentrations, the Allchar deposit is the first The first results concerning the miner­ Carlin-type depo it found in the Balkan Pen­ als from Allchar Iocality were published by Foul­ insula during the mid 1980's. Ion, 1890, 1892, 1904; Hofmann, 1891 ; Pelikan, The latest mining activities started in 1881, 1891; Goldschmidt, 1896; Hackman, 1897; Ste­ and with some interruptions, lasted till 1913 (Jan­ vanovic, 1904). kovic, 1960). During that period mainly arsenic ore During the end of the nineteenth (Vrba, 1894; was excavated and exported to Thessaloniki, Greece Krener, 1895;' Goldschmidt, 1899) and the begin- and Gem1any. Small amounts were mined out in the 2 B. Boev, V. Bennanec, T. Serafimovski, S. Lepilkova, S. MikuNHi, M Soufek, G. Jovanovsk,; T. SlafiJov, M Najdoski

ning of the twentieth century (Jannasch, 1904; Lo­ 1994; Sotirovski and Boyer, 1993; Stafilov et aI., czka; 1904; Jezek, 1912, 1913a) the first thallium 1993,1995; Trajkovska et aI., 1993). minerals were discovered ( and vrbaite, re­ Some adits as no. 21 have been re-opened to spectively) as constituents of arsenic-antimony ore. enable taking the samples. This activity lasted from Exploration for antimony carried out from 1987 through 1993. Later it was restricted to labo­ 1953 to 1957 and from 1962 to 1965 resulted in the ratory investigations. . discovery of significant reserves of low grade ore The mineral potential of tballium in the AlI­ (Ivanov, 1965). However, high arsenic content in char deposit has been estimated at 500 tons (order Sb-concentrations has precluded economic exploi­ of magnitude) (Ivanov, 1986). tation. The latest exploration for antimony was car­ The possible presence of gold in the Sb-As-TI ried out in 1970-1973 (Ivanov, 1986). association at Allchar was initially suggested by Mineral potential of the Allchar deposit, both different authors (Stafilov, 1985; Ivanov, 1986; mined out and available ore, exceeds 20,000 tons Stafilov and Todorovski 1987). During the 1986­ of antimony with 0.5 % Sb as cut-off grade (Janko­ 1989 period gold mineralization was systema­ vic et aI., 1997). tically explored. The results of both field and labo­ The name of the deposit pronounces as AUchar, ratory studi e showed that the geological, geo­ being derived from the names Allatini (a bank institu­ chemical, mineralogical and hydrothermal altera­ tion, owner of the concession) and Char teau (a min­ tion features are strikingly similar to those which ing engineer who worked in the mine). characterize Carlin-type mineralization of the Special interest for thallium as possible solar · Western United States (Percival and Radtke, 1990; neutrino detector (Freedman, 1976, 1979) gave a Percival et aI., 1992). new impulse for systematical investigations of Unlike the Carlin-type gold deposits in the thallium mineralization in the north part of the All­ Western USA, the Allchar mineralization is hosted char deposit (i.e. the Crven Dol ore body). This not only by sediments, but volcanics as well. was an international LOREX (LORandite EXeri­ It should be emphasized that the Allchar de­ ment) Project aiming to establish reliability of the posit is not fully explored and that the metalloge­ mineral lorandite from this deposit as thallium so­ netic studies are not completed. The current inves­ lar neutrino detector (Ernst et aI., 1984; Pavi cevie, tigations are still in progress. 1986, 1988, Morinaga, 1986; Pavieevie and EI For the results of previous studies of the All­ Goresy, 1988; Palme et aI., 1988; Pavieevie and char deposit, the reader is referred to Ivanov (1965, Korschinek, 1993; Anovski et aI., 1993; Frantz et 1986); Jankovic (1960, 1988, 1993); Percival and aI., 1994; Grzetie, 1993; Hejl et aI., 1993; Ivanov­ Boev 1990); Stieglitz (1990); Percival et al. (1992); ski et aI., 1993; Lazaru and Stafilov, 1993; Balie Percival and Radtke (1994); Boev and Serafimovski Zunie et. aI., 1993a, 1993b; Makovicky and Balie (1996); Boev et al. (1993a); Rieck, 1993; Caubel Zunie, 1993; Mihaj lovie, 1993; MijatoviC et aI., and Galvier (2000). 1993; Petrov and Andonova, 1993; Petrov et aI.,

REGIONAL GEOLOGIC SETTING

Spatially the Allchar deposit is located along The terrain adjacent to the deposit is com­ the western flank of the unstable Vardar zone and posed of several litho-stratigraphy members. the Dinarides or rigid Pelagonian crystaUine block The wide vicinity of the Allchar deposit is on the west, about 50 km south-west of the town of characterized by complex tectonic relations in Kavadarci in close proximity to the Greek-Mace­ which N-S structures of deep fractures along the donian border. contact of the Vardar zone and the Pelagonian Mineralization is associated with a Pliocene massif play an important role. Volcanic structures volcano-intrusive complex of calc-alkaline suites, and subvolcanic intrusions of calc-alkaline magma controlled by deep fractu res striking mostly N-S are formed at their intersections with neotectonic and SW-NE. fractures SW-NE. The age of subvolcanic intru­ This igneous complex formed on a basement sions in all parts of the Kofuf area is the same, the composed predominantly of Triassic ediments, Allchar deposit intrusions belonging to the young­ Jurassic ophiolite (gabbro-peridotites prevail) and est phases (3.9 - 5.1 m.y.). Cretaceous sediments.

Geologica Macedonica. 15-16, \-23 (2001-2002) Suppl. Allchar mineral assemblage 3

All geological units, except those of the Plio­ Upper Cretaceous sediments are significantly cene shallow basin, ' demonstrate an elongation spread in the vicinity of Allchar. They occur in with north-south trend and are tectonically rather several facies such as: dislocated. - Barremian-Albian conglomerates and - Turronian limestones Precambrian albitic gneisses with sporadic These rocks make up' the hanging-wall in the amphibolite lenses belong to the oldest rocks in the Ni-Fe RZanovo deposit. wide vicinity of Allchar. Sporadic marble masses occur in the gneisses. Upper-Eocene series consists of basal con­ glomerates covered by flysch sediments (alevro­ Paleozoic schists, phylites, local~ cipolines, lites, clays, sandstones and limestone intercalationsr metasandstones, argilloschists and quartzites 'are not widespread. Pliocene lacustrine sediments and pyroclas­ tites are wide spread in the vicinity of Allchar. Triassic sediments comprise a large portion Pliocene sediments consist of conglomerates and of the terrain in the All char area. They occur in clayey-sandstone facies with local occurrences of two basic facies: (i) as marbleized limestones and marls. Small deposits of diatomaceous earths are dolomites and (ii) claystones and sandstones with occasionally noticed. Volcano-sedimentary suites sporadic masses of diabases and local green schists. with pyroc1asts and clayey-saud tone sediments (Kojcov Rid north ' of AJlchar) are developed in Jurassic rocks are represented by diabase­ individual Pliocene basins. chert formations composed of li mestones, sand­ stones, clayshists, quartzites, cherts sedimentary Quaternary sediments occur in the form of facies as well as strongly serpentinized gabbro­ terraces, and as tuffs locally. peridotite complexes of harburgitic-dunitic compo­ ition. SmaJl deposits with podiform chromite bod­ The volcano-intrusive complex of calc-alkali­ ies have been found in the latter. Serpentinites also ne rocks of Pliocene age is part of the wide Kozuf OCC\Jf as separated narrow hands with tectonic bor­ area. Its petrologic features are shown in detail by ders on surrounding rocks. They appear in this area Boev (1988). as a result of processes associated with diapirism. Latites, minor ·latites and andesites (near This is indicated by intensive tectonic fracturing as Studena Voda) occur in the wide area of Allchar. well as by the appeared dislocations in the western margin of the Vardar zone.

LOCAL GEOLOGIC SETTING

Deposition of sandstone and claystone, fol­ the central part is built of dolomite, marble, and spo­ lowed by bedded and massive carbonate rocks radically limestone. (limestone, dolomite, marble) took place in the The dolomite series underlies marble. Based Middle and Upper Triassic. These rocks are the on fission traces the age of dolomite was deter­ basement of the Allchar deposit. mined to amount about 250 (Lepitkova, 1995). The quartz-sericite-feldspar schists are devel­ m.i oped along the eastern fl ank of the deposit, whereas

MINERAL ASSEMBLAGE OF INDIVIDUAL TYPES OF MINERALIZATION IN THE ALLCHAR DEPOSIT

Microscopic and X-ray spectral laboratory the most widespread and occurs as massive aggre­ studies carried out on samples from the Allchar gates. Grains are 0.5 mm in size. It is closely asso­ deposit determined the mineral assemblages as fol­ ciated with marcasite and . Chemi­ lows: cally, pyrite is relatively pure. However, low man­ The pyrite-marcasite mineral assemblage ganese and content$' have been found. Ar­ hosts pyrite, marcasite and arsenopyrite. Pyrite is senic content is high, reaching 5 % which is an

Geologicu Macedonica, 15-16, 1-23 (2001-2002) Suppl. 4 B. Boev, V. Bennanec, T. Seralimovskl; S. Leplikova, S. Miku/tii, M Soukk, G. Jovanovskl; T. Slali/ov, M Nl/jdoski

indicator of the large activities of this element dur­ 1993b; Lazaru and Stafilov, 1993, 1998; Stafilov et ing the process of forma tion of the deposit. Taking ai., 1995). in consideration the occurrence of arsenopyrite in -orpiment-Iorandite assemblage is association with pyrite makes arsenic content in rather variable. The assemblage was formed during pyrite logical. 'the later stages of hydrothermal activity in the area. Marcasite is less common. It can be found in Orpiment is the most common in the assem­ the form of spheroids in silicified mass or as pe­ blage. It forms aggregates of massive texture oc­ ripheral zones in pyrite. Grains vary from 0.005 to curring as large cry tals of 10 to 15 mm in size. 0.1 mm in size. It contains lower amounts of ele­ Small quantities of iron and copper occur as impu­ ment impurities compared to pyrite. Marcasite is rities (Boev et ai., 1993b; Lazaru and Stafilov, characterized by the presence of low arsenic and 1993, 1998; Frantz et aI., 1994; Stafilov et aI., antimony concentrations. 1995). Arsenopyrite is not very common. Its dis­ Realgar forms individual aggregates or occurs crimination from pyrite is in general based on col­ in association with orpiment, lorandite and other ored dispersion in crossed nicols, which is blue to thallium minerals. It occurs as large grains of 3 to yellowish-brown. 5 mm in size. Its composition is stoichiometric Stibnite assemblage includes only mineral containing low quantities of iron and copper as stibnite. It occurs in the form of fairly large crys­ impurities. Orpiment corrodes realgar indicating tals of 2 x 5 mm in size. It possesses idiomorphic that realgar has been formed earlier than orpimeni. grain structure with individual grains connecting Thallium minerals in this assemblage are very quartz aggregates with marcasite. This indicates common. The most common is lorandite occurring that stibnite has been formed later compared to in grains of up to 5 mm in size. It occurs in asso­ pyrite-marcasite assemblage. Stibnite is not associ­ ciation with both realgar and orpiment. Chemically ated with any other minerai. Significant concentra­ it is relatively pure (Boev et aI., 1993b; Lazaru and tions of other elements in stibnite are not regis­ Stafilov, 1993, 1998; Frantz et aI., 1994). tered. Iron and copper are common impurities, Minerals present at the Allchar deposit are whereas thallium occurs sporadically (Boev et aI., given in Table 1.

Table I Minerals present at the Allchar deposit

No. Mineral Formula Crystallographic system

Elements Gold Au Cubic 2 S Monoclinic/orthorhombic

Sulfides and sulfosalts -_._---...-.-._-_...__._._--..--_._--"...----_.__....._..._._-_...._...... _.._--_ .._...._....._..•..._.._....__._----_._._----­ 3 Arsenopyrite FeAsS Monoclinic 4 Bernardite TI(AsSb)sSg Monoclinic 5 HgS Hexagonal

6 Jankovicite* TIsS ~(AsSb)4S22 Triclinic

7 Lorandite TIAsS 2 Monoclinic 8 Marcasite FeS2 Orthorhombic

9 Orpiment As2SJ Monoclinic 10 Parapierrotite* TI(Sb,As)sSg Monoclinic 11 Pararealgar AsS Monoclinic 12 Picotpaulite* TIFe2SJ Orthorhombic 13 Pyrite FeS2 Cubic/orthorhombic

Geologica Macedonica.15-16, 1-23 (2001-2002) Suppl. Geo AJJchar mineral assemblage 5

No. Mineral Fonnula Crystallographic system

14 Raguinite TIFeS2 Orthorhombic

15 Realgar AS4S4 Monoclinic 16 Rebulite* TIsSbsAssS22 Monoclinic 17 Simonite* TIHgAs,JS6 Monoclinic

18 Stibnite Sb2S,J Orthorhombic

19 Vrbaite* TI4Hg,JAsgSb2S2o Orthorhombic 20 Weissbergite TISbS2 TricJinic

21 Filngite TI 3AsS4 Otrhorhombic

Oxides

22 (or Claudetite) AS20 3 Cubic 23 Cervantite Sb20 4 Orthorhombic 24 Goethite FeO(OH) Orthorhombic 25 Quartz a-Si02 Hexagonal (trigonal) 26 RomCite (Ca,Fe,Mn,NahCSb,Tih06(O,OH,F) Cubic

27 Stibiconite Sb30 6(OH) Cubic

28 Va1entinite Sb20 3 Orthorhombic Carbonates

29 Aragonite CaC03 Orthorhombic 30 CaCOJ Hexagonal (rhombohedral)

31 Dolomite CaMg(C03h Hexagonal (trigonal) - -_.. _....._---_ .. _--_•...... _._--_._ ...... _.__.­ Sulfates ....__.__..--_._- _..._._-_._-.._....- _._....._._.._--..... _._-----_._---_...... _...... _.._._----_.-.__._--_._-­ 32 Barite BaS04 Orthorhombic

33 Dorallcharite* Tlo.sKo.2FeJ(S04hCOH)6 HexagonaJ (trigonal) 34 Epsomite MgS04'7H20 Orthorhombic

35 Fibroferrite FeS04(OH)'5H20 Trigonal 36 Gypsum CaS04·2H20 Monoclinic 37 Melanterite FeS04·7H20 Monoclinic

38 Rozenite PeS0 4 '4H20 Monoclinic

39 Slorkeyite MgS04 '4HzO Monoclinic ------_._--_.__ ..._. _._- - _._------_._ --­ Arsenales ---­ _._-_ .----_..._...__._._._-­ --- --_.._------_.._------_._.... - --- 40 Hl:lmesite MgJ(As0 4)2'8H20 Monoclinic

41 Pharmacol ite CaHAs04 ·2H2O Monoclinic

42 Picropharrnacolite Ca4Mg(AsOJOHh(As04h ·IIH2O Triclinic 43 Unnamed new mineral* FC2TJ[(Aso.asSO.lS)04h·4H20 ...... _------_.------_._ --_.__..._...._ .. Molibdates ...,-,------:::-:--:-:--:::--_...... __._._--_.. _._._-- - -_._------_.­ 44 Wulfenitc PbMo04 Tetragonal

Allchar thallium minerals are marked in bold • Thallium mincrals present only at Allchar deposit ' -

Geologica Macedonica, 15-16, 1-23 (2001-2002) Supp!. 6 B. Boev, V. BClTTll1nec, T. Sr:raJjmovski, S. Lepitkol'8, S. Mikul6i, M. $oufek, O. JOl'anovski, T. S/aJilov. M. N8jdoski

MINERAL ASSAMBLAGE

Elements and sulfosalts

GOLD, Au ARSENOPYRITE, FeAsS

The presence of gold in the Sb-As-TI associa­ Among marcasite and pyrite only a unique Lion at Allchar was suggested by Stafilov, 1985; occurrence of arsenopyrite ha been mentioned in Ivanov, 198~, and Stafilov and Todorovski 1987. the northern part of the A -rich deposit. H. von During the 1986-1989 period gold mineralization Foullon (1882) has reported this occurrence as was systematically explored. Percival and Radtke small lustrous crystals embedded in massive orpi­ (1990) and Percival et aJ. (J 992) showed thal the ment. geological, geochemical, mineralogical and hydro­ thermal alteration features are similar to those, which characterize Carlin-type mineralization of BERNARDITE, Tl(AsSb)sSs the Western United State. Bernardite was fou nd in only one of the nu­ merous specimens that were collected by group of SULFUR, S Czech mineralogists in 1975 and 1976. The name was given in honour of Jan Bernard, Czech miner­ Sulfur forms a small bright yellow well de- . alogist and metallogenist, who tirst recognized the veloped crystals up to 1 mm. n is also found as new mineral and drew attention to it. Pasava et al. earthy yellow masses. On the exposure to sunlight (1989) have published the work with detailed de­ it i.5 unstable and tends to become millcy earthy. cription of its physical, chemical and structural characteristics. It forms thick tabular crystals, which are usually smaller than 1 mm the largest reported being 4 mm in size. The crystal faces are commonly corroded or striated and dull. The min­ eral i black with occasional dark red internal re­ flections and a red . No has been observed and is subconchoidal to uneven. The mineral occurs in associations with orpiment and realgar. Its position in the general mineral se­ quence is unclear. Holotype specimens have been deposited in the Narodnf Museum in Praha and in the Naturhistorisches Museum in Vienna.

Fig. 1. One of the crystal forms of sulfur Fig. 2. One of the crystal forms of bemardite Geologica Geologica Macedooica, 15-16, 1-23 (2001 - 2002) Suppl. AI/char mineral assemblage 7

CINNABAR, HgS LORANDITE TlAsS2

Rick (1993) mentioned cinnabar as very rare Lorandite is world famous mineral described mineral detectable only in polished sections as as the firSt thallium-bearing mineral. Since its first grains up to 150 micrometers. Some inclusions in discovery in Allchar in 1884 (Krenfler, 1894, 1895, realgar belong to cinnabar as well. Among the 1897) its smaller quantities have been found in samples which were deposited in Croatian Natural only a few other localities worldwide. The mono­ History Museum in Zagreb there are single crystals clinic tabular aggregates of lorandite are typically of cinnabar up to 2 mm in size. These samples are dispersed throughout realgar and orpiment hosts. the subject of recent study. Well-developed crystals are much more seldom. They show many different forms. Krenner (1895), Goldschmidt (1899) and Baric (1958) described up to 32 forms. Lorandite can easily be distinguished from realgar by its darker red color, its semimetal­ lic luster and its perfect cleavage on (001 ) (201) and (110). Some crystals are coated by a brownish yellow crust. Lorandite crystals of 1 cm are ty pical for this locality, although exceptionally single crystals up to 5 cm in size have been found. Lo­ randite is named after the Hungarian physician Lo­ rand Eotvos (1848-1919).

Fig. 3. One of the crystal forms of cinnabar Chemical composition of lorandite has been well established (Jannasch, 1904). The investiga­ tions in connection with the LOREX program have JANKOVICITE, TlsSb9(AsSb)4S22 revealed some interesting features. The Allchar lorandite is pure, containing only traces of K, Cr, A new sulfosalt mineral from the Allchar de­ Fe, Cu and Zn (Palme et aI., 1988). The ore-grade posit has been described by Libowitzky et al. (1994). in the richest zone contains about 18,000 cubic The determination has confirmed meters of ore with an average Tl content of 0.35 %. As that the sites are partially substituted by Sb. The Microprobe analyses in the recent investigations structure shows close similarities with those of rebu­ show presence of Hg. lite. Named in recognjtion of Prof. S. Jankovic for his work on the mineralogy and geology of Allchar.

Fig. 4. Some of the crystal forms of lorandite

Geologica Macedonica, 15-16, 1-23 (2001-2002) Suppl. 8 B. Boev, V. Bennnnec, T. Serafimovsk,; S. Lcpitkov.1, S. Mikllk'ii, M Soufek, G. Jovallovski. T. Stafilov, M Najdoski

MARCASITE, FeS2 of moisture) altering to other minerals of iron sul­ fide type. It is oflen associated with realgar and Marcasite appears as black botryoidal nod­ stibnite containin g rather high quantity of arsenic. ule . It is very dull, crumbly and (in the presence

Fig. 6. Marcasite

Geologica Macedonica. 15-16. 1-23 (2001-2002) S~ppl. A I/c/mr (mncro/assemb/age 9

low, elongated idiomorphic crystals with adaman­ tine luster faces are very rare. Orpiment usually P Ime J.t al. (1988) described orpiment as a forms fa n~shaped aggregates or hemispheres, stoichion Lricall rather pure mineral, alth ugh it mainly ha iog brownish yellow color and dull lus­ does contain traces of K, CI, Cr, Mn, Fe an Cu. It ter. The crystal size of a few mm is typical. The occurs mainly as ompact masses sometimes presence of lorandite ne r the realgar and orpiment weighing several hundred kilograms. Bright yel­ zones i observed.

Fig. 1. orne of the cry'anl forms of orpimcnl

PARAPIERROTITE, TI(S ,AshS~

arupl rrotite usually appears as single elon­ gated ' rvslals in c'lvitics of rna. ive realgar. The length of th ~ cry.taL is usually about 3 mm, but Fig. 9. Some of the cr\,qal rtlm\~ of pumpicrmtitc exceptionally th size can reach up to 1 cm. (Johun et aI., 1975). They re b ack ith a semimetallic PARAREALGAR. AsS luster. The mineral '" I amed on account of its rela­ Pnrarealgar occur ' as a result of decomposi­ tions with pierotitc. Holotypes have been deposited tion of realgar, which has be n exposed, to in the mineralogical colic tion of Ecole nali onale sunlight. The mineral appears as very tiny yellow supcrieurc des mines de Paris. coloured crystals.

GeologlclI Muc.:donica. 15- 16. 1-23 (2001-2002) Suppl. lOB. Boev, V. Bt:rTI1IJnCC, T St:roJimovski, S. LcpitkoV8. S. Miku/t!it!. M. Soufi:k, G. Jovanovsk,; T. Sltlfilov. M. Nil}doski

1969). In the Laurent's paper raguinite has been described as pseudomorphs after an unknown spe­ In the lorandite bearing zone of the depo ii, cies later described and named picotpaulite. Like .especial ly in the zone of pyrite and raguiniLe. pi­ picotpaulite it i found in the central zone of thal­ cotpauliLe was found as inclusions mainly up to 0.5 lium ore body. as ociated with orpiment, realgar mm. Lt is bronze colored but in polished section and lorandjte. Raguinite crystals are elongated in under reflected light it appears creamy white with ' the form of fi bers. Such bunille of fibers has bril­ very strong anisotropi character. Often it is at li ant bronze color. Usually it is intimately inter­ least partly replaced pseudomorphically by ra­ grown wi th pyrite. In reflected light i a gray white guinite. Picotpaulite is rhombic, but the crystals are to pinkish white. Mineral shows very strong po­ LlSU8': j pseudohexagonal because penetration larization colors with a dominant orange color. twinning on it is common (Johann et aI., 1970). It Only small quantities of thi mineral have been is named after the French mineralogist Paw Picot. recovered to date. Holotypes have been deposited Holotypes have been depo ited in the mineralogi­ in the mineralogical collection' of Ecole nationale cal collection of Ecole nalionale superieure des superieure des mines de Paris. mines de Paris.

Fig. 10. One of the crystal forms of piCOlpJulitl

PYRITE, FeSz

The pyrite itself i very unattractive, It has been the fi rst crystallized in AlI­ char being of high importance for the formation of some of the rare iron be~ring thallium sulfosalts. Pyrite is responsible (as in the other CarHn-type deposits) for the precipitfltion of gold. It is mainly found as corroded grains and in the core of marca­ site nodules.

RAGUINlTE. TlFeS2

Raguinite has been named according to the French scholar Eugene Raguin (Laurent et aI., Fig. 11. Some of the crystal forms of pyrite

Geologica Macedonica, 15-16, 1-23 (2001-2002) Suppl A/lchar miners/assemblage 11

gated red coloured prisms which (exposed to light) decompose and transform to yellow pararealgar. It Realgar was mentioned in the papers of Foul­ is worth mentioning that realgar is the host for Ion (1892 and 1904) where its phy ical and chemi­ mineral lorandite. Liquid inclusions can be fo und cal characteristics are described. It occurs as crys­ in some crystals (Beran et al., 1994). tals of up to 2 em in size. The crystals are elon­

Fig. 120. Crystal forms of realgar

Geologica Macedonica. 15-16. 1-23 (2001-2002) Suppl. 12 B. Boev, V BC17nancc, T Serafimovski, S. Lcpitkova, S. Jl/iku/66, M. Svuiek, G. JOI'lJnOlsk,. J: Sro/l/o v, ft.!-....:.... N:yJoskl-----­

Fig. 12b. Crystal fonns or realgar

Geologjc~ Macedonica, 15-16, 1- 23 (2001-2002) Suppl. AI/charminerol asscmblage 13

Fig. 13. Realgar with lorandite . faces of the zone lOlO] are stri ated. Well devel­ oped cry tal., up to 2 mm m . lze are described. Re­ his mineral is named in honor of well known bulite is associated vi th realgar and simonite. The geologl. t B ris Rebula from Macedonia who has identity of the studied by Balie Zunic et al. (1 982) ha dly wor 'cd on Allchar mineral characterization. samples of rebulite was established by mean" of fh crystal., of rebulite are dark gray with a metal­ EDX analysis, and powder patterns were calcu­ lic Itl\ter and a brownish red streak. They exhibit lated according to the crystal structure. Allchar is the d JnIll:1nt forms [100}, (00 I} and {Ill}. The the type locality for this mineral.

Fig. 14. Som of the cry~lul fll rnlS of rchultll

Geologica Mtlcedonica. 15-16. 1-23 (2001-2002) Suppl. 14 B. Boev, V. Bemwnec, T. Serafimovsk,; S. Lepilkova, S. Mikuitic. M Soufek, G. Jovanovski, T. Slafiio v, M Najdoski

SIMONITE, TlHgA 3S6 tal structure of this mineral was solved by Ohmasa and Nowacki, 1971. Engel et al. (1982) published the result of the crystal structure determination of a new sulfosalt mineral named simonite. The small orange-red crystals of simonite were found only as inclusions in rebulite. They have irregular shape with dimen­ sions from 0. 1 to 0.2 mm. Its light orange-red col­ our can easily be confused with realgar. Allchar is the type locality for this mineral.

Stibnite was mined especially at the turn of 19th to 20th century. The entire production of ma­ nually upgraded 'ore (with an antimony content of 60 %; the Sb content of pure stibnite is 71.68 %) was sold to England to use in the hardening of and - alloys. Stibnite occurs as groups of well-de­ veloped crystals in cavities of massive tibnite. Crystals of stibnite are elongated prizmatic with high luster. Tl\ey reach a length up to 10 cm. The most attractive specimens of stibnite are often ac­ companied by sprinkled small realgar crystals on it.

Vrbaite is a very rare sulfosalt which was no­ ticed for the fu t time in 1903 by Wilhem Maucher (JeZek, 1912). He identified in small cavities in realgar existence of a new, as yet undescribed min­ eral and he analyzed major con tituents of these samples: thallium, arsenic. antimony and sulfur. Later Jezek (1 9 12, 19 J3a) des ribed it as a new mineral and named it in honor of his teacher Karl Fig. 16. Stibnite Vrba (1845-1922). Vrbaite occurs as dark gray minute crystals with a bluish sheen and semimetallic luster. Usually they are tabular or flat bipyramidal having a pale yel­ lowish streak. In thi nnest sections vrbaite is dark red translucent. Its good cleavage on {.o 10} is usu­ ally observable and can be used for identification. Previously the chemical formula TlAs2SbSs or Tl(As, SbhS5 has been propo ed based on the re­ sults of the chemical analysis (Tl 29.52, Fe lo85, Sb 18.34, A 24.06, and S 25.20 %) (KI'ehhK, 1912, 1913). More than 50 years later this composition was found to be incomplete. The re ults of micro­ probe work (Caye et aI., 1967; Nowacki, 1968) have shown that Hg is major constituent of the composition leading to the now commonly ac­ cepted chemical form ul a: T14Hg3AssSb2S2o. All­ char is the type locality for this mineral. The crys­ Fig. 17. Vrbaitc

Geologica Maccdonica, 15-16, 1-23 (2001-2002) Suppl. Allchllr minera/assemb/.7gc 15

Fig. 18. Crystal fo rms 0f vrbaitc

WEISSBERGlTE, T1SbS2 was first described from the Carlin mine by Dick­ son and Radke in 1978. Rieck has identified Rieck (1993) has reported for the first time weissbergite on a single spedmen of realgar, in the weissbergite from Allchar, whi ch is now the sec­ form of elongated pri, matic crystals with a maxi­ ond known location for this mineral. Weissbergite mum size of 0.5 mm. It is steel gray, and has a me-

Geologica Macedonica. 15-16,1-23 (2001-2002) Suppl. 16 B . Hoev, V. Berm.,ncc, T. Semfil11ovskl: S. LepitkoViJ, S. Mikll!(!k; M. SOllrek, G. Jo vano I ski T. '(;,Jifov. M. Niljdo!ii.'i

tallic luster, with deeply striated face . Its well de­ QUARTZ, u-Si02 eloped cleavage in four different directions helps to distinguish it from U1C tber thal li um sul­ The well developed clear LO Illi lky crystals of phosalts. quartz are found in th central z ne associ at d with stibnite and realgar Such up to 2. em in size dru­ zas are found sporadically. The cryst I si7c u ually does not exceed 2 mm. In mo l parts of the dep sit quartz is also found in the form of chalcedony and This new mineral form rims around loralldite ja per. eEl oresy an Pavicevic J 988) and has s far only been identified u. ing refl ected light micro­ scopy and microprobe I1n aly ~ is. Frantz et at. (1994) confirmed its chemical composition. Later Wilson et al. ( 1993) found the mineral with the same chemical compo ition in Mereur gold deposit in Utah. USA. giving a name fangite.

Oxides

ARSENOLlTE (or CLAUDETITE), AS203

Frantz et a1. ( 199 ) identifi ed a mineral wi th the chemical compo:llion AS103. It has been de­ scri bed as a small vein between realgar gr.lin. It is Fig. 19. Sum or lht: crystnl f nns of

GOET}IIT E, FcO(Oll) In the past these ubiquitous minerals from Allchar depo it have een considered to be a new Foullon predicte the OCC lln-ence of lhis anti­ mineral being conseguentl y described as "all­ mony and later ( oullon. It 90) proved charite" (Jezek, 191 3; Cecil fi nd J hann, 1967). It it exisl nce on material he ree ived from a mine appears like a dark brown to earthy masses and engineer. No further description or Allchar valen­ minute crystals. P eudom rph. after pyrite crystals Li nite has been given by any other aulhor. 'consisl almo t entir Iy of goethite.

Geolugica Mnccdonica, 15-16. 1--23 (2otll - 2002) Suppl. ( AI/char mineral assemblage 17

Carbonates-.

ARAGONITE, CaC03

Aragonite has been reported in Allchar's min­ eral paragenesis usually as white crusts consisting of fibrous tiny crystals. They are visually interest­ ing when occurring in association with stibnite and realgar.

Fig. 20. One of the crystal fonns of aragonite Fig. 22. Some of the crystal fonns of calcite

CALCITE, CaC~

Calcite is widely spread in the form of marble The major host rock of the deposit is massiv as a part of the host rock. Calcite has been also dolomite. Crystals have been found in cavities found in grains and veins of dolomite where it ap­ the massive dolomite. They are usually brownisl pears as fine-grained masses of minute scaleno­ colored by iron-bearing weathering. Mostly the hedral crystals. are small and do not exceed 1 mm in size. Dol mite is partly or wholly replaced by silica by lat hydrothermal processes.

Fig. 21 . Calcite Fig. 23. Onc lIf the crystal fonn:. of dolomite

Geologica Macedonica. 15-16. 1'-23 (2001-2002) Suppl. 18 B. Boev, V. Bemwnec, T. Serafimovski. S. Lepitkov.1, S. Mikuk'id, Nf. .sol/rek, G. Jo vlmavski. T Sralilol'. M Naidoski

Sulfates

BARITE, BaS04

Barite has been mentioned by Baric (1958) and Stieglitz (1990). Tn both papers it is pointed out that this mineral appears a platy, colorless clear to milky colored crystals to a maximum size ( of 6 mm. Although it ho not been discussed in their papers, it is interesting to mention that the Fig. :?.t. OIlC ol' thc cry~lal form' of harilc quantity of barium in this mineral is far a way from the value that is expected in Carlin-type ore depos­ its.

DORALLCHARITE, Tlo,gKo,2Fe3(S04)2(OH)6

Dorallcharite is fo und in the oxidation zone of the are body (Balie Zuni6 et aI., 1993b, 1994). It appears as yellow earthy mas es of submicroscopic crystals. This mineral is a member of the alunite­ jarosite family being isomorphous with jarosite KFe3(S04MOH)6. It· is often associated with an amorphous Fe-Mn suIfate..'brsenate free of TI. The mineral specimen is depo ired in the Geological Museum of Copenhagen. AJ1char is the type local­ ity for this mineral.

f n EPSOMITE, MgS04·7H20

Epsomite appears in the fonn of the white fi­ brous aggregates. Stalactite forms of this mineral are also present inside of the ore deposit (Ber­ manec, 1999)."

FIBROFERITE, FeS04(OH)'5H20

Rieck (1993) has for the first time reported the presence of this mineral in Allchar paragenesis. He described fibroferrite as hemispheres of yel­ low fibers. It is associated with homesite (Mg3(As0 4h'8H20), rozenite (FeS04'4H20) and gypsum (CaS04'2HzO) on altered host rock in the vicinity of re~lga.r vein .

GYPSUM, CaS04,'2H20 .:'

Gypsum is spread on all types of ore and host rock. Single crystals are rather small with typical flat habit on {OlO}. In large quantity it appears as an efflorescence on wall rock and even on ti mber­ ing. Stalactitic masses sometimes exceed 25 cm.

Geologica Macedonica, 15-16, 1-23 (2001-2002) Suppl. ologiea Mac~ A !Ichor minetti' i/sscmbMgc 19

ROZENlTE FeS04AH20 It is found as white crusts of prismatic crys­ tals or stalactitic aggregates throughout the deposit on altered host rock and ore in association with melanterite, home ite, gyp ti m and fibroferrite. Rozenite is in fact product of the decomposition of melanterite, pyrite and marcasite.

STARKEYITE, MgS04 AH20 Rieck (1993) has for the first time identified starkeyite as fibrous aggregates partly filling the Fig. 27. Gypsum space between the realgar crystals. The crystals are white with a silky sheen.

MELANTERlTE, FeSO~· 7H20 Arsenates

Melanterite is a typical post mining product, like rozenite. Highly al tered parts of the ho t rock are traversing with melanterite. Thj mineral was The firs report concerning this mineral be­ found in Allchar for the first time by Baric (t958) longs to Rieck (1 993). Its small crystals (up to 50 11m) are prismatic and elongated. They are usually who described green crusts and stulactitic aggre­ gates without observing the crystals . In 1993, Ze­ aggregated to cru. ts and stalactites. It is a sociated bec at al. (1993) published the result of measure­ with other efflorescent minemLs. It is sometimes ment of three melanterites crystals. They are green­ intimately intergrown with gypsum. Its identifica­ ish - blue transparent crystals from 2 to 3 mm in tion can be confirmed only by means of chemical size. In atmospheric conditions melanterite decom­ or X-ray analysis. poses in rozenite (FeS04'4H20) by loosing three molecules of water. PHARMACOLlTE, CaHA 04·2H20 Rieck (1993) has for the first time reported the presence of phannacolite in this deposit. He described it as radiating acicular coating on real­ gar, orpiment and host rock. Single crystals are rarely observed.

PICROPHARMACOLITE,

Ca4Mg(AsOl OHMAsO.j)f I t H20 Rieck (1993) has identified picropharmaco­ lite, which occurs as den~ coatings with a maxi­ mum thickness of 0.5 rum along fracture surfaces. The crystal sizes up to 50 /lm are bladed and give the specimen a silky white or colorless sheen.

UNNAMED NEW MINERAL·, Fe2TI« Aso.asSo.ls)04)3 AH10

This mineral is found near pyrite globules, which are altered and partly or completely replaced

• Foonally it is incorrecl to use the teon "new minernt" as long as Fig. 28. One of the crystal fomlS or melim(erite the species has not been accepted by the IMA Commission on New Mineral and Mineral Names.

Geologica Mncedonica. 15-16. 1-23 (2001-2002) Suppl. 20 B. BlM", V. Bt:rmanec, T. SerafimovskJ; S. Lepitkova, S. Mikultic, M Soufek, G. Jovano vskJ; T. Sfllfilov, M. Najdoski

by this new mineral, suggesting that it was formed U and Th and not as a result of transformations of through the alteration of pyrite by thallium - bear­ 205T1 to 20sPb caused b~ '1eutrino interaction with Tl. ing weathering solutions. The sizes of the grains encountered varied from 30 ~m to over 100 ,.. Im. In the course of reflected light investigations Frantz et a1. (1994) discovered a phase with a radial struc­ ture. M1croprobe analysis yielded the tentative stoichiometric composition that is given above.

B Molibdates

WULFENITE, PbMo04

Wulfenite is the first discovered (Soufek et aI., 1998) lead bearing mineral in the deposit. Sev­ eral. authors have investigated the Pb content in Allchar minerals. According to Stafilov and To­ Ce dorovski (1990) and Boev at a1. (1993b) it is often present within the range of 0.3 to 10 ppm in the Die main sulfides. Wulfenite crystals were observed on one sample built of microcrystalline quartz. Such quartz aggregates fiU cavities in stibnite - realgar ore body. Orange-yellow crystals of wulfenite up to 8 mm in size together with well developed crys­ tals of realgar have crystallized over such micro­ Eng crystals of quartz. Wulfenite is obviously the very late mineral in this part of are body. The lead pre­ sent in the wulfenite is due to a previ ous decay of Fig. 29. Some of (he crystal fonns of wulfenite ~~ M t~ tri CONCLUSION Foullo Me 31 : minerals species in this paper does not mean thai The studies carried out on tbis mineral as­ Foullol semblage indicate that the Allchar deposit is a real these studies have discovered all mineral assem· Vr/ challenge for investigation in the field of mineral­ blages present in the deposit. It is certain that fur· Foullor ogy. The total number of to nowadays discribed 44 ther studies will discover new minerals.

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Geologica Macedonica, IS-I6, 1-23 (2001-2002IS ologica Macedonica, l~ ------. ~------::--:--====~r===~

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Stieglitz, H., 1990: Abcnteuer AUchar. Lapis, 15 (2), 11-19. Wilson, 1. R. , Gupta, P. K. S., Robinson, P. D., Criddle, A. 1., SOllfek. M., Billstro, K... Tiblj~, D., Bennanec V., 1998: Dis­ 1993: Fangile, TI}AsS4, a new tballium arsenic slIlfosalt tri bution of lead isotopes in wul fenite from Allchar, Ma­ rrom the Mercur Au deposit, Utah, and revised optical cedonia. N. Jb. Miner. Mh. 1998, 10,462--468. data for gillulyile. Amer. Miner., 78, 1096. Trnjkovska, M., Soptraj anov, B., Stafilov, T. Jova novski, G., Vrba, K., 18 4: 0 ni!klcrych lIliner:ilech z Allcharu v Mace­ 1993: Detennination of lorandite and realgar in mineral donii, Vcstnik Kr. ccsk6 spol. nuuk . Ir. math. pfir. pojedn., 48. using infrared spectroscopy. Geologica Maccdonica, 7, Zebec, V., Bennanec. V. TibljaS, D., 1993: Melanterilc lind roze­ 55-59. nite from Allchar mine, Macedonia. Nal. Croal., 2, 83. 8.

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Macedonica. 15-16, 1-23 (2001-2002) Supp!.