Preliminary data on the mineralogy of limestone and skarn-hosted caves from Băita (Bihor County, Romania)

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Preliminary data on the mineralogy of limestone and skarn-hosted caves from Băita (Bihor County, Romania)

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Preliminary data on the mineralogy of limestone and skarn-hosted caves from Băita (Bihor County, Romania)
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Onac, Bogdan P.
Damm, Paul
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Anthropology ( local )
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"This paper presents the mineralization of five medium-size limestone-caves and eleven skarn-hosted caves from the upper part of Crişul Băitei River (Bihor Mountains). Apart from berlinite -- AlPO4, the other minerals reported from the limestone caves are common carbonates, phosphates or oxy-hydroxides. In turn, the skarn-hosted caves contain a diversity of minerals, including wittichenite, luzonite, natrolite, norsethite, rosasite, glaukosphaerite, aurichalcite, azurite, malachite and chalcanthite. Five of these minerals have never before been identified in a cave environment and moreover, three are new occurrences in Romania. Some of these minerals are hydrothermal in origin, whereas alteration and/or hydration of primary hydrothermal minerals formed the others. Considering the mineral assemblage, the morphology and the position of cavities within the skarn bodies, we assume these minerals formed during one of the following stages: hydrothermal, hydrothermal/vadose or vadose." -- Authora
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"This paper presents the mineralization of five
medium-size limestone-caves and eleven skarn-hosted caves
from the upper part of Criul Bitei River (Bihor Mountains).
Apart from berlinite --
AlPO4, the other minerals reported from the limestone
caves are common carbonates, phosphates or oxy-hydroxides. In
turn, the skarn-hosted caves contain a diversity of minerals,
including wittichenite, luzonite, natrolite, norsethite,
rosasite, glaukosphaerite, aurichalcite, azurite, malachite
and chalcanthite. Five of these minerals have never before
been identified in a cave environment and moreover, three are
new occurrences in Romania. Some of these minerals are
hydrothermal in origin, whereas alteration and/or hydration
of primary hydrothermal minerals formed the others.
Considering the mineral assemblage, the morphology and the
position of cavities within the skarn bodies, we assume these
minerals formed during one of the following stages:
hydrothermal, hydrothermal/vadose or vadose." --
Authora



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STUDIA UNIVERSITATIS BABE -BOLYAI, GEOLOGIA, XLVII, 1, 2002, 93-104 PRELIMINARY DATA ON THE MINERALOGY OF LIMESTONE AND SKARN-HOSTED CAVES FROM BIA (BIHOR COUNTY, ROMANIA) BOGDAN P. ONAC1 & PAUL DAMM2 ABSTRACT. This paper presents the mineralization of five medium-size limestone-caves and eleven skarn-hosted caves from the upper part of Criul Biei River (Bihor Mountains). Apart from berlinite AlPO4, the other minerals reported from the limestone caves are common carbonates, phosphates or oxyhydroxides. In turn, the skarn-hosted caves contain a diversity of minerals, including wittichenite, luzonite, natrolite, norsethite, rosasite, glaukosphaerite, aurichalcite, azurite, malachite and chalcanthite. Five of these minerals have never before been identified in a cave environment and moreover, three are new occurrences in Romania. Some of these minerals are hydrothermal in origin, whereas alteration and/or hydration of primary hydrothermal minerals formed the others. Considering the mineral assemblage, the morphology and the position of cavities within the skarn bodies, we assume these minerals formed during one of the following stages: hydrothermal, hydrothermal/vadose or vadose. Keywords: karst, skarn, hydrothermal, mineralogy, speleogenesis, Bia Bihor, Romania. INTRODUCTION The mineralogy of limestone caves is straightforward, as the main mineral species found are calcite, aragonite and gypsum. In addition, the presence of bat guano deposits is responsible for the pr ecipitation of various phosphate minerals. However, caves lo cated adjacent to metamorphic or volcanic terrains or those hosted wi thin skarn bodies, volcanic tuffs, s andstones or evaporite rocks may show a complex and dive rse mineralogy. It is this situation of the skarn-hosted cavities we are pr esenting in this paper. The objectives of the present study are to pr esent the preliminary result s on the mineralogy of caves from Bia-Bihor region and to assess what processes led to the deposition of the identified minerals. To accomplish our goal we collect ed twenty-six samples representing crusts, corraloids, crystals and various type of aggregates from seven limest oneand eight skarn-hosted caves, all locat ed in the upper part of Criul Biei River. Their mineralization was studied usi ng a combination of optical microscopy 1 Department of Mineralogy, Babe-Bolyai University, Koglniceanu 1 & Emil Racovi Institute of Speleology, Clinicilor 5, 3400 Cluj, Romania (bonac@bioge.ubbcluj.ro). 2 Transilvania General Company Teatrului 1-2, 3700 Oradea & Speleological Club Z 14/4, 3576 Atileu, Bihor, Romania.

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BOGDAN P. ONAC, PAUL DAMM (Nikon Optiphot 2-POL), scanning electron microscopy (Stereoscan 250 MK3-Cambridge equipped with energy-dispersive spectrometer), and stable isotope analysis (Finnigan MAT 251 mass spectrometer). Step-scan CuK (1 = 1.5405) X-ray powder diffraction data (XRD) were collected with a standard Philips PW1800 diffractometer fitted with a curved graphite diffracted-beam monochromator. The step-scan data were collected over the range 5-70 2 using a step interval of 0.02 2. Minerals were characterized solely based on XRD data when the spectrum was complete and well resolved. When multiple minerals phases occurred in the sample, additional investigations were conducted. GEOGRAPHIC & GEOLOGIC SETTING The investigated area lies in the south-western part of the Bihor Mountains, in the well-known metallogenetic district of Bia-Bihor (Fig. 1, inset). The landscape in the region has high relief and is heavily forested. Fig. 1. Synthetic lithostratigraphic columns showing the formations that host caves and the location of Bia-Bihor karst region. 1: quartzites & hornfelses (Triassic); 2: Frsinel marble; 3: Bia marble; 4: Couri Beds; 5 & 7: Upper Jurassic limestones; 6: Permo-Triassic formations; 8: Lower Cretaceous limestones. 94

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PRELIMINARY DATA ON THE MINERALOGY OF LIMESTONE AND SKARN-HOSTED CAVES The bedrock geology consists of a complex tectonic setting bringing into contact several nappe systems belonging to the Bihor and Apusenides structural units (Balintoni, 2001). In the Bia-Bihor area, the lowermost unit of the Codru Nappe system is the Vetre Nappe, which shows a complete Triassic sequence. The formations of interest for our investigations consist of quartzites and hornfelses of Ladinian to Lower Carnian age, Frsinel dolomite marble (Carnian), and Bia marble (Norian) (Bleahu et al., 1994). Within this area, outcrops of slightly or unmetamorphosed limestones of Upper Jurassic and Lower Cretaceous age occur. In several sectors of the upper Criul Biei basin, the Triassic metamorphosed carbonate rocks (Vetre Nappe) are in tectonic contact with quartzites and hornfelses of Couri Beds (Vlani Nappe) (Matyasi et al., 2001). The geological column is shown in Fig. 1. The rich calcic and/or magnesian skarn bodies from this region host economic deposits of Mo, W, Bi, Cu, Pb etc. that have been mined since the Middle Ages. Their genesis is related to a deep-seated Laramian pluton of granitic to dioritic composition (Stoici, 1983). Several scientific reports and papers have been published on the geology of this important mining district of Romania (Stoicovici & Stoici, 1972; Cioflica et al., 1974, 1995, Cioflica & Vlad, 1979; Stoici, 1983 and Matyasi et al. 2001, among others). Stoici (1983) mentions a number of caves accidentally discovered during mining of the skarn ore deposit and comments on the genesis of these cavities and their mineralogy. The only karst papers that describe this region are those by Posepny (1874), Vlena et al. (1977), Oreanu (1997) and Damm (1998, 2000). None, however, contains information on cave mineralogy or speleogenesis of the skarn-hosted caves. SPELEOLOGICAL SETTING The most important category of caves we studied within the Bia-Bihor region are those formed within the skarn bodies. Thirteen cavities (for 4 of them we have data obtained from published or unpublished old geological reports) were investigated with respect to their mineralogy. With few exceptions the caves are poorly decorated and short (none of them exceeding 100 m), but often show notable positive or negative relief. A striking feature is the way their galleries closely follow the metasomatic contact between Couri Beds and the mineralized skarn bodies. The other category of caves includes those formed by classical solution processes. These eight caves are formed either in the Upper Jurassic or Lower Cretaceous, unmetamorphosed and metamorphosed limestone or at the boundary between these formations and the Couri Beds. The length of these caves may exceed 1,000 m and are well decorated. All known caves from this karst region are listed in Table 1. 95

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BOGDAN P. ONAC, PAUL DAMM RESULTS OF MINERALOGICAL ANALYSES Our analyses led to the identification of two sulfides (luzonite and wittichenite), two silicates (natrolite and quartz), two hydroxides (romanechite and goethite), six hydrous carbonates (aurichalcite, azurite, glaukosphaerite, hydromagnesite, malachite, and rosasite), three carbonates (calcite, aragonite, and norsethite), two phosphates (berlinite and hydroxylapatite), and one sulfate (chalcanthite). Out of these eighteen minerals, six are for the first time identified in caves worldwide and prior to our study three have never been reported in anz mineral occurrence from Romania. Table 1. List of limestoneand skarn-hosted caves of Bia-Bihor mining district (the caves we sampled are shown in italics). Cave name hosting mining galleries Length & relief (m) Host host rock The cave from Aloisie Mine 56/+16 Water Cave from Codreanu Mine 65/26 (-11, +15) Crystals Cave from Codreanu Mine 44/20 (-13, +7) The cave from Elena Mine 110/+8 Water Cave from Karoli Mine 32/-14 The cave from Iohann Mine 47/+3 The cave from Gustav Mine 60/-16 The cave from Franz Mine unexplored Small Cave from Bolfu III Mine 93/+3 Big Cave from Bolfu III Mine 402/58 (-25, +33) Surprise Cave from Tony Mine ca. 550 The cave from Schachtadel shaft unexplored Izbuc Cave from Couri Valley 80/+5 skarn Izvorul Criului Negru 1,155/+45 Pereii Corlatului 247/29 (-18, +11) Tunnel Cave from Corlatu Valley 38/3 (-1.5, +1.5) Condorului 110/+8 Schmidl 141/+7 Mare 75/-8 The cave from Quarry 500/-60 Porile Bihorului 220/-65 limestone, dolomite & marble Sulfides The antimonian variety of luzonite Cu3(As0.64Sb0.36)S4 was identified by means of XRD when analyzing thin grayish-black crusts (< 4 mm in thickness) collected from the walls of Crystals Cave (Codreanu Mine). In some parts newly formed calcite crusts or clusterites coat these dark crusts. The diffraction spectrum of luzonite is shown in Fig. 2. 96

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PRELIMINARY DATA ON THE MINERALOGY OF LIMESTONE AND SKARN-HOSTED CAVES Wittichenite Cu3BiS3 form lead-grey granular aggregates in Big Cave from Bolfu III Mine. The strongest 14 XRD lines of this mineral are identical or closely match those reported by Nuffield (1947). The chemical composition obtained by AAS analysis (wt%) gave Cu 37.54, Bi 41.72, S 19.22 and Pb 1.14. Without any doubt the two minerals are of hydrothermal origin. They may have been deposited either within the carbonate host rock and displayed later when solution processes cut across the skarn or in pre-existing hydrothermal or meteoric karst channels. This problem is still open, but is clear that both luzonite and wittichenite under oxidizing conditions may have altered to various hydrous carbonates. 0 500 1000 1500 2000 2500 3000 10 20 30 40 50 60 70counts /a.u.2 theta /deg. raw data Fig. 2. The diffraction patterns of luzonite. Silicates Natrolite Na2[Al2Si3O10]2H2O was found in the Big Cave from Bolfu III Mine as millimeter size patches of granular crusts or fibrous aggregates associated with calcite. It appears as glassy and opaque-white. The identification relies solely on XRD analysis. Fine quartz SiO2 crystals build up concentric layers intermixed with calcite crystals, being an indication of past hydrothermal conditions. This mineral has been identified in the clusterites that grow on the walls of Water Cave from Codreanu Mine. The clusterites never exceed 1 cm in length and appear either as colorless or shades of yellow-brown colors. Carbonates Calcite is by far the most common and abundant mineral forming a large variety of speleothems. These include coatings, crusts, stalactites, stalagmites, columns, flowstones, moonmilk, helictites and spars. However, only Surprise 97

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BOGDAN P. ONAC, PAUL DAMM Cave and the two cavities from Bolfu III Mine are well decorated with calcite speleothems. The cavities from Codreanu Mine were almost completely devoid of speleothems due to the ore mining. Depending on the quantity of inorganic or organic trace impurities, the color of calcite speleothems in these caves varies from pure white to dark brown, including yellow and orange shades. Investigations carried out on some of the calcite speleothems (e.g., clusterites) suggest some are of hydrothermal origin. Isotopic analyses showed depleted 18O values (i.e., between and .7 PDB) for the suspected hydrothermal calcite whereas the 18O values are less negatives (i.e., -4 to 8.3 PDB) in the low-temperature cave environment calcite speleothems. Botryoidal corraloids made up of aragonite were found in the two caves from Bolfu III Mine. Aragonite was identified by means of XRD analyses and microscope observations. Hydromagnesite Mg5(CO3)4(OH)2H2O is the prime constituent of moonmilk and nodules found on the floor and walls of two cavities from Bolfu III Mine and Izvorul Criului Negru Cave. The color of hydromagnesite speleothems is cream to chalk white. The diffraction patterns obtained on our samples are complete and well resolved, fitting exactly the reference patterns of hydromagnesite (corresponding to the trigonal system, space group R32). Except for the three minerals presented above all the other carbonates were found only in the skarn-hosted caves. Malachite Cu22+(CO3)(OH)2, azurite Cu32+(CO3)2(OH)2 and aurichalcite (Zn,Cu2+)5(CO3)2(OH)6 are widespread secondary minerals in the oxidation zones of copper-bearing ore deposits. These three mineral species (identified by means of XRD analyses) were found in cavities from Elena and Karoli mines. In all of these locations, bright green to olive-green malachite and intense blue lustrous azurite generally stains and coats the bedrock, the calcite crusts, and the pebbles along the stream. A fragile pale-green or light-blue crust of aurichalcite lines the sectors of the walls. In some parts of the cavities these minerals fill or line small fissures or corrosion pockets in the cave walls (Pl. I, Figs. 1, 2). Both malachite and azurite were also identified by their optical properties. In the Water Cave from Codreanu Mine, malachite is closely associated with rosasite (Cu2+,Zn)2(CO3)(OH)2 and glaukosphaerite (Cu,Ni)2(CO3)(OH)2. Rosasite appears as bluish-green needles, 0.05 to 2 mm in length, forming efflorescences on bedrock and calcite crusts. Glaukosphaerite, a mineral of the rosasite group (Mandarino, 1999), typically occurs in this cave as thin coatings of deep green color. Although many authors cite glaukosphaerite appearing alongside rosasite, it has never been previously reported in an association from a cave environment. The identification of the two minerals is based on X-ray diffraction and chemical analyses (Table 2). As seen in Table 3, the diffraction data of rosasite and glaukosphaerite differ significantly, hence, easily distinguishing them when appearing in the same sample. The unit cells of rosasite and glaukosphaerite closely correspond to those reported on their ICDD files. The small differences between the cell parameters obtained in this study and the reference are interpreted as a slight difference in their chemical composition. 98

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PRELIMINARY DATA ON THE MINERALOGY OF LIMESTONE AND SKARN-HOSTED CAVES Table 2 Average wet-chemical analyses (wt%) for three samples of rosasite and glaukosphaerite. Rosasite Glaukosphaerite CuO ZnO CO2 H2O+ Total 42.21 30.87 19.82 7.27 100.17 CuO NiO CO2 H2O+ Total 41.87 30.77 18.64 8.51 99.79 Table 3 Comparison of X-ray powder diffraction data for rosasite and glaukosphaerite from Bia-Bihor. Rosasite Glaukosphaerite d () I d () I 7.4618 6.071 5.118 3.7425 3.059 2.892 2.545 2.478 2.199 2.146 1.963 1.911 1.799 1.685 1.4823 17 43 94 100 14 73 60 29 10 18 15 10 6 13 14 7.3998 5.976 4.713 3.702 3.033 2.978 2.84 2.781 2.596 2.521 2.461 2.318 2.189 2.129 1.999 1.935 1.676 1.647 1.587 1.497 1.474 1.3006 1.267 20 40 11 70 17 80 29 25 100 54 38 13 9 20 7 17 11 6 13 10 8 5 5 a = 9.33210.043 b = 11.99050.081 c = 3.13750.088 = 88.312.93 a = 9.43950.023 b = 11.94210.019 c = 3.05240.014 = 90.520.5 The last of the carbonates identified is norsethite BaMg(CO3)2 a rare rhombohedral double carbonate. It appears as well crystallized white nodular aggregates on the walls of Crystals and Surprise caves. The X-ray reflections seem to be closer to those of dolomite. However, the essential 99

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BOGDAN P. ONAC, PAUL DAMM difference between the two species is that the reflections of norsethite, located between 46 and 49 2, are shifted about 2.5 2 from the dolomite spectrum where they appear from 48.5 to 51.5 2. Moreover, norsethite posses three distinct lines at 21.02, 33.52, and 41.84 2 respectively, which are missing on the calcite spectrum. Least-squares refinement using the diffraction data yields the following R32 rhombohedral cell parameters for Bia-Bihor norsethite: a = 5.04940.0487; c = 16.99280.2251. Further investigations are to be conducted to understand the way this mineral was precipitated in the cave environment. Phosphates Hydroxylapatite Ca5(PO4)3(OH) appears in Pereii Corlatului and Izvorul Criului Negru caves as millimeter-thick, fragile brown to black crusts. It precipitates only in areas were bat colonies are to be found. Hydroxylapatite was identified by means of XRD. The other phosphate mineral, berlinite AlPO4 was found in a remote passage in Pereii Corlatului Cave forming small crusts made up of tiny gray crystals. The location where the sample was collected is situated in the vicinity of the geological contact between limestone and the metamorphosed rocks of Couri Beds. Knowing that berlinite typically forms at temperatures above 186C (Bass & Sclar, 1979) we believe it has a hydrothermal origin. The X-ray diffraction data for the sample are as follow d()/I: 4.269/22; 3.981/2; 3.648/2; 3.367/100; 2.472/9; 2.305/10; 2.253/5; 2.131/6; 1.987/7; 1.681/4; 1.552/7; 1.461/2; 1.388/5, 1.301/2; 1.235/2; 1.195/2. Presently, we cannot discriminate whether it is a true cave mineral or not. Berlinite was recently reported for the first time in a cave environment from Cioclovina Cave (Onac et al., 2002). Sulfates Blue, millimeter size crystals of chalcanthite have been found in the close vicinity of the secondary copper carbonates in the Water Cave from Codreanu Mine. The XRD patterns of our sample are sharp and overlap almost all reflections recorded in the ICDD card no. 11-646 of chalcanthite (Fig. 3). In this occurrence, the copper comes from chalcopyrite, whereas sulfate is supplied by strongly acidic water (from pyrite oxidation). Hydroxides Either goethite -Fe3+O(OH) or romanechite (Ba,H2O)(Mn4+,Mn3+)5O10 have been found in most of the investigated caves (except for Condorului and Schmidl) as orange, red-brown and black coatings on alluvial clasts and cave walls close to the water level. The XRD spectra were poorly resolved; therefore, our identification was based on IR and chemical analysis. The presence of goethite in these caves is attributed to oxidation of Fe-rich minerals, while romanechite may have been directly precipitated in oxidizing environments from underground streams or seeping waters. 100

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PRELIMINARY DATA ON THE MINERALOGY OF LIMESTONE AND SKARN-HOSTED CAVES 0 2500 5000 7500 10000 12500 0 10 20 30 40 50 60 70counts /a.u.2 theta /deg. raw data Fig. 3. The diffraction patterns of chalcanthite. CONCLUSIONS The minerals presented in this paper were assigned to the following three genetic categories: (1) minerals deposited from hydrothermal solutions (wittichenite, luzonite, berlinite, quartz, and partly calcite); (2) minerals that are hydration or alteration products of primarily hydrothermal deposited minerals (natrolite, goethite, malachite, aurichalcite, rosasite, glaukosphaerite, chalcanthite etc.); (3) minerals precipitated from low-temperature vadose solutions (calcite, aragonite, hydromagnesite, hydroxylapatite, goethite etc.). The question we have to answer is which of the above-mentioned minerals are true secondary minerals formed in caves? (see Hill & Forti, 1997 for details). If all those included in the third category fulfill the condition requested for a cave mineral, some of the others listed in the first group are questionable. Quartz and calcite speleothems of hydrothermal origin are well documented from many caves around the world. Moreover, various sulfides were often found associated with quartz crystals in cavities hosted by skarn bodies (Dublyansky, 1997). Even so, we are still searching for more evidence before including luzonite and wittichenite into the cave minerals group. As already mentioned, except for the particular occurrence from Cioclovina Cave, berlinite was only documented from hydrothermal mineral assemblages. The minerals grouped in the second genetic category are in our opinion likely to be all true cave minerals. 101

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BOGDAN P. ONAC, PAUL DAMM Although still preliminary, this paper reports and partly characterizes 18 minerals assigned to 6 chemical classes. Three of them, rosasite, glaukosphaerite, and norsethite are not included in Udubaas (1999) checklist of valid mineral species known in Romania. Furthermore, five of the mineral species (true or not cave minerals), luzonite, wittichenite, natrolite, glaukosphaerite and norsethite are new for the cave environment worldwide. Acknowledgements. Permission for sampling the caves was granted by Emil Racovi Institute of Speleology. Minvest Deva Company gave permission to enter the old mining galleries. We thank the members of the Speleo Club Z and the following persons for assistance in the field: M. Petrescu, M. Zotescu, N. Feier, T. Brad, and S. Matyasi for useful discussions on the local geology. J. Kearns is thanked for proof reading. We acknowledge the support of the European Community Access to Research Infrastructure action of the Improving Human Potential Programme, contract HPRI-CT-1999-00008 awarded to Prof. B. J. Wood (EU Geochemical Facility, University of Bristol) that enabled us to perform part of the XRD and electron-microprobe analysis. REFERENCES BALINTONI, I.C. 2001, Short outlook on the structure of the Apuseni Mountains. In 4th Regional Meeting of IFAA, Field trip guide (I.I. Bucur, S. Filipescu & E. Ssran, eds.), Cluj, Romania, pp. 9-17. BASS, J. D. & SCLAR, C. B. 1979, The stability of trolleite and the Al2O3-AlPO4-H2O phase diagram. American Mineralogist 64, pp. 1175-1183. BLEAHU, M., MANTEA, G., BORDEA, S., PANIN, S., STEFNESCU, M., SIRIC, K., HAAS, J., KOVACS, S., PERO, C., MAKK-BERCZI, A., KONRAD, G., NAGY, E., FELGENHAUER-RALISCH, E. & TOROK, A. 1994, Triassic facies types, evolution and paleogeographic relations of the Tiszia Megaunit. Acta Geologica Hungarica 37, pp. 187-234. CIOFLICA, G. & VLAD, S. 1979, Bi-sulfosalts related to Laramian skarns of the Bihor Mountains (Northern Apuseni Mountains). Revue Roumain Gologie, Gophysique et Gographie, Gologie 23, pp. 15-21. CIOFLICA, G., VLAD, S., IOSOF, D. & PANICAN, A. 1974, Thermal and metasomatic metamorphism of the Paleozoic rocks belonging to the Arieseni Unit (Baita Bihorului). Studii i Cercetri de Geofizic, Geografie, Geologie 19, pp. 43-68. CIOFLICA, G., JUDE, R., LUPULESCU, M. & SIMON, G. 1995, New data on the Bi-minerals from the mineralizations related to Paleocene magmatites in Romania. Romanian Journal of Mineralogy 76, pp. 9-23. DAMM, P. E. 1998, La relation karst parakarst dans la gnse de la grotte de Pereii Corlatului (Monts du Bihor, Roumanie). Travaux de lInstitute de Spologie Emil Racovitza XXXVII. DAMM, P.E. 2000, Petera de la Izvorul Criului Negru. Speomond 5, pp. 27-28. 102

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PRELIMINARY DATA ON THE MINERALOGY OF LIMESTONE AND SKARN-HOSTED CAVES DUBLIANSKY, Y.V. 1997, Hydrothermal cave minerals. In Cave Minerals of the world (C.A. Hill & P. Forti, eds., 2nd ed.), NSS, Huntsville, Alabama, pp. 252-255. HILL, C.A. & FORTI, P. 1997, Cave Minerals of the world. 2nd ed., NSS., Huntsville, Alabama. MANDARINO, J.A. 1999, Fleischers Glossary of Mineral Species 1999. The Mineralogical Record, Inc., Tucson, Arizona. MATYASI, S., MATYASI, L. & VLAS, G. 2001, Studiul mineralogic i structural al mineralizaiilor polimetalice la nivelul orizontului XVIII Zona Antoniu i orizontul XVI zonele Baia Roie i Terezia din cadrul Zcmntului Bia Bihor n vederea stabilirii potenialului economic. Arhiva S. M. Baia & GeoProspect Ltd., tei. NUFFIELD, E.W. 1947, Studies of mineral sulpho-salts: XI-Wittichenite (Klaprothite). Economic Geology 42, pp. 147-160. ONAC, B.P., BREBAN, R., KEARNS, J. & TMA, T. 2002, Unusual minerals related to phosphate deposits in Cioclovina Cave, ureanu Mts. (Romania) Theoretical and Applied Karstology 15, pp. 27-34. OREANU I. 1997, Contributions to the hydrogeology of karst areas of the Bihor-Vldeasa Mountains (Romania). Theoretical and Applied Karstology, 9, pp. 185-214. POSEPNY F. 1874, Geologisch-montanishe Studie der Erzlagerstattenlehre von Rzbnya, Budapest. STOICI, S. 1983, The Baita Bihor metallogenic district. Academiei RSR, Bucureti (In Romanian with extended Engl. abstr.). STOICOVICI, E. & STOICI, S. 1972, Contributions to the investigation of the boron ores from superior area of the Black Cris (Baita, Bihor). Studia Univ. Babes-Bolyai, Geologia-Mineralogia, fasc. 1, pp. 3-10. UDUBAA, G. 1999, Advances in mineralogy of Romania. Romanian Journal of Mineralogy 79, pp. 3-30. VLENA, L., BLEAHU, M., BRIJAN, P. & HALASI, G. 1977, Inventarul speologic al Munilor Bihor, Nymphaea, 5, pp. 209-335. Plate I. Fig. 1. Fissures lined by fibrous crystals of malachite (Water Cave from Codreanu Mine, crossed nicols, x10). Fig. 2. Azurite crystal (Water Cave from Codreanu Mine, plane-polarized light, x40). 103

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BOGDAN P. ONAC, PAUL DAMM Plate I. Fig. 1 Fig. 2 104


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