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ACTA MINERALOGICA-PETROGRAPHICA ABSTRACT SERIES HU ISSN 1589-4835 HU ISSN 0324-6523
Editor-In-Chief Tibor Szederkényi University of Szeged, Szeged, Hungary E-mail: [email protected]
Associate Editor Elemér Pál-Molnár University of Szeged, Szeged, Hungary E-mail: [email protected]
EDITORIAL BOARD
Magdolna Hetényi Gábor Papp University of Szeged, Szeged, Hungary Hungarian Natural History Museum, Budapest, Hungary
Péter Árkai Dr. Csaba Szabó Laboratory for Geochemical Research, Hungarian Eötvös Loránd University, Budapest, Hungary Academy of Sciences, Budapest, Hungary
György Buda Gyula Szöőr Eötvös Loránd University, Budapest, Hungary University of Debrecen, Debrecen, Hungary
Imre Kubovics István Viczián Eötvös Loránd University, Budapest, Hungary Hungarian Institute of Geology, Budapest, Hungary
Tibor Zelenka Hungarian Geological Survey, Budapest, Hungary
Abbreviated title: Acta Mineral. Petrogr. Abstr. Ser., Szeged
The Acta Mineralogica-Petrographica is published by the Department of Mineralogy, Geochemistry and Petrology, University of Szeged
On the cover: Lamellar limestone, Létrás-tető, Bükk Mountains, Hungary. Photo: Attila Kovács.
Designed by: Elemér Pál Molnár & György Sipos A forum for giving an insight in the state of the art of Mineral Sciences in the Carpathian–Pannonian Region…
MCC2 2nd MINERAL SCIENCES IN THE CARPATHIANS INTERNATIONAL CONFERENCE Miskolc, Hungary, 6–7 March 2003
ABSTRACTS
Edited by
Béla Fehér and Sándor Szakáll
English text was revised for major grammatical problems by
Erzsébet Tóth, Tamás Váczi and Tamás G. Weiszburg
Sponsored by
Koch Sándor Foundation (Miskolc) Mineralholding Ltd. (Budapest) Foundation for Hungarian Minerals (Miskolc) Socrates/Erasmus Curriculum Development Programme (CDA) on a Co-ordinated European Curriculum in Mineral Sciences
Szeged, Hungary
2003 Organizers
Herman Ottó Museum, Miskolc University of Miskolc
Co-organizers
Austrian Mineralogical Society Hungarian Geological Society Mineralogical Society of Poland Mineralogical Society of Romania Slovak Geological Society Ukrainian Mineralogical Society CBGA Commission on Mineralogy and Geochemistry
INTERNATIONAL SCIENTIFIC BOARD
Martin Chovan Comenius University, Bratislava, Slovakia
Aleksandra Gawęda University of Silesia, Sosnowiec, Poland
Friedrich Koller University of Vienna, Vienna, Austria
Victor M. Kvasnytsya Institute of Geochemistry, Mineralogy and Ore Formation, National Academy of Sciences, Kyiv, Ukraine
Milan Novák Masaryk University, Brno, Czech Republic
Gábor Papp Hungarian Natural History Museum, Budapest, Hungary
Gheorghe Udubaşa Geological Institute of Romania, Bucharest, Romania
LOCAL ORGANIZING COMMITTEE
Sándor Szakáll (Chairman) University of Miskolc, Miskolc, Hungary
Béla Fehér Herman Ottó Museum, Miskolc, Hungary
Ferenc Mádai University of Miskolc, Miskolc, Hungary
Timea Tóth-Szabó Herman Ottó Museum, Miskolc, Hungary
Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
INCORPORATION OF “INVISIBLE GOLD” TO THE SULPHIDE MINERALS FROM TATRIC UNIT (WESTERN CARPATHIANS, SLOVAK REPUBLIC)
ANDRÁŠ, P.1, CHOVAN, M.2 & OZDÍN, D.2 1 Geological Institute, Slovak Academy of Sciences, Severná 5, SK-974 01 Banská Bystrica, Slovak Republic. E-mail: [email protected] 2 Deparment of Mineralogy and Petrology, Comenius University, Mlynská dolina G, SK-842 15 Bratislava, Slovak Republic.
The main gold carriers among the sulphide minerals of As, S, Sb with Au usually follow the temporary increase of the Tatric Unit are arsenopyrite and pyrite. They are usually the As-content during the dynamic varying crystallization enriched in Sb and their characteristic feature is the strong conditions, the suitable temperature and pH conditions. The inhomogeneity caused preferentially by negative As-Au vs. quiet stable crystallization conditions seems to be not very S-(Sb, Fe) correlation. The Au contents in arsenopyrite reach suitable for Au-incorporation. up to 6700 ppm (point analyses from the Trojárová deposit) After some common assumptions the submicroscopic and in pyrite vary from 0 to 62 ppm (from the Pezinok de- gold is situated in lattice deformations. WAGNER et al. posit). Mössbauer spectroscopy proved that the dominant (1988) and CATHELINEAU et al. (1989) published opinion part of the Au content in gold-bearing sulphide minerals is that Au is incorporated to the sulpides in “non-metallic” (with the exception of the Jasenie deposit) represented by anion form. BOYLE (1979) and COOK & CHRYSSOULIS invisible gold. (1990) suggested that Au substitutes for As in arsenopyrite. The incorporation of Au into the crystals show many ir- This hypothesis is based on comparison of ionic radii of regularities. We cannot define any definite scheme but we covalently bonded As and Au. JOHAN et al. (1989) used can present several relatively expressive trends: electron-probe data from gold-rich arsenopyrite and stoichi- It is possible to distinguish three types of gold-bearing ometric calculations to propose that Au is substituting for the sulphide crystals: with more or less homogeneous distribu- excess As, which actually is present in Fe sites. SCHOONEN tion of Au, with Au-enriched crystal cores and Au enriched et al. (1992) and FLEET et al. (1993) show the great impor- crystal rims. The Au-enrichment shows an important positive tance of adsorption-redox reactions on surface of the sul- correlation with As contents. This correlation is usually ab- phides growth zones in the gold-bearing sulphide ores form- sent in homogeneous sulphide crystals. Au-As enrichment of ing process. The Au transport is possible in form of miscel- crystal rims was described from the Malé Karpaty Mts. re- laneous fluids (by diffusion too) and Au is not incorporated gion (Pezinok, Trojárová deposits) and from some occur- to sulphide structure but to pores, vacancies and on surface rences of Nízke Tatry Mts. (Mlynná dolina Valley). Opposite of mineral growth-zones. According to this assumption py- trend was observed at the Dúbrava, Vyšná Boca and Nižná rite and arsenopyrite contain in aqueous fluids at the growth
Boca deposits (Nízke Tatry Mts.). plain surfaces oxidizable S-H and Sx-H surface groups (≡ 0 Incorporation of Au into the sulphide minerals depends SSH), so they can reduce AuOH(H2O) ligands and create on various factors: stoichiometry, stability of the aqueous Au-S complexes on surface of arsenopyrite and pyrite complexes, presence of a suitable bonding-relations. Impor- crystals (SCHOONEN et al. 1992). tant supposition of gold incorporation to the sulphides is the The last mentioned mechanism is the most probable one high arsenic concentration. The presented process is usually for the investigated Western Carpathian deposits. Such as- accompanied by Sb, S and Fe content decrease in connection sumption could explain nearly any As:Au correlation in with the acidification of the ore-forming fluids. Critical value ICP/MS-laser ablation and microprobe point analyses and on of this decrease is different at various deposits but is usually the other hand an important As:Au correlation in AAS bulk- approximately constant within one single deposit. analyses of distinct growth zones of gold-bearing sulphide Au enters into the crystals during favourable conditions minerals (there were realised parallel analyses of separately from CO2 containing aqueous solution of low salinities (from dissolved crystal rims and crystal cores). 1 to 11 weight equiv. % NaCl). Homogenization tempera- tures vary from 230 to 325 °C and the crystallization tem- peratures are about 330-450 °C. The coprecipitation of Fe,
3 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
WESTERN CARPATHIAN AND SELECTED EUROPEAN Sb-MINERALIZATIONS; Pb -ISOTOPE STUDY
ANDRÁŠ, P.1, CHOVAN, M.2, SCHROLL, E.3, NEIVA, A. M. R.4, KRÁL, J.5 & ZACHARIÁŠ, J.6 1 Geological Institute, Slovak Academy of Sciences, Severná 5, SK-974 01 Banská Bystrica, Slovak Republic. E-mail: [email protected] 2 Deparment of Mineralogy and Petrology, Comenius University, Mlynská dolina G, SK-842 15 Bratislava, Slovak Republic. 3, Institute of Mineralogy and Crystallography, University of Vienna, Althanstrasse 14, A-1090 Vienna, Austria. 4 Departamento de Ciencias da Terra, Universidade de Coimbra, P-3000 Coimbra, Portugal. 5 Slovak Geological Office - Geological Survey of Slovak Republic, Mlynská dolina 1, SK-817 04 Bratislava, Slovak Rep. 6 Institute of Geochemistry, Mineralogy and Mineral Resources, Faculty of Science, Charles University, Albertov 6, CZ-128 43 Praha 2, Czech Republic.
The Pb-isotope study of Sb-mineralizations from the of ore formation during Variscan orogeny. The oldest model Western Carpathians show a polycyclic character of the ore ages determined from Krásna Hora deposit (510–435 Ma). forming process. Pb-isotope data from Hynčice deposit correspond with De- Tatric Unit - the oldest model ages (corresponding to vonian age – 380 Ma and the sample from Příbram with uranogenic lead) were determined in samples from the Nízke Carboniferous (or Lower Permian?) age – 295 Ma. With the Tatry Mts (about 400 Ma). The second group of the data exception of the data from Krásna Hora deposit the samples from this region vary between 300-330 Ma and the third one indicate average crust origin of lead (µ1 < 9.80). about 200 Ma (ANDRÁŠ et al., 1998). The main field of the The oldest 206Pb/204Pb model ages both from Dúrico – results from the Malé Karpaty Mts. is clustered round time- Beirão district and from Trás-os-Montés (Galicia-Trás-os- linea at 200-250 Ma (Pezinok deposit). The second group of Montés zone, Northern Portugal) correspond with Devo- the model ages is about 110-120 Ma (Pezinok and Pernek nian age. They range from 405 (Alto do Subrido, Dúrico – deposits). Kriváň occurrence (Vysoké Tatry Mts.) belongs to Beirão district and Coitadinha-Grijó, Trás-os-Montés) up to the last group (155-160 Ma). The Sb-mineralization from the 320 Ma (Alto do Subrido and Medas, Dúrico – Beirão dis- Helcmanovce, Poproč and Grexa deposits (Gemeric Unit) is trict). The majority of the data is concentrated to the field connected with some younger events (110-140 Ma), includ- bordered by values from 390 to 320 Ma (Alto do Subrido, ing Permian volcanism. The special position (negative model Aguiar de Sousa-Abelheira, Moinho do Picão, Dúrico – age) have the samples from Zlatá Baňa neovolcanic deposit. Beirão district). Two samples: from Pinheirinhos and from The source of the lead from Sb-deposits of the Western Car- Borralhal (both from Dúrico – Beirão district) show some pathians is not homogeneous and could be connected with younger mineralization formation about 245 Ma. One an- the wall rocks. The lead is derived from crustal rocks, or other sample from Borralhal gives model age at about 120 related material. Ma (Cretaceous?) which represent the result of partial Eastern Alps. The model ages calculated from the lead remobilization of the original mineralization . isotopes of stibnite from Schlaining (Penninic Rechnitz Win- The Pb in stibnite mineralizations is derived from ho- dow) deposit correspond with the young Alpidic age. The mogenous crustal source. The lead gives µ1 values between model ages of the other mineralizations can be interpreted as 9.66 and 10.04 which is higher than the average crust value pre-Alpidic. The oldest model ages give stibnite from Drau (9.74). Only the µ1 values from 2 samples (from Grijó and range: Obertilliach (440 Ma), Radlbergalm (up to 385 Ma) from Medas) are close to the upper crustal lead (µ1 > 10). In and Rabant (360 Ma). The most important part of the results the Dúrico-Beirão district were the metals mobilized from indicate model ages around 250 Ma. Data from Guginock metamorphic complexes during the regional metamorphosis (Drau range) and Brückl (Gurktal thrust system) indicate and during the intrusion of granitoides (304–280 Ma). influences of younger events and ore-mobilization processes. Data from Northern Portugal and from Bohemian Massif The large spread of the data is partly due to the presence of (in contradiction to Western Carpathian and Eastern Alpine 206 208 young upper crustal Pb enriched in Pb and Pb in Varis- area) present the features of the old Variscan terrains without can vein type deposits, partly also due to the addition of significant younger Alpine overprint. radiogenic Pb during remobilization of ores under metamor- phic conditions of the Alpine orogenic process. The lead Reference isotope data show the importance of the fluid mixing in the ANDRÁŠ, P., CHOVAN, M. & SCHROLL, E. (1998). Car- origin of the veins and suggest that the lead was leached pathian - Balkan Geological Association XVI Congress from the wall rocks (ANDRÁŠ et al., 1998). (Vienna), 4. The Pb model ages for the Sb-mineralizations of the Bo- hemian Massif coincide by and large with the assumed time
4 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
EVOLUTION OF ORE-FORMING FLUIDS AT PEZINOK-KOLÁRSKY VRCH Sb-Au DEPOSIT (WESTERN CARPATHIANS, SLOVAKIA)
ANDRÁŠ, P.1, LUPTÁKOVÁ, J.1 & KOTULOVÁ, J.2 1 Geological Institute, Slovak Academy of Sciences, Severná 5, SK-974 01 Banská Bystrica, Slovak Republic. E-mail: [email protected] 2 Slovak Geological Institute of Dionýz Štúr, Mlynská dolina 1, SK-817 04 Bratislava, Slovak Republic.
Pezinok-Kolársky vrch Sb-Au deposit belongs to the secondary two-phase fluid inclusions. Salinity of included group of Sb-Au-FeS2 ore deposits of Malé Karpaty Mts. fluid is between 6 and 11 wt. % NaCl equiv. Nevertheless, associated with basic volcanism. The deposit is situated in eutectic temperature values (-45 to -55°C) suggest the pres- about 3500 m long tectonic zone of NW-SE direction. The ence of divalent cations such as Ca2+. Inclusions homoge- mineralised structure is 25-70 m thick and about 430 m long nised to the liquid in the temperature range of 140-275°C. at the surface. Two types of ore mineralisations have been Calculated fluid density is around 0,88 g/cm3. The estimated distinguished: 1 – metamorphosed, primarily volcano- pressure is about 3 kbar. Fluids were probably endogenous- sedimentary pyrite mineralisation, genetically related to metamorphogenous in origin. Quartz coexisting with stib- Devonian basic submarine volcanism, and 2 – epigenetic nite-sulphosalts mineralisation of 2nd and 3rd stage contained hydrothermal Sb (Au-As) mineralisation located mostly in primary two-phase fluid inclusions. These inclusions en- tectonically deformed black shales. Metallic elements could closed NaCl-H2O±CaCl2 solutions with moderate to high have been mobilised from the black shales by the circulation salinity (7 – 25 wt. % NaCl equiv.) as resulted from low of fluids released during regional and periplutonic metamor- temperature measurements. Presence of bivalent cations phism caused by granitoid rock intrusion (CHOVAN et al., (Ca2+) is indicated by eutectic temperatures below -45°C. 1992). Homogenisation to liquid phase occurred between 145- Four stages of epigenetic mineralisation have been rec- 200°C. According to various independent thermometers, ognised: 1. - gold-bearing quartz-arsenopyrite-pyrite, 2. - temperature of crystallisation ranges from 350 to 390°C. quartz-pyrite-arsenopyrite±löllingite, tetrahedrite, chalcopy- Two-phase aqueous fluid inclusions from 4th stage quartz rite, 3. - quartz-carbonate-stibnite± gudmundite, pyrrhotite, contained CaCl2-NaCl-H2O solutions with salinity of 8-25 pyrite, sphalerite, Pb-Sb sulphosalts, berthierite, 4. - stibnite- wt. % CaCl2 equiv. Inclusions homogenised to the liquid in kermesite±antimony, valentinite, bismuth, Bi-Sb sulphosalts the temperature range from 89 to 199°C. Density of included (CAMBEL, 1959; ANDRÁŠ, 1983). fluid varied between 0,96 and 1,16 g/cm3. Obtained results Lead in stibnites is of upper crustal origin. The young show that of hydrothermal fluids were similar in character model ages (220-230 and 110-130 Ma) are caused by the during whole ore-forming process. However, decrease in younger metamorphic processes and rejuvenation of Sb (- homogenisation temperatures indicates apparent cooling of Au) ores. Isotope distribution shows at least two sources of the hydrothermal system. sulphur. Biogenic sulphur had an important role predomi- The investigations Pezinok-Kolársky vrch deposit sup- nantly in metamorphosed, primarily volcano-sedimentary ported the increasing role of meteoric water and its intensive pyrite mineralisation and in Sb hydrothermal minerals with mixing with endogenous fluids while penetrating wall rocks Fe content (gudmundite, berthierite). Sulphur isotopes in during the metamorphic process. gold-bearing sulphide mineralisation are differentiated: the light biogenic sulphur is incorporated into pyrite while sul- References phur from deep lying source into arsenopyrite. Hydrothermal ANDRÁŠ, P. (1983). Thesis. Manuscript, 159 p. fluids (mainly 3rd and 4th stage) were probably meteoric in ANDRÁŠ, P., KOTULOVÁ, J., HAŠKOVÁ, A & DUBAJ, origin but they incorporated predominantly magmatic sul- D. (1999). Uhlí-Rudy-Geologický průzkum, 11, 6: 24-30. phur that could have been derived from the older plutonic CAMBEL, B. (1959). Acta geol. geogr. Univ. Comen., rocks or of juvenile origin. Distribution of carbon and oxy- Geogr., 3, 338 p. gen isotopes in carbonates and distribution of oxygen iso- CHOVAN, M., ROJKOVIČ, I., ANDRÁŠ, P. & HANAS, P. topes in quartz of Sb mineralisation is inhomogeneous. The (l992). Geol. Carpath., 43/5: 275-286. values show a relatively wide range and indicate predomi- nantly meteoric origin of fluids (ANDRÁŠ et al., 1999). The character of ore-forming fluids was specified by means of fluid inclusion study. Quartz of 1st stage contained
5 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
APPLICATION OF THE SURFACE ENERGIES OF A CRYSTAL FOR THE CALCULATION OF THE RELATIVE FORMATION TEMPERATURE
BABIĆ, D. Faculty of Mining and Geology, University of Belgrade, Djušina 7, YU-11000 Belgrade, Yugoslavia. E-mail: [email protected]
In this paper the results of the application of the Gibbs- Wulff’s theorem upon some crystal morphological types and Table 1: Calculated relative formation temperature for pyrite the dependence of the surface energies on temperature are {100}{111} crystal form combinations, Lipe deposit, East presented. We obtained an expression that enables us to Serbia. calculate the relative formation temperature of the
{100}{111} crystal form combination for pyrite, fluorite and Ymeas.(mm) X meas.(mm) T (ºC) Number of galena. The results for pyrite and galena crystals are pre- crystals sented in details. 1.8 0.43 315 21 Applying the Gibbs-Wulff’s theorem on the {100}{111} 1.8 0.42 270 15 crystal form combination in the cubic system we obtained the 2.0 0.47 260 18 following expression: 2.2 0.53 316 12 3 n 3.0 0.40 316 2 51 ()k −−= YTT.X 2 3.0 0.70 331 6 In this expression X is the size of the (111) planes (mm, cm); Y is the size of the (100)-planes (mm, cm); Tk is the critical temperature of the crystal formation (K); T is the unknown Table 2: Calculated relative formation temperature for ga- relative temperature of formation (K) and n is an exponent lena {100}{111} crystal form combinations, Ravnaja de- that has different values for different minerals (n = 0.062 for posit, West Serbia. pyrite and galena etc.). The relative temperature of formation o can be calculated from the above mentioned expression if we Ymeas.(mm) X meas.(mm) T C Number of measure the values X and Y on the real crystal and if we crystal 2.62 0.62 276 15 know Tk. The calculated values for the relative formation tempera- 1.45 0.36 262 23 ture of pyrite {100}{111} crystal form combinations from 1.36 0.31 223 27 Lipe (copper deposit, East Serbia) are given in Table 1. For pyrite, Tk is 1014 K in the Fe-S system. For galena, the {100}{111} crystal form combination ex- pression is the same as for pyrite, but Tk is different. For galena, Tk is 989 K in the Fe-Pb-S and Pb-S systems. Table 2 presents the calculated values for the relative formation tem- perature of galena {100}{111} crystal form combinations from the Ravnaja Pb-Zn-deposit (West Serbia).
6 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
THE MORPHOLOGICAL STABILITY OF GROWING CRYSTALS
BABIĆ, D. Faculty of Mining and Geology, University of Belgrade, Djušina 7, YU-11000 Belgrade, Yugoslavia. E-mail: [email protected]
The morphological stability of growing crystals is a very number of lamina growth. If we solve the above function, old problem preoccupying many scientists. The primary we get four symmetrical solutions for l =1, 2 that are pre- problem of the morphological stability of growing crystals is sented in Fig. 1a. the recovery of the mathematical expression that depicts The growth of the {100}{111} combination can be de- crystal growth. To solve this problem, we start in this paper dd 4 2 from the perturbation of field concentration in the interphases scribed by the function l =Y-()lai =0 . If we dtd border that is represented by a Laplace equation. The field l concentration at the interphase border is a real physical field, solve this function, we get eight symmetrical solutions for upon which mathematical physics can be applied. By partial l =1, 2 that are presented in Fig. 1b. solution of the Laplace equation, and the presentation of that solution as Legendre polynomial, we can get a complex Growth of the {111} and {111}{100} crystal forms function that describes the growth of several crystal forms in The growth of the {111} crystal form can be described by the cubic system. dd 3 g(111) the function l =Y-()lbi =0 , b = ; the Growth of the {100} and {100}{111} crystal forms dtd RTd Growth of the {100} crystal form can be described by the l growth of the {111}{100} crystal form can be described by following function (perturbation of field concentration) at the dd 2 dd l 3 l 4 the function =Y-()lbi =0 . If we solve these interphase border: =Y-()lai =0 ; ψ = (Ck-C0), dtd dtd l l functions, we get adequate solutions for =1, 2. The solu- where Ck is the density of a crystal, C0 is the density at the l g tions for the growth of the {111} and {111}{100} crystal (00)l forms are presented in Fig. 1c and Fig. 1d, respectively. interphase border; a = , where γ(100) is the interphase RTd surface energy at the (100)-plane (erg/cm2), R = 8.314·107erg/mol K, T is the temperature in K and d is the thickness of an interphase border; l is the fundamental
Fig. 1a Fig. 1b Fig. 1c Fig. 1d
7 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
PHOSPHATE-BEARING MINERALS IN EPITHERMAL SYSTEMS – A FEW EXAMPLES FROM THE CARPATHIAN-PANNONIAN REGION
BAJNÓCZI, B.1, SERES-HARTAI, É.2 & SZAKÁLL, S.3 1 Laboratory for Geochemical Research, Hungarian Academy of Sciences, Budaörsi út 45, H-1112 Budapest, Hungary. E-mail: [email protected] 2 Department of Geology and Mineral Resources, University of Miskolc, H-3515 Miskolc-Egyetemváros, Hungary. 3 Department of Mineralogy and Petrology, University of Miskolc, H-3515 Miskolc-Egyetemváros, Hungary.
Sulphate minerals have a significant role in the alteration other phosphate minerals, augelite and crandallite were also zones of epithermal systems, as sulphate-containing solutions found. of different origin are present in both HS and LS systems. Near Legyesbénye, Tokaj Mountains, Hungary, alunite The most typical sulphate mineral in these systems is alunite. appears in strongly silicified rocks, filling fissures and closed It is not widely known that during these processes phos- vugs. Electron microprobe studies proved the enrichment of phate-bearing minerals are also formed - though in a less Pb, Al, and P in the core of the alunite crystals (SZAKÁLL amount. The phosphate-bearing minerals in the alteration et al., 1986). The elongated forms of minerals suggest that zones of epithermal mineralizations appear in a wide range the alunites are pseudomorphs of apatite. The chemical com- of genetic environment, from hydrothermal to supergene position indicates a transition for hinsdalite (a mineral in processes. relation with woodhouseite). It seems that the formation of While the sulphur is abundant in the hydrothermal solu- the APS minerals took place before the crystallization of tions of epithermal systems, the phosphor is subordinate. alunite. Thus, the main source of phosphor can be the apatite of However, we suppose that the APS minerals occurring magmatic rocks, which is dissolved in strongly acidic fluids along the opened fractures in spherical or radial, needle-like at high temperature (STOFFREGEN & ALPERS, 1987). clusters are of supergene origin. These are crandallite (Pod- An early-formed mineral is the woodhouseite (alumin- polom, Slovakia and Recsk-Parádfürdő, Hungary), wavellite, ium-phosphate-sulphate or APS mineral), which is isostruc- faustite and variscite (Parádfürdő) and plumbogummite tural with alunite. Two new occurrences of woodhouseite (Pátka and Nadap, Hungary). In association with these min- were found in the Carpathian–Pannonian region (BAJNÓCZI erals jarosite and clay minerals are common. et al., 2003). One of these occurrences is at the eastern part of the Velence Mountains (Hungary), in the quartz-alunite References zone of the HS system related to Paleogene volcanites. The BAJNÓCZI, B., SERES-HARTAI, É. & NAGY, G. (2003). other occurrence is at Podpolom, Javorie Mountains (Slova- Acta Geol. Hung. (in press) kia), in the siliceous breccias of the HS system, which is STOFFREGEN, R. E. & ALPERS, C. N. (1987). Can. Min- developed in a Neogene volcanic complex. In both areas the eral., 25: 201-211. woodhouseite occurs in the core of the magmatic- SZAKÁLL, S., TAKÁCS, J. & WEISZBURG, T. (1986). hydrothermal alunite or in the siliceous matrix, which means Natura Borsodiensis, 1: 20-34 that it was formed prior to alunite. Beside woodhouseite, two
8 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
SOURCE MINERALS OF RADON ANOMALIES – HUNGARIAN CASE STUDIES
BARABÁS, A.1, BURJÁN, Zs.1, BREITNER, D.1, SZABÓ, Cs.1, NAGY-BALOGH, J.1, GÁL-SÓLYMOS, K.1 & MOLNÁR, Zs.2 1 Department of Petrology and Geochemistry, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary. E-mail: [email protected] 2 Institute of Nuclear Techniques, Budapest University of Technology and Economics, Hungary.
Introduction Methods Radon, a radioactive noble gas, has three isotopes found We have collected samples from both the surface (S, N, in natural environments, which originate from decay series of SH, T) and from shallow drills (N, SH). The samples in all uranium or thorium. The 222Rn radioisotope, having a half cases were sieved and subsequently sorted and subjected to a life of 3.8 days, enter the atmosphere of ground-level bed- wide range of examinations as follows: heavy mineralogy, rooms and living rooms of houses and may cause, in a long gamma-spectrometry, trace element analysis (by instrument term scale, serious health problem as snipped into lung then of neutron activation and optical emission spectrometry), attacking the tissues by emitting alpha particles. In Hungary, electron microprobe and Roentgen diffraction analysis. due to extended measurement of indoor radon level has been Furthermore, at the N locality outdoor radon measurements carrying out by the RAD Lauder Lab (Budapest), now sev- were carried out in soil gas and in groundwater. eral villages and towns are known characterized with ele- vated radon activity concentration. Three of these settlements Results and conclusions and an additional one have been taken under a serious study Neutron activation analysis showed no elevated amounts in order to determine the potential sources of radon entering of radioactive elements (basically U and Th) in the bulk the houses. For this reason, detailed sedimentological, pet- samples such as granite and granite rubble (up to 5.37 ppm rographical and geochemical study was performed on differ- U, 23.26 ppm Th), different kinds of soils (up to 3.2 ppm U, ent materials (e.g. granite, soils) collected from the settle- 12.8 ppm Th) and loess (up to 2.4 ppm U, 9.5 ppm Th) com- ments chosen. pared to the Clarke values of these rock types. Electron microprobe analysis show in micrometer scale, potential Geological background source minerals such as monazite, xenotime, allanite, zircon The areas studied were as follows: villages of Sukoró (S) and zirkelite, which contain the parental elements (U and Th) in the Velence Mountains, Nézsa (N) at the foot of one of the of radon. Among these minerals the monazite occurs most Mesozoic blocks on the left bank of the Danube (Cserhát frequently and believed to be the most important radon Mountains), Sajóhídvég (SH) (along Sajó River, North East emitter in the rocks and soils studied. Our petrographical and Hungary), and Tápiószentmárton in the Great Hungarian geochemical results suggest that monazites could have Plain (T). All of them represent significantly different geo- formed by near-surface alteration from allanite. This indi- logical environments such as Paleozoic (carboniferous) cates that these physical and chemical processes, which pro- granite (S), Mesozoic limestones and dolomites surrounded duce monazites may act recently, too. However, minerals and partly covered by Oligocene and young sediments (N) found at the T locality show no alterations which can be and alluvial fan of River Sajó (SH), which consists mostly of related to the low radon activity concentration at that loca- sand, loess, silt and gravel, and in the case of locality T, loess tion. and running sand cover the surface.
9 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
USING WOLLASTONITE FROM BĂIŢA BIHOR (APUSENI MOUNTAINS, ROMANIA) FOR FAST-FIRING CERAMIC GLAZES
BENEA, M. & GOREA, M. Department of Mineralogy, Babes-Bolyai University, 1 Kogalniceanu St., RO-3400 Cluj-Napoca, Romania. E-mail: [email protected]
Wollastonite (CaSiO3) with a theoretical chemical com- deposits, contain about 100 various mineral species. Among position 48.25% CaO and 51.75% SiO2 is particularly suit- them, wollastonite aggregates (up to 20 cm in diameter) able for reducing shrinkage and increasing strength during locally form nearly monomineralic bodies. fast-firing as well as for improving gloss and reducing sur- Fibrous white wollastonite aggregates were characterized face defects in glazes. During firing, a minimum volume of by means of X-ray diffraction (XRD) and optical micros- gas is generated as compared to other traditional materials, copy. resulting in a smooth surface with diminished pinholing. In order to test the wall tiles ceramic glazes, 5, 10 and Wollastonite is the main source of CaO flux in glazes (and 15% wollastonite were introduced into the recipe. The ther- bodies) instead of lime. Since wollastonite contains silica as mal treatment was conducted for 45 minutes between 1130- well, glaze recipes employing it do not need as much raw 1140 °C. silica powder. In fast-fired glazes wollastonite smooths out The obtained ceramic glazes showed an increased me- rapidly and completely, and the SiO2 and CaO react more chanical strength, a better resistance again acid corrosion and readily to form silicates. an improved gloss. The polymetallic skarn ores from Băiţa Bihor, Bihor Mts., developed in fractures cutting carbonate-rich Triassic
10 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
STRUCTURAL CONTROLS OF FLUID MOBILIZATION PROCESSES CONNECTED TO THE VARISCAN AND ALPINE IGNEOUS ACTIVITY IN THE VELENCE MTS. (WESTERN HUNGARY) ON THE BASIS OF STUDIES OF FLUID INCLUSION PLANES
BENKÓ, Zs. & MOLNÁR, F. Department of Mineralogy, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary. E-mail: [email protected]
The Velence Mts. is a part of a largely covered NE–SW fractures that have N–S strike-direction and were developed oriented belt that consists of Variscan granitoid intrusions due to a N–S oriented compression. The late Variscan fluids and Palaeogene andesitic-dioritic intrusive and volcanic with carbonic-aqueous composition (300–400 °C at 1.5–2.5 complexes (among other sedimentary and metamorphic kbars pressure) were channelled by NW–SE oriented frac- rocks) along the southern margin of a crustal unit that has tures. been escaped from the Alpean collision zone due to north- The Palaeogene fluids circulated under low pressure east-oriented lateral movements of Neogene age. In the area conditions (20–300 bars) that resulted in their boiling. Two of the Velence Mts., both Variscan and Alpine igneous rocks stages of Palaeogene hydrothermal fluid circulation that are strongly mineralized and there are field, mineralogical- affected the Variscan granite have been recognised. The geochemical, as well as fluid inclusion evidences of the in- older Palaeogene fluid circulation event took place mostly teraction of the Palaeogene hydrothermal system with the along E-W oriented fractures and it was associated with granitoid intrusion that has already been mineralised during intense illitic alteration of granite. These fluids are charac- the Variscan post-magmatic activity. Fluid inclusion studies terized by about 250°C temperature and low salinities. The on granite-related pegmatite, quartz-molybdenite stockwork second phase of Palaeogene fluid mobilization may be con- and base-metal bearing vein-filling mineralization as well as nected to a second generation of intermediate intrusions. This on the porphyry-copper and high-sulphidation type epither- phase of fluid circulation was connected to a NW–SE ori- mal mineralization connected to the emplacement of intru- ented shear-zone and is characterised by the occurrence of sions and volcanic rocks of Palaeogene age revealed signifi- high temperature (around 400°C) and low salinity, as well as cant differences in chemical and phase compositions of fluids low-temperature (around 250–300°C) and low and high sa- of these various hydrothermal systems (MOLNÁR et al., linity hydrothermal solutions. 1995; MOLNÁR, 1996, 1997). In the eastern part of the The post-Palaeogene fracturation of granite is character- Velence Mts., there are small intrusions and dikes of Palaeo- ized by NE–SW orientation of joints and can be connected to gene age that intrude into the old granite, and outcrops and the NE-oriented large scale lateral movements of Neogene quarries excellently expose their tectonised and hydrother- age. A second generation of young open fractures is NW–SE mally altered zones. Fracturation of granitic rocks and type oriented and they can be connected to the recent-subrecent of fluids that circulated along fractures can be reconstructed stress field of the Pannonian Basin. on the basis of orientation (dip direction and dip angle) This work was supported by the OTKA (HNSF) T measurements and microthermometric analyses of secondary 035095 research grant to F. Molnár. planes of fluid inclusion assemblages in rock-forming quartz together with the evaluation of field observations on joints References and faults. MOLNÁR, F. (1996). Plate tectonic aspects of the metal- The tectonic regime at the time of the emplacement of the logeny in the Carpatho-Balkan region (Popov et al. Eds). Variscan intrusion is characterized by the orientation aplite UNESCO-IGCP project No. 356, vol. 2.: 29-44. and granite-porphyry dikes which is NE–SW in the recent MOLNÁR, F. (1997). Földt. Közl., 127: 1-17. position of the granite. Analyses of field data and data of MOLNÁR, F., TÖRÖK, K. & JONES, P. (1995). Acta Geol. fluid inclusion planes revealed that the high temperature Hung., 31: 57-80 (400–600°C at 2 kbar pressure) and relatively dilute early magmatic fluids of the Variscan system circulated along
11 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
SOME FEATURES OF NEOGENE VOLCANIC STRUCTURES AND METALLOGENIC PRODUCTS FROM VOIA AREA, METALIFERI MOUNTAINS, ROMANIA
BERBELEAC, I. Institute of Geodynamics, Romanian Academy, Jean-Louis Calderon Str. 19-21, RO-70201 Bucharest, Romania. E-mail: [email protected], [email protected]
Voia area is situated in the central part of the Brad- types are known in Voia area, such as: 1) pyrite-calcium and Sacaramb Tertiary Basin, Metaliferi Mountains (MM), calcium-magnesian skarns and hornfelses have been found South Apuseni Mountains. This basin is coupled with open- in some boreholes and formed through heat and pyro- and ing of the Pannonian Basin. It is the result of an extensional hydrometamorphism processes, probably close to Eo- prevail period (17–14 Ma) followed by a period (14–11 Ma) Cretaceous intrusions and VADSB; 2) the porphyry copper– of strike-slip faulting with accommodation of extension pull- gold ore body with a side like porphyry iron ± copper-gold apart structures (DREW & BERGER, 2001). The subvol- ore (BERBELEAC et al., 1985) and the argillic, propylitic canic intrusions and volcanic rocks form Voia area, as well and potassic alteration types genetically related with as in other parts of MM, are preferentially localized in the VADSB; 3) the Mo-base metal brecciated structure presents extensional stepovers relate with this younger deformation on the north-western contact of Macris-Cetras andesitic dyke period (14–11 Ma). (borehole no. 24); 4) the epithermal HS mineralization and Voia area represents a region of about 20 km2. It is built alteration types such as Cu-As-Au quartz-clay minerals- up of Jurassic ophiolites – calc-alkaline volcanics and their barite veins (Paraul lui Avram) and marcasite-pyrite-clay covers represented by Upper Jurassic-Paleogene sedimen- minerals-gypsum (anhydrite)-alunite-diaspore dissemina- tary formations, by Badenian-Sarmatian sedimentary and tions and veins in magmatic and sedimentary rocks and 5) volcano-sedimentary formations and by Sarmatian- the epithermal LS mineralization and alteration types as Au- Pannonian volcanic rocks. At the surface only small patches pyrite disseminations in magmatic and sedimentary rocks, of Lower Miocene sedimentary and volcano-sedimentary probably Au-base metal veins (borehole no. 17) and pyrite- rocks are present. The Pre-Tertiary E–W and NE–SW (reac- marcasite breccia body from Lazuri stream. In the Voia area tivated) faults and the Tertiary NW–SE normal and strike- some particular features are emphasized: 1) the abundance slip faults controlled the Neogene volcanic structures. of the gypsum-clay minerals-marcasite-pyrite assemblage in Concerning Voia Neogene volcanic activity it is impor- argillic alteration zone from the upper part of Voia subvol- tant to note the followings: 1) the Neogene magmatic rocks canic body and anhydrite-pyrite±base metal sulfides towards (11.7-11.54 ± 0.5 Ma, ROSU, 2001) are calc-alkaline in the depth of this structure; 2) within VADSB there is a zone composition and consist of quartz amphibole ± biotite ande- with very chloritized rocks, richer in iron oxides and like sites, quartz amphibole biotite ± pyroxene andesites, por- iron porphyry±Cu-Au ore and 3) there is a genetic link and phyry microdiorites and amphibole-quartz ± pyroxene ande- partial spatial superposition between the skarn occurrences, sites; 2) the volcanic structures show a great diversity of porphyry Cu-Au and hydrothermal mineralizations. forms such as simple volcanoes (Buha, Momeasa, Geamana) and stratovolcanoes (Cetras, Macris) with extrusive domes, References lava flows ± talus and avalanche deposits; 3) the volcanic BERBELEAC, I., ZAMARCA, A., DAVID, M., necks describe a circle with some subvolcanic bodies within TANASESCU, I., BERINDE, N. (1985). D. S. Inst. it like in the Sacaramb area and 4) a multi-stage Voia ande- Geol. Geofiz., LXIXL/2: 8-26. sitic-dioritic subvolcanic body (VADSB) and other andesitic DREW, J. I. & BERGER, R. B. (2001). Min. Deposits at the dikes have been recognized in some boreholes. The metallo- beginning of the 21st Century, Pietrzynski et al (eds), genic processes are dominantly related with high fluid con- Swets & Zeitlinger Publishers, 519-522. tent of Neogene calc-alkaline magmas; the mineral reactions ROSU, E. (2001). ABCD-GEODE 2001 Workshop Vata in extensive fluid-rock interactions with basement and cover Bai, Romanian J. Mineral Deposits, 79,/Suppl. 2: 19-22. formations must be taken into account. In spite of the very small area great varieties of the mineralization and alteration
12 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
GEOPHYSICAL SETTING OF THE DEEP WELL 6042 DELENI IN CENTRAL TRANSYLVANIA, ROMANIA
BESUTIU, L.1, GORIE, J.2 & DORDEA, D.2 1 Institute of Geodynamics, Romanian Academy, Jean-Louis Calderon Str. 19-21, RO-70201 Bucharest, Romania. E-mail: [email protected] 2 SC “Prospectiuni” SA, Caransebes Str. 1, Bucharest-32, Romania.
Deep well 6042 Deleni was drilled for hydrocarbon ex- tively low densities. The fact was attributed to the presence ploration in the central part of Transylvanian Depression of some deep fracture zones located at the basement level, (TD). It penetrated at a depth of about 4700 m and went hidden beneath the TD Mesozoic and Cenozoic cover. Grav- through for more than 350 m, some basic rocks (basalts, ity and geomagnetic data processing allowed outlining sev- basaltic-andesites, etc.), located beneath Tithonian carbonate eral regional deep faults striking eastward and north–north- series (dolomites). The mafic sequence was considered by eastward in the borehole area. The presence of the fracture several authors as the ophiolite suture of the Transylvanian zone is confirmed in the well logging data reflected in the branch of the Tethys Ocean. combined γ-ray highs, low resistivity, and larger neutron The paper is intended to present airborne/surface geo- porosity values, which are completely unusual for basalt physical data related to the area in correlation with well- rocks. logging data (caliper logs, electric, gamma-ray, and neutron Based on gravity and geomagnetic data, under the con- logs) and previous regional geotectonic framework. It was straint of seismics and rock physics laboratory determina- aimed at adding geophysical and tectonic setting to the thor- tions, attempts were made to model the borehole environ- ough mineralogical studies dedicated to the mafic rocks ment. encountered by this well (HOECK & IONESCU, 2003). Finally, some concluding remarks and speculations are Gravity, magnetics (both ground and airborne), geother- made on the regional geotectonic framework of the 6042 mal gradient (heat flow), as well as seismics were taken into Deleni deep well. account in this analysis. Various filtering techniques (matrix smoothing, polynomial regression, etc.) were extensively References used in order to improve the signal/noise ratio in separating AIRINEI, ST., STOENESCU, SC., VELCESCU G., RO- effects made by sources of different extent and/or located at MANESCU, D., VISARION, M., RADAN, S., ROTH, various depths. M., BESUTIU, L., BESUTIU, G. (1983). An. Inst. Geol. Airborne data (CRISTESCU & STEFANCIUC, 1968) Geofiz. (ser. Geofizică, Hidrogeologie şi Geologie in- clearly outlined a large regional geomagnetic anomaly over ginerească), LXIII: 5-11. the whole central part of the TD. Later on, it has been fully AIRINEI, ST., STOENESCU, SC., VELCESCU G., RO- confirmed in the images provided by the ground vertical MANESCU, D., VISARION, M., RADAN, S., ROTH, component geomagnetic map of Romania (AIRINEI et al., M., BESUTIU, L., BESUTIU, G. (1985). St. Cerc. Geol. 1983, 1985). Geofiz. Geogr., Geofizica, 23: 12-19. Several previous geological interpretation (BESUTIU, BESUTIU, L. (1984). An. Inst. Geol. Geofiz., LXIV: 361- 1984) considered this regional geomagnetic effect as a com- 368. posite anomaly mainly due to sources located at least at three CRISTESCU, T. & STEFANCIUC, A. (1968). The aero- levels: (i) Dej tuffs, located in the upper part of the section; magnetic map of the Romanian territory: The 5th Na- (ii) basic to intermediate igneous rocks located at the level of tional Symposium of Applied Geophysics and Physics of the TD basement; (iii) a large wavelength component due to the Earth, Bucharest. the basaltic layer geomagnetic expression in the “colder” part HÖCK, V. & IONESCU, C. (2003). Acta Mineralogica- of TD. Petrographica, Abstract Series 1 (this volume). It should be noted that analyses made on core samples from the 6042 Deleni borehole clearly exhibited high mag- netic susceptibility for the above mentioned basalts, but rela-
13 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
LEONITE IN PRE-CARPATHIAN EVAPORITES AND ITS TRANSFORMATION UNDER INCREASED TEMPERATURES
BILONIZHKA, P. National University of Lviv, Hrushevskogo 4, UA-79005 Lviv, Ukraine. E-mail: [email protected]
Leonite is a rare mineral in Precarpathian evaporites. It Heating time was 30 minutes. Heating products were studied has been discovered as small admixture in the kainite and by X-ray powder diffraction. polymineral rocks and as fibrous streaks in the clayey salif- On the X-ray powder diffraction patterns of leonite erous breccia near and among potassium salt deposits. heated to 100 and 150°С all the reflections typical of natural Leonite is a light yellow, transparent, bitter-tasting min- leonite were present, but peak intensities became smaller. eral with high solubility in water. Its lustre is waxy to vitre- At 200°С the crystal structure collapses. The new phase ous. The mineral is firm in dry air. Under the microscope is most probably K2Mg[SO4]2 • 2H2O (dhkl: 6.7; 5.6; 3.56; leonite grains are colourless with low interferential colours 3.36; 3.33; … Å). That crystalline phase exists only in a (grey). Polysynthetic twins are sometimes visible. Some narrow temperature range and we do not know it from na- leonite grains have wavy extinction. The refractive indices of ture. Some admixtures of langbeinite (K2Mg2(SO4)3; 3.15; leonite are: Nx=1.479; Ny=1.482; Nz=1.487; Nz-Nx=0.008. 3.91; 2.67; 2.43; … Å) and arcanite (K2SO4; 3.36; 3.01; 2.91; On the X-ray powder diffraction patterns of the fibrous 2.87; … Å) phases appear as well. leonite from Stebnyk potassium mine the following reflec- Further heating to 250°С leads to the complete loss of the tions appear: 6.1; 5.9; 5.25; 4.93; 4.77; 4.21; 3.97; 3.71; 3.52; structural water and to the formation of langbeinite (5.7; 3.49; 3.42; 3.30; 3.04; 2.87; 2.75; 2.62; 2.50; 2.46; 2.38; 4.05; 3.15; 3.01; 2.76; 2.66; 2.41; 2.28; 2.17; … Å) and ar- 2.29; 2.21; 2.17 Å. They are similar to the reflections of the canite (5.0; 4.18; 3.76; 3.51; 3.39; 3.15; 3.01; 2.91 (100); standard X-ray powder diffraction pattern (JCPDS № 21- 2.85; 2.66; 2.51; 2.43; … Å). These two phases remain stable 995). also at 300 and 400°С. The chemical composition of the studied leonite is The transformation process of leonite can be represented K2O=25.30; MgO=11.01; SO3=43.75; H2O=19.66; with the help of the following equation: Na2O=0.36; Cl=0.06 (wt%). Chlorine is connected with 2K2Mg[SO4]2 • 4H2O=K2Mg2[SO4]3 + halite admixture. The crystallochemical formula of leonite 733.37 419.99 (after subtraction of halite) is K1.96Na0.04Mg1.00[SO4]2.00 • 100% 56.59% 4H2O. The sodium in the formula may be connected to the presence of blödite (Na2Mg(SO4)2 • 4H2O), that is in close K2[SO4]+8H2O paragenetic association with leonite. Leonite and blödite are 174.25 144.13 very similar because their refractive indices are close to each 23.76% 19.65% other. It is important to note that potassium may also substi- tute in blödite. Domain isomorphism (inclusions of blödite Leonite admixtures in potassium salts are primary while microlayers in the leonite structure and vice versa) is quite its interlayers in the clayey saliferous breccia are secondary possible between them, too. formations. Based on the TG data, the loss of structural water of the On the basis of these investigations we may assume that studied leonite starts around 130°C. A bump on the dehydra- during catagenesis, under increasing pressure and tempera- tion curve around 200°C testifies some delay in the process. ture, leonite decomposes and transforms through an unstable, About 10% of water is lost under that temperature. Dehydra- intermediate dihydrate phase into langbeinite and arcanite. tion of the mineral is completed at about 240°С. The DTA Considering also geological time, this process may take curve shows two endothermic effects at 167 and 212 °С, place in evaporites at temperatures even lower than the tem- respectively. peratures suggested by the above experiments. Experimental investigations were run to study the nature of these thermal reactions. Samples of the fibrous leonite from Stebnyk mine were heated in a regulated oven at tem- peratures of 100, 150, 200, 250, 300 and 400°С, respectively.
14 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
REE ACCESSORY MINERALS IN THE FELSIC SILICIC ROCKS OF THE WEST- CARPATHIANS: THEIR DISTRIBUTION, COMPOSITION AND STABILITY
BROSKA, I. Geological Institute of the Slovak Academy of Sciences, Dúbravská cesta 9, P.O. Box 106, SK-840 05 Bratislava 45, Slovak Republic. E-mail: [email protected]
The paragenesis of the accessory minerals in the granitic Stability of the principal REE-bearing accessory miner- rocks depends on the water or volatile content, and very als, as monazite or allanite, is in the fluid regime restricted. strongly on aluminosity and alkalinity of the primary melt. The alteration of monazite is possible already by subsolidus From among the different accessory minerals, the typomor- magmatic fluids in the low temperature conditions. In such phic REE-bearing accessory minerals currently help to dis- conditions monazite breaks down and newly-formed LREE- criminate (by their presence or absence or physico-chemical enriched apatite occurs on the monazite grains. It is known character) following granite genetic suites in the Western from the S-type granitic rocks presented e.g. in Suchý. The Carpathians: Palaeozoic orogenic I- and S- type and anoro- new apatite usually forms only very tiny rims on monazite, genic A- and S-type. Generally, the REE-rich accessory but sometimes the alteration is much less complete. Other mineral assemblages typical for the I-type granites is formed alteration also on the rim of monazite grains is the result at by allanite, apatite, and sphene on the other hand the par- formation of huttonite. This is accompanied by the increased agenesis characteristic for the S-type granites contains mobility of the actinides as U and Th, and this was described mainly monazite, apatite, xenotime and garnet. in the Western Carpathians e.g. in the Tribeč Mts. within the The allanite / monazite antagonism, which is important S-type granite suites. Formation of rhabdophane on monazite for the recognition of the S / I-type granite suites is very surface is also possible. Monazite from the felsic silicic rocks distinctly developed in the West-Carpathian granites. The overprinted in the amphibolite facies breaks down to allanite relationships between monazite and allanite are explained by often with formation of an intermediate zone of apatite different solubilities of these minerals when the solubility of (FINGER et al., 1998, BROSKA & SIMAN, 1998). This allanite in peraluminous granites is higher than monazite. assemblage is associated with the reaction between biotite, Generally, allanite precipitated rather in metaluminous (or anorthite and monazite-(Ce) with high activity of Ca. The slightly peraluminous) than peraluminous granitic rocks, so apatite in such transition zone in monazite-allanite-epidote allanite is typical for the I-type granitic rocks, on the other coronas or grains contains usually low amount of the REEs. hand, monazite for the S-types. The highest content of allan- Similar to monazite, xenotime is also unstable during over- ite is observed in the Lower Carboniferous Sihla I-type printing under the amphibolite metamorphic conditions. granitoids, which is known in the Slovak Ore Mts, Tribeč Xenotime alteration is resulted in formation of REE-rich Mts. and Čierna Hora Mts. In comparison with the I-type epidote in the form of coronas around the xenotime grains. granitic rocks, total Al in allanite increases with whole rock Such alteration of xenotime is known from the orthogneisses peraluminosity, usually being above 2.0 Al pfu in allanites in the Western Tatra Mts., during retrogression events from S-type granites. Monazite is characteristic for the S- (JANÁK et al., 1999). Allanite breakdown is also common type granites, only more evolved I-type or late differentiated and usually REE-rich epidote is the product of such disinte- I-type granitic rocks contain beside allanite also monazite. gration. Titanite shows interesting alteration, because allanite The monazite composition, as solid solution of the monazite and REE epidote represents the breakdown products. Usually s.s. component, brabantite and huttonite, show some depend- these minerals form small patches within the titanite grains ency on the primary melt composition and physicochemical and this effect reflects the mobility of the REEs or REE- conditions. The proportion of brabantite increases with per- leaching processes. aluminosity and peralkalinity as can be demonstrated on the The stability of the REE-bearing accessory minerals is in example of the Spiš-Gemer granites, while huttonite content most aspects still unknown phenomenon, although their in the monazite increases with temperature. Apatites from the distribution is crucial for the understanding of the REE mo- S-type granites show pronounced Eu-negative anomaly, in bility in the granitic rocks. contrary to I-type granites, where higher redox conditions in the melt caused the presence of Eu mainly in the trivalent References form. The S-type granites contain more Eu in divalent form BROSKA, I. & SIMAN, P. (1998). Geol. Carpath., 49: 161- due to the reduction regime, state this valence being easier 167. incorporated into plagioclase. Except REEs, apatite is typo- FINGER, F., BROSKA, I., ROBERTS, M. P & SCHER- morphic mineral also due to the presence of other elements MAIER, A. (1998). American Mineralogist, 83: 248-258. which discriminate the granite rocks between the S or I- JANÁK, M., HURAI, V., LUDHOVÁ, P., O’BRIEN, P. I. & types. More peraluminous granites, like orogenic West- HORN, E. E. (1999). J. Metamorphic Geol., 17: 179-195. Carpathian S-type granites produce apatites with higher content of Mn and Fe compared to the I-type of granites.
15 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
ANOMALOUS GRANDITE GARNET FROM BĂIŢA BIHOR, ROMANIA
BÜKÖS, M. CS.1 & DÓDONY, I.2 1 Babeş-Bolyai University, Kogalniceanu 1, RO-3400 Cluj-Napoca, Romania. E-mail: [email protected] 2 Department of Mineralogy, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary.
Garnets are expected to crystallize in the cubic Ia3d space Although the anisotropy seems to be proportional to the Al group. Many of the calcium garnets formed during contact content, the microprobe did not reveal an exact relationship. metamorphism or in hydrothermal environments proved to Beside the expected cubic structure (Ia3d) X-ray powder be optically anisotropic. Mostly the intermediate members of diffraction showed also a triclinic (I1) component in the the andradite-grossular series reveal anomalous birefrin- studied samples. gence, meanwhile the end-members are expected to be opti- TEM studies also proved a lower than Ia3d symmetry. In cally isotropic (SHTUKENBERG et al., 2002). accordance with the published interpretations, the origin of The analysed samples are postmagmatic products of a birefringence is explained by the Fe3+/Al3+ ordering in the lamprophyric intrusion from Băiţa Bihor. Compositionally octahedral position. they are close to the pure andradite member of grandite solid solutions. The optical anisotropy is mostly related to zona- SHTUKENBERG, A. G., POPOV, D. Yu. & PUNIN, Yu. O. tion with oscillatory zoning of the Fe3+/Al3+ ratio. Addition- (2002). Mineral. Mag., 66: 275-286. ally, there are minor anisotropic areas in pure andradite, too.
16 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MORPHOLOGY AND GEOCHEMISTRY OF ZIRCON FROM THE METAMORPHIC ROCKS OF THE WESTERN TATRA MTS. (S-POLAND)
BURDA, J. Department of Paleogeography and Paleoecology of Quaternary, Faculty of Earth Sciences, University of Silesia, Będzińska st. 60, PL-41-200 Sosnowiec, Poland. E-mail: [email protected]
In the Polish part of the Western Tatra Mts. metamorphic prism and {211} pyramid. The most common types are S1, complex, migmatites predominate forming the northern en- S2, S6, S7, L1, L2, with a distinguished maximum at S1. velope of the Rohace granite. They are both heterophanic In CL images of the mesosome zircons inner cores, sur- (mainly stromatitic) and homophanic (schliere-type) ones. rounded by the outer magmatic rims are commonly observed. The P-T evolution of the metamorphic complex shifted from The outer rims represent the magmatic recrystallization event the medium pressures (7.5–9 kbar) and temperatures in the in the metamorphic complex. Many rounded zircons are range of 700–730oC (Ky + St stability field) to the stability completely diffuse in the CL images, with neither an old core of sillimanite (750–780oC) and than to andalusite nor the outer magmatic zoning observed. (GAWĘDA et al., 1999). Among the migmatites two gen- Among the zircons from leucosome euhedral, transparent, erations were distinguished: the first generation was formed light-coloured crystals predominate, with elongation 2:1 to during differentiation in the Ky+St stability field and the 4:1. They are mostly S1, S2, S21, S22 forms according to Pu- second one due to the partial melting in the sillimanite sta- pin’s classification (PUPIN, 1980). In the typological distri- bility field (BURDA & GAWĘDA, 1999). bution two maxims can be observed, suggesting the occur- Zircons, being accessory minerals in migmatites, have rence of two generations of zircons. been affected by the metamorphic events, occurring in this CL investigations often revealed subtle oscillatory zon- area and they may be considered as good petrogenetic indi- ing, due to heterogeneous distribution of trace elements dur- cators of the rock evolution. To observe the zircon response ing the crystal growth (HOSKIN & BLACK, 2000). The for the partial melting of the host metasedimentary rocks, the intensity of CL signal shows no major variations. It is possi- zircon crystals from both leucosome and mesosome from the ble that the chemical environment during crystallization stromatitic migmatite were investigated. remained fairly stable. These zircons grew during a single The population of zircons from mesosome is dominated magmatic event. Some zircons exhibit inner cores, which are by the normal prismatic crystals, differing in colours (col- relics from the protolith. ourless, grayish, yellowish-grayish and abundant brown and Chemical analyses of zircons from mesosome revealed dark grey crystals). The length of single crystals varies in the that Zr/Hf ratio varies in a wide range: from 24 to 110,2. range of 20 to 60 µm and the aspect ratio (length : width) However, about 50% of the analysed zircons show the Zr/Hf ranges from 1:1 to 2:1. The degree of crystal roundness ratio in the range of 24–39. There are no major changes in changes in the large scale, but in general subhedral crystals major element distribution in the zircon crystals. predominate. The percentage of anhedral zircons with rounded edges and tops is difficult to determine because of References the transitional stages from euhedral to anhedral forms. Eu- BURDA, J. & GAWĘDA, A. (1999). Arch. Miner., LII/2: hedral zircons can be both short and prismatic and elongated 163-194. ones. In the population of short, isometric crystals the GAWĘDA, A., DEDITIUS, A. & PAWLIK, A. (1999). rounded, subhedral to anhedral forms are more popular. Miner. Pol., 30/2: 63-82. Different forms of zircon corrosion are observed in the ana- HOSKIN, P. W. O. & BLACK, L. P. (2000). J. Metamorphic lysed grain population. Fine-grained zircon aggregates are Geol., 18: 423-439. abundant in mesosome but rare in leucosome. The morphol- PUPIN, J. P. (1980). Contr. Miner. Petr., 73: 207-220. ogy of zircons from mesosome is dominated by the {110}
17 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
LOST MINERALS?
BURKE, E. A. J. Chairman of the IMA-CNMMN, Faculty of Earth and Life Sciences, Vrije Universiteit Amsterdam, De Boelelaan 1085, 1081 HV Amsterdam, The Netherlands. E-mail: [email protected]
The Commission on New Minerals and Mineral changes in existing nomenclature) should publish descrip- Names (CNMMN) of the International Mineralogical tions of the minerals covered by these proposals within two Association (IMA) was established in 1959 for the purpose years of being notified of the approval by the chairman or of controlling the introduction of new minerals and mineral the vice-chairman. This period of two years is probably too names, and of rationalising mineral nomenclature. The short, it is well known that it takes on average about one year CNMMN consists of representatives appointed by national from the submission of a manuscript to the appearance of the mineralogical bodies (currently 30 voting members) and an hard copy of a journal, a considerable delay due to the time executive committee consisting of chairman, vice-chairman needed for the peer review and the printing process. Of the and secretary. The CNMMN repartitions its workload 48 new minerals approved in 2000, only 24 have been pub- amongst the three officers: the chairman prepares the new- lished until November 2002. mineral proposals, the vice-chairman handles the proposed But we have also much older new minerals that have not changes to existing nomenclature (discreditations and redefi- been published yet. According to several databases kept by nitions), and the secretary coordinates the subcommittees CNMMN officials, we lack the publication of 30 or so min- created to examine the nomenclature of mineral groups. The erals approved between 1988 and 1999. One of the CNMMN 30 members of the CNMMN evaluate all nomenclature pro- members (Michel Deliens of Belgium) regularly contacts the posals (new minerals, changes in existing minerals, mineral ‘slow’ authors by proxy of the chairman, and these actions groups), and cast their votes on these, on a monthly basis for sometimes result in the ‘rescue’ of these new minerals, which the new-mineral proposals, and as they come for the other would otherwise be lost to our science. proposals. About 70-80% of the members participate actively A completely different case is represented by the phases in the monthly new-mineral proposals, and about 60% in the on which research has been carried out, but that for some others. The work of the CNMMN has gained since 1959 reason or other have never reached the stadium of submis- overwhelming support from the international mineralogical sion to the CNMMN for approval, e.g., by lack of data asked community. for by the CNMMN. In many cases these phases are pub- The CNMMN handles about 50-60 new-mineral propos- lished as ‘unnamed minerals’, giving partial descriptions. als per year (52 proposals in 2000, 70 in 2001, 57 in the first The CNMMN has an active subcommittee working on an ten months of 2003). The CNMMN has voted on 300 new- annotated list of these unnamed minerals published since mineral proposals in the period from January 1998 to Octo- 1960. Most of these published unnamed minerals, however, ber 2002. Approximately 80% of these were approved, the will never be fully characterised. remainder being either rejected, or suspended pending further The present author has been involved between 1969 and information. The CNMMN has also adjudicated in the same 1977 in a cooperation with Slovak and Russian colleagues on period 22 proposals to discredit, redefine or revalidate min- an interesting phase on which the work has remained incom- eral species or to amend nomenclature in mineral groups plete. It concerns a sulphosalt with a particular composition (e.g., amphiboles, micas, zeolites). About 50% of these were (Pb-Hg-Sb-S) from the locality Zenderling near Gelnica approved, with the remainder being rejected, withdrawn or (Slovakia). Almost all work was ready, even X-ray work was pending. Since 1959 the IMA-CNMMN has officially taken carried out on the specially made synthetic equivalent of the a decision on 3,500 or so minerals and mineral names on mineral, but the final description was never submitted to the their approval, discreditation and/or redefinition. The list CNMMN, and only fragmentary descriptions have been with these 3,500 or so decisions is available as a PDF file published, although even recently with a name (HÁBER et from the recently established IMA-CNMMN web site al., 1999) not approved by the CNMMN. (www.geo.vu.nl/users/ima-cnmmn). This official IMA list only gives name, formula and one reference for each species; References the reference supplied is for the published announcement of HÁBER, M., JELEN, S., KRIZÁNI, I., SOTÁK, J. & the CNMMN decision regarding the mineral’s status, for new SPISIAK, J. (1999). Exkurzný sprievodca II, Banská minerals usually the publication by their authors. Bystrica 21.-22.mája 1999. And here we have a first problem. According to the NICKEL, E. H. & GRICE, J. D. (1998). Canadian Mineralo- CNMMN procedures and guidelines (NICKEL & GRICE, gist, 36: 1-14. 1998) authors of approved proposals (new minerals or
18 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
CHEMICAL COMPOSITION OF Ni, Co AND Fe SULPHOARSENIDES AND ARSENIDES IN THE HYDROTHERMAL SIDERITE VEINS IN THE WESTERN CARPATHIANS (SLOVAKIA)
CHOVAN, M. & OZDÍN, D. Department of Mineralogy and Petrology, Faculty of Natural Sciences, Comenius University, Mlynská dolina G, SK-842 15 Bratislava, Slovak Republic. E-mail: [email protected]
There are Ni-Co minerals occurring mainly in the hy- sented by gersdorffites from Vyšná Boca and Dobšiná. In drothermal siderite veins of Alpine age in the Western Car- these samples a smooth transition to krutovite is observed, pathians. The mineral succession scheme is the following: with strong variation of As vs. S and a less characteristic alteration → siderite → alpine paragenesis → Ni-Co-Fe-As isomorphic substitution of Fe vs. Co. Both minerals crystal- minerals → quartz with Cu-Bi-Fe-Sb-Hg sulphides. The lized in the space group P213, a space group of gersdorffite most abundant are in the sulphide (sulphoarsenide, arsenide) of temperature lower then 300 °C (KLEMM, 1965). In the stage with less contents of carbonates and silicates. There euhedral crystals intensive oscillatory zoning is typical. The are often occurred with the Cu minerals – tetrahedrite, ten- cores of the crystals are formed by krutovite and the rims by nantite, chalcopyrite and with the others sulphides mainly gersdorffite. Krutovite was identified by X-ray diffraction. pyrite and galena. Those were described on numerous de- Gersdorffites from Častá belong also to that type. They were posits and occurrences in the Slovak Republic. Ni-Co-Fe-Cu- formed together with ullmannite by solid solution decompo- As minerals are represented by gersdorffite, cobaltite, arse- sition. They show strong isomorphous substitution of Sb, As nopyrite, rammelsbergite, pararammelsbergite, krutovite, and S. Space group is P213. Their formation temperature was ullmannite, skutterudite, nickeline and carrollite which were relatively low, probably under 300 °C. studied in details at the following localities: Vyšná Boca, Most arsenopyrites contain no isomorphous substitution Dobšiná and Častá. and are close to stoichiometric formula. Isomorphous sub- Optical zoning is a characteristic feature of all the men- stitution of Fe vs. Co or Ni respectively indicated a higher tioned Ni-Co minerals, but mainly of the sulphoarsenides and temperature of formation (KLEMM, 1965). Antimony rarely diarsenides. It may be oscillatory, concentric or sector zon- substitute in the arsenopyrite crystal lattice. Arsenopyrite- ing. The typical oscillatory zoning was developed probably gudmundite smooth transition was not observed (Vyšná in a non-steady system under the influence of locally chang- Boca), but zonal arsenopyrite contains zones, mainly in the ing physico-chemical conditions or by diffusion in solid crystal core, enormously enriched in Sb (up to 11.81 wt.% state. The dominant components in the chemical zoning in Sb; (=5.59 at.% Sb)). This is the maximum Sb substitution in the sulphoarsenides are As and S over the also varying Ni, arsenopyrite reported from the Western Carpathians. Sb Co and Fe. replaces As in the lattice. These Sb substituted arsenopyrites The most abundant minerals are sulphoarsenides repre- might formed at a lower temperature. sented mainly by arsenopyrite and gersdorffite. Based on Based on this chemical variation, (successive precipita- chemical composition of sulphoarsenides we described 3 tion from solid solution; substitution of cations (Ni, Co, Fe) basic types of gersdorffite. The 1st type is represented by and anions (As, Sb, S)), we can say, that with increasing euhedral, homogenous gersdorffite from Vyšná Boca, with temperature arsenopyrite began to precipitate; later gers- typical strong isomorphism of Ni vs. Co (± Fe) and a less dorffite and cobaltite, with strong substitution of cations. On pronounced variation of As vs. S. That type forms rims the reverse path ullmannite and gersdorffite was crystallized around arsenopyrite crystals and was crystallized close to the by solid solution decomposition. Fluid inclusion studies of temperature of the arsenopyrite formation. Higher tempera- these hydrothermal veins (HURAI et al., 2002) confirmed a ture sulphoarsenides, including cubic gersdorffites and co- temperature increase during the crystallization of quartz and baltites with strongly disordered structure and space group siderite from the core to the rim. Pa3, were formed at a temperature of 500–550 °C (KLEMM, 1965). The 2nd type from Dobšiná deposit is characterized by References smooth transition from arsenopyrite to gersdorffite. Gers- ČVILEVA, T. N., BEZSMERTNAYA, M. S. & SPIRI- dorffite formed by metasomatic replacement of arsenopyrite, DONOV, E. M. (eds.) (1988). Nedra, Moskva, 1-504. thus both minerals might have crystallized in the triclinic HURAI, V., HARČOVÁ, E., HURAIOVÁ, M., OZDÍN, D., space group P1 (ČVILEVA et al., 1988), at temperature of PROCHASKA, W. & WIEGEROVÁ, V. (2002). Ore 550–650 °C (KLEMM, 1965). During that replacement the Geology Reviews, 21/1-2, 67-101. primary crystal shape of arsenopyrite is preserved. The inten- KLEMM, D. D. (1965). Neues Jahr. für Miner., Abh., 103, sive zonal (but smooth) arsenopyrite-cobaltite transition 205-255. samples may also belong to this type. The 3rd type is repre-
19 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
VESUVIANITE AND GROSSULAR FROM THE SKARN NEAR SUSULA, EAST SERBIA
COCIĆ, S.1, ERIĆ, S.2 & SRECKOVIĆ-BATOCANIN, D.2 1 Institute for Copper-Bor, Zeleni Boulevard 33-35, Bor, Yugoslavia. 2 Faculty of Mining and Geology, University of Belgrade, Djušina 7, YU-11000 Belgrade, Yugoslavia. E-mail: [email protected]
Intrusive rocks are common in the Timok Eruptive Com- Chemical analyses of vesuvianite show that FeO-content plex (TEC). They are usually intruded into the andesites of ranges between 2.49–3.57%, while TiO2-content is in the the TEC, or in the sedimentary rocks (Jurassic and Creta- 0.14–0.95% range. Contents of the same oxides in garnet ceous limestones) of the TEC or in the marginal parts of the range from 3.93 to 5.76% for FeO, and from 0.06 to 1.58% TEC. They mostly form small bodies that are present all over for TiO2. this complex between Majdanpek, on the north, and Bucje, Mineral chemistry coefficient activity (Kd), i.e. molar on the south. fraction rate of Ti and Al was also determined. The Kd value In the contact zones between the intrusive bodies and the ranges from 0.310 to 0.330, suggesting that these minerals sedimentary formations skarns were formed. They are pre- were formed in a system poor in CO2, and at temperatures dominantly built up of vesuvianite and garnet. Subordinately around 400 °C (LOBOTKA et al., 1988). quartz, epidote, wollastonite, magnetite and pyrite can also As the Susula Skarn has a more complex composition be found. Very rarely chalcopyrite, bornite and chalcocite compared to the association of a simple “wollastonite zone”, occur. The Susula Skarn, one of these skarn formations, was with Al being present in both vesuvianite and grossular, the discovered in the western part of the TEC, in the mountain primary rock was probably not a pure limestone. Considering area between the Crni Vrh and Kucaj. At that locality euhe- the low mobility of aluminium, it is assumed that it was dral vesuvianite crystals (tetragonal prisms + bipyramid) up already present in the clay fraction of the original sedimen- to 5 cm in size, and euhedral grossular-andradite type gar- tary rock, rather than being brought by the intruding magma. nets, up to 1 cm in size can be found. Morphology of the vesuvianite crystals (Fig. 1) is the same as in the skarn of the Reference Potoj Cuka locality. LOBOTKA et al. (1988). Amer. Mineral., 73: 1302–1324.
Fig. 1: Vesuvianite crystal.
20 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
BRIEF OVERVIEW ON THE SiO2 VARIETIES OF GEM-QUALITY FROM SOUTHERN APUSENI MOUNTAINS (ROMANIA)
CONSTANTINA, C.1 & POP, D.2 1 Department of Mineralogy, Institute of Gemology, Babeş-Bolyai University, 1, Kogălniceanu St., RO-3400 Cluj-Napoca, Romania. E-mail: [email protected] 2 Mineralogical Museum, Babeş-Bolyai University, 1, Kogălniceanu St., RO-3400 Cluj-Napoca, Romania.
The Southern Apuseni Mts. were known as hosting gem- usually formed as veins, but currently they can be collected th quality SiO2 varieties since the second half of the XIX cen- from the alluvia. Under the optical microscope, the presence tury (KOCH, 1885; PRIMICS, 1886). Several occurrences in of calcite and epidote in contact with chalcedony indicates the region provide some of the most beautiful chalcedonies, transformation processes due to the circulation of hy- even agates in Romania. The present study provides a brief drothermal solutions (MÂRZA & CONSTANTINA, 2000). overview of the main areas where such materials were identi- Măgura Bradului Hill (Brad, Hunedoara district) is well fied, arranged chronologically according to the genetic types known for its jaspers mentioned in early papers on the re- of the host- (and generating-) rocks. In each case new geo- gion. Coarse andesitic pyroclastic agglomerates host sili- logical and microscopic data on the gem materials are given, ceous sinters (geyserites). The generating epithermal silica- based on recent results of one of the authors (CC). rich solutions were deposited within small lakes, as proved by the fossil fauna and flora. The local prevalence of various 1. Gem materials associated to the “ophiolitic” volcanism impurities (Fe oxy-hydroxides, Mn oxy-hydroxides etc.) lead “Ophiolitic” complexes containing gem materials (mainly to the local formation of variously coloured jaspers, domi- represented by coloured chalcedonies, jaspers and rarely nated by the brown-reddish varieties. Mineralogical data on agates) consist of basalts, spilites, microgabbros, andesites, these jaspers were given by GHERGARI & IONESCU latiandesites, alkaline trachites, dacites, and rhyolites. The (1999). Silicified woods from Prăvăleni (Hunedoara district) formation of the SiO2 varieties was mainly related to pyro- are hosted by Sarmatian cinerites; they show a reduced clastic deposits that provided relatively more porous and gemological value. permeable substrates for the circulating solutions. The most representative occurrence of this type is Rachiş 4. The gemological-field Techereu (Hunedoara district) (Alba district) (GHIURCĂ, 2000). The chalcedony is of On a relatively small area five genetic types of gems are vein-type, rarely nodular - in this case mainly consisting of present: chalcedonies associated to the Mesozoic “ophiolitic” the agate variety. The typical colour is white, and reddish- complex, polychromatic jaspers in Cretaceous conglomer- grey; gem-quality materials are usually translucent. Micro- ates, variously-coloured chalcedonies in Paleogene rhyolites, scopically, a nucleus of microgranular quartz (grey and/or siliceous nodules, jaspers and silicified wood within the white in colour) is surrounded by concentric reddish bands of Almaşu Mare Gravel (Badenian), as well as reworked chal- fibrous quartz; the intensity of the red colour depending on cedonies and jaspers in Quaternary deposits (MÂRZA, the concentration of iron oxy-hydroxides. Gem-quality mate- 1999). This complex geology confers a unique position rials can be collected from the host-rock or from alluvia. among the above-mentioned locations to the Techereu occur- rence. 2. Gem materials associated to the banatitic volcanism Pyroclastic agglomerates and tuffs represent mainly the References volcanic rocks of a Paleocene age. The SiO2-type gem mate- GHERGARI, L. & IONESCU C. (1999). Anal. Univ. Bu- rials are very diverse and abundant: chalcedony, agate, opal, cureşti, Min. Petr. (Abstract volume), 48: 32. jasper, silicified wood. The type locality is Gurasada (Hun- GHIURCĂ, V. (2000). Studii si Cercet. (Geol.-Geogr.), 5: 9- edoara district), and materials can be typically collected from 17. Muz. Jud. Bistriţa-Năsăud, Bistriţa. alluvia. The chalcedony shows a massive texture and has KOCH, A. (1885): Erdély ásványainak kritikai átnézete. usually lighter colours (white-bluish) than the chalcedony Orv.-Term. Társ., Kolozsvár, p. 211. from the “ophiolitic” complex. MÂRZA, I. (1999). Studia Univ. Babeş-Bolyai, Geol. 44/1: 78-86, Cluj-Napoca. 3. Gem materials associated to the Neogene volcanism MÂRZA, I. & CONSTANTINA, C. (2000). Studia Univ. The generating rocks are represented by andesitic pyro- Babeş-Bolyai, Geol., 45/1: 91-104, Cluj-Napoca. clastics in Brad area and pyroxenic andesites in Hărţăgani PRIMICS, Gy. (1886). Földt. Közl., 16: 308-313, Budapest. area, both complexes having a Sarmatian age. The white to dark-grey chalcedonies from Hărţăgani (Hunedoara district)
21 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
SHALLOW SUBVOLCANIC ANDESITIC MAGMATISM IN THE EAST BORSOD BASIN, HUNGARY: AN EXAMPLE OF MAGMA/WET SEDIMENT INTERACTION
CSÁMER, Á. Department of Mineralogy and Geology, University of Debrecen, P. O. Box 4, H-4010 Debrecen, Hungary. E-mail: [email protected]
Already from the 1970s but mainly from the 1990s many Epiclastic tuff-breccias and lapilli-tuffs are drab or grey, authors published examples where magma comes in contact poorly bedded or unbedded, with tuffaceous matrix, and with wet sediment, generating hyaloclastites, peperites, in- consist of andesite blocks, fragments and epiclasts of various situ breccias, etc. (LYDON, 1968; YAMAGISHI, 1991; size. By the major element composition of the andesite HANSON & HARGROVE, 1999). These works make it blocks, they belong to the calc-alcaline series; the range of clear that phenomena of magma/wet sediment interactions contents of SiO2 and K2O varies between 56.85–58.22 wt% are common in geological environments where thick sedi- and 1.86–2.10 wt%, respectively. These rocks are highly ment sequences accumulate during active volcanism. Mio- porphyritic with phenocrysts mainly consisting of plagio- cene palaeogeographic environment (HÁMOR, 2001) and clase, orthopyroxene (ferrosilite), clinopyroxene (augite). neutral volcanism of the East Borsod Basin allowed the for- The groundmass of andesite blocks is felsitic containing mation of different types of these rocks. mineral assemblage of plagioclase, orthopyroxene, clinopy- The East Borsod Basin (EBB) is mainly built up from roxene, magnetite and titanomagnetite. The texture is micro- Cenozoic sequences. Paleo-Mesozoic rocks, represented holocrystalline-porphyritic or pilotaxitic. mostly by limestones, siliceous shales and derived volcano- Andesite intrusions and dykes are small (max. 15 m in clastics, cover small areas. The greater part of EBB is cov- diameter), and often show columnar, slab jointing or coarse ered by Cenozoic clastic sediments, volcanic-subvolcanic blocked structure (CSÁMER & NÉMETH, 2000). Their rocks, pyroclastic and volcaniclastic deposits, and the Paleo- chemical and mineralogical composition is similar to that of Mesozoic basement is situated within a few hundred meters the pyroclastic andesite blocks. Andesite intrusions were below the surface. emplaced into wet unconsolidated sediments during or The Lower and Middle Miocene (Ottnangian-Karpatian) shortly after their deposition. The host sediment is domi- sequences (Salgótarján Lignite Formation – SLF) are repre- nantly lapilli-tuff, tuff-breccia. On the margins of the intru- sented by sandstones, aleurolitic sandstones, argilliferous sions aureole and hyaloclastite occur containing angular or aleurolites, clays and redeposited acidic tuffs with interca- partly rounded andesite fragments of varying quantity in a lated coal seams. These sediments were deposited in shallow tuffaceous matrix. Beside the regular chaotic texture (cluster marine and near-shore environments. of angular andesite fragments), jigsaw-fit texture can be also The Upper Badenian–Sarmatian–Pannonian sequences recognized recording in situ fragmentation. building up the Sajóvölgy Formation (SF) are deposited with unconformity on the SLF. These sediments were deposited in Acknowledgement fluvial, deltaic or near-shore environments. The upper part of This work was supported by the Hungarian National Sci- the formation consists mainly of cross-bedded medium- or ence Research Foundation (OTKA) under Res. Contracts No coarse-grained sands, polymict gravels or conglomerates; the T-029058. lower part contains shallow marine–offshore tuffites and sands. Sediments of the SF are unconsolidated or poorly References consolidated, therefore, erosional valleys and canyons are CSÁMER, Á. & NÉMETH, G. (2000). Földtudományi barely found, while derasional and erosional-derasional val- Szemle, 1: 85–90. leys are more abundant. HÁMOR, G. (2001): Explanation to the Miocene palaeo- Interbedded Sarmatian–Pannonian andesitic pyroclasts geographic and facies maps of Carpathian Basin. Geo- and volcanic-subvolcanic rocks are present in patches on the logical Institute of Hungary, Budapest, p. 66. (in Hun- surface, because most of them are covered by younger de- garian) posits. Their characteristics, habits and facies could be inter- HANSON, R. E. & HARGROVE, U.S. (1999). Bull. Vol- preted as a separate volcanic formation (Dubicsány Andesite canol., 60: 610–626. Formation – DAF) formed by pyroclastic tuff-breccias, lap- LYDON, P. A. (1968): Geology and lahars of the Tuscan illi-tuffs, and shallow subvolcanic intrusions, dikes, in situ Formation, Northern California. In: Studies in Volcanol- breccias and hyaloclasts. The age of the neutral volcanic ogy, The Geological Society of America Inc., Boulder, activity in the EBB ranges from 9.5 ± 0.8 to 13.73 ± 0.76 Ma Colorado: 441–473. (Upper Badenian–Sarmatian–Pannonian) according to K/Ar YAMAGISHI, H. (1991). Sediment. Geol., 74: 5–23. radiometric data.
22 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
BOURNONITE FROM HYDROTHERMAL ORE DEPOSITS IN THE BAIA MARE AREA, ROMANIA
DAMIAN, F. & DAMIAN, Gh. Department of Geology, North University of Baia Mare, 62/A Dr. Victor Babes Street, RO-4800 Baia Mare, Romania. E-mail: [email protected]
The most frequent occurrences of bournonite in Romania Table 1: Atomic proportions based on 3 atoms of sulphur are related with the Neogene hydrothermal mineralizations. for the Baia Mare bournonites. In the hydrothermal mineralizations associated with the Neo- gene subduction type magmatism at the Baia Mare area, No Atomic proportions Sample bournonite was identified at Ilba-Alunis, Dealul Crucii, 1Pb1.03Cu1.1Ag0.003Sb0.98S3 Ţiganul vein, Herja, Baia Sprie, Cavnic, Băiuţ and Toroiaga-Borşa. In the Toroiaga base metal mineralizations bournonite appears as inter- 2Pb1.02Cu0.95Bi0.004Sb1.11S3 Caterina vein, growths with galena and less frequently with chalcopyrite, Toroiaga sphalerite and pyrite. Among the sulphosalts the mineral 3Pb0.98Cu0.99Sb1.05S3 Caterina vein, frequently associated with bournonite is tetrahedrite. Bour- Toroiaga nonite is present as prismatic crystals of 2–3 mm size with 4Pb1.02Cu0.98Sb1.03S3 Caterina vein, vertical striations. These crystals are disposed on galena and Toroiaga sphalerite. Bournonite forms crystal aggregates with different 5Pb092Cu1.17 Ag0.0005Fe0.004- Baia Sprie spatial arrangements, of several centimetres in diameter. In Sb1.09S3 reflected light they show fine characteristic lamellar twins 6Pb0.86Cu1.12 Fe0.002Sb1.02S3 Baia Sprie (0.05-0.10 mm) in one or two directions. The value of Vick- 7Pb1.004Cu1.02Bi0.002Sb1.02As0.01- Ignaţiu vein, ers microhardness determined for a standard print of 20 µ is 2 Te0.001S3 Herja 150–190 kg/mm . The bournonites from the Baia Mare area 8PbCu Sb S Dealul Crucii were studied by electron microprobe analyses. The formulae 0.96 0.95 0.95 3 9Pb Cu Fe - Băiuţ 101 of the studied bournonites have been recalculated on the 0.933-0.96 0.95-0.98 0.02-0.034 Sb As Sn S basis of 3 sulphur (Table 1). 0.92-0.99 0.013-0.085 0.004-0.01 3 10 Pb Cu Fe - Băiuţ 602 Besides the major elements Cu, Pb, Sb, S small quantities 0.97-0.99 0.96-0.98 0.011-0.05 Sb As Sn S of As, Fe, Bi, Ag, Sn and Te also appear. Arsenic appears as 0.723-0.98 0.08-0.3 0.003-0.005 3 11 Pb Cu Fe Sb S Baia Sprie substitute for Sb. This shows the existence of a solid solution 099 0.98 0.018 0.95 3 12 Pb0.98Cu1.15Fe0.072Sb0.91As0.027S3 Cavnic between CuPbSbS3 (bournonite) and CuPbAsS3 (seligman- nite). Fe, Ag and Sn appear as substitutes for metallic cations 1–4 after GÖTZ & DAMIAN (1990); 9–10 after DAMIAN Cu and Pb. The presence of Sn can indicate a high formation & COSTIN (1999); 11 after SIPŐCZ (1886); 12 after temperature of the paragenesis. Bi and Te appear as substi- HIDEGH (1881). tutes for Sb. References DAMIAN, Gh. & COSTIN, D. (1999). Studia Universitatis Babeş-Bolyai, Geologia, XLIV/1: 138-149. GÖTZ , A. & DAMIAN, Gh. (1990). Revista Minelor, 41/9: 467-471. HIDEGH, K. (1881). Akad. Közlem., 8: 17, Ref. Z.K., 8. SIPŐCZ, L. (1886). Tschermak’s Mineral. Petrol. Mitt., 7, Z.K., 11.
23 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
Mn-RICH TETRAHEDRITES IN THE ROMANIAN TERRITORY
DAMIAN, Gh. & DAMIAN, F. Department of Geology, North University of Baia Mare, 62/A Dr. Victor Babes Street, RO-4800 Baia Mare, Romania. E-mail: [email protected]
Tetrahedrite–tennantite is the most common sulphosalt Ag0.19-0.24Sb2.73-3.15As0.8-1.40S13. The tetrahedrites from Gura present in the majority of hydrothermal ore deposits. Man- Barza contain Sb and especially large quantities of Ag, which ganoan tetrahedrites appear in some hydrothermal ore de- include them in the argentian tetrahedrites group. These 2+ posits from South Apuseni Mts. MAKOVICKY & KARUP- tetrahedrites contain more Me2 than would normally result 2+ MØLLER (1994) showed that Mn can be incorporated in the from the substitution of Cu2 by Fe and Zn. The tetrahedrites synthetic tetrahedrite structure. The stoichiometric formula from Coranda-Hondol contain As and Sb and a very small 2+ 2+ of tetrahedrite is Cu10Me2 (Sb,As)4S13. Incorporation of Mn amount of Ag. In these tetrahedrites Cu2 is almost totally in tetrahedrites is possible by substituting cations in the substituted by Fe and Zn. Under these circumstances we structure. Mn can substitute Cu2+ in the structure. Manganese assume that Mn substitutes Cu+ together with Ag. BASU et was indicated in all publications, but not exceeding 0.5 wt %. al. (1984) claims that once the Me3+ content increases the BASU et al. (1984) described an occurrence of man- Me+ content lowers. This statement is not applied to some ganoan tetrahedrite with 1.5–1.7 Mn atoms per formula unit. tetrahedrites from South Apuseni Mts. Because Fe and Zn 2+ These tetrahedrites are As varieties containing between 0.7 substitute most of Me2 , we assume that Mn together with + + and 2.2 atoms, alongside with 0.1–0.2 Pb, 0.1–0.3 Fe, and Ag substitutes Cu10 in the formula unit. According to minor amount of Zn and Hg. BURKHART-BAUMAN MAKOVICKY & KARUP-MØLLER (1994), the presence (1984) described at Quiruvilca (Peru) two intimately inter- of Mn in synthetic tetrahedrites contributes to the increase of grown tennantites. One variety had Pb-bearing manganoan the unit cell parameter a. This increase is due to the much tennantite, and the other had tennantites rich in Mn with 1.48 higher value of Mn2+ (0.67 Å) cationic radius compared to atoms per formula unit. Another occurrence of manganoan that of Fe2+ (0.64 Å) and Zn2+ (0.637 Å). The presence of Ag tetrahedrite was described by DOBRE (1992) from the in tetrahedrites also determines the increase of the a pa- skarns of the Tunaberg Cu-Co deposit, Bergslagen, Central rameter (RILEY 1974). The high amount of Mn and Ag, Sweden, and had 0.61 to 0.86 Mn per formula unit. present in the studied tetrahedrites, can determine essential In Romanian territory the richest analyses in Mn were changes in the tetrahedrite structure. As the structure is very communicated by HIDEGH (1881) at Săcărâmb (South much modified, we do not exclude the possibility of having a Apuseni Mts) with 1.23 wt % Mn. This tetrahedrite is inter- new mineral, a tetrahedrite with manganese. Further investi- mediary between tetrahedrite-tennantite with 1.77 wt % Fe, gation of these tetrahedrites will either confirm or reject our and 5.55 wt % Zn. Other manganoan tetrahedrite occurrences suppositions. were described at Boteş-Bucium, Arama vein by LOCZKA (1901) with 0.69 wt % Mn and KRETSCHMER (1911) with References 0.26 wt % Mn. BASU, K., BORTNIKOV, N., & MOOKHERJEE, A. We have identified new occurrences of manganoan tetra- (1984). N. Jb. Miner. Abh., 141: 280-289. hedrites in the South Apuseni Mts. Two occurrences are BURKHART-BAUMAN (1984). N. Jb. Miner. Abh., 150: certain at Gura Barza (Brad) and Coranda Hondol. The Gura 37. Barza tetrahedrites contain 3.04–4.16 wt % Mn, and the DOBRE, R. T. M. (1992). Miner. Mag., 56: 113-115. Coranda-Hondol ones, between 0.74–6.31 wt % Mn. Micro- HIDEGH, K. (1879). Tschermak’s Mineral. Petrol. Mitt., 2, scopically, some varieties have been identified. At Coranda- Ref. Z.K., 1881, 5. Hondol the intergrowings between different varieties are KRETSCHMER, A. (1911). Zeits. Kryst., 9. highly evident and UDUBAŞA et al. (1982) signalled them. LOCZKA, J. (1901). Zeits. Kryst., 34. These intergrowings are more evident when they are built up MAKOVICKY, E. & KARUP-MØLLER, S. (1994). N. Jb. of varieties with manganoan tetrahedrites and non- Miner. Abh., 167: 89-123. manganese varieties. RILEY, J. F. (1974). Mineral. Deposita, 9: 117-124. Formulae units for Gura Barza tetrahedrites are Cu6.82- UDUBAŞA, G. et al. (1982). D. S. Instit. geol. geofiz., Bu- 7.45Zn0.98-1.65Fe0.33-1.01Mn0.95-1.31Ag1.56-1.9Sb3.89-3.93S13 and for cureşti, LXVII/2: 197–232. Coranda-Hondol are Cu8.32-9.58Zn1.45-1.74Fe0.21-0.2721Mn0.22-1.87
24 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
THE USE OF THE ZEOLITIC TUFFS IN THE DETOXIFICATION OF HEAVY METAL CONTAMINATED SOILS
DAMIAN, Gh. & DAMIAN, F. Department of Geology, North University of Baia Mare, 62/A Dr. Victor Babes Street, RO-4800 Baia Mare, Romania. E-mail: [email protected]
Zeolitic tuffs are used in a various range of activities. the treated soil have been planted with Lolium perenne. The MUMPTON (1973) has drawn attention upon their great germination was accomplished in proportion of 90% in the potential regarding industrial applications. During the last 40 treated soil and approximately 40% in the original soil. The years, many research studies were carried out concerning the growth of the plants has demonstrated that the soil treated use of natural zeolites in many areas including environmental with organo-zeolitic material allows the growth of vegetation protection (MUMPTON, 1999). The excellent ion-exchange much faster than the original soil. selectivity of clinoptilolite for ammonium has been Growth has been possible because the organo-zeolitic emphasized recently (LEGGO, 2000). Zeolitic tuffs can be material supplies all the necessary substances for the plants used at large scale in the detoxification of the heavy metal (nitrogen, humus, potassium, and calcium). During growth, + contaminated soils produced by mining and metallurgical the plants take up NH4 and some cations from the soil solu- + industry. These contaminated soils are a serious problem at tion. Cations and NH4 taken up by the plants emerge into an international scale. For the remediation of these soils in the soil solution from the structure of the organo-zeolitic + such a way that pollution is avoided, research with natural material. The same way, cations and NH4 ions included in zeolites has been carried out in the last few years. Heavy the zeolitic structure are exchanged with the heavy metal metal contaminated soils have been treated with a mixture of cations, which are fixed in the zeolitic structure. All this organic substance and zeolite (organo-zeolitic materials). cationic exchange is adjusted by the growing plants, which + Organo-zeolitic material has been obtained by fermenta- create a permanent NH4 cation deficiency in the soil solu- tion of 2/3 fresh organic substance with 1/3 zeolitic tuffs. tion. The experiment was carried out in the laboratory and The tuffs were prevailed from Bârsana and Ocna Şugatag the plant growth was observed for 4 months. We noticed a areas (Maramureş Basin). They are vitroclastic tuffs con- pH increase in the treated soil, in comparison with the origi- taining 1–5% crystalloclasts (quartz, plagioclase, biotite), nal soil, which indicates that the organo-zeolitic material also glass and volcanic ash that are strongly vitrified and substi- has a pH correction role, improving its value from 4.4 to 5.9 tuted by: clinoptilolite, heulandite, mordenite, montmorillo- and from 4.1 to 5.4. nite, celadonite and silica. Clinoptilolite is the predominant Considering the results obtained during the experiment zeolite and appears as compact masses of tabular and pris- we can conclude that the maximum plant growth was ac- matic micron-sized crystals that are evident in SEM images. complished in the cases when the soil was treated with or- The medium ion exchange capacity ranges between 125 and gano-zeolitic material. This growth was possible because the 142 mvals/g. The contact surface is 15–18 m2/g. organo-zeolitic material mixed with soil provides the sub- Zeolitic tuffs were roll crushed and ground in small stances necessary for the plants to develop (ammonium, grains with dimensions between 0.08 and 2.5 mm, then humus, potassium, calcium). At the same time heavy metals sieved to obtain 0.5–2 mm-sized fraction. This material was that inhibit the plant development are blocked through the homogeneously mixed with two parts of organic material and cationic exchange mechanism that makes them enter the the mixture was put in a plastic container for fermentation. zeolite structure and they no longer have direct access to the Ammonia that results from bacterial discomposition changes plant roots. the zeolitic structure. In this way, Ca2+ and K+ got incorpo- rated in the organic substance. This final product is excellent References for inhibiting heavy metal cations from soils and promotes LEGGO, P. J. (2000). Plant and soil, 219, p. 135–146, Klu- vegetation growth. wer Academic Publishers. The experiments were made in pots, each containing 2 kg MUMPTON, F. A. (1973). Industrial Minerals, 73/2: 30-45. of polluted soil with organo-zeolitic material. In the mixture, MUMPTON, F. A. (1999). Proc. Natl. Acad. Sci. USA, 96: the polluted soil represents 83% and the organo-zeolitic 3463-3470. material represents 17%. The soil used in the experiment contains 4% Pb and a pH = 3.77–4.44. The original soil and
25 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
CRYSTALCHEMISTRY OF CLAY-MINERALS AROUND THE BORDER OF AN OVER- PRESSURE ZONE IN ONE OF THE DEEP SUB-BASINS OF THE SOUTHERN PART OF THE GREAT HUNGARIAN PLAIN
DÓDONY, I. & LOVAS, Gy. A. Department of Mineralogy, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary. E-mail: [email protected]
In this contribution the smectite to illite transition and the sponding vitrinite reflectance values showed also a sharp maturation of organic matter have been studied with in- change. The estimated pore pressure data for this depth range creasing temperature and pressure, i. e. with increasing depth indicated an overpressure zone between 4500 and 6000 m, in one of the sub-basins of the Pannonian Basin (Hungary) that could result in interrupting the continuos dehydration of called Hódmezővásárhely-Makó trench. Hódmezővásárhely-I smectites and could be responsible for the stagnation of the is the deepest borehole (5842.5 m) in Hungary traversing smectite content of the I/S in this zone. The increase of only Pannonian (s. l.) sedimentary formations built up smectite content, however, could certainly not be explained mainly of marls, marly shales, shales and sandstone. Clay by the pressure conditions. A possible explanation lay in the fractions extracted from the core samples were studied by actual crystalchemistry, that is the real structure, the in situ XPD using method given by Reynolds and Moore (1997) in interlayer and/or octahedral, tetrahedral co-ordinated cation order to estimate the smectite content of mixed-layered il- distribution, that is the individualism of this clay mineral lite/smectite. Orientated air-dried ethylene-glycolated and assemblage, resulting in a decreased reactivity. Another glycerolated, Mg-saturated air-dried ethylene-glycolated and possible approach is the supposition of an abrupt change of glycerolated, and heated to 350 and 550ºC <2 µm fraction the source (containing smectite-like clay of a different kind) mounts were measured in order to determine the mineral of the sedimentary rock. A nanometer scale crystalchemical assemblages, the smectite % (S %) and the order of the I/S study has been carried out on the undisturbed in situ smec- phases. In the course of diagenesis the regular pattern of the titic material using analytical TEM technique the revealed smectite content of I/S is diminishing with increasing depth. several interesting facts that will be discussed. In the present case, however, an anomalous change – in- This research project is financially supported by the Hun- creasing, than stagnating S% – in this sequence was detected garian National Research Fund (OTKA) under contract no. in the depth of 4500-5800 m, where dominantly pelagic T032450, which is greatly acknowledged. marls and marly shales occur. In the same zone, the corre-
26 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
SLOVAKIAN MINERALS – THE CURRENT STAGE OF KNOWLEDGE
ĎUĎA, R. Eastern Slovakian Museum, Hviezdoslavova 3, SK-041 36 Košice, Slovak Republic. E-mail: [email protected]
From the beginning of the evolution of mineralogy, the Table 1 area of Slovakia had an important position. Many minerals of historical names were described from the area of Banská Class 1980 2002 Increase % Štiavnica, Smolník, Špania Dolina etc. already in the times Elements 17 26 34.6 of AGRICOLA (1556). A more complex review of the min- Sulfides etc. 94 175 46.3 erals of Slovakia can be found in the works of ZIPSER Halides 7 11 36.4 (1817), JONAS (1820), ZEPHAROVICH (1859, 1873, Oxides etc. 63 94 33.0 1893), TÓTH (1882) and others. Carbonates etc. 23 32 28.1 Throughout the 19th century and in the beginning of the Sulfates etc. 52 69 24.6 20th. century many new minerals were first described from Phosphates etc. 41 69 40.6 Slovakian localities (evansite, euchroite, libethenite, szomol- Silicates 129 180 28.3 nokite etc.). The Mining Academy in Banská Štiavnica Organic minerals 4 5 20.0 (Schemnitz, Selmecbánya) was a rather important scientific Summary 430 661 35.0 centre of mineralogy of that time, many world-famous min- eralogists worked there. References th During the 20 century, the mineralogical studies were AGRICOLA, G. (1556). De re metallica libri XII. Froben, concentrated at universities and in research institutes in Slo- Basileae. vakia and in the Czech Republic. The results of an almost JONAS, J. (1820). Ungerns Mineralreich orycto- 100-year-old continuous research activity were summarized geognostisch und topographisch dargestellt. Hartleben, in the 1980’s, in the three volumes of the book by KODĚRA Pesth. et al., (1986, 1990): Topografická mineralógia Slovenska KODĚRA et al. (1986, 1990). Topografická mineralógia (Topographical mineralogy of Slovakia). Since that time Slovenska I-III. SAV Veda, Bratislava. there has been an intense progress in mineralogical research, TÓTH, M. (1882). Magyarország ásványai. Hunyadi Mátyás thanks to the development of laboratory methods applied in Int., Budapest. mineralogy (microprobe techniques, electron microscopy, ZEPHAROVICH, V. VON (1859, 1873, 1893). Mineralogis- infrared spectroscopy, chemical analytical methods etc.). ches Lexicon für das Kaiserthum Oesterreich. Braumüller That development is also proved by the intense increase of (1859, 1873), Tempsky (1893), Wien. the number of mineral species described from Slovak locali- ZIPSER, CH. A. (1817). Versuch eines topographisch- ties: from the 430 species in 1980 (KODĚRA et al., 1986) mineralogischen Handbuches von Ungern. Wigand, we arrived to 661 species by the end of 2002. That increase Oedenburg. of more than 50% in average shows a more or less homoge- nous distribution over the mineral classes (Table 1).
27 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
CALCIUM PHOSPHATES IN THE BAT GUANO DEPOSIT FROM PEŞTERA MARE DE LA MEREŞTI, PERŞANI MOUNTAINS, ROMANIA
DUMITRAS, D.-G.1, MARINCEA, Ş.1, DIACONU, G.2 & BILAL, E.3 1 Geological Institute of Romania, Caransebeş 1, RO-78344 Bucharest, Romania. E-mail: [email protected] 2 “Emil Racoviţă” Institute of Speleology, Bucharest, Romania. 3 Ecole Nationale Supérieure des Mines, Saint-Étienne, France.
The cave from Mereşti (Peştera Mare de la Mereşti) is lo- of the composition and stoichiometry, the Mereşti material cated at the northern margin of Perşani Mountains, in the closely matches the CaHPO4·2H2O end-member. Its mean Vârghiş Gorges, at about 18 km north–northwest of Baraolt, composition, taken as an average of five ICP-AES analyses Covasna County, Romania. The cave, which has, including of samples whose purity was proved by XRD analysis is (in the divergent galleries, 1527 m in length, is developed in wt.%): K2O = 0.02, Na2O = 0.02, CaO = 32.09, MnO = 0.07, Tithonian-Neocomian algal micritic limestones with cal- MgO = 0.21, FeO = 0.16, P2O5 = 40.26, SO3 = 1.11, H2O (as carenite levels. A bat guano deposit, with limited extension, calculated for the charge balance) = 26.05. This composition, was identified inside the cave. normalized on the basis of 2 (P+S) and 8 (O) in the anhy- Calcium phosphates (i.e., hydroxylapatite, carbonate- drous part of the compound, leads to the chemical-structural hydroxylapatite, brushite and ardealite) are the most repre- formula: 2+ sentative mineral species in the bat guano pile, but the asso- [K0.001Na0.002Ca1.969Mn0.003Mg0.018Fe 0.008](HPO4)1.952 ciated minerals also include calcite, gypsum, alpha (low) (SO4)0.048 • 4H2O. quartz, illite and interstratified kaolinite-illite. The average unit-cell parameters, taken as mean of the Hydroxylapatite, or more precisely carbonate- values obtained by least-squares refinements from 7 sets of hydroxylapatite, is the most common mineral species in the X-ray powder data including 51-93 reflections unequivocally lower part of the guano pile. It occurs as creamy white crusts attributable to brushite are a = 5.812(5) Å, b = 15.169(5) Å, c composed of fine platy crystals up to 15 µm in diameter and = 6.239(4) Å and β = 116.35(13)°. 1 µm in thickness. Ardealite occurs as cream white, thin and porous crusts An inductively coupled plasma - atomic emission spec- that overcoat hydroxylapatite or as small nodules, up to 0.5 trometry (ICP-AES) analysis of a carefully handpicked sepa- cm in diameter, surrounded by a mass composed of hy- rate, recalculated to 100% after the deduction of water in droxylapatite and brushite. order to assess the charge balance, gave (in wt.%) the fol- The average ICP-AES composition, obtained as mean of lowing results: K2O = 0.01, Na2O = 0.01, CaO = 54.87, MnO three individual analyses of representative samples yielded = 0.03, MgO = 0.27, FeO = 0.39, P2O5 = 42.03, SO3 = 0.53, (in wt.%): K2O = 0.01, Na2O = 0.01, CaO = 32.45, MnO = H2O = 1.86. This composition, normalized on the basis of 6 0.02, FeO = 0.05, MgO = 0.04, P2O5 = 21.05, SO3 = 22.76, (P + S) and 26 (O,OH) per formula unit (pfu), leads to the H2O (calculated in order to assess the charge balance) = chemical-structural formula: 23.60. The resulting chemical-structural formula, calculated 2+ [K0.002Na0.003Ca9.804Mn0.004Mg0.067Fe 0.054](P5.934S0.066) on the basis of basis of 2 (S+P) and 8 (O) in the anhydrous O23.929(OH)2.071. part of the compound, is: 2+ Note that the presence of carbonate substituting for phos- [K0.001Na0.001Ca1.992Mg0.004Fe 0.002](HPO4)1.021(SO4)0.979 • phate groups was ignored, because CO2 was not checked for. 4H2O. The infrared spectrum of the same sample gave, however, a The cell parameters, taken as mean of least-squares re- pattern typical for carbonate-hydroxylapatite, characterized finements on 6 different sets of X-ray powder reflections, are -1 -1 by OH stretching (3570 cm ) and librational (635 cm ) a = 5.718(3) Å, b = 30.998(24) Å, c = 6.248(5) Å and β = -1 -1 -1 bands, CO3 (ν3 1466 cm , ν3’ ~1430 cm , ν2 872 cm ) 117.17(5)°. -1 -1 -1 bands, and PO4 (ν3 1086 cm , ν3’ 1042 cm , ν1 955 cm , ν4 The textural relationships between the three calcium -1 -1 -1 604 cm , ν4’ 564 cm , ν2 472 cm ) bands. phosphates, observed by scanning electron microscopy and The cell parameters obtained by least-squares refinement energy-dispersive electron microprobe analysis suggests that of 59 X-ray powder (XRD) reflections obtained for a repre- their sequence of crystallization was from (carbonate-) hy- sentative sample are a = 9.438(3) Å, c = 6.868(3) Å and V = droxylapatite to brushite and finally ardealite. All the three 529.8(3) Å3. species clearly resulted from the reaction between the Brushite occurs as snow white powdery coating on hy- strongly acidic solutions derived from the guano mass and droxylapatite or as nodular earthy masses (several mm to 2 the cave floor or moonmilk flows. cm in diameter) in the bat guano mass, in which case the mineral is generally surrounded by hydroxylapatite. In terms
28 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MINICOLLECTIONS OF MINERALS – A CONTRIBUTION TO EDUCATING THE YOUNG GENERATION
EDELSTEIN, O. V. Babes 30A, RO-4800 Baia Mare, Romania. E-mail: [email protected]
Due to many reasons, the collections of minerals have an • No. 1 Volcanic rocks and minerals from the Baia important role in the education of the young generation. Mare region - Romania These collections contribute greatly to increasing the knowl- • No. 2 Minerals from Baia Mare – Romania and edge in various fields: Atacama – Chile • In chemistry, due to the fact that all minerals repre- • No. 3 Copper minerals sent chemical compounds, • No. 4 Semiprecious and ornamental gems from • In geography, due to the fact that a collection in- around the world I volves a clear specification of the location of the • No. 5 Semiprecious and ornamental gems from sample, around the world II • In history of civilization, because some minerals are • No. 6 Native elements part of ore deposits and they have influenced the • No. 7 Ore minerals from Romania evolution of people, geographic regions and periods • No. 8 Minerals from Romania – A field guide in human history. • No. 9 Aesthetic mineral samples from the Baia Collection of the minerals also involves collecting trips, Mare region – Romania which lead to new knowledge, better understanding of new • No. 11 Natural and synthetic gemstones. areas, and requires spending more time outdoors. The poster presents several mineral collections as fol- lows:
29 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
KAMPHAUGITE-(Y), A RARE HYDROUS Ca-Y-CARBONATE MINERAL FROM SZARVASKŐ, BÜKK MOUNTAINS, HUNGARY
FEHÉR, B.1, SZAKÁLL, S.2 & NAGY, G.3 1 Department of Mineralogy, Herman Ottó Museum, Kossuth u. 13, H-3525 Miskolc, Hungary. E-mail: [email protected] 2 Department of Mineralogy and Petrology, University of Miskolc, H-3515 Miskolc-Egyetemváros, Hungary. 3 Laboratory for Geochemical Research, Hungarian Academy of Sciences, Budaörsi út 45, H-1112 Budapest, Hungary.
Known localities of kamphaugite-(Y) 0.63, Dy2O3 4.91, Ho2O3 0.99, Er2O3 2.74, Tm2O3 0.50, Kamphaugite-(Y) – ideally Ca2Y2(CO3)4(OH)2 • 3H2O – Yb2O3 1.65, Lu2O3 0.43, Σ 70.47, which corresponds to was first described by RAADE & BRASTAD (1993) from Ca1.94(Y1.43Dy0.14Gd0.10Er0.08Nd0.07Sm0.05Yb0.05Ce0.03Ho0.03 Hørtekollen, Oslo region, Norway. The Hørtekollen deposit Eu0.02Tb0.02Pr0.01 Tm0.01Lu0.01)Σ=2.05 (CO3)4.03 (OH)1.97 • xH2O, is a contact metamorphic skarn deposit, where kamphaugite- where x = –1.94. CO3 and OH were calculated from charge (Y) is a late-stage phase in cavities of the rock. There are two balance and H2O was calculated from the difference. other occurrences of the mineral in Norway: a) Høydalen We can’t determine the degree of hydration of the Szar- granite pegmatite, Tørdal (RAADE et al., 1993); b) Tangen vaskő kamphaugite-(Y) from the electron microprobe analy- pegmatite quarry, Kragerø. ses, because ca. 10 wt% CO2 and H2O eliminated from the Outside Norway some additional localities of kamphau- sample when it decomposed under the electron beam. From gite-(Y) are known: 1) A Ca-Y-carbonate mineral was re- the chemical analyses a formula with 3H2O per 4CO3 has corded and identified as “tengerite” by STEPANOV (1961) been proposed by RAADE & BRASTAD (1993), but only from an undefined locality in Kazakhstan. 2) An unnamed 2H2O is implied from the structural investigation (RØM- Ca-Y-carbonate was discovered in a quartz-barite vein within MING et al., 1993). The 004 and 008 reflections of the XRD the carbonatized Goudini volcano, Transvaal, South Africa powder diagrams may have strongly variable intensities (VERWOERD, 1963). 3) The next locality is in the Evans- probably depending on water content. For the kamphaugite- Lou pegmatite, Quebec, Canada (HOGARTH, 1972), where (Y) with a lower water content the 004 reflection is always it was designated as UN-21. According to RAADE & BRA- clearly visible and 008 is strongly enhanced, whereas the 004 STAD (1993) the Ca-Y-carbonate minerals from the three reflection may or may not visible on X-ray films for water- localities given above represent kamphaugite-(Y). Recently rich kamphaugite-(Y) (RØMMING et al., 1993). Because on kamphaugite-(Y) was recorded by GAMBONI & GAM- the X-ray film of kamphaugite-(Y) from Szarvaskő the 004 BONI (1998) from Cala Francese, La Maddalena Island, reflection is visible and 008 is rather strong, this mineral Italy. There are some other unpublished localities of kam- contains probably less than 3H2O per formula unit. phaugite-(Y) without any additional data, e. g. Paratoo cop- In Szarvaskő kamphaugite-(Y) is a low temperature late per mine, Yunta, Olary Province, South Australia; Mt. Plo- stage mineral formed in the fissures of metagranite. There are skaya, Keyvy, Kola Peninsula, Russia. not any other members of this low temperature paragenesis except for calcite, however, it is never associated with kam- Kamphaugite-(Y) from Szarvaskő phaugite-(Y). The only primary REE-mineral of metagranite In Hungary kamphaugite-(Y) was found in the Tóbérc is an REE-bearing epidote group mineral (allanite?), which quarry (formerly Forgalmi mine) at Szarvaskő, Bükk Moun- could be the source of yttrium in the hydrothermal system. tains. It forms white globular aggregates up to 0.5 mm in Investigated kamphaugite-(Y) sample from Szarvaskő is diameter and white coatings on the walls of fissures of gran- preserved in the mineral collection of Herman Ottó Museum ite. Globular aggregates consist of 10–20 µm sized thick (Miskolc, Hungary) under catalogue number 25257. tabular crystals on {001}. Kamphaugite-(Y) is tetragonal with space group P41212 References (RØMMING et al., 1993). Observed reflections on the X-ray GAMBONI, A. & GAMBONI, T. (1998). Rivista Miner- powder pattern of Szarvaskő specimen are [d in Å (int., hkl)]: alogica Italiana, 1998/2: 27-28. 6.344 (s, 102), 5.438 (w, 004), 5.126 (w, 111), 4.405 (m, HOGARTH, D. D. (1972). Mineral. Record, 3: 69-77. 104), 3.534 (m, 202), 3.295 (w, 211), 3.198 (w, 212), 2.906 RAADE, G. & BRASTAD, K. (1993). Eur. J. Mineral., 5: (m, 107), 2.835 (m, 214), 2.742 (m, 008), 2.637 (s, 220), 679-683. 2.449 (w, 216), 2.033 (mw, 322), 1.926 (w, 324) and 1.890 RAADE, G., SÆBØ, P. C., AUSTRHEIM, H. & KRIS- (ms, 228). The experimental pattern was obtained with a TIANSEN, R. (1993). Eur. J. Mineral., 5: 691-698. 114.6 mm Gandolfi camera using CuKα radiation. Unit cell RØMMING, C., KOCHARIAN, A. K. & RAADE, G. data are a = 7.515 Å, c = 21.898 Å, V = 1236.5 Å3. (1993). Eur. J. Mineral., 5: 685-690. Six chemical analyses were carried out with JEOL JXA- STEPANOV, A. V. (1961). Trudy Kazakhskogo Nauchno- 733 electron microprobe operated at 20 kV and 40 nA. H2O Issledovatel. Instituta Mineralnogo Syrya, 5: 147-161. and CO2 couldn’t be directly determined because the amount VERWOERD, W. J. (1963). Ann. Geol. Surv. S. Africa, 2: of available material was very limited. A representative ana- 119-129. lytical result is the following (in weight per cent): CaO 20.07, Y2O3 29.72, La2O3 0.10, Ce2O3 0.93, Pr2O3 0.33, Nd2O3 2.13, Sm2O3 1.55, Eu2O3 0.53, Gd2O3 3.26, Tb2O3
30 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
TRACING GLAUCONITE FORMATION IN OLIGOCENE–MIOCENE SANDSTONES IN HUNGARY
FEKETE, J., WEISZBURG, T. G. & TÓTH, E. Department of Mineralogy, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary. E-mail: [email protected]
Glauconite formation has been a subject of lively debate of the clastic sedimentary rocks; (2) study the relationship for many decades. The results of recent seafloor studies between the iron content, density, magnetic behaviour, grain (ODIN, 1988) demonstrated the complexity of this process. size, structure and maturity of the glauconitic grains. In the frame of a larger research project on celadonite- The results confirmed the complexity of glauconitization. glauconite minerals the process of glauconite formation on The green grains, formerly handled as single phase clastic substrate was studied in details. “glauconite” (characterized by one chemical and XPD data Two glauconite-bearing clastic sedimentary formations set in one geological horizon) of the profiles showed high were selected for detailed study: the Upper Oligocene Eger variability in their physical, chemical and structural proper- Formation (south-western foreland of the Bükk Mountains, ties. North Hungary; two samples from different locations) and For example in one of the Oligocene samples (Nyárjas-1) the Lower Miocene Pétervására Sandstone Formation (north- the green grains were distributed over a density range of ern foreland of the Mátra Mountains, North Hungary; one 2.83–2.53 g/cm3. Their colour, even if it has faded a bit, was sample). The current presentation is to report the final results still characteristically green around the 2.53 g/cm3 density of the separation process and the preliminary results of the fraction. Even the lowest density fraction (<2.43 g/cm3) got a study of these separated mineral fractions. light green tint. The studied rocks are mostly cemented by calcite, thus The data indicate a density-grain size correlation, in the the first step of separation was acetic acid treatment (10% larger grain size fractions the population of the larger density solution). Each studied sample weighed approximately 1 kg. glauconitic grains is higher. After the treatment acetic acid was washed out of the sam- While the morphology of the different colour grains in ples. the different size fractions is very similar, the XPD patterns The second step was the separation upon grain size. The show a clear separation of the lowest density fraction (poorly following grain size fractions were obtained by wet sieving: crystallized, smectite-like pattern) and the fractions above >800 µm, 800–400 µm, 400–250 µm, 250–125 µm, 125– 2.53 g/cm3 (mica-like, still not very well crystallized struc- 63 µm, <63 µm. To enhance the disintegration of the grains, ture). the obtained fractions were gently shaken in an ultrasonic In some of the studied samples glauconitic grains repre- cleaner (for 5 minutes), then wet sieving was repeated. After senting a complete series of the stages of the glauconitization drying the samples, dry sieving was also applied. The frac- process could be found, while in others glauconite grains tions >800 µm and <63 µm were not subjected to further were present in only one dominant density/size fraction. separation due to their reduced importance concerning glau- Based on these differences autochthonous and allochthonous conitization. positions of glauconite could be assumed. The third separation step was magnetic separation. Each With the help of that systematic and complex separation grain size fraction was separated at (0.5), 0.6, 0.7 and procedure it has become possible to study glauconitic grains (0.8) A, depending on the magnetic behaviour of the sam- of different size, density and magnetic property separately. ples. Magnetic behaviour was different in the different grain We suppose that glauconitic grains of different size, density size fractions of the different samples. and magnetic character from the same glauconite population The fourth separation step was the separation upon den- represent different stages of glauconitization. By this highly sity. For this purpose, bromoform (tribromomethane) diluted differentiated study of a single glauconite population we by different amounts of ethyl alcohol was applied, resulting hope to get a deeper insight into the formation process of in the following density fractions in each formerly separated glauconites. fraction: (>2.83 g/cm3), 2.83–2.78 g/cm3, 2.78–2.73 g/cm3, This work was supported by the OTKA (Hungarian Sci- 2.73–2.68 g/cm3, 2.68–2.63 g/cm3, 2.63–2.58 g/cm3, 2.58– ence Foundation) grant #T25873. 2.53 g/cm3, 2.53–2.48 g/cm3, 2.48–2.43 g/cm3 and <2.43 g/cm3. Reference The fifth, last, step was the purification of samples by ODIN, G. S. (ed., 1988). Green marine clays. Development hand picking under the binocular. in sedimentology, 45. Elsevier, Amsterdam. This minute and rather time-consuming procedure en- abled us to (1) get an overview on the mineral composition
31 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MORPHOLOGY OF QUARTZ FROM PALEOGENE SEDIMENTS AT THE LOCALITY VEĽKÝ LIPNÍK, SLOVAKIA
FULÍN, M. Eastern Slovakian Museum, Hviezdoslavova 3, SK-041 36 Košice, Slovak Republic. E-mail: [email protected]
Marmarosh diamond (originally described as quartz phology of crystals the following types are distinguished crystals of pseudocubic shape) is one of the genetic types of (BAJOVÁ & FULÍN, 1989): quartz. In the north-eastern part of Slovakia, in the Inner- - Crystals with short prisms (length of prisms smaller Carpathian Klippen Belt Zone several occurrences of Mar- than 1/3 of the whole length of the crystals) marosh diamond have been described. The region of Veľký - Crystals with long prisms Lipník is one of the registered Marmarosh diamond locali- - Crystals with subordinate prisms ties. The clear crystals of quartz occur here in joints in grey- - Skeleton crystals black slates and in sandstones. The occurrence of Marmarosh With the study of crystal faces we tried to find out, diamond is here the result of a low-temperature (140– whether all the four morphological types described can be 190 °C) mineralization. An important condition for the regarded as Marmarosh diamonds (in genetical sense) or they mineral growth was the diagenesis of flysch. Water and represent other genetical types of quartz (ZACICHA et al., methane, products of diagenesis, influenced the crystal 1984). We studied 52 crystals above the size of 1.0 cm. We morphology. The variability of quartz crystals depends on calculated the reciprocal ratio of the crystal faces and com- changes at the joints during the growth. By the opening of pared these data between the crystals, so that we obtained the the joints the pressure and the chemical character of the character of the dominant crystal form. The results confirm solutions changed. The andesite volcanism in Poland near that the big crystals have the character of Marmarosh dia- Szczawnica played an important role, too (BAJOVÁ, 1987). monds, too. At Veľký Lipník quartz crystals of the range 0.5–5.0 mm predominate. Centimeter-size crystals are common here, too. References The largest crystal from this locality was 6.0 cm long and 4.0 BAJOVÁ, Ľ. (1987). Diploma thesis, KGaM BF VŠT cm wide. With the increasing crystal size, the typical mor- Košice. phological characteristics of Marmarosh diamonds (short BAJOVÁ, Ľ. & FULÍN, M. (1989). Zborník Výcho- ditrigonal resp. pseudohexagonal prism, two sides closed doslovenského múzea v Košiciach, XXX: 11–15. with area of positive and negative rhomboedra) change, their ZACICHA, B. V. et al. (1984). Naukova dumka, Kiev/Lviv: lustre and clarity decreases. The larger crystals show parallel 83–100. intergrowths and also skeleton habit. Very frequent are inclu- sions of methane and carbon dioxide. According to the mor-
32 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
POLISHED BASALT STONE TOOLS FROM HUNGARY
FÜRI, J.1, SZAKMÁNY, Gy.1, KASZTOVSZKY, Zs.2 & T. BÍRÓ, K.3 1 Department of Petrology and Geochemistry, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary. E-mail: [email protected] 2 Institute of Isotope and Surface Chemistry, Chemical Research Centre, Hungarian Academy of Sciences, P. O. Box 77, H-1525 Budapest, Hungary. 3 Hungarian National Museum, Múzeum krt. 14-16, H-1088 Budapest, Hungary.
Volcanic rocks were very popular as raw materials for samples. The first and second group has fluidal texture. stone tools in the Neolithic Age in the Carpathian Basin and There were clinopyroxene and sometimes a few olivine phe- its environs. Basalt and andesite were considered very good nocrysts, too, in the first group. The second group is similar for polished stone tools due to the good mechanical qualities to the first group, but with smaller pyroxene phenocrysts. In and the common occurrence of the raw material in the Car- the third group there were a lot of olivine phenocrysts, but pathian Basin. The main aim of our study was to determine their size and quantity were smaller than the clinopyroxenes. and characterise the different types of basalt polished stone In both cases the plagioclase formed the skeleton in the tools and localise the source region of the different types of groundmass, and there were small-size opaque minerals, basalt in Hungary by Prompt Gamma Activation Analysis clinopyroxene, apatite, chlorite and a variable quantity of (PGAA). Macroscopical, petrographic microscopical and glass among the plagioclase laths. geochemical studies were made on archaeological as well as The Prompt Gamma Activation Analysis measurements geological samples. Geochemical studies were made using were carried out at the Budapest Research Reactor, Hungary. PGAA which is a relatively new, sensitive and non- This measurement technique is based on the detection of destructive analytical method, therefore it may be useful on prompt gamma rays originating from neutron radiative cap- archaeological finds. ture or (n, γ) reaction. The method is suitable for determina- We have investigated 30 samples (17 archaeological tion of all the elements at the same time, however, with dif- samples; 14 basalt and 3 andesite, moreover 13 basalt sam- ferent sensitivity. PGAA measurements gave reliable data for ples from outcrops). The samples are from different geologi- the main components of basalt (SiO2, TiO2, Al2O3, Fe2O3, cal and archaeological age and locality. MnO, MgO, CaO, Na2O, and K2O) and some trace elements Basalt stone tools from several archaeological collections (B, Sc, V, Cr, Sm, Eu, Gd and Dy). Moreover, we could were selected from different parts of Hungary. All samples detect Cl, too. The advantages of the method are: it is abso- were studied by PGAA and petrographic investigation. The lutely non-destructive and the measurement requires no sam- examined samples originated from the Miháldy collection, ple preparation. 7 samples were measured in powder and Laczkó Dezső Museum (Veszprém), some pieces from Wo- massive form too, to check reproducibility and we got much sinszky Museum (Szekszárd), from Tápé-Lebő, Szolnok and more consistent data on the main element composition than Szentgál (Hungarian National Museum, Budapest; Dam- for the trace elements. janich Museum, Szolnok and Laczkó Dezső Museum, Vesz- Macroscopical investigation did not show a significant prém) and from a private collection from Mórágy. We col- difference between the samples. Moreover, the archaeologi- lected basalt from outcrops of the 4 main areas in Hungary, cal implements are typically heavily altered on the surface, where significant basalt occurrences suitable for tool-making because of being buried for a long time. The differences in can be found: notably, in the Mecsek Mts., the Balaton texture and mineral composition observed in the microscopi- Highlands, the Little Hungarian Plain and in the Nógrád- cal studies did not show any connection with the previous Gömör Unit. macroscopical grouping. Seemingly meaningful groups The archaeological basalt samples are macroscopically could be made on the basis of microscopical observation and grey or dark-grey, black in their colour, the cut surface is PGAA. usually darker, almost black. They are massive, fine-grained, We could form three groups of basalt by geochemistry and homogenous. The surface is sometimes heavily altered; and petrography. Two of them are clearly distinct and corre- therefore it has a lot of tiny holes because of the dissolution spond, on one hand, to Mecsek Cretaceous basalt (Group 1), of olivine and pyroxene. We can see small black (pyroxene) on the other hand, to young alkaline basalt (Group 3). Group and dark green (olivine) phenocrysts in the grey matrix. In 2 shares more features of the former, its interpretation, how- general, the smaller finds have more elaborate surface than ever, needs further studies. Another question raised was the larger pieces. We have investigated 3 fine grained dark separating macroscopically similar andesite polished stone andesite archaeological samples too, which were macro- tools from basalt. It was possible by microscopical investi- scopically very similar to the geological samples. gations and PGAA too, but the unbroken polished stone tools The mineral composition of basalt can be characterised can be studied preferentially by non-destructive methods, by plagioclases and clinopyroxenes, olivine, amphibole, and like PGAA. ore minerals also present. On the basis of microscopical features, we could distinguish three groups among the basalt
33 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MINERAL ASSEMBLAGES AND CRYSTALLIZATION OF THE KOSMAJ GRANITOIDS AND ITS ENCLAVES (SERBIA)
GAJIĆ, B.1 & VASKOVIĆ, N.2 1 Faculty of Forestry, University of Belgrade, Kneza Viseslava 1, YU-11000 Belgrade, Yugoslavia. E-mail: [email protected] 2 Faculty of Mining and Geology, University of Belgrade, Djušina 7, YU-11000 Belgrade, Yugoslavia.
On the southwestern slopes of the Mt. Kosmaj (North Su- can be considered as the temperature at which GRD and MD madija, Serbia) in an area of about 2.5 km2 a few smaller or magmas were completely crystallized or as a temperature of re- larger outcrops of granitic rocks are discovered. These occur- equilibration. rences expose a part of a granitoid pluton that intruded during The thermo-sensitive cation content in amphiboles (Ti Oligocene (29–30 Ma) into Upper Cretaceous flysch sediments. and AlIV) projected on the empirical temperature scale of The pluton occurs in the Vardar Zone Composite Terrane NABELEK & LINDSEY (1985) showed that temperatures (KARAMATA & KRSTIC, 1996). Its intrusion caused a 400– are not significantly different from those calculated from the 550 oC thermal contact aureole over an area of about 11 km2 at a amphibole–plagioclase geothermometer. pressure of 0.5–1.5 kbar. Among the mentioned granitoid occur- In order to place thermal constraints on the late-magmatic rences the most interesting one is outcropping in the Radovac crystallization at excess fluid composition CIPW normative of creek and its tributaries and can be traced for about 1 km. It is the Ab, Or, Qtz components of the Kosmaj granitoid rocks were characterized by a number of mafic igneous enclaves and frag- projected via an into the ternary residual system for PH2O = 3 ments of contact metamorphosed flysch sediments. kbar (JOHANNES, 1985). MD and D enclaves plot above the The granitoid rocks are medium- to fine-grained with binary Ab-Or minimum (765 °C) and close to M2, indicating megacrysts of K-feldspar (1–6 cm in length). The main min- lower water pressure (1–2 kbar). However, plotting these data eral constituents are K-feldspar (Or70.5-92.8), rarely microper- on to haplogranite diagram of PH2O = 2 kbar and aH2O = 1 thite and mirmekite, plagioclase (An39.7-14.8), quartz, amphi- (HOLTZ et al., 1992) results in a little bit different tempera- boles (magnesio-hornblende, edenite, actinolitic hornblende, tures, suggesting plagioclase fractionation joined by alkali- actinolite, XMg = 0.63–0.75), biotite (XMg = 0.53–0.57), and feldspar in the porphyritic types. Cotectic near minimum com- accessories are zircon, apatite, titanite and magnetite. Ac- position in rocks with An < 28% indicates water-excess crystal- cording to major element composition these rocks corre- lization which probably did not exceed 3 vol. % at temperatures spond to granodiorite (GRD) and tonalite (TON). between 720 and 680 °C. The mostly elliptic mafic igneous enclaves are irregularly The obtained results suggest that the main rock type (grano- distributed throughout the exposed mass. The enclaves usu- diorite) of the Kosmaj pluton crystallized in the temperature ally have a size of 1–10 cm. Their structure is quite different range of 640 ± 70 °C, and enclaves in the temperature range of from that of the incorporating granitoids: fine-grained or 760 ± 20 °C, under the pressure range of 0.5 to 1.5 kbar, indi- porphyritic. They are composed of plagioclase (An51.8-21,8), cating shallow-level emplacement (cca. 1.5 to 3 km) and con- K-feldspar (Or79-85), quartz, amphibole (magnesio- solidation under H2O-saturated conditions. hornblende, actinolitic hornblende; XMg = 0.65–0.76), biotite (XMg = 0.53–0.59); accessories are titanite, apatite and mag- References netite. Major element composition exhibits monzodioritic HOLLAND, T. & BLUNDY, J. (1994). Contrib. Mineral. (MD) and dioritic (D) character. Petrol., 116: 433-447. Pressure of 0.5 to 1.5 kbar and temperatures from 668 to 529 HOLTZ et al. (1992). Amer. Mineral., 72: 321-239. oC were calculated for GRD and TON and 740–620 oC for the JOHANNES, W. (1985): In”Migmatites” (Ed. Ashwort, MD enclaves, using hornblende and co-existing hornblende and J.R.), Blackie, 36-85. plagioclase compositions, respectively. The two feldspar geo- KARAMATA, S. & KRSTIC, B. (1996): In “Terranes of thermometer was calculated applying an average pressure of 0.5 Serbia and neighbouring areas” 25-40. to 1.5 kbar. The calculated temperatures range between 583 and NABELEK, C. R. & LINDSEY, D. H. (1985). Geol. Soc Am. 565oC (± 50oC) for GDR and 648–573oC (± 50oC) for MD Prog. Abst. 68384, 673. enclaves. These temperatures are lower than those calculated for the equilibrium of the amphibole–plagioclase assemblage and
34 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MIGRABITUMENS – THE LINK BETWEEN THE PODHALE TROUGH AND THE CRYSTALLINE BASEMENT OF THE WESTERN TATRA MTS.
GAWĘDA, A.1, MARYNOWSKI, L.1 & KĘPIŃSKA, B.2 1 Faculty of Earth Sciences, University of Silesia, ul. Bedzińska 60, PL-41-200 Sosnowiec, Poland. E-mail: [email protected] 2 Mineral & Energy Economy Research Institute, Polish Academy of Sciences, ul. Wybickiego 7, PL-30-950 Cracow, Poland.
The Tatra Mts. form one of the uplifted crystalline cores the lowest in the bitumens from the crystalline rocks and present in the Inner Western Carpathians. The allochtonous much higher in the Mesozoic and Tertiary rocks. That fact, crystalline basement is overthrusted by folded Mesozoic together with vitrinite reflectance measurements, point out unmetamorphosed sedimentary sequences. From the north the differences in maturity between bitumens and organic block of the Tatra Mts. is bordered by the Podhale Trough. matter from the Podhale and Tatra sedimentary rocks. The That structure is built up of Mesozoic basement (adequate to high level of organic matter maturity in the Podhale Trough the Tatra Mesozic cover) and Tertiary filling: Podhale Flysch caused the decomposition of biomarkers, so it is not possible and nummulitic Eocene limestones (KĘPIŃSKA, 1997). to compare the characteristics of source rocks for migrabitu- Several boreholes drilled the structure of the Podhale mens and Mesozoic and Tertiary rocks of Podhale. The pres- Trough. Apart from gas and oil manifestations sulphide ence of n-alk-1-enes was stated in both Mesozoic rocks and, thermal waters were stated here, too. Both the Tatra Mts. in lower concentrations, in bitumens from the tectonic zones. block and Podhale Trough are cut by the NE-SW trending The n-alk-1-enes are important markers of rock-oil migration tectonic zones. Some of the boreholes, cutting Podhale and secondary expulsion, especially in the rocks which un- Trough, are located roughly on/near the tectonic lineaments derwent the maturation processes to the level higher than Ro (Zakopane IG-1, Poronin PAN-1, Biały Dunajec PAN-1). = 1.2 %. They are usually enriched during the last stages of In the crystalline basement the presence of bitumens, en- crude oil expulsion. trapped in the quartz-sealed tectonic zones, were stated. Both Mesozoic basement rocks and Tertiary fill of the Bitumens are at oil window stage of transformation (RCS = Podhale Trough underwent the intensive maturation (level of 0.75–0.82) and contain biomarkers (steranes and hopanes), late catagenesis to early metagenesis) after the hydrocarbons conventionally used for the oil-source rocks correlation. expulsion. In this complex situation the correlation of the Possible source rocks for the bitumens were Upper Triassic – migrabitumen and source rocks was enabled only by the Lower Jurassic sedimentary rocks, deposited in the marine, occurrence of n-alk-1-enes and δ13C isotope data. The simi- oxic to suboxic environments (MARYNOWSKI et al., larity of isotope data and consequent changes of n-alk-1-enes 2001). along the NE-SW-trending tectonic lineaments, together with Rock-Eval analyses showed that rock samples from the the characteristics of Mesozoic sedimentary rocks led to the Podhale Flysch have the total organic carbon (TOC) content conclusion that Mesozoic (T, J) sedimentary rocks were the in the range 0.6–1.4 wt% and Tmax varying in the range from source of the investigated bitumens. 430 °C to 445 °C. All investigated Tertiary samples represent The migrabitumens from the tectonic zone of the crystal- the usually non-generative, III type of kerogen. Additionally, line basement of the Tatra Mts. are much less mature than the extractable bitumens from the Tertiary Podhale Flysch con- dispersed organic matter in the Mesozoic source rocks. The tain significant amounts of oleanes, which are absent in the preservation of primary molecular constitution was possible migrabitumens as well as in the extractable organic matter due to quartz sealing of the tectonic fractures and/or due to from the Tatra Mesozoic cover and Podhale Mesozoic base- the differences in heat flow in the western part of the Tatra ment. and Podhale complex. The Mesozoic basement rocks reached the transformation of dry gas window stage, with Ro changing from 1.1% (north References of Podhale) to 1.51% and 2.3% (south of Podhale). Organic KĘPIŃSKA, B. (1997). Polish Academy of Sciences – matter from the Mesozoic rocks of the Tatra block cover Monographs, CPPGSMiE, 48, Cracow. showed the mean Ro = 1.23%. MARYNOWSKI, L., GAWĘDA, A., CEBULAK, S. & GC-MS investigations revealed that thermally stable iso- JĘDRYSEK, M. (2001). Geol. Carpathica, 52: 3-14. mers of phenantrenes, terphenyls and phenylonaftalenes as well as the aromatic sulphur compounds concentrations are
35 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
TOURMALINES FROM THE CRYSTALLINE BASEMENT OF THE WESTERN TATRA MOUNTAINS (POLAND) – INDICATORS OF PARTIAL MELTING PROCESSES
GAWĘDA, A.1 & PIECZKA, A.2 1 Faculty of Earth Sciences, University of Silesia, ul. Bedzińska 60, PL-41-200 Sosnowiec, Poland. E-mail: [email protected] 2 Department of Mineralogy, Petrography and Geochemistry, University of Mining and Metallurgy, al. Mickiewicza 30, PL-30-059 Cracow, Poland.
Tourmaline is the most important mafic mineral in the The speculations about the source of boron resulted in pegmatites and leucogranites present in the crystalline base- two conclusions: ment of the Western Tatra Mts. Tourmalines are very ir- 1. the source of boron can be the decomposition of primary regularly distributed, spatially bound to the leucogranites B-bearing minerals (i.e. muscovite), (alaskites) and their pegmatites (GAWĘDA, 1993). They are 2. introduction of B-rich fluid could have occurred along the usual component of leucogranite pegmatites – as idiomorphic shear zone. and/or xenomorphic crystals, ranging from 0.3 cm to 8 cm in The temperature of crystallization, calculated according length. Tourmaline-rich lenses at the contact between leu- to tourmaline-biotite geothermometer (COLOPIETRO & cogranite and mica schists can be also found. Tourmalines FREIBERG, 1987) ranged from 490 to 515 °C. The 3+ are rarely present as small (up to 3 mm) dispersed crystals in Fe /Fetotal ratio varies in all investigated samples. The possi- folded mica schists, defining L2 lineation. Both leucogranites ble explanation for the different Fe-oxidation states can be and associated tourmaline occurrences are located in the presented in two ways: shear zones, cutting the metamorphic complex of the West- 1. Oxygen fugacity differed from place to place in the source ern Tatra Mts. which acted as a migration path both for the rocks due to their inhomogeneity and presence or lack of escaped melt and fluids. graphite. Because separate magma batches had no contact All tourmalines, found in the Western Tatra Mts., belong with each other, and there was no equilibrium in the to the schorl-dravite solid solution. They are saturated with metamorphic complex the original differences in oxygen respect to Al (Al in Y sites = 0.182–0.631 a.p.f.u.), poor in Li fugacity could have been preserved. (0.001-0.003 wt.%), with X-sites occupied mainly by Na 2. The magmatic/post-magmatic fluid interacted with the (0.564–0.801 a.p.f.u.), relatively poor in F (0.18–0.19 host rocks, forming a chemical gradient. Such gradient a.p.f.u.). The crystal zoning, typical of tourmaline group, is produced the internal zoning in the tourmaline nest and 3+ very poor. Some crystals are nearly homogeneous. But the the differences in the Fe /Fetotal ratio in the tourmalines. +3 chemistry and Fe /Fetotal ratio differ in different localities. Both possibilities are applicable for different localities. Fm parameter, defined as FeT/(FeT + Mg), of the investi- The irregular distribution of tourmalines is interpreted as gated tourmalines varies in the range 0.362–0.652. The low- a result of limited boron and water availability in the melted est values are typical of the internal zone of tourmaline-rich metasedimentary rocks and restricted mobilization of mafic lenses, while tourmalines from the outer part of the same lens (Fe, Mg) components. The escape of (B, H2O)-rich fluid are characterized by the Fm values in the range of 0.427 to phase along a zone of shearing was an additional factor, 0.508. The highest Fm values (0.513–0.652) are reported controlling the occurrences of tourmaline-bearing rocks. from tourmaline-bearing pegmatites. The origin of tourmalines is interpreted, in general, as References crystallization of B-rich portions of fluid, separated from the COLOPIETRO, M. R. & FREIBERG, L. M. (1987). Geol. anatectic leucogranite magma, formed by partial melting Soc. Amer. Abstr. Progr. 19: 264. (dehydration-melting of muscovite) of metasediments GAWĘDA, A. (1993). Arch. Miner. XLIX/2: 113-144. (GAWĘDA, 2001). The main factor was the reaction be- GAWĘDA, A. (2001). Monographs of the University of tween the B-rich fluid/melt and (Fe, Mg)-rich host rocks: Silesia, No. 1997, Katowice. + + Bt + AS + 0.5 Pl + V(BO3, H2O, Na2O ) = 0.7 Tr + K + 0.1 Ilm + 1.2 Qtz + Fe2O3.
36 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
NOTE ON THE RECORD OF AN UNKNOWN METEORITE FALL NEAR THE ORADEA FORTRESS (TRANSYLVANIA, ROMANIA) AT THE END OF THE 17TH CENTURY
GEORGIŢĂ, M. The National Archives of Romania, Cluj Branch, 10, Kogălniceanu St., RO-3400 Cluj-Napoca, Romania.
During the preparatives for a new siege of the Oradea seums and other collections that host fragments of some of fortress by the Austrian imperial army, an astronomical event these meteorites. was noticed by the upper-rank officers, who soon after that Until now, the oldest record of a meteorite fall in Roma- officially reported it to the emperor Leopold II. nia concerns the meteorite from Buzău (Magnus meteoriticus At the end of a long report on the current evolution of the Bozaianus), January 1714, that was mentioned by S. Köleséri war from Transylvania and on the requirements of supplies in his work “Auraria Romano-Dacica” but of which no sam- and equipment forwarded by general Veterani to the emperor ple was preserved (MAXIM, 1968). The Catalogue of Mete- on 20th April, 1692, a brief version of a note by general Au- orites (GRAHAM et al., 1985) indicates a meteorite fall near ersperg on a meteorite fall near Oradea was also included. Oradea, at Tăuţi, but the date of the fall is 1937 (p. 343); Count Auersperg was in that time the leader of the blockade Oradea refers in that case to the former district at the time of against the fortress, still occupied by the Turks. There he the fall, the present-day administrative affiliation of Tăuţi mentioned about a „fire ball” that was noticed in the skies on village being Arad district. April 8th around 10 p.m., that went beyond the blockade, If the information presented above is confirmed, the fall fortress and the army forefront, and finally landed in the from Oradea (1692) would represent the 11th and at the same woods in the neighborhood (…“Übrigens hat der Graff von time the oldest record on meteorite falls in Romania. Auersperg berichtet, dass den 8th dieses nachts um 10 Uhr bei Waradein ein feurige Kugel an dem Himmel gesehen worde, References welche sodann über unsere Schantz, die Festung und unsere GRAHAM, A. L., BEVAN, A. W. & HUTCHISON, R. Feldwachte in dem aldortige Wald gefallen seye”…)1. (1985). Catalogue of Meteorites. British Museum, Lon- Attached to the report there is a sketch showing the tra- don. jectory of the meteorite until the impact with the soil where, MAXIM, I. A. (1968). Studia Univ. Babeş-Bolyai, Ser. according to the drawing it was fragmented into several Geol.-Geogr., 13/1: 3-6. pieces. The meteorite in flames occurred from the clouds, its STANCIU, V. & STOICOVICI, E. (1943). Revista Muzeului trajectory being marked by „a fire tail” consisting of a multi- Mineralogic-Geologic Univ. Cluj, 7/1-2: 121-152. colored bright path. By comparing the sketch with a military map realized in May 1692, it can be concluded that the di- rection of the fall was probably NW-SE. Presumably Auer- sperg and his officers did the sketch. The size of the meteorite was compared to that of a 200 kg bomb. It may be assumed that the original size was larger, keeping into account the distance from where it was ob- served and the fact that the meteorite could not be recon- structed from its pieces after the landing. One can expect that supplementary data could be found in the military archives from Austria. Little chance exists to find geological evidence in the field, the place of the fall been now probably within the area covered by the present- day town of Oradea. Our note is also intended to be a signal for museums in the region that posses meteorite collections, where in a fortunate case, fragments of this meteorite could be identified. The importance of this information consists of the rarity and value of a meteoritic fall itself, but more than that, it could be the first mention of this type on the present-day territory of Romania. There are two reference papers con- cerning the meteorite falls in the Romanian territory: STANCIU & STOICOVICI (1943) give, besides the list of falls known at that time, a detailed description on the features recorded by eye-witnesses during the fall of six meteorites (Mădăraş, Cacova, Ohaba, Jădani, Mociu, Şopot) as well as petrographical and geochemical data. MAXIM (1968) adds to the previous list of falls four additional ones: Buzău, Târ- govişte, Târgu-Jiu – Câmpina, Tăuţi) and indicates the mu-
1 The National Archives, Bucharest (microfilms)
37 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
THE MINERALOGY OF THE NEOLITHIC CERAMICS FROM UNGURULUI CAVE (SUNCUIUS, ROMANIA)
GHERGARI, L., IONESCU, C. & LAZAR, C. Department of Mineralogy, Babes-Bolyai University, 1, Kogalniceanu Str, RO-3400 Cluj-Napoca, Romania. E-mail: [email protected]
The paper presents the mineralogical features of the rem- The arrangement of the lamellar minerals (micas, clay nants of Neolithic pottery found in clayish deposits covering minerals) inside the ceramic wall gives the structure, which the floor of the Ungurului Cave, located on the left side of can be: Crisului Gorge (Apuseni Mts.). From archaeological and • oriented, with the minerals arranged in rows parallel to mineralogical points of view, the ceramics from Ungurului the ceramic body surface; Cave is similar to the ceramics of same age, also found in the • non-oriented, with the minerals randomly arranged. western part of Transylvania, at Salca-Oradea, Piscolt-Carei, The surface of the pottery was smoothed and covered Zauan-Zalau (the archaeological characterization belongs to with a coloured slip, prepared from clay and calcite. SEM C. Ghemis from Oradea Museum). studies identified the presence of kaolinite, illite and il- The colour of the ceramic body varies from reddish- lite/montmorillonite. yellow to red, brown or reddish-brown. Granulometrically, the ceramics is mainly of semifine, rarely coarse and fine type. The fabric of the ceramic body (observed in thin sections) is microcrystalline-amorphous, reflected by a highly trans- formed clay matrix, which contains different clasts. The clasts belong either to the raw materials or were added as temper (sands). The clasts are represented by: • lithoclasts (fragments of andesites, quartzites, quartzitic schists, granodiorites, garnet mica schists, rhyolites and volcanic glass); • crystalloclasts (quartz, feldspars, biotite, muscovite as well as epidote-zoisite, calcite, zircon, garnet, titanite, tourmaline and amphiboles); • ceramoclasts (potsherds). Vegetal remnants (transformed into carbon) were also identified. The changes of the mineral compounds during the firing are mainly of middle-to-high temperature type, as: sinteriz- X-ray diffractometry reveals the presence of clay miner- ing, partial melting, recrystallizations, and changes of the als, quartz, calcite, feldspar, micas, magnetite (see figure). optical features. The clay minerals melted partially and gen- The changes noticed in the X-ray pattern for clay minerals, erated amorphous material or even supported some recrys- as well as microscopic studies, allow us to conclude that the tallizations. The iron oxides and hydroxides formed magnet- firing temperature for the Neolithic ceramics was around o ite and hematite. The birefringence of clay minerals changed 800 C (half-opened pits). as a function of the temperature of firing. At least three sources of raw materials were used: In cross section, the ceramic wall presents in general a bi- • a Jurassic kaolinitic clay from Suncuius deposits; layered texture, marked by an outer layer (lighter colour; • a Neogene kaolinitic-illitic clay with tuffs fragments oxidizing firing) and an inner layer (darker colour; reducing (from Borod Basin); firing). • soil formed on metamorphic rocks (Piatra Craiului area).
38 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
GEOARCHAEOLOGICAL STUDY ON LOCAL FINE CERAMICS FROM II-III CENTURY (NAPOCA SITE, ROMANIA)
GHERGARI, L.1, IONESCU, C.1 & RUSU-BOLINDET, V.2 1 Department of Mineralogy, Babes-Bolyai University, 1, Kogalniceanu Str, RO-3400 Cluj-Napoca, Romania. E-mail: [email protected] 2 National History Museum of Transylvania, 2, Daicoviciu Str, RO-3400 Cluj-Napoca, Romania.
Ceramic pottery made in Roman times and found in the The fabric (the arrangement of lamellar minerals) is in Napoca archaeological site (Transylvania, Romania) is ana- general oriented, as the ceramics is a wheel-made one. lyzed to establish a real classification as well as sources of The changes in the microscopic characteristics of the raw materials. minerals, the diffraction spectra and the SEM analyses indi- The colours of the ceramic body are quite homogenous: cate the temperatures of firing, which reached various do- red to yellowish-red or gray. The surface of the pottery is mains, between 850 and 1000oC for the red ceramics and smoothed and in general is not decorated, rarely vegetal about 1100 oC for the gray one. With few exceptions, the motifs being carved or pressed. The pottery is covered with a calcite is partly or totally decomposed. The feldspars and black or white, glassy slip. clay minerals show changes of their optical properties. The Granulometrically, the ceramics is lutitic-siltic, the ceramics fired over 950oC contains high amounts of glass as maximum diameter of the particles being less than 0.1 mm. the result of melting processes. In the gray ceramics, fired at The porosity of the ceramic body is low. higher temperatures, around 1100 oC, mullite crystals are also The microscopic studies, performed on thin sections, present. identified a microcrystalline-vitreous fabric, as well as the The provenance studies, based on the comparison of the main compounds: various clasts in a clayish matrix. The mineralogical–petrographical compounds (as temper, litho- clayish matrix present sinterizing or vitrification processes, clasts, bioclasts) and the features of the clayish rocks found in various degrees, function of the firing temperatures and nearby the location of the ancient city suggest the using of a the composition of the raw materials (SHEPARD, 1976). kaolinitic-illitic clay, with calcite content. Similar rocks of The lithoclasts (magmatic and metamorphic rocks), Badenian age occur to the north of the archaeological site. crystalloclasts (quartz, plagioclase feldspars, orthoclase, biotite, muscovite, heavy minerals), bioclasts (fragments of Reference globigerinid forams, echinid plates, nannoplankton) and SHEPARD, O. A. (1976): Ceramics for the archaeologist. ceramoclasts (potsherds) indicate both the composition of 9th ed. Carnegie Inst. of Washington, 414 p. raw materials and the temper used for ceramic paste.
39 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
TECHNOGENIC GEOLOGY – A NEW BRANCH OF EARTH SCIENCES
GOROVOY, A., DOROFEEV, V. & GOROVAYA, N. Donbass Mine-Metallurgical Institute, Lenin prospect 16, UA-94204 Alchevsk, Ukraine. E-mail: [email protected]
Huge quantities of industrial wastes have been accumu- multiple of limiting-allowable concentration (industrial con- lated in many countries of the world. Up to now, 2–3 x 1012 t centration) shows how many times the content of the toxic of industrial wastes have accumulated all over the world. (useful) element exceeds the limiting-allowable concentra- Wastes cover an area of approximately 16 x 106 hectares. Its tion (industrial concentration). The sum is the result of sum- quantity increases by 1010 t every year, 106 t every hour. ming the excess multiples of all toxic (useful) elements in the The wastes are objects of geological study, because geo- analysis, average is obtained by the division of the sum by logical processes (mainly weathering; in coal mine waste the number of the toxic (useful) elements. The chemical type dumps also reduction) take place in them. The study of of toxicity is defined by the most widespread element fol- wastes must form a new branch of earth sciences, which we lowed by its prevalence to a class and then subclass. Toxity offer to call technogenic geology. General task of this sci- (usefulness) can be presented as the formula of the three ence is the studying of geological processes in wastes. In that most widespread elements among toxic (useful) elements. frame we can list several processes, among others those The chemical symbol is surrounded by some parameters: the which depend on the composition (wastes of coal, ore, met- coefficient showing specific frequency of occurrence the allurgical and other industry) and on climate (humid, arid element is disposed in front of the chemical symbol; behind, etc), those which provoke the generation of mobile chemical in subscript the excess multiple of limiting-allowable con- compounds. The new branch can be further subdivided for centration (industrial concentration); behind, in superscript e.g. technogenic geochemistry (studying migration and ac- the element role among others. The graphical plot consists of cumulation laws), technogenic mineralogy (formation of new the general number of elements on the vertical axis and the minerals as it takes place e.g. in burning coal mine waste excess multiples on the horizontal axis. The received indices dumps), technogenic economic geology and metallogeny allow to determine the typomorphism, model, metallogenic (studying the concentration of elements etc. of industrial speciation of useful elements and the chemical composition importance), technogenic geoecology (studying the concen- (type, class and subclass) of toxic elements, quantities, com- tration of toxic elements). parison maps, chemical formulae and diagrams. Wastes may be the “technological” deposits of elements We studied the chemical composition of industrial wastes of major economic importance (e.g. workable concentrations (containing rocks, rock-coal mixture, pure coal and coal of scandium, germanium, lithium, silver and other elements ashes of Donbass mines, dumps, slags, slimes, soils around have been discovered in coal ashes), but may also be sources Donbass metallurgical plants and slags of some power sta- of environment pollution (by arsenic, lead, molybdenum and tions). We found very high concentrations of useful and toxic other toxic elements). elements (scandium up to 700 g/t, germanium up to 2000 g/t, We worked out methods for the evaluation of wastes lithium over 10000 g/t, arsenic up to 5000 g/t in coal ashes (usefulness/toxicity). and others). In the Northern Donbass mines coal ashes The offered estimation methods are based on the estab- “reserves” of antimony, beryllium, yttrium, cadmium, nio- lishment of useful and toxic indices and the determination of bium and silver are estimated to be around thousands of tons; several parameters. The useful and toxic indices are the gen- bismuth, zinc, copper, cobalt, molybdenum, vanadium, ger- eral number, composition, quantity, sum and mean of spe- manium, strontium, zirconium, scandium, gallium and ytter- cific frequencies of occurrence, sum and mean of the excess bium around tens of thousands of tons; titanium and lithium multiple of limiting-allowable concentration for toxic ele- around hundreds of thousands of tons. In reality the stocks ments (industrial concentration for useful elements), ranges can be even higher (by 25–30%). of useful and toxic indices, mean combined index (rating). It is possible to recover some metals simultaneously by The general number of toxic (useful) elements is the sum of one technology. In some coal mine fields up to 10 metals those chemical elements the contents of which exceed the have been revealed. Economic profit is obvious. If we as- limiting-allowable concentration (minimum industrial con- sume that 1 t of coal contains 20–30% coal ashes, in which centration). The specific frequency of occurrence shows how scandium content is 300 g/t, we can extract 60–90 g of scan- frequently the element is present in the analyses. The sum of dium from the ashes of 1t coal. The minimum price of 1 g of specific frequencies of occurrence is obtained by summing scandium is 10 USD. The price of 1 t coal is 20–25 USD, the specific occurrence frequencies of all elements in the while that of the extracted scandium is 600–900 USD. analyses, while the average is the result of the division of the sum by the number of toxic (useful) elements. The excess
40 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
THE PARTICIPATION OF MICRO-ORGANISMS AT THE FORMATION OF TODOROKITE FROM OXIDATION ZONE (TERÉZIA VEIN, BANSKÁ ŠTIAVNICA DEPOSIT, SLOVAK REPUBLIC)
HÁBER, M.1, JELEŇ, S.1, SHKOLNIK, E. L.2, GORSHKOV, A. A.3 & ZHEGALLO, E. A.4 1 Geological Institute, Slovak Academy of Sciences, Severná 5, SK-97401 Banská Bystrica, Slovak Republic. E-mail: [email protected] 2 East Geological Institute, Russian Academy of Sciences, Vladivostok, Russia. 3 Institute of Geology of Ore Deposits, Petrography, Mineralogy and Geochemistry, Russian Academy of Sciences, Moscow, Russia. 4 Institute of Palaeontology, Russian Academy of Sciences, Moscow, Russia.
Todorokite has been identified at the Terézia vein in the (probably glycokalyx, i.e. recrystallized microbial liquid) Banská Štiavnica ore field. Todorokite belongs to the young- was probably partially preserved, metasomatised by todoro- est minerals of the vein filling, confirmed by its position in kite. The well-preserved spheroidal remainders have an aver- the central part of the cluster cavities, often formed by per- age size of 3 to 10 µm. The various maculose clusters fect crystals of quartz. The grey-brown coloured, fine- (probably septa), cumulates, or the vertical off shoots can be grained aggregates of todorokite, having a characteristic observed on some fungus-like structures. metallic lustre, frequently fill the space among the crystals of Closely vertical layers with systems of oval cavities–gal- quartz and often form crusts up to 4 cm thickness. Some- leries, with fungus-like structures at the upper part of thal- times they form also spheroidal and reniform aggregates with luses and strongly cellular structures with the fungi (probably radial to fibrous texture, built up of very small needle-like basidia) of spheroidal shape, with a size up to 15 µm, were crystals. also observed. The cohesion’s knitting-through is observed The SEM images from reflected (back-scattered) elec- among the relatively compact thalluses, where the fibrous trons, obtained from various parts of sample under relatively structure is clearly seen. The thin fibres of the fungus-like great magnification, show that the sample is formed by structures are not always totally mineralised. plates, needles and tables of various length and width, and Up to now not exactly identified euhedral rhombohedral also by fibres and spheroidal aggregates of todorokite. crystals (probably Ca-Mn carbonates) were been formed at By scanning electron microscope (CAM SCAN-4) the the cavities of the cellular structures of the above described typical gradual stratifying of the aggregate of todorokite was aggregates. observed, which corresponds to the gradual natural forming The quantitative analyses of the sample were converted to of more layers within the aggregate. the following empirical formula of todorokite: 4+ 2+ 2+ Some layers are characterised by vertically curved basalt- (Na0.25K0.15Ca0.45Zn0.16)1.01(Mn 5.20Mn 0.45Mg 0.34)5.99O12·3 shaped crystals and among them are situated the cohesionless H2O. The quantity of water in the given formula and the interwoven mass of very thin fibres (probably mineralised distribution of cations within the formula is analogous with basidia). Their presence is confirmed by their carbon content the formula given by STRACZEK et al. (1960). The basic (Corg = 0.10–0.22%). Vertical structures with variable posi- diffraction lines are 9.58 Å (100), 4.82 Å (50), 2.45 Å (40), tion of bacteria-like structures are often also present and/or 2.360 Å (30), 1.971 Å (20), 1.422 Å (40). The structure is fungus-like structure clusters at upper parts of the layers. The nearest to the orthorhombic lattice with parameters: a = 9.75 thickness of the fungus-like structures is several tenths of µm Å, b = 2.84 Å and c = 9.6 Å (Z = 1). Nevertheless, at basic and the length several hundred µm. masses this todorokite is characterised by the disordered Other layers form remicated, strongly cellular and porous structure. It appears, that in the oxidised zone micro- fungus-like structures (thalluses) with marginal feathered and organisms participate also in the creation of todorokite (pres- globular termination, which probably correspond to basidia. ence of todorokite pseudomorphs of various parts of fungi, The thickness of these bacteria-like and/or fungus-like seldom a woodruffite mass). structures is up to 40–50 µm, the length of individual uni- cellular bodies is up to 200–300 µm. The terminal basidia reach the size of 15 to 30 µm. Reference Typically, there are also relatively large (20 to 40 µm) STRACZEK, J. A., HORER, A., ROSS, M. & WAR- spheroidal forms (clusters of identical, partly disturbed) SHAWCH, M. (1960). Amer. Mineral. 45: 1174-1184. spheroidal remainders of micro-organisms or bacteria-like and/or fungus-like structures. Here the bacterial mucilage
41 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
PETROGRAPHIC EVIDENCE TO EXTENSION OF THE PANNONIAN BASIN
HIDAS, K., FALUS, Gy. & SZABÓ, Cs. Lithosphere Fluid Research Lab, Department of Petrology and Geochemistry, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary. E-mail: [email protected]
Introduction mum similar to that of (001). The pattern of the (100) plains The Pannonian Basin is thought to have formed as a re- displays a single maximum perpendicular to the lineation in sult of a complex deformation history in the Middle-Late the foliation plain. Only very few orthopyroxenes display Miocene. Two major tectonic events have been recognized “normal” LPO pattern: (001) parallel to the lineation and the which determined the evolution of the basin: 1/ a rollback foliation and (010) perpendicular to both plans. Olivine effect of subduction in the Early-Middle Miocene (thinning LPO’s are normal, (100) plains are in the foliation parallel to factor was nearly the same for both the lithospheric mantle the lineation, whereas (010) is perpendicular to the lineation and the crust: β = δ = 1.4-1.6); and 2/ an asthenospheric and foliation, both show single maximum. mantle upwelling in the Late Miocene which caused a large- The orthopyroxenes are more resistant to recrystallization sized extension in the lithospheric mantle (thinning factor: than olivines (PASSCHIER & TROUW, 1998; MERCIER, δ = 4-8) at the central portion of the basin (HUISMANS et 1985) and may preserve earlier deformation states of the al., 2001). Subcontinental lithospheric mantle xenoliths col- mantle. Our results suggest that the observed orthopyroxene lected from the Bakony-Balaton Highland Volcanic Field patterns might be due to a deformation predating the defor- (central part of the Pannonian Basin) have been studied pet- mation that recrystallized the olivines in the mantle. The rographically to trace textural evidence of the large-scale orientations of the stress fields of the two deformations were mantle deformation events described. significantly different, almost perpendicular. These results correspond to geophysical modeling of Sample and techniques formation of the Pannonian Basin, as summarized HUIS- After looking at more than 300 mantle xenoliths from the MANS et al. (2001), and might provide the first petrographic Bakony-Balaton Highland Volcanic Field, one spinel lher- evidence that a two-stage deformation process formed the zolite xenolith from Szentbékkálla with a unique, special basin. tabular texture was chosen for a detailed microscopic study using universal stage. We measured lattice-preferred orienta- References tion (LPO) of orthopyroxenes and olivines on more than 100 HUISMANS, R. S., PODLADCHIKOV, Y. Y. & grains, respectively and our data have been projected and CLOETINGH, S. (2001). Tectonics, 20: 1021-1039. evaluated on a stereographic projection. MERCIER, J-C. C. (1985). Deformed Metals and Rocks: An Introduction to Modern Texture Analysis, Academic Results and conclusions Press, Inc., p. 471. LPO patterns of orthopyroxene show a (001) maximum PASSCHIER, C. W. & TROUW, R. A. J. (1998). parallel to the lineation in the foliation plain and another Microtectonics, Springer-Verlag, p. 251. maximum perpendicular to the lineation and the foliation. The pattern of the (010) plains also displays a double maxi-
42 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MINERALS AND MINERAL VARIETIES FROM METAMORPHOSED Mn DEPOSITS OF BISTRITA MOUNTAINS, ROMANIA
HÎRTOPANU, P.1 & SCOTT, P.2 1 Geological Institute of Romania, Caransebeş 1, RO-78344 Bucharest, Romania. E-mail: [email protected] 2 Camborne School of Mines, Redruth, Cornwall, United Kingdom.
The Bistrita Mountains belong to the Crystalline Meso- mation of some amphiboles and some pyroxenes into other zoic Zone of the East Carpathians, which consists of super- phases, there are drastical transformations of pyroxenes into posed Variscan and Alpine Nappes, overthrusted eastwards pyroxenoids (johannsenite into rhodonite), pyroxenoids into over the Flysch Zone. The manganese ore is contained by pyroxenoids (pyroxmangite into rhodonite), pyroxmangite Tulghes Group (Tg2 level) of the Variscan Putna Nappe, into manganogrunerite, garnets into garnets (spessartine- situated over the Pietrosu Bistritei Nappe and supporting the calderite into spessartine, spessartine into anisotropic spes- thrusting of the Rebra Nappe. All these Variscan nappes sartine-andradite-grossular), calderite into pyroxmangite- constitute the Alpine Sub-Bucovinian Nappe localised be- magnetite, etc. are the best evidences of continuous variation tween Alpine Infrabucovinian Nappe in the East and the of formation conditions. Alpine Bucovinian Nappe in the West. The Mn ore have a predominant carbonate rather than The mineralogy of Mn metamorphosed deposits from silicate mineralogical composition, which means a great CO2 Bistrita Mts. includes 328 minerals and mineral varieties. fluid control in the carbonation and dehydration processes They may count among the mineralogically the most com- along the many stages of the whole history of the ore and the plex deposits of the world. Prior to 1970 there were known Tg2 level. The mineral reactions for the tephroite assem- ca. 50 minerals. The mineral number grew in 1970-1976 blages were of decarbonation type, their temperatures were period to 70 minerals and in very recent period (1994-2002) strongly influenced by composition of metamorphic fluid, the mineral number reached 328. Minerals and mineral va- that is, the decarbonation reactions took place at high tem- rieties from almost all mineral classes have been identified: perature and high XCO2 (corresponding to amphibolite fa- carbonates 17, silicates 157, oxides 47, sulphides 48, sul- cies). phates 5, phosphates 11, wolframates 2, borates 1, arsenates The olivines, carbonates, Mn-humites, garnets, pyrox- 5, vanadates 1, native elements 1 and 33 minerals from oxi- enes, pyroxenoids, amphiboles, some oxides, some phyllo- dised zone. silicates and some sulphides offer useful petrological infor- The minerals and mineral varieties were determined by mation. Metamorphic reactions and P-T path of the Bistrita combined methods: X-ray, IR, AAS, SEM analysis and opti- ores suggest that they have undergone at least five stages of cal microscopy. Several of them are very rare species (nam- recrystallisation in a subduction zone. The clockwise trend of bulite, natronambulite, norrishite, bannisterite, parsettensite, metamorphism is in agreement to the structure of the compli- manganpyrosmalite, friedelite, schallerite, nelenite, minne- cated tectonic setting of the Crystalline Mesozoic Zone. sotaite, kellyite, etc.). A lot of determined minerals have Mn Many minerals are accessory phases having a scientific im- as major constituent: tephroite, manganese humite group portance, enriching the national mineralogical patrimony. (manganhumite, sonolite, alleghanyite), leucophoenicite In the Bistrita Mn-deposits three types of assemblages group (ribbeite, leucophoenicite, jerrygibbsite), some of the were determined on the basis of the bulk oxidation ratios: oxide group, manganiferous phyllosilicates group, etc. Many oxidised (i.e. containing Fe3+ and Mn3+), reduced (with Fe2+ are secondary, as they occur in veins or are product of retro- and Mn2+) and neutral, with Mn2+ and Fe3+. gressive transformation from the granulite to amphibolite Closely associated assemblages of diverse mineralogy facies, from the amphibolite to blueschist or greenschist from Bistrita Mn ore suggest that XMn and Xfluid rather than facies. Each metamorphic event was a source for new miner- physical conditions of metamorphism are the decisive factors als. Frequently, each mineral grain presents chemical varia- in forming the observed mineral diversity. The Bistrita tional function of P, T, fO2, fCO2, fCl2 etc. on the route of pro- metamorphosed Mn-rich mineral assemblages evolved under grade and retrograde polyphasic metamorphism. The zona- a variety of constraints, including the diversity in the char- tion of the pyroxenes and amphiboles – marginal and sectoral acter of the protolith and the nature of buffering of the fluid – is a good evidence of changes of metamorphic conditions. phase during metamorphism. Such a rich mineralogy when In the case of zoned amphiboles, the core is man- compared with the limited number of minerals occurring in ganogrunerite (amphibolite facies) and the rim is constituted the country rocks, make manganese ore from BM very of alkali blue amphiboles (blueschist facies). The sector- promising potential markers for P,T, fO2, fH2O, fCl, fB, fAs, etc. zoned arrangement of pyroxenes developed during rapid reconstructions, to supplement the country rocks mineral crystal growth and involved differences of both composition records (Tg2 level), strongly transformed or even erased by and cation order. It consists of bands or hour-glass texture of metamorphism. sodic augite and omphacite pyroxenes. Beside the transfor-
43 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MINERALS OF THE METAMORPHOSED Mn-Fe DEPOSITS IN ROMANIA: OLD DEPOSITS, NEW SPECIES
HÎRTOPANU, P.1, UDUBAŞA, G.1 & SCOTT, P.2 1 Geological Institute of Romania, Caransebeş 1, RO-78344 Bucharest, Romania. E-mail: [email protected] 2 Camborne School of Mines, Redruth, Cornwall, United Kingdom.
The main metamorphosed Mn-Fe deposits in Romania pore, groutite, etc. V. Carbonates: calcite, dolomite, rhodo- are hosted by metamorphic sequences of Upper Precambrian chrosite, kutnohorite, witherite, aragonite, magnesite, sid- (South Carpathians) and Lower Cambrian ages (East Car- erite, ankerite, Fe-rhodochrosite, smithsonite, azurite, mala- pathians) and their mineralogical composition is quite differ- chite; Borates: tusionite. VI. Sulfates: barite, khademite, ent, although the major minerals are the same, i.e. the oli- jarosite, rozenite, szomolnokite, gypsum, etc.; Wolframates: vines, rhodochrosite, pyroxmangite, rhodonite, etc: (1) Ra- hübnerite, ferberite; VII. Phosphates: hydroxylapatite, car- zoare Mn-Fe deposit (Preluca Mts, East Carpathians), sili- bonate-hydroxylapatite, Mn-apatite, chlorapatite, fluorapa- cate-carbonate-oxide-suphide (2) Dadu, Colacu, Oita, Tolo- tite, switzerite, brushite, monazite-(Ce), monazite-(La), evan- vanu, Puiu, Caprarie, Arsita, Argestru, Todireni, Sarisor, site, xenotime-(Y) (with Eu and Gd), variscite, etc.; Arsen- Dealu Rusului, Mandrileni, Ulm-Sihastria, Holdita, Brosteni, ates: magnussonite, sarkinite, johnbaumite, manganarsite, Borca Mn deposits (Bistrita Mts, East Carpathians), carbon- hedyphane, etc. Vanadates: Ba-vanadates. VIII. Silicates: ate-silicate-oxide-sulphide; (3) Pravat, Leucus, Bretan, A. Nesosilicates : 1.Olivine group: Mn-fayalite, Fe-tephroite, Strambu, Jigureasa, Valea Untului, Cugir Valley, Rovina, tephroite, Mg-tephroite; 2. Manganese humites: sonolite, Rascoala Mn-Fe deposits (Sebes Mts., South Carpathians), alleghanyite, manganhumite; 3. Leucophoenicite humites silicate-carbonate (subsaturated, queluzite) and silicate- group: ribbeite, leucophoenicite, jerrygibbsite; 4. Garnets: quartz (saturated, gondite); (4) Paltinis, Sadu Valley, Sadurel spessartine, spessartine-calderite, grossular, Ti-spessartine- Valley Mn deposits (Cibin Mts, South Carpathians), spessar- grossular, almandine, Mn-almandine, spessartine-andradite- tine type (gondite); (5) Delinesti Mn-Fe deposit (Semenic grossular, anisotropic spessartine-andradite, etc. 5. Zircon, Mts, South Carpathians), silicate-carbonate-oxide. About 350 thorite, titanite, greenovite, etc. B. Sorosilicates: 1. Yoshi- mineral species and mineral varieties have been identified in muraite, bafertisite, etc.; 2. Epidote-zoisite group: epidote, the mentioned deposits. By far the Bistrita occurrences are piemontite, allanite, Mn-allanite, zoisite, “thulite”, androsite- the richest in minerals, including rarities such as silicates- (La), etc. C. Cyclosilicates: 1. Tourmaline group: dravite, arsenates (schallerite, nelenite, etc.), Cl-bearing phyllosili- schorl, etc. D. Inosilicates: 1. Pyroxenes: Mn-ferrosilite, cates (manganpyrosmalite, friedelite, mcgillite, etc.), nambu- Mn-hedenbergite, johannsenite, Fe-johannsenite, augite, lite, bannisterite, androsite-(La), etc. not found yet in South diopside-augite, Na-augite, aegirine-augite, Ti-aegirine- Carpathian occurrences. In addition, the Bistrita minerals augite, aegirine, namansilite, etc.; 2. Pyroxenoids: pyrox- commonly show compositional zoning, which was used to mangite, rhodonite, nambulite, natronambulite, inesite, py- reconstruct the metamorphic evolution. roxferroite (?); Amphiboles: grunerite, manganogrunerite, The minerals from Romanian Carpathian metamorphosed manganocummingtonite, kozulite, magnesioriebeckite, mag- Mn-Fe ores belong to the following mineral classes: I. Na- nesiocummingtonite, “crocidolite”, riebeckite, winchite, tive elements: gold , bismuth, graphite; II. Sulphides: ala- ferroferriwinchite, ferro-anthophyllite, Li-eckermannite, bandite, hauerite (?), pyrite, chalcopyrite, galena, pyrrhotite, richterite, K-richterite, magnesiohornblende, arfvedsonite, cattierite, bornite, löllingite, tetrahedrite, tennantite, ferroglaucophane, “crossite”, Mn-actinolite, ferroactinolite, matildite, bournonite, semseyite, freibergite, boulangerite, Mn-tremolite, etc. E. Phyllosilicates: phlogopite, Mn- molybdenite, Bi arsenide with Cl, sulphide-arsenide with Cl, phlogopite with Ni, norrishite, biotite, Ti-biotite, Mn-biotite, Bi-telluride, tetradymite, skutterudite, matildite, nickeline, muscovite, kinoshitalite, anandite, illite, annite, chloritoid, cobaltite, linneite, kësterite, arsenopyrite, safflorite, geerite, bannisterite, Ba-bannisterite, ganophyllite, parsettensite, breithauptite, stannite, wurtzite, carrollite, glaucodot, ram- manganpyrosmalite, friedelite, caryopilite, schallerite, su- melsbergite, etc. III. Oxides: primary oxides: jacobsite, gilite, nelenite, minnesotaite, ottrélite, pennantite, clino- magnetite, bixbyite, braunite, neltnerite, hausmannite, pyro- chlore, greenalite, antigorite, kellyite, nimite, lennilenapeite, phanite, iwakiite, hematite, ilmenite, senaite (with Sr, Ca, V, coombsite, bementite, sepiolite, etc. F. Tectosilicates: 1. Nb and Zn), cassiterite, thorianite, högbomite, rutile, perov- Feldspar group: albite, microcline, celsian, hyalophane, or- skite, samarskite; quartz group: α-quartz, stishovite (?), coe- thoclase. 2. Helvite group: helvite, genthelvite, homilite. site (?), opal, moganite, etc. and secondary oxides: nsutite, For all the occurrences the metamorphic evolution is pyrolusite, ramsdellite, manganite, hollandite, lithiophorite, quite complex, generally showing several metamorphic manjiroite, goethite, ranciéite, todorokite, birnessite, coro- events, mainly of retrograde character. nadite, crednerite, cryptomelane, pyrochroite, asbolane, dias-
44 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
SUPRA-SUBDUCTION ZONE (?) BASALTS FROM THE DELENI-6042 DEEP WELL (TRANSYLVANIAN DEPRESSION, ROMANIA)
HÖCK, V.1 & IONESCU, C.2 1 Institute of Geology and Palaeontology, University of Salzburg, Hellbrunnerstr. 34, A-5020 Salzburg, Austria. E-mail: [email protected] 2 Department of Mineralogy, Babes-Bolyai University, 1, Kogalniceanu Str, RO-3400 Cluj-Napoca, Romania.
The Transylvanian Depression contains a number of gas such as plagioclase, pyroxene and olivine. The micro-ophitic fields, which were frequently drilled. Only a small number of groundmass, highly altered, contains microlites of plagio- drill holes penetrated the pre-Badenian formations. One of clase, small grains of pyroxenes and olivine as well as the deep wells, 6042-Deleni, was set up in the northern part opaque minerals (Ti-magnetite, hematite, goethite, etc.) and of the major Deleni gas field. Initially it was planned to reach altered glass. The structure is fluidal with the orientation of a depth of 6000 m for the well, but finally it stopped at 5062 the feldspar microlites in the direction of the flow. Basalts, m in Jurassic (?) basalts. The whole stratigraphic range of the brecciated basalts, basalts with olivine, vesicular and amyg- well involves Cenozoic (Sarmatian, Badenian) and Mesozoic daloidal basalts are the main petrographic types. Basaltic (Cretaceous and Upper Jurassic) rocks (Romgaz Archives, andesites occur subordinately. Media; unpublished data). It is shortly outlined as follows: Nineteen samples of the basaltic sequence between a Down to the depth of 2997 m the well penetrates Sarma- depth of 4742 and 5015 m were chemically analyzed for tian sands, sandstones and marls and Badenian rocks, repre- major, minor, as well as trace and RE elements. After some sented mainly by marls, and subordinately by sands. Several correction for the alteration (see also IONESCU et al., 2003) tuff levels were crossed for example the “Ghiris Tuff” in 924 the volcanics classify as basalts, basaltic andesites and ande- m and another tuff level at 1688 m. The presence of salt and sites with partly a low content of alkalies. Three groups can tuffs (“Dej Tuff”) levels marks the boundary between Ceno- be distinguished from top to bottom: a low Cr/high Zr group, zoic and Mesozoic rocks (2997 m). The Cretaceous deposits, a high Cr/low Zr group and finally a low Cr/low Zr group. mainly siliciclastics (marls, sandstones, silts, clays) are be- Other elements such as Ni, Y, Sr, Th etc. fit also with this lieved to include the Late Cretaceous and partly the Early grouping. The generally low contents of Zr, TiO2, Y as well Cretaceous. Beneath the Lower Cretaceous deposits, at a as a low Ti/V ratio (<20) argue for a formation of these ba- depth of 3660 m, Upper Jurassic carbonate rocks occurred in salts and basaltic andesites in a supra-subduction zone envi- the well. The oldest rocks overlaying the volcanic sequence ronment. The high Th/Yb ratio as well as the high Ce/Yb belong to the base of Kimmeridgian as exemplified by Al- ratio combined with a relatively low Ta/Yb ratio suggest a veosepta jaccardi, SCHRODT. calc-alkaline nature of these volcanics. Comparison with Starting with a depth of 4698 till 4742 m, strong under- other basaltic and andesitic volcanics in the South Apuseni ground eruptions of salt water and gases prevented the re- Mountains shows that the Deleni volcanics are obviously not covery of the drill cores. For the first two meters of the inter- genetically related with the ophiolitic basalts described by val, fragments of dolomites mixed with fragments of basalts SACCANI et al. (2001). On the other hand they might be were caught in the well-screens, but beneath the depth of quite well compared with some basaltic and andesitic vol- 4700 m only basalt fragments appeared. The first massive canics described by NICOLAE (1995) partly from the Ca- drill cores of the basaltic rocks are taken from the depth of palnas-Techereu Nappe and partly from Rimetea (Bedeleu) 4742 and continued till the depth of 5015.5 m. Because of Nappe (BALINTONI, 1997). technical problems, the recovery of the drill cores between the depth of 5015.5 and the final depth of 5062 m was very References poor, only basaltic fragments remained on the well screens. BALINTONI, I. (1997): The geotectonics of the metamor- The basaltic rocks, crossed by the well between the depth phic terraines from Romania. Ed. Carpatica, Cluj- of 4742 and 5015 m, are represented mainly by dark- Napoca, 176 p. (in Romanian) coloured, blackish-greenish basalts, in general with various IONESCU, C., HÖCK, V. & TOPA, D. (2003). Acta Miner- degrees of alteration, macroscopically marked by numerous alogica-Petrographica, Abstract Series 1, Szeged (this veins, nests and pseudomorphs with calcite ± iron oxides, volume). chlorite and serpentine minerals, microquartz, chalcedony NICOLAE, I. (1995). Rom. J. Tec. & Reg. Geol., 76: 27-39. and smectites (see also IONESCU et al., 2003). The volcanic SACCANI, E., NICOLAE, I. & TASSINARI, R. (2001). sequence is represented by massive basaltic lava flows; Ofioliti, 26: 9-22. sometimes they are brecciated, mainly in the upper part of the interval. In general, the rocks are poor in phenocrysts
45 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
REFINEMENT OF THE SYNGENITE STRUCTURE AND INVESTIGATION OF ITS HEATING AND MOISTURING PRODUCTS BY MEANS OF IR-SPECTROSCOPY
IL’CHENKO, K. O. Institute of Geochemistry, Mineralogy and Ore Formation, National Academy of Sciences, Palladine Avenue 34, Kyiv, Ukraine. E-mail: [email protected]
We studied the sulphate mineral syngenite, other type of SO4-groups has no water molecules in its near- K2Ca(H2O)[SO4]2, from Kalush, Ukraine, by IR- est surrounding. spectroscopy. On the IR-spectrum (obtained on KBr pellet) Six maxima in the region of ν3 vibrations and four in the the following absorption bands related to the S–O bonds of region of ν4 vibrations of the IR-spectrum of the deuterated the SO4-tetraheda were observed: ν3 (asymmetric stretch- sample represent a further argument in favour of the struc- -1 ings) 1190, 1138, 1126 and 1110 сm ; ν1 (symmetric tural non-equivalency of two SO4-groups. -1 stretchings) 1005 and 985 сm ; ν2 (bendings) 470 and The fractional loss of water on heating at 200 °C causes -1 -1 442 сm ; and ν4 (bendings) 675, 645, 605 cm and a shoul- some structural changes and at 250 °C anhydrous sulphate der near 620 сm-1. The broad band with the main maximum phases (?) forms. at 3315 cm-1 and the shoulders at 3520 and 3385 cm-1 are The mineral, moistened by water on air, slowly trans- usually attributed to the stretching vibration νОН of the water forms into gypsum. molecule, while the band at 1675 cm-1 to the bending vibra- tion δОН of the water molecule. The interpretation of the band at 750 cm-1 is not as obvious as those of the previous bands, since it could be caused both by one of the vibrations of the SO4-tetrahedra or the librations of the water molecule. The presence of four bands in each of the ν3- and ν4- regions and two bands in the ν1-region is possible if the two SO4-tetrahedra in the syngenite structure are not equivalent (CORRAZA & SABELLI, 1967). The factor-group calcula- 2 tion for Р21/m (C2h ) group, Z=2 yields two independent sets of vibrations: 2·[ν1(Вu) + ν2(Au+Bu) + ν3(Au+2Bu) + ν4(Au+2Bu)] that would be active in IR-spectra. However, the number of bands observed in the powder spectra is less than that of the calculated bands. To refine the structural position of the SO4-tetrahedra, IR-reflection spectra of the (100), Fig.1: IR-reflection spectra of the different faces of syn- (110) and (101) faces of a single crystal were obtained genite single crystal. (Fig. 1). Five out of six possible bands in the ν3-region were registered. The IR-spectra of deuterated syngenite display not only Reference the isotopic shift to the low frequencies of all bands related CORRAZA, E. & SABELLI, C. (1967). Zeit. Kristal., 124/6: to the water molecule, mentioned above, but also the shift of 398–408. a rather intense band from 750 cm-1 to 550 cm-1
(νОН/νOD=750/550=1.36). This allows assigning the latter band undoubtedly to the librating vibrations of the water molecule involved in hydrogen bonds with sulphate oxygen atoms belonging to one of the two different SO4-groups. The
46 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
ALTERATION PROCESSES ON BASALTS FROM THE TRANSYLVANIAN DEPRESSION, ROMANIA (DEEP WELL 6042-DELENI)
IONESCU, C.1, HÖCK, V.2 & TOPA, D.2 1 Department of Mineralogy, Babes-Bolyai University, 1, Kogalniceanu Str, RO-3400 Cluj-Napoca, Romania. E-mail: [email protected] 2 Institute of Geology and Palaeontology, University of Salzburg, Hellbrunnerstr. 34, A-5020 Salzburg, Austria.
A lot of boreholes were drilled in the Transylvanian De- feldspar microlites and a low amount of former glass in the pression (Romania) as it contains a number of gas fields. In groundmass. The phenocrysts as well as the groundmass the northern part of the Deleni gas field one of the deeper exhibit intense alteration processes, expressed by the forming wells (6042-Deleni) penetrated sedimentary formations and of smectite (Fe-rich saponite), microquartz and quartz with volcanics, reaching finally the depth of 5062 m. A more than disordered structure (chalcedony; FLÖRKE et al., 1991), 320 m thick pile of volcanic rocks underlays the Cenozoic magnetite, hematite, pyrite, chalcopyrite and calcite. and Mesozoic sediments between the depth of 4742 and 5062 The intermediate group with high Cr/low Zr also has a m. From the whole range of the volcanics a total of 34 m homogenous appearance, marked by the prevalence of were cored by Romgaz. From that, a total of 20 core samples amygdaloidal basalts with olivine (?) as well as with clinopy- could be studied in details by the courtesy of Romgaz. roxenes and plagioclase. The highly altered sub-ophitic and Various petrographic types were observed macroscopi- intergranular groundmass as well as numerous vesicles filled cally and microscopically, such as basalts, brecciated basalts, later with minerals, such as Fe-rich clinochlore, Fe-rich porphyritic basalt with phenocrysts of olivine (?), clinopy- saponite, nontronite, serpentine minerals, chalcedony, zeo- roxene and mainly plagioclase, vesicular and amygdaloidal lites, calcite, are characteristic. The phenocrysts of plagio- basalts. Combined with geochemistry basalts, basaltic ande- clase, olivine and clinopyroxene present highly different sites and andesites were identified. The general appearance is degrees of alteration. As opaque minerals, magnetite, chro- that of more or less compact, hydrothermally highly altered mite and pyrite occur. volcanics, with blackish-greenish colour, frequently crossed The uppermost level with low Cr/high Zr includes basal- by white, pinkish-white or greenish-grey veins and nests. tic breccias, basalts, basaltic andesites and andesites, the Spheroidal and ellipsoidal vesicles, empty or filled (amyg- latter displaying a higher amount of plagioclase microlites dales) with white, reddish or greenish-grey minerals (calcite, and no olivine phenocrysts. The intergranular to sub-ophitic chlorite, smectite and chalcedony) are also frequently pres- groundmass exhibits transformation processes, mainly into ent. The groundmass displays a sub-ophitic to intergranular calcite, chlorite minerals and subordinately into smectites. texture and contains microlites of plagioclase randomly ori- Oxide minerals are represented by magnetite, chromite, chal- ented or oriented in the direction of the flow. Furthermore, copyrite, hematite and pyrite. small grains of clinopyroxenes, titanite, opaque minerals Geochemically, the most conspicuous alteration is the (magnetite, ilmenite, chromite, hematite, pyrite, chalcopyrite, addition of calcite as expressed by a clear positive correlation goethite, etc.) and sometimes olivine occur. The former glass of CaO and CO2. Other elements such as Na, K, Rb, and Ba is changed to smectite. The phenocrysts of plagioclase and were also clearly affected by the alteration processes. All of clinopyroxene show often a glomerophyric structure. The them may be depleted or enriched. The observed mineralogi- phenocrysts change from very well preserved, slightly al- cal changes argue for relatively low temperature events. The tered, to completely replaced by calcite, chlorite and smec- causes for the hydrothermal alteration can be assigned either tite. to the postmagmatic fluids or to seawater. The temperatures Based on their geochemical features, three groups can be of 110–117 °C (4502 m depth), 122–130 °C (4902 m depth) distinguished (HOECK & IONESCU, 2003). They are from measured in the drill hole indicate that alteration processes bottom to the top: a low Cr/low Zr group, a high Cr/low Zr may still continue. group and finally low Cr/high Zr group. The differences between the groups are not very pronounced at a macro- References scopic scale. Nevertheless, some variability and various FLÖRKE, O. W., GRAETSCH, H., MARTIN, B., RÖLLER, degrees of alteration were identified in thin sections, by K. & WIRTH, R. (1991). Neues Jahrb. Min. Abh., 163: means of X-ray diffractometry, TEM and microprobe analy- 19-42. ses. HÖCK, V. & IONESCU, C. (2003). Acta Mineralogica- The lowest low Cr/low Zr group, is relatively homoge- Petrographica, Abstract Series 1, Szeged (this volume). nous with only microphenocrysts mainly of plagioclase. In general the basalts are characterized by a high quantity of
47 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
METASOMATIC-HYDROTHERMAL PROCESSES ALONG THE CONTACT ZONE OF A TEPHRITIC SILL AND BLACK SHALE IN THE EASTERN MECSEK MTS., SOUTH- HUNGARY
JÁGER, V. & MOLNÁR, F. Department of Mineralogy, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary. E-mail: [email protected]
In the Mecsek Mts., alkaline basaltic-phonolitic volcanic aggregates and infillings in amygdules. In the zone of ap- rocks and dykes of Lower Cretaceous age are widespread. pearance of biotite in knots, pyroxene disappears from the The alkaline igneous activity is related to rifting events con- rocks. Closer to the contact pyrite replaces biotite. About ten nected to the opening of Central European branches of the centimetres from the contact quartz appears in association Tethys Ocean. Alkaline dykes intrude into Lower-Middle with the amygdule-filling calcite. The maximum size of Mesozoic sedimentary rocks at many places of the Mecsek amygdules (1 cm diameter) occurs about 3–4 cm from the Mts. In the Réka valley, the area of this study, a tephritic sill contact. In addition to amygdules, occurrences of tubular intruded into a Toarcian, organic-material rich black shale. gas-cavities (also filled by calcite) are also typical to this This paper summarizes the mineralogical and petrographical zone which therefore can be considered as the zone of maxi- characteristics of the contact between the upper margin of the mum enrichment in volatiles. In the chilled margin, right sill and the covering shale. along the contact, amygdules are absent and the texture of Rock-forming minerals in the black shale are clay-, car- rock is microintersertal. The gradational change of texture bonate- and feldspar minerals associated with small amounts and mineral composition, together with the appearance of of quartz and pyrite. The sill consists of oligoclase, analcime, amygdules and their variation in size point towards the proc- Ti-augite and biotite as major minerals with apatite, pyrite ess of volatile enrichment of the crystallizing melt. The and titanomagnetite as accessories. Texture of the rock is source of excess H2O, CO2, and S is evidently the clay- ophitic-subophitic. Occurrence of small pegmatoid lenses mineral, carbonate and sulphide rich country rock. The (ca. 10 cm in diameter) is also typical for the sill. The peg- cooling fractures in the sill are parallel with the bedding of matoid lenses consist of anorthoclase, aegirine, aegirine- the black shale, thus not only chemical, but physical effect of augite, Ti-augite with aegirine coronas, biotite, analcime, the country rock on the sill can be recognised. The thermal titanomagnetite and apatite. Occurrence of these pegmatoids effect on the pore fluids of the black shale resulted in a vig- indicates enrichment of magmatic fluids in pockets during orous fluid circulation yielding hydrothermal brecciation of the final stage of crystallization. the shale along the contact. The breccia is cemented by The first signs of contact-metasomatic alteration can be quartz and calcite. Secondary fluid inclusions of these miner- found about 2 meters from the black shale in the tephritic als have homogenization temperatures around 120 and 130 sill. Here, calcite appears in the groundmass of the igneous °C. These inclusions with about 4–5 NaCl equiv. wt % salin- rock that develops intergranular texture. Towards the black ity mark the final stage of pore-fluid circulation. shale, the amount of calcite increases and calcite also appears The secondary mineral paragenesis was developed during in the form of infillings of amygdules which also start to weathering of primary and metasomatic-hydrothermal as- develop towards the contact. Increase of the amount of cal- semblages and it consists of hematite, limonite and gypsum. cite is also associated with the change of the rock texture The Ni-content of pyrite resulted in the formation of from intergranular to intersertal and then to intersertal- dwornikite during these late processes. amygdaloidal. Biotite occurs in groundmass far from the contact; however, close to the contact it forms knot-like
48 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
ORE MINERALIZATION OF THE BANSKÁ ŠTIAVNICA STRATOVOLCANO, SLOVAKIA
JELEŇ, S.1, HÁBER, M.1, KODĚRA, P.2 & LEXA, J.2 1 Geological Institute, Slovak Academy of Sciences, Severná 5, SK-974 01 Banská Bystrica, Slovak Republic. E-mail: [email protected] 2 Geological Survey of Slovak Republic, Mlynská dolina 1, SK-817 04 Bratislava, Slovak Republic.
The region of the Central Slovakian Neogene Volcanic of the Rozália mine and occurs as subhorizontal veins at the Field, with the biggest andesitic volcano Banská Štiavnica, base of pre-caldera stage andesites. Au mineralization is has served as an important source of precious and base met- represented by quartz, carbonates, sulphides, rhodonite, rho- als for a long time. The Banská Štiavnica stratovolcano, dochrosite, adularia and gold. It evolved during two stages, including an extensive subvolcanic intrusive complex, large both associated with the boiling of low salinity fluids (0–3 caldera and remarkable resurgent horst, hosts the following wt.% NaCl eq.) and moderate temperatures (290–310 ºC). types of mineralization: 1. High-sulphidation system at Šo- Variable pressure conditions (114–45 bars) indicate continu- bov, related to the subvolcanic diorite intrusion, 2. Magnetite ous opening of the system and transition from hydrostatic + skarn deposits and occurrences at contacts of a subvolcanic lithostatic towards hydrodynamic conditions at shallow granodiorite pluton with Mesozoic carbonate rocks, 3. depths. δ18O and δD values suggest mixing of magmatic Stockwork/ disseminated base metal mineralisation along an fluids with meteoric waters that have intermediate composi- irregular network of fractures in apical parts of the granodio- tion between granodiorite-related and horst-related hy- rite pluton and in remnants of basement rocks, 4. Por- drothermal systems in the ore district (KODĚRA et al., phyry/skarn Cu±Mo, Au deposits and occurrences related to 2002). granodiorite/quartz-diorite porphyry dyke clusters and rock Horst-related vein type low sulfidation epithermal pre- around the granodiorite pluton, 5. Caldera collapse related cious and base metal mineralization in more than 120 veins epithermal gold deposit in the andesitic environment just mainly occur in propylitized pyroxene andesites, diorites, above the granodiorite pluton, 6. Hot spring type advanced quartz-diorite porphyries and granodiorites. In the ores argillic systems in caldera filling, 7. High sulfidation system sphalerite, galena, pyrite, chalcopyrite and hematite are of Varta related to an assumed granodiorite porphyry stock, widespread, accompanied by sulfides, selenides and tellu- 8. Vein type low sulfidation epithermal precious/base metal rides of Ag, sulfosalts of Ag-Cu-Pb-Bi-S and Ag-Cu-Sb-As- deposits and occurrences at faults of the resurgent horst, 9. S, native gold, silver, electrum etc. The ore-forming proc- Replacement precious /base metal mineralization of a limited esses evolved during five stages and were accompanied by extent in the Mesozoic carbonate rocks next to epithermal concomitant decrease in temperature, salinity, oxygen and veins, 10. Carlin-like Au±Hg, Tl, Sb, As mineralization in sulphur activities. The minerals precipitated from low-to- Triasic dolomites at Bukovec, 11. Low temperature Au±Hg, moderately saline aqueous solutions (0.2–11.5 wt.% NaCl Sb, As mineralization in rhyolite extrusive domes around the eq.) with NaCl, CaCl2 and MgCl2 as the major solute compo- resurgent horst (LEXA, et al., 1999; LEXA, 2001). nents. Different eutectic temperatures estimated in the upper Precious and base metal, vein-type mineralization and parts of the veins indicate mixed sulphate-carbonate compo- iron skarn mineralization were the most abundant and eco- sition of the mineral-forming solutions. Mineralization was nomically most important mineralizations in this region. formed at temperatures from 380 to 50 ºC, pH from 3.5 to Magnetite skarn deposits and occurrences are situated 7.6 in depth from 0.4 to 1.6 km. The assumed age of the mostly in the western part of the horst and were the subject mineralization is 12.1–11.2 Ma (K-Ar method), resp. 12.8– of medieval mining. Two types of skarns are present: the 11.2 Ma (Rb-Sr method) (HÁBER et al., 2001). magnesian type and calcic type. Mineralization formed dur- ing three basic stages: initial, with the garnet, diopside and References wollastonite assemblage (epidote and tremolite further from HÁBER, M., JELEŇ, S., KOVALENKER, V. & the contact), metasomatic, with the epidote, tremolite, andra- ČERNYŠEV, I . (2001). Miner. Slov., 33: 215-224. dite and magnetite assemblage and retrograde, with the zonal KODĚRA, P., LEXA, J., RANKIN, A. H. & FALLICK, A. garnet, hematite and minor magnetite assemblage. Fluid E. (2002). Geol. Carpath., 53: 94-96. inclusions from skarn garnets show a large variation in salin- KODĚRA, P., RANKIN, A. H. & FALLICK, A. E. (1999). ity (4–23 wt.% NaCl eq.) and Th (220–370 ºC), independent In: Mineral deposits: processes to processing, Stanley et of the garnet types, reflecting variable amounts of magmatic al. (eds). Proc. joint SGA-IAGOD conf. vol. 1, 51-54. fluids and low salinity meteoric waters. Inclusions in retro- (Balkema Press) grade stage minerals showed boiling and dilution processes, LEXA, J. (2001). Miner. Slov., 33: 203-214. further indicated by O and H stable isotope data (KODĚRA LEXA, J., ŠTOHL, J. & KONEČNÝ, V. (1999). Miner. et al., 1999). Depos., 34: 639-654. Caldera collapse related epithermal Au-mineralization is located at depth of 400–500 m below the surface at the area
49 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
THE PECTOLITE SKARN FROM MIĘDZYRZECZE (BIELSKO-BIAŁA REGION) IN THE POLISH CARPATHIANS
KARWOWSKI, Ł. & WŁODYKA, R. Department of Geochemistry and Petrology, University of Silesia, ul. Będzińska 60, PL-41-200 Sosnowiec, Poland. E-mail: [email protected]
In the western part of the Outer Polish Carpathians, be- There are two genetic types of pectolite: open-space fill- tween Bielsko-Biała and Cieszyn, the occurrence of ing and metasomatic. Pectolite, like datolite, can crystallize teschenite sills and related rocks (diabase, picrite and lam- only from solutions with very low concentrations of CO2, i.e. prophyre) were observed. They are widely distributed in the in zones of reduced pressure, where degassing of CO2 takes flysch sediments of the Cieszyn Subnappe (Cieszyn beds, place. In the veins intersecting the skarn body pectolite forms Upper Kimmeridgian to Hauterivian). irregular massive aggregates of radial or fan-arranged crys- In Międzyrzecze Górne near Bielsko-Biała, close to the tals with size between a few millimeters and 12 cm. Large, top of the picrite sill, the presence of a pectolite skarn was up to 6 cm long, fibrous (with diameter below 0.01 mm) or stated. The pectolite endoskarn forms a lenticular body that is needle-shaped (up to 0.03 mm) crystals are white and silky. up to 2 m thick, 5 m wide and 12 m long. Abundant carbon- The second, metasomatic type of pectolite forms the endo- ate veins (up to 30 cm thick) intersect the central part of the skarn body. The formula of the fibrous pectolite from the skarn filling the tectonic fissures and cracks. The pectolite centres of vein in endoskarn is Na0.98Ca2.00H1.01Si2.99P0.01O9. skarn consists mainly of elongated (up to 2 mm long and to There are small chemical differences between two genetic 0.5 mm wide) pectolite crystals which poikilitically enclose types of pectolite. The metasomatic type is enriched in abundant inclusions of Ti-garnets, diopside, analcime and Al2O3, FeO, MnO, and MgO compared to the open-spaces aegirine. Poikilitic biotite crystals with inclusions of Ti- filling type. Pectolite from the Międzyrzecze sill is triclinic garnets sometimes coexist with other minerals such as natro- with the following lattice parameters: a = 7.986 Å, b = 7.017 lite, calcite, apatite and titanite. Veins cutting the skarn body Å, c = 7.021 Å and α = 90.399o, β = 95.208o, γ = 102.554o. contain calcite, pectolite, natrolite, analcime, datolite, Ti- In the pectolite skarn, two types of Ti-bearing garnet can garnet and apophyllite. The spatial relationships between the be distinguished: above mentioned minerals suggest that natrolite and anal- 1. Brown-black euhedral crystals (<0.02 mm) forming in- cime were the first to crystallize forming the vein margins, clusions in pectolite, biotite, titanite and diopside or filling being followed by calcite. Pectolite, likewise datolite and open spaces in veins. apophyllite always formed after calcite had filled open 2. Larger (up to 0.7 mm across) atoll-shaped garnets spaces in the vein centres. showing narrow black-light brown rims completely distinct Datolite from Międzyrzecze occurs mainly as granular from cores consisting of spicular aegirine and a cryptocrys- aggregate, rarely as automorphic crystals up to 1 cm in size, talline mixture of natrolite and analcime. These garnets are pale green in colour. Three morphological types of datolite clearly metasomatic type Ti-garnets. Both types of garnet crystals were distinguished: pseudo-bipyramidal, prismatic from the pectolite skarn show very restricted changes in TiO2 and pinacoidal. Most of the datolite crystals are 0.5–0.8 cm content (12–15 wt%). Textural and chemical evidence shows in size and belong to the second type. They crystallized on that the atoll garnets reflect replacement, mainly by analcime the walls of miarolitic cavities within calcite. On basal pina- and natrolite, progressing from the garnet interior towards coid faces of datolite numerous fluorapophyllite crystals the garnet margins. The garnet compositions plotted on the appear. Its chemical composition follows the crystallochemi- schorlomite (2R4+) – andradite (2R3+) – morimotoite (R2+R4+) cal formula (K0.86Na0.03)0.89 Ca4.03 (Si7.91Al0.04P0.03)7.98 (F0.83 diagram show that they are titanian andradites according to OH0.17)1.00O19.92 • 8.08 H2O. The datolite habit changes from the nomenclature of DEER et al. (1982). The data obtained pseudo-bipyramidal through prismatic to pinacoidal with pH support the conclusion that the schorlomite substitution was decrease. In the Międzyrzecze skarn, in individual cavities, the major factor in the formation of Ti-bearing garnet in the datolite crystals of different habit coexisted. This situation skarn from the Międzyrzecze sill. may reflect the local, labile conditions of datolite crystalliza- tion in the open system. The studied datolite has monoclinic References symmetry with the following lattice parameters: a = 4.8316 DEER, W. A., HOWIE, R. A. & ZUSSMAN, J. (1982). Å, b = 7.6054 Å, c = 9.6287 Å and β = 90.143o. Its chemical Rock-forming minerals. Vol. 1A. Orthosilicates (2nd ed.) composition is close to the theoretical one, among trace ele- KUDĚLÁSEK, F., MATYSEK, D. & KLIKA, Z. (1987). ments barium and strontium predominate. Datolite from Čas. Mineral. Geolog., 32(2): 169-174. Międzyrzecze is similar in composition to those from Žer- manice and Řepiště (Northen Moravia) (KUDĚLÁSEK et al., 1987).
50 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
PALEOCLIMATOLOGICAL STUDIES ON TRAVERTINES FROM BUDAKALÁSZ (BUDA MTS., HUNGARY): EVIDENCE FROM STABLE ISOTOPIC DATA
KELE, S.1, VASELLI, O.2 & SZABÓ, Cs.1 1 Lithosphere Fluid Research Lab, Department of Petrology and Geochemistry, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary. E-mail: [email protected] 2 Department of Earth Sciences, University of Florence, Florence, Italy.
Introduction Results and conclusions Travertines from the Pannonian Basin have been studied Based on petroghraphic and microfacies analyses, the for almost one hundred years. However, principles, concepts Budakalász travertine samples of the three sections studied and technical background in geology have been dramatically can be divided into two stratigraphic groups. The lower part changed during the past decades. As a consequence, beside of each section (approx. 15 meters thick) consists of massive stratigraphic and microfacies descriptions, valuable informa- travertine that represents smooth slope facies, and in the tion can be contributed to paleohydrological and paleocli- terrace pools, shrub facies as the result of bacterial activity. matological studies by using geochemical and stable isotope The whole lower part of the sections is characterized by data obtained on travertines. The major goal of this work is values of δ13C(PDB) = 2.2‰ and δ18O(PDB) = –12.1‰. The to carry out a detailed C and O stable isotope study on Buda- upper part of the beds studied represents marsh pool facies, kalász travertine (Buda Mts., Hungary) in agreement with deposited from a small lake, and has values of δ13C(PDB) = previous microfacies analyses (KOVÁCS, 1995) to find out 1.7‰ and δ18O(PDB) = –10‰. Between the lower and upper the origin of CO2 in water from which travertine deposited. parts of the sections calcareous mud layers were observed inferring to terrestrial period and could have been a relatively Geological background, sampling and applied techniques long break in deposition. Based on the isotopic data, and The Pleistocene Budakalász travertine deposit lies on using PENTECOST’s (1995) classification, the Budakalász early Oligocene Hárshegy Sandstone and Kiscell Clay For- travertine is thermogene fresh water limestone which formed mations. Early Pleistocene limnic clay and gravel terrace can presumably associated with late activity of the Miocene be found under the limestone suggesting a former limnic and volcanism widely recognized around the studied area. fluvial environment (SCHEUER et al., 1987). The travertine is covered by a few meters thick loess and overlain by a thin References humus layer. The Ezüsthegy quarry is approximately 800 KOVÁCS, A. (1995). M.Sc. thesis, Eötvös University, Bu- meters long and 15–20 meters high. Sixty travertine samples dapest, Department of Applied and Environment Geol- have been collected at three vertical sections of the travertine ogy. quarry. Microfacies and petrographic analyses have been PENTECOST, A. (1994). Quaternary Science Review, 14: performed on some samples. Selected travertines were ana- 1005-1028. lyzed for δ13C and δ18O using Finningan 250 MAT Delta-S SCHEUER, Gy., SCHWEITZER, F., & SZLABÓCZKY, P. mass-spectrometer. (1987). Építőanyag, 39: 102-107.
51 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
ENVIRONMENTAL RADIOLOGICAL ASPECTS OF THE COAL MINING IN PÉCSBÁNYA (SOUTH HUNGARY)
KÓBOR, B.1, GEIGER, J.2 & PÁL MOLNÁR, E.1 1 Department of Mineralogy, Geochemistry and Petrology, University of Szeged, P. O. Box 651, H-6701 Szeged, Hungary. E-mail: [email protected] 2 Department of Geology and Paleontology, University of Szeged, P. O. Box 651, H-6701 Szeged, Hungary.
It has been known since the first set of Hungarian radio- mer, and 85 nGy/h in the wet, cold winter. The values of logical and geochemical research carried out in connection total-gamma dose-capacity in the areas currently being with uranium prospecting that the radioactive element con- stripped are 45–55% and on the waste stockpiles 20–25% centration of some coals (some brown coals in the Tatabánya higher than those of the distant surroundings. Those waste Basin, the coal of Ajka, and the Liassic coal in the Mecsek stockpiles which are permanently landscaped and covered Mts.) are significantly above the average (SZALAY, 1962). with a 40–60 cm thick soil layer absorb the radioactive over- During the 200 years of coal mining in the vicinity of Pécs dose almost entirely: values measured there are higher than (Mecsek Mts., South Hungary) materials with radioactivity the radioactive “zero level” by a mere 2–5%. The highest levels higher than that of the environment were brought to levels of total-gamma radiation were measured on old the surface in vast quantities. The exact radiological assess- burned, parched dumps, which are often left uncultivated. ment of the areas in question, the maintaining of the radioac- Mining raises the radioactivity levels of the close surround- tive “zero level” of the territory, and the determination of the ings by 20–25%. quality and quantity of the radioactive over-radiation of the The gamma-spectrometric measurements of the collected population is necessary for the successful and effective re- rock specimens under laboratory conditions reveal that the cultivation of the areas affected by mining. higher level of radiation is caused by the high K40-content in We carried out total-gamma dose-capacity scaling and the case of claystones, aleurolites and sandstones, and by gamma-spectrometry survey in a 50 x 50 metre grid in ac- high uranium and thorium content in the case of coal and cordance with the proposals of the International Atomic coal sandstones rich in organic matter. Out of the rocks of the Energy Agency (IAEA), in the Pécsbánya Karolina opencast opencast mine, those rich in clay minerals and organic matter mining area, in the neighboring uncovered, landscaped, and at the same time, have the highest K40 and Th content above uncultivated dumps, coal stocks, as well as in the entire area the global average (SWAINE, 1990). of the town of Pécsbánya. As a result of our winter-summer “in situ” measurement series we constructed the total-gamma References dose-capacity map of the Karolina opencast mine and its SWAINE, D. J. (1990) Trace elements in coal. Butterworths. surroundings for winter and summer, characterised by sig- London. 278 p. nificantly diverse meteorological conditions. According to SZALAY, S. (1962): Papers of the Engineering Department our findings the radioactive “zero level” of the distant sur- of the Hungarian Academy of Sciences. Budapest, pp. roundings of the opencast mine in relation to the total- 168-185. gamma dose-capacity is 90–92 nGy/h in the dry, hot sum-
52 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
PETROLOGICAL AND GEOCHEMICAL ARGUMENTS FOR THE NATURE AND SOURCE OF THE SZARVASKŐ COMPLEX (NE-HUNGARY)
KOLLER, F.1 & AIGNER-TORRES, M.2 1 Institute of Petrology, Geo-Center, University of Vienna, Althanstraße 14, A-1090 Vienna, Austria. E-mail: [email protected] 2 ETH-Zürich, Sonneggstraße 5, CH-8092 Zürich, Switzerland.
The Szarvaskő complex exposes a fragment of Jurassic magmatic mineral assemblages cannot be related solely by mafic and ultramafic igneous rocks (DOWNES et. al., 1990). fractionation of a common MORB source only. They repre- They have been described as a dismembered portion of a sent a combination of a MORB-like fractionation of oli- Mesozoic ophiolitic sequence formed in a narrow basin of vine+plagioclase+clinopyroxene±chromite and a minor, but the Vardar Ocean (AIGNER-TORRES & KOLLER, 1999). still important influence of assimilated terrigeneous sedi- The magmatic sequence consists mainly of extrusive basaltic ments abundantly present in the area. The most interesting pillow lavas together with gabbroic sills intruding into terri- minerals in the plagiogranites are strongly zoned almandine geneous shales, and minor ultramafic and plagiogranite rocks rich garnets and an Fe-rich epidote with high amounts of (BALLA et al., 1983, AIGNER-TORRES & KOLLER, REE, both are of magmatic origin. 1999). The basalts and some of the gabbros show fraction- The presence of the rare ultramafic cumulates and the ated N-MORB-like patterns with a low Nd, indicating a plagiogranites beside the common pillow lavas and various possible enriched source component. Some of the gabbros gabbros with N-type MORB composition are still the best and the unusual ultramafic rocks, described originally as arguments for an ophiolitic nature of the Szarvaskő complex. wehrlites, have rather low REE pattern and are regarded as Although, based on the geochemistry data, there is no sub- cumulates (AIGNER-TORRES & KOLLER, 1999). duction-related component, AIGNER-TORRES & KOLLER These wehrlites contain according to AIGNER-TORRES (1999) suggest a back-arc basin affinity for this complex. (1996) dominant olivine (Fo0.51-0.49) and rare orthopyrox- The secondary mineral assemblages with prehnite and pum- ene (Fs0.38), higher amounts of a variable clinopyroxene pellyite are either part of the oceanic metamorphism or more (XMg 0.82-0.58) and minor brown amphiboles with a wide possibly related to the Alpine overprint and define clearly the compositional range from tschermakite to magnesiohorn- post-magmatic history and the limits of the emplacement blende. Besides minor An-rich plagioclase high amounts of mechanism for the Szarvaskő complex. ilmenite and titanium magnetite up to more than 20 vol% are the main features of this rock type. The wehrlite samples can References be classified as hornblende peridotites or as olivine-ilmenite AIGNER-TORRES, M. (1996). Diploma thesis, University cumulate. In any case these samples represent a member of a of Vienna, NAWI Faculty, 128 p. classical tholeiitic fractionation trend with high Fe- and Ti- AIGNER-TORRES, M. & KOLLER, F. (1999). Ofioliti, 24: enrichment. The low Cr- and high V-contents in contrast can 1-12. be only explained by a fractionation from an evolved basic BALLA, Z., HOVORKA, D., KUZMIN, M. & VINOGRA- melt indication also rather high oxidation state. DOV, V. (1983). Ofioliti, 8: 5-46. On the other hand the plagiogranites show an inverse DOWNES, H., PANTÓ, Gy., ÁRKAI, P., & THIRLWALL, pattern with overall high trace element contents and remark- M. F. (1990). Lithos, 24: 201-215. able negative Eu anomalies. This sample suite with clear
53 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MINERALS OF GYÓD SERPENTINITE BODY, HUNGARY
KOVÁCS, G.1, RAUCSIK, B.2 & HORVÁTH, P.3 1 Environmental Inspectorate of Lower Tisza Region, Felső-Tisza part 17, H-6721 Szeged, Hungary. E-mail: [email protected] 2 Department of Earth and Environmental Sciences, University of Veszprém, Egyetem u. 10, H-8200 Veszprém, Hungary. 3 Laboratory for Geochemical Research, Hungarian Academy of Sciences, Budaörsi út 45, H-1112 Budapest, Hungary.
In the earlier studies different mineral composition of eral samples we analysed chrysotile (probably 2Orcl symme- Gyód serpentinite body were determined from which differ- try orthochrysotile) and 1T-lizardite were surely determined. ent conclusions were drawn concerning the ultramafic proto- Most samples consist of more than one serpentine mineral, lith and its alteration processes. On the basis of X-ray dif- but antigorite was not detected. The most important minor fraction analysis ERDÉLYI (1970) determined numerous phases are the dolomite, ferrite-spinel, quartz, calcite, ortho- minerals (Table 1) of the serpentinized peridotite. SZED- pyroxene and olivine. Regarding phyllosilicates, the sepa- ERKÉNYI (1974) and GHONEIM (1978) claimed that the rated, oriented samples of < 2 µm fraction represent Mg- protolith of the serpentinite must have been pyroxenite or chlorite, and swelling phase is not detected. On the base of lherzolite or dunite. According to PAPP (1989) the most peak maxima between 7.06–7.10 Å and 3.48–3.53 Å, the frequent serpentine minerals are lizardite, chrysotile and presence of kaolinite can be precluded. polygonal serpentine. BALLA (1985) established that the By means of microprobe analysis we tried to determine chemical composition of Gyód serpentinite body is harzbur- the chemical composition of the relict minerals. Olivine has gitic, and stated a multi-step metamorphic evolution path of 90–91% forsterite content, orthopyroxene can be character- it. ised by 90–92% enstatite component and spinels consist of 57–59% chromite and 22–28% magnetite, respectively. Gen- eral occurrence of plagioclase, clinopyroxene and amphi- Table 1: Mineral composition of the Gyód serpentinite body. boles were not pointed out. Although completely serpen- tinized amphiboles can be seen as bastites, these can not be Author Minerals identified. Fresh amphiboles can only be found in one sam- Erdélyi, 1970 lizardite, hydrochrysotile, clino- ple where they occur together with talc in the alteration rim chrysotile, chlorite, talc, montmorillo- of enstatite. Unaltered anthophyllite was found only in a nite, biotite, muscovite, albite, by- special location, near an aplite dyke. townite, clinoenstatite, tourmaline, The high ratio of forsterite component in olivine may magnetite, böhmite, diaspore, lepido- suggest that by the partial melting of a lherzolitic protolith, a crocite, brucite, wilkeite, calcite, dolo- residuum of harzburgitic composition could have formed in mite, ankerite the upper mantle, representing the lower part of an ophiolite Ghoneim, 1978 enstatite + olivine, lizardite + chrysotile, sequence. chlorite + dolomite, chromite, magnet- ite, pentlandite, pyrrhotite References BALLA, Z. (1985). In Dobrecov, N. L. ed.: Rifeysko- Balla, 1985 enstatite1, olivine, enstatite2, anthophyl- Nizhnepaleozoyskie ofiolity. Severnoy Evrazii, 136-148. lite, talc1, magnetite1, antigorite, talc2, ERDÉLYI, J. (1970). Manuscript, Hung. Geol. Survey, T. 2574. carbonates, magnetite2, chlorite, Cr- magnetite, chrysotile, lizardite GHONEIM, M. F. (1978). Candidate Thesis, Hung. Acad. Sci., Budapest. Twelve samples were chosen for X-ray powder diffrac- KOVÁCS, G. & M. TÓTH, T. (2000). Acta Mineral. Pet- tion and microprobe analyses from the whole drilling se- rogr., Supplementum, Szeged, XLI: 64. quence of the borehole No. Gy-2 on the basis of the prelimi- PAPP, G. (1989): Doctoral Thesis, Dept. of Petrol. Geo- nary petrographic studies (KOVÁCS & M. TÓTH, 2000) in chem., Eötvös Univ., Budapest. order to resolve the contradictions of literature. SZEDERKÉNYI, T. (1974). Acta Geol. Sci. Hung., 18: 305- The main phases of the examined rocks are Fe-Mg phyl- 313. losilicates, mostly serpentine minerals (30–60 %), talc (10– 30%) and chlorite (10–20%). The determination of multiphase serpentine minerals is rather uncertain, however, in the several samples we analysed chrysotile (probably 2Orcl
54 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
COMPOSITION AND PROVENANCE OF THE PONTIAN SAND AT SUPURU DE JOS (ROMANIA)
KOVÁCS-PÁLFFY, P. & THAMÓ-BOZSÓ, E. Geological Institute of Hungary, Stefánia út 14, H-1143 Budapest, Hungary. E-mail: [email protected]
The studied sand formation at Supuru de Jos (Romania) By the microprobe analysis ferroan-enstatite and ferro- is situated in the NE part of the Pannonian Basin, the NW hornblende were determined among the minerals, which have area of the Şimleului Basin, which is surrounded by the Bâc, “hacksaw” terminations. In a ferrohornblende grain one gold the Plopiş, the Meseş Mountains, and further by the NE- inclusion appeared too. Ferro-actinolite and spinel (hercynite, Carpathians. In the basin the Quaternary sedimentary rocks ulvöspinel) also occurred in the sand. The cement contains are underlain by alternating Pontian lignite and dark grey mainly Si, and sometimes it has relatively high Mn content. sand layers, their thickness varies between 150–200 meters (CHIVU et al., 1966). The detailed examination of the min- Conclusions erals in this sand is very useful to determine its source rocks Facies: The studied Pontian immature, very well sorted, and the post-depositional processes, and to the study of the medium sand was formed in a littoral environment in the provenance of the Pliocene and Quaternary sedimentary stringing lagoons of the Şimleului Basin, which subsided and rocks in the Great Hungarian Plain. uplifted from time to time, and the sand altered with swampy sediments. Methods Provenance: Most of the minerals in the sand originated We used wet sieving, optical microscopic examination, from different Neogene volcanic rocks of the NE- X-ray diffraction, microprobe, chemical analysis and SEM. Carpathians (e.g. volcanic pebbles and rock fragment, partly the quartz, feldspars, garnet, opaque minerals and most of the Results pyroxenes and amphiboles), and the nearest metamorphic We studied the upper part of the Pontian sandy sequence formations (e.g. metamorphic pebbles and rock fragments, at Supuru de Jos, borehole 123 H2P, in the interval of 41.8– staurolite, muscovite, partly the quartz, feldspars, biotite, 46.7 m. It comprises dark grey, very well sorted, medium garnet, spinel). Jacobsite, rhodochrosite, and partly the mag- sand. It is loose, but partly it is cemented to hard sandstone. netite came from Precambrian metamorphic carbonate rocks, The few pebbles and rock fragments (bigger than 2 mm) are because these minerals are described from the Răzoare For- max. 30 mm in size, and they are subangular quartzite, vol- mation of the Preluca Mountains (HÂRTOPANU et al., canic rocks (andesite) with different colours and roundness, 1993). Some minerals and rock fragments originated from metamorphic and sedimentary rocks. recycling of older sedimentary sequences. Among the sand-size grains the most frequent minerals Diagenesis: The strong etching of some minerals, the are quartz (some have characteristic pyroclastic origin), feld- “hacksaw” terminations of pyroxenes and sometimes the spars (plagioclases, and some K-feldspars, most of them are amphiboles, and the cementation of the sand caused by post- strongly altered), muscovite, pyroxene (hypersthene, clinoen- depositional processes. Diagenesis was related to the statite, augite), amphibole (green and brown hornblende) and swampy, organic material rich environment, the carbonate- opaque minerals. Garnet, spinel, biotite, staurolite and rutile and volcanic rock fragment content of the sand, and subsi- appear too. On the bases of the earlier data sphalerite, ga- dence and uplifting of the basin from time to time. lenite, tetrahedrite, melnikovite and native copper also occur in the sand (KOVÁCS-PÁLFFY et al., 1986). Pyroxenes and Acknowledgements sometimes the amphiboles have “hacksaw” terminations, This research was fund by Hungarian National Scientific which are produced by post-depositional dissolution. The Fund (OTKA T-035168). grains are frequently covered by thin silica cement layer in patches, and sometimes small zeolite crystals can be seen on References the cement layer too. In the fraction of 0.1–0.2 mm the sand CHIVU, M., DRAGU, V., ENACHE, GH., ISAC, D. & has high heavy mineral content (19 wt%), low quartz / feld- MĂRGĂRIT, E. (1966). Dări de seamă, LII/1: 239-253. spar ratio (1.4), and it contains high amount of magnetic HÂRTOPANU, P., UDUBAŞA, G., UDRESCU, C. & fraction (20 wt%). CRISTEA, C. (1993). Rom. Jour. Miner., 76: 15-21. According to the results of X-ray diffraction analysis, KOVÁCS-PÁLFFY, P., DAMANIA, GH., POP, V., RO- clay minerals (illite-sericite), zeolite (clinoptilolite), rhodo- MAN, M., ROMAN, G. & NICOLOCI, AL. (1986). chrosite, calcite, magnetite, zircon, chlorite, maghemite, IPEG ilmenite, goethite, chalcopyrite, jacobsite, bustamite, frank- linite and ulvöspinel also occur.
55 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MINERALOGICAL ASPECTS OF SOME HYDROTHERMAL ZEOLITES FROM COPACENI, ROMANIA
KRISTÁLY, F., STREMTAN, C. & TÓTH, A. Department of Mineralogy, Babes-Bolyai University, 1, Kogalniceanu Str, RO-3400 Cluj-Napoca, Romania. E-mail: [email protected]
The studied area is situated in the NE part of Trascau silica, clay minerals, and zeolites. The methods of investiga- Mountains, 20 km SE from Cluj-Napoca, in the close prox- tion we have used (transmission polarizing microscope, ste- imity of the European road E60 near Copaceni village, Cluj reomicroscope, X-ray diffraction) helped distinguish the County. presence of six zeolites (analcime, heulandite, wairakite, The geological formations occur in the area belong to the stilbite, barrerite, chabazite), associated with both micro- and ophiolitic type Mesozoic island-arc magmatism from Trascau macro-crystalline calcite and silica. Mountains. These formations are characterized by the pres- The goal of this study is to perform the mineralogical de- ence of pillow-lava basalts and massive basalts, included scription of the area and also to emphasize the occurrence of from a tectonical point of view in the Rimetea Nappe new zeolites. For the near future, our aim is to begin a de- (NICOLAE et al., 2001). The analyzed samples were col- tailed case study to determine physical and mineralogical lected from an abandoned quarry, where an alternating suc- properties of one of the zeolites we found (barrerite) with cession of compact basalts and basalt flow sequences can be extremely rare occurrence in general. observed easily. In the upper part of this sequence a layer of volcanoclastics occurs. Reference The post-magmatic mineral association – hydrothermal NICOLAE, I., SACCANI, E. & TASSINARI, R. (2001). and supergene – crystallized along the fractures and void Ofioliti, 26(1): 9-22. spaces of the basaltic rocks, especially volcanoclastics. Neo- formation minerals are basically represented by carbonates,
56 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
BIOMOBILIZATION AND BIOACCUMULATION OF HEAVY METALS IN MONTANEOUS LANDSCAPE (BANSKÁ ŠTIAVNICA, SLOVAK REPUBLIC)
KRIŽÁNI, I.1, ANDRÁŠ, P.1 & DANÁKOVÁ, A.2 1 Geological Institute, Slovak Academy of Sciences, Severná 5, SK-974 01 Banská Bystrica, Slovak Republic. E-mail: [email protected] 2 County Office, Križovatka 4, SK-969 00 Banská Štiavnica, Slovak Republic.
The most legible manifestation of exploitation activities dump areas with fine-grained substrate originate plant groups in mining regions are rests of mining dumps, which represent in mosaic position: Tussilago farfara, Agrostis tenuis and dumping grounds of dessintegrated rocks, fine-milled ores Artemisia vulgaris, Tripleurospermum perforatum, Daucus and chemical matters used during the dressing activities. carota and Tanacetum vulgare. On places where there is Until now were these dumping grounds perceived only as a more humus, we can find next species: Avenella flexuosa, “memorials of the technical work“ or as an anthropogenic Nardus stricta, and mainly species from the surroundings: relief-creating elements. Arrhenatherum, Tithymalus cyparissias, Veronica chamaed- The surrounding of Banská Štiavnica is a very good rys, Phleum pratense and Festuca rubra. model area. All this region, is even during the Ancient times The oldest dumps from 14. to 16. centuries, worked as (maybe even during Primeval Age), extensively remarked by meadows, are covered by grass, which consists of species mining activity. resistant to heavy metals: Acetosella vulgaris, Luzula cam- To confirm that the origination of the percolating waters pestris, Arrhenatherum elatius, Avenella flexuosa, Leucan- acidity is the activity of chemical-litotrophic thionic bacteria themum vulgare, Dianthus carthusianorum, Pilosella cy- there were isolated the following species Thiobacillus ferro- mosa. The soil in this stage has well developed two or three oxidans, Thiobacillus thiooxidans, Leptospirillum ferrooxi- soil horizons. dans and Bacillus cereus. The mentioned bacteria in dump- Dumps from 18. and 19. centuries are predominantly ing grounds are metabolically connected with sulphides. The planted by trees Pinus nigra, Pinus sylvestris and more rarely dominant part of these sulphides is represented by fine- by Picea abies. On the youngest dumps subsist by auto- grained pyrite. It was proved that in percolating waters and in sowing Betula pendula, Alnus glutinosa, Salix caprea and the influenced soils micro-fungi are present. One of the some other plants. Analyses of plant tissues show high con- products of the metabolism of microorganisms are organic centrations of heavy metals, e.g. in acid soil (pH = 4) contain acids. It is assumed that these acids have an important role in Acetosella vulgaris up to 3500 mg Al in kg of dry sample. the process of silicates and alumosilicates decay. The Little mammals represent due their short living and lim- mechanism of biological oxidation under influence of thio- ited, max. of 1–2 ha extent life-area an extraordinary con- bacteria initiates the hydrolytic process of sulphide minerals venient group for monitoring the contamination of environ- and cause creation of complex compounds of heavy metals. ment. 142 mammals of 5 species were caught: Apodemus These acid percolating waters extensively damage and flavicollis (54.2%), Microtus arvalis (23.9%), Clethrionomys destroy the entire biotope, contaminate the underground glareolus (18.3%) and rare Pitimys subterraneus and waters by Zn, Cu, Cd, Fe, Bi, Mn... The extraordinary nega- Clethrionomys suaveolens. tive influence has Al. Its concentration in acid water is very There were determined contents of Fe, Mn, Cu, Pb, Zn, high. The result of biological-chemical environmental events Cd, Bi (Ni) in tissues of kidneys, livers and spleens of mostly is the biological transformation of the original sulphidic as abundant species. High contents of heavy metals were de- well as of the alumosilicates. The main consequence of these scribed in liver dry-tissues of Apodemus flavicollis (mg.kg-1): processes is the pelitization and illitization. The affectation Fe 3028, Ni 337, Mn 26, Cu 26, Zn 45, Pb 60, Cd 4 ppm and of H2SO4 and of the products of metabolism of species Ba- in spleen dry tissues of Microtus arvalis: Fe 952, Ni 2498, cillus cause releasing of Si, Al, Cr, Au, Ag... to the solution. Cu 1371, Zn 295, Pb 122, Cd 5 ppm. Between heavy metal The study of gold grain surfaces shows that the products of contents in plants and internal organs of little mammals from the bacterial metabolic processes reacted with Au and caused surface levels of dumps was found a trend of important posi- Au migration in the form of water-soluble complexes. tive correlation but it will be very convenient verify these We recorded the following evolutionary vegetation stages data on the larger set of samples. on dumps and soils influenced by heavy metal pollution. On
57 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
DIFFERENT MOBILITY OF HEAVY METALS IN HYDROQUARTZITE AND IN SEDIMENTS OF TEILING POUNDS (BANSKÁ ŠTIAVNICA, WESTERN CARPATHIANS, SLOVAK REPUBLIC)
KRIŽÁNI, I.1, ANDRÁŠ, P.1 & DLUHOLUCKÁ, L.2 1 Geological Institute, Slovak Academy of Sciences, Severná 5, SK-974 01 Banská Bystrica, Slovak Republic. E-mail: [email protected] 2 Secondary school, SK-969 01 Banská Štiavnica., Slovak Republic.
The pit quarry at the south slope of Malý Šobov Hill is rainwater (pH 4.5). Contents of selected heavy metals in situated in lense of hydrothermal quartzite (HQ). Fine leaching were determined by atom absorption spectrometry. grained waste from flotation plant of Banská Štiavnica Ore The primary source of Fe, Cu, Zn, Pb, Ag and Cd in HQ Mine State Plant is deposited in setting pit Sedem Žien at the in the sediments of the setting pit are sulphide minerals and contact of village landmark of Banská Štiavnica and Banská sulphosalts. Source of the Mn are in both cases carbonates Belá. and silicates. The average sample of HQ (A) was prepared by homog- The important reason of the intensive leaching of the enization of crushed material from three bore holes for bench selected elements from HQ is caused by lower carbonate blasting in the low level of the quarry and from sediments of content in comparison with sediments of the setting pit. The setting pit (B) after mixing of mentioned three samples from second reason is the long time activity of three species of the external part of the dam. Nine portions of grain size <1 thio-bacteria and of products of their metabolism on the high mm with volume <25 cm3 from each sample were washed by reactive mineral phases of HQ. In the sediments of the set- 250 ml solutions of destilled water (pH 6.5), solution H2SO4 ting pit dam was isolated already only Thiobacillus ferrooxi- + HNO3 and NaHCO3 in destilled water (pH 4.5) and in dans.
Table 1: Contents of the most important oxides in wt.% in HQ and in sediments from the setting pit
SiO2 TiO2 Al2O3 Fe2O3 FeO MnO MgO CaO Na2OK2OP2O5 A 92.32 0.44 0.97 3.26 0.26 0.02 0.04 0.11 0.05 0.08 0.12 B 71.68 0.31 7.72 2.36 2.20 1.03 1.14 2.28 2.22 3.79 0.10
Table 2: Contents of selected heavy metals (g/t) in HQ and in sediments from the setting pit
Cu Zn Pb Ag Cd A 25 52 64 8.27 0.10 B 478 3632 1138 5.50 18.40
Table 3: Average contents of heavy metals (mg/l) in leachings from samples A and B
Fe Mn Cu Zn Pb Ag Cd xA 330 8.10 0.52 5.70 2.30 0.23 0.018 xB 1.10 14.20 0.06 3.40 1.04 0.03 0.045
Table 4: Overview of thio-bacteria from Šobov and Nová šachta dumps and from setting pit Sedem Žien
Samples Sample Bacteria Locality pH Medium number Tf Lf Tt Šobov quarry and dump drainage water 6 2.0-2.4 + + + Nová Šachta dump drainage water 3 5.6-6.8 + + + Setting pit Sedem Žien leaching from sand 1 5.7 +3 – – Explanations: Tf – Thiobacillus ferrooxidans, Lf – Leptospirillum ferrooxidans, Tt – Thiobacillus thiooxidans + present, – not present
58 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
OPAL VARIETIES IN CARPATHIAN VOLCANIC ROCKS
KULCHYTSKA, G.1 & PAVLYSHYN, V.2 1 Institute of Geochemistry, Mineralogy and Ore Formation, National Academy of Sciences, Palladine Avenue 34, Kyiv, Ukraine. E-mail: [email protected] 2 National University, 90 Vasylkivska, str., Kyiv, Ukraine.
A fair amount of water is a typical constituent of opal, a OH-groups, and “organo-opal”, with CH-groups, respec- short range order form of silica. Opals are distinguished by tively. structural attributes (opal-A, -C, -CT); their name may vary These two opal varieties were found also in Carpathian by colour (milky and black opal, chrysopal), by transparency volcanic rocks, but separately. Opal present in altered tuffs (hyalite, hydrophane, cacholong) or by gem value (common (Table 1, #5) resembles “hydroxyl-opal” the most, as vacuole and noble opal). There is no opal classification based upon water dominates in it and there are very little hydrocarbons the water content, though it varies from 1 to 30%. We do not present. “Ungvarite”, a mixture of opal and nontronite (Ta- have enough information about the role of water in opal, not ble 1, #6), is similar to them, too. Precious opal from Dubnik speaking about the amount and role of other volatile compo- (Table 1, #2–3) is similar to “organic-opal” in the amount of nents present. hydrocarbons. On the other side the larger amount of Gas analysis of pyrolysed opal showed that during heat- “absorbed” and the fewer amount of “adsorbed” water in it ing not only the dominant water (vapour), but also hydrogen gives us the reason to interpret that variety as a mixture of and volatile compounds of carbon (СО2, СО, СН4, СnHm) “hydroxyl-” and “organic-opal”. Kinetics of water separation leave the samples. While degassing, many opal samples suggests the very small size of both the open and the closed generate compounds of nitrogen (N2, NO), and some of them pores. The amount of hydrocarbons, and also СО2 and par- also compounds of sulphur (H2S, SO2, COS). The amount of ticularly СО decreases noticeably. from the translucent to the non-water phases in the leaving gas mixtures decreases from vitreous variety. The similar trends of changing of the СО, the opaque to the transparent opals. (causing a reverse de- СnHm and H2 content suggests the common source of these pendence for water). compounds. In the current study we analysed the gas composition of Based on the data of the parent rocks (Table 1, #1, 4) it different opal varieties and that of their volcanic parent rocks can be pointed out that 1) there is an inverse correlation be- (from the Carpathians) on heating and compared these results tween the amount of organic groups in opal and in its (vol- with analyses of opals from the Ukrainian Shield (Table 1). canic) parent rock; 2) there is much nitrogen in the pyrolysed The two opals from the Ukrainian Shield gave interesting products of volcanic rocks, even without adsorbed nitrogen. results (PAVLYSHYN et al., 1993; KULCHYTSKA et al., (up to 0,005%). 1997). They are closely connected, form a zonal structure. To our point of view the differentiation of silica (caused Their non-volatile chemical composition do not differ, while by temperature and pressure changes), the formation of the their volatile composition differ considerably. The differ- opal varieties, was influenced also by the composition of ences in the volatile composition were interpreted in the these volatile admixtures. following way: The “amorphous” silica contains open or closed pores. Opals with open pores contain less water than References opals with closed pores. In the first case water is considered KULCHYTSKA, G., VOZNYAK, D. K., EGOROVA, L. N. as „adsorbed”, while in the second case as “absorbed” (in the MELNIKOV, V. S. & PAVLYSHYN, V. I. (1997). Min- vacuole). Typical characteristic of opals with open pores is a eral. Zhurnal, 19/1: 18-37. fair amount of carbon compounds and hydrogen in its py- PAVLYSHYN, V. I., VLASYUK, S. A., INDUTNY, V. V., rolysed gas. The different composition of volatile admixtures KVASNYTSYA, V. M., KULCHETSKAYA, A. A., on the surface of silica globules was suggested to lead to the MELNIKOV, V. S. & RAKHMANGULOVA, D. Z. formation of two opal varieties, called “hydroxyl-opal”, with (1993). Mineral. Zhurnal, 15/4: 5-16.
Table 1: The amount of some components in the pyrolysed products of opals and their parent rocks. Temp. of pyrolysis (°C) 1 2 3 4 5 6 7 8 50–1050 3.60 3.59 3.45 6.67 7.26 6.65 1.49 4.95 H O (wt%) 2 50–250 0.72 0.85 0.32 0.86 0.54 1.18 1.06 0.26 CH4 (ppm) 50–1050 0.53 7.30 4.35 54.98 0.13 0.53 7.73 0.87 C2H4+C2H6(ppm) 50–1050 0.38 16.50 2.94 64.70 1.03 0.10 16.00 1.30 N2 (ppm) 250–1050 17.44 7.09 16.16 49.12 9.39 7.13 4.22 1.07 No. of analyses 1 3 1 2 3 2 11 18 1) andesite, Dubnik, Slovakia; 2) milky and frost opal (from andesite), Dubnik, Slovakia; 3) vitreous opal from andesite, (from andesite), Dubnik, Slovakia; 4) altered volcanic (crystal/vitritic) tuff, Slovakia; 5) translucent opal from altered volcanic tuff, Slovakia; 6) „ungvarite” (opal-nontronite intergrowth), Transcarpathians, Ukraine; 7) „organo-opal”, the Ukrainian Shield, Ukraine; 8) „hydroxyl-opal”, the Ukrainian Shield, Ukraine.
59 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
SIMPLE FORMS OF SYNGENITE (KALUSZITE) CRYSTALS
KVASNYTSYA, I. V. Kyiv National University, Kyiv, Ukraine. E-mail: [email protected]
Syngenite crystallography has been sufficiently studied based on the crystallographic data published by GOLD- by J. Rumpf in 1872, V. Zepharovich in 1872, 1873, K. Ubra SCHMIDT (1922), PALACHE et al. (1951), LAZARENKO in 1873, A. Laskiewicz in 1927, 1934, 1936 (KO- et al. (1962) and GOROGOTSKAYA (1966). Theoretical ROBTSOVA, 1955) and L. Gorogotskaya in 1966. Our in- dhkl have been calculated by us according to X-ray data vestigations of many syngenite crystals from Dombrove (JCPDS 28-739, a0 = 9.777(2), b0 = 7.147(2), c0 = 6.250(2), β occurrence (Kalush area, Precarpathians) give evidence that = 104˚01’(2)). It is clear that the forms with big values of dhkl their habit is often determined by {100} pinacoid (Fig. 1). are most frequently occurring and well-developed faces on
Fig.1: Main morphological types of syngenite crystals from Dombrove quarry. Syngenite crystals of {100} + {110} pinacoidal-prismatic syngenite crystals. habit and {110} prismatic habit are rare. Owing to peculiari- ties of syngenite structure (GOROGOTSKAYA, 1966) References crystals are often prolonged along [001]. Well-developed and GOLDSCHMIDT, V. (1922): Atlas der Krystallformen. widespread forms on investigated crystals are represented by Band VIII. Carl Winters Universitätsbuchhandlung, Hei- {100}, {010}, {001}, {101}, {101}, {110} and {011}. delberg. List of all known simple forms of syngenite crystals, their GOROGOTSKAYA, L. I. (1966). Collection of L’vov Uni- distribution and development according to their interplanar versity, 20/4: 481–489. distances is next: {100} - dhkl, 9.486 (9.490) (theoretical data KOROBTSOVA, M. S. (1955): Mineralogy Potassium salts and in brackets X-ray data, JCPDS 28-739); {010} – 7.147; deposits of Eastern Precarpathians. In: Problem of Miner- {001} – 6.064; { 1 01} – 5.784; {110} – 5.708 (5.710); alogy of Sedimentary Formations. Vol. 2. L’vov National {101} – 4.626; {011} – 4.624 (4.624); { 1 11} – 4.496 University Publ., L’vov, Ukraine, p.3–137 (in Russian) (4.496); { 2 01} - 4.271; {210} - 3.952 (3.954); {111} – LAZARENKO, E. K., GABINET, M. P. & SLYVKO, E. P. 3.883 (3.887); { 2 11} – 3.667; {120} – 3.344 (3.347); {211} (1962): Mineralogy of Sedimentary Formations of the – 3.042; {310} – 2.892 (2.891); { 1 12} – 2.856 (2.855); Precarpathians. L’viv National University Publ., L’viv, { 2 21} – 2.741 (2.741); {221} – 2.448 (2.447); {410} – Ukraine. – 482 p. (in Ukrainian) PALACHE, C., BERMAN, H. & FRONDEL, C. (1951): 2.251 (2.250). The other forms {411}, {510}, {203}, {430}, th {520}, {610}, { 3 04}, {124}, {710}, {720}, {304}, {810}, Dana’s system of mineralogy. 7 Ed., vol. II. { 7 04}, {504}, {650} and {10.3.0} are very rare. This list is
60 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
NEW DATA ON SYNGENITE (KALUSZITE)
KVASNYTSYA, V. M.1, VOZNYAK, D. K.1, IL’CHENKO, K. O.1, KVASNYTSYA, I. V.2 & HRYNIV, S. P.3 1 Institute of Geochemistry, Mineralogy and Ore Formation, National Academy of Sciences, Palladine Avenue 34, Kyiv, Ukraine. E-mail: [email protected] 2 Kyiv National University, Kyiv, Ukraine. 3 Institute of Geology and Geochemistry of Combustible Minerals, Ukrainian National Academy of Sciences, L’viv, Ukraine.
More than 50 mineral species were first discovered in the equal or less then 60–67 ˚C (± 1 ˚C). Eutectic temperature is Carpathian region. Only two of them were found in the in the range from –8.3 to –9.0 ˚C (± 0.2 ˚C). Ukrainian part of the Carpathians: syngenite from Kalush The second group of primary inclusions (0.2–0.3 mm in area (the Precarpathians, Miocene molasse sedimentary size) consists of tubular and tabular negative crystals, which rocks) and karpatite from Oleneve area (the Transcarpathi- coincide with [001]. Gaseous bubble appears at cooling and ans). Syngenite was described almost simultaneously by J. disappears at the temperature 40–47 ˚C. Teutectic is between – Rumph and V. Zepharovich in 1872 (KOROBTSOVA, 22.4 and –22.6 ± 0.2˚C. Tice melting is from –8.3 to 12.8 ˚C. 1955). The former author had discovered this mineral on half Liquid inclusions in syngenite with Teutectic. is similar to the year earlier and named it as kaluszite, the later one named his system NaCl–H2O (Teutectic.= –21.1 ˚C) and NaCl–KCl–H2O find as syngenite. Later syngenite was found in other occur- (Teutectic.= –22.9˚C). Its concentration is from 12.1 to 16.7 rences of the Precarphathians (Morshyn, Stebnyk). These wt% NaCl equiv. crystals were described by R. Zuber in 1904, J. Tokarski in Syngenite formation is a result interaction of the anhy- 1910, 1913 and Cz. Kuzniar in 1934. In 1955 considerable drite and halite rocks with solution enriched in KCl and progress has been made in the systematical research of syn- K2SO4. For growth of syngenite high concentration of KCl in genite (KOROBTSOVA, 1955). solutions is necessary (more 8% of KCl after Lepeshkov I. Our main goal in this study is to present results of com- M.) (KOROBTSOVA, 1955); it is in good agreement with plex investigations of syngenite from new occurrence and to our data on fluid inclusions. compare them with already published data. New find of syngenite crystals was made in sediments of Golyn’ syncline Concluding remarks (Kalush-Golyn’ group of potassium-magnesium salt depos- The syngenite crystals from Dombrove quarry often show its). Here potassium-bearing strata has a thickness of 300- a combination of simple forms with big values of dhkl. Most 600 m. It contains layered and breccial clays with lens of of the crystals have {100} pinacoidal habit. Main simple halite and potassium salts which are represented by langbe- forms of the crystals are {100}, {010}, {001}, {101}, inite-kainite rock and sylvinite. Statistically representative { 1 01}, {110} and {011}. Obtained infrared spectra of the set of syngenite crystals (about 500 samples) from gypsum – syngenite crystals are typical for syngenite and confirm its clay cap (sole mark 265–270 m) of Dombrove quarry was structure peculiarities. Therefore the crystallization condi- examined. Syngenite crystals were extracted from gray clay. tions of syngenite were optimal. At the beginning the syn- The crystal sizes are 0.5–30 mm along [001]. genite crystals grow from KCl-enriched solutions at the tem- perature equal or less then 60–67 °C (KCl–H2O system has New data the Teutectic. = –10.8 ˚C). At the end of syngenite crystalliza- Some groups of fluid inclusions (primary and secondary) tion it was held from NaCl-enriched solutions at the tem- have been determined in the syngenite crystals. Primary perature equal or less then 40–47 ˚C. Concentration of solu- inclusions of the first group have either isometric form of tions was 12.1–19.7 wt. % NaCl equiv. negative crystals (50–70 µm in size) or complex one with a size up to 1–3 mm. Most of big inclusions have high degree Reference of filling. All inclusions take place in the central part of the KOROBTSOVA M. S. (1955) Mineralogy Potassium salts crystals. Inclusions composition is: aqueous solution (90–95 deposits of Eastern Precarpathians. In: Problem of Miner- %) + gas (1–2 %) + solid phases (3–9%, isotropic minerals alogy of Sedimentary Formations. Vol. 2. L’vov National prevail). Homogenization temperature of gaseous phase is University Publ., L’vov, Ukraine, p.3 – 137 (in Russian)
61 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
PHYSICO-CHEMICAL CONDITIONS OF QUARTZ AND CARBONATE VEIN FORMATION FROM THE CALDERA OF THE KELCHEY VOLCANO (TRANSCARPATHIANS, UKRAINE)
LAZARENKO, He., BLAZHKO, V. & KULIBABA, V. Institute of Environmental Geochemistry, National Academy of Sciences, Kyiv, Ukraine. E-mail: [email protected]
Zonal veins of 3–5 cm thickness cut andesite which fills Cl ion, F-hydrocarbon are determined in “quartz I” and up the caldera of the Kelchey volcano (Kvasovo ore field). “quartz II” by the water-extract method. These components The main minerals of the veins are “quartz I”, “quartz II” are absent in carbonates. (amethyst) and “quartz III” (amethyst similar to quartz I) and A large temperature range (375–165 ºC) of “quartz I” and carbonates (calcite and rhodochrosite) crystallized in the “quartz II” crystallisation shows an unbroken evolution proc- sequence listed. ess of hydrothermal solution. The gas phase is prevailing at On the basis of homogenisation temperature and gas- the high temperature stage (>300 ºC). phase content the following generations of fluid inclusions The increase of reduced gases in the later stage of mineral may be distinguished: in “quartz I”: 375 ºC (60% gas), 230– formation (“quartz II”) shows that at low temperatures the 205 ºC (20% gas); in “quartz III”: 300 ºC (25–30% gas); in oxygen fugacity was lower. The bulk crystallisation of rho- “quartz II”: 225–180 ºC (20% gas) and 170–165 ºC (10% dochrosite suggests that Mn2+ was stable under these condi- gas). Fluid inclusions are not present in carbonates. tions. By gas chromatography the following components of the The high homogenisation temperature of the gas inclu- gas-liquid inclusions have been determined: Ar + O2, N2, sions indicates that mineral formation in early stages oc- CH4, CO, CO2, C2H6, and H2S. curred within pneumatolytic conditions. The composition of 3 CO and H2S contents (in cm /kg) are different: in “quartz this phase may reflect the volcanic gas composition. I” (CO 0.6, H2S 1.7) are less than in “quartz II” (CO 85, H2S 87).
62 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MINERALS OF THE JÓZSEF HILL CAVE, BUDAPEST, HUNGARY
LEÉL-ŐSSY, Sz. & SURÁNYI, G. Department of Physical and Historical Geology, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary. E-mail: [email protected]
In 1984, spelaeologists under the guidance of Szabolcs needlegrass are living formations that precipitate from the Leél-Őssy and Péter Adamkó explored the József Hill Cave, infiltrating water and the cave aerosol. the most beautiful and most abundant in minerals member of With its 13 separate forms of appearance in the cave, the the cave group in the environs of Budapest. As to its charac- calcite occurs most frequently as common peastone. The 5– ter and formations, this typical thermal karst cave, known at 15 cm long sheaf-like clusters, standing out perpendicularly present in a length of 5.6 km, is similar to the Lechuguilla from the side wall, are built up of green pea-sized deformed Cave (New Mexico, USA), called the most beautiful cave in spheres of layered structure. There are angular and coral the world – even if the dimensions of the mineral precipita- peastones, as well. All of these peastones came into being tions and the passages are not to be mentioned in the same from the mist above the evaporating warm water cave lake breath. that condensed on the side walls some tens and hundreds of In the laboratory of Stein-Erik Lauritzen, University of thousand years ago, respectively. Bergen, Norway, in 1996, as well as in the laboratory of the The glass ball peastones are regularly spheroidal yel- Eötvös Loránd University of Budapest during 2001–2002, lowish formations of about 0.3–0.8 cm diameter with a uranium series dating measurements were carried out on the smooth surface. Unlike the most peastone varieties, they formations. The obtained data helped a lot in determining the precipitated from the slowly flowing or dripping cold water. genetics of the precipitations. According to the results of the uranium series dating, they On the main passage level of the cave, the host rock can are only some thousand years old. be investigated only at a few places, as the mostly white From the point of view of age determination, the 0.2–3.0 crystal coating covers uninterruptedly the wall almost eve- cm thick cave raft and several cm thick flowstone rywhere. Altogether 7 minerals can be examined and distin- (multigenerational calcite crust) accumulations, covering the guished with the unaided eye. The presence of 6 minerals side wall at a lot of places, are the most important, as they was demonstrated by X-ray powder diffraction examinations were precipitated shortly after the dissolution of the cave, and further 3 minerals were detected by heavy mineral analy- near the surface of the warm water, filling the cavity. The sis. Among them, mainly carbonates and sulphates, as well results of their examination refer to the fact that the passages as oxides–hydroxides and silicates could be found. The two of the József Hill Cave were dissolved about half a million dominant mineral species (gypsum and calcite) can be ob- years ago. served in very diversified forms of appearance. In the cave, the calcite is represented by several other Out of the 9 forms of appearance of the gypsum crystals, precipitation types (e.g. dripstone, dog teeth, tetaratas, basin the 0.5–1.0 m gypsum chandeliers that hang down from the fingers, etc.), as well. ceiling are the most spectacular ones. Generally, the side As to the spectacle, a determinant representative of the walls are covered by small crystalline gypsum coating. At crystals of the cave is the aragonite, the 1–2 mm thick crys- several places, on the top of the some cm thick gypsum crust talline needles of which form hemispheres of 1–3 cm di- 1–5 cm gypsum crystals, while at other places 1–3 mm wide, ameter and 4–8 cm long clusters. The 30,000–200,000 years 1–2 cm long needles are sitting. The pencil-thick, 10–15 cm old crystalline needles are sitting generally on the top of the gypsum flowers and gypsum snakes as well as the straggly peastone grains. The infiltrating waters in the cave have agglomeration of the hair-thin but locally 50–90 cm long already re-dissolved the considerable part of the aragonite crystal needles, called needlegrass, are precious gypsum needles. formations. Besides the spectacular crystal formations, the clay min- The material of the gypsum precipitations may be derived erals: kaolinite and illite, accumulating from the detritus of partly from the sulphate content of the former thermal the carbonate rocks, occur on the bottom of the passages in a springs, partly from the pyrite content of the more than 10 m considerable (locally several m) thickness. thick marl layer covering the cave. The coatings and the
63 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
OFFRETITE FROM THE BALATON HIGHLAND, HUNGARY
LÓRÁNTH, Cs. Department of Mineralogy, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary. E-mail: [email protected]
Offretite, a rare zeolite mineral was found in Bazsi X-ray powder (Table 1) and selected area electron- (Karikás Hill quarry) near Sümeg. This zeolite was unknown diffraction. Regarding structural characterisation of offretite in hydrothermal zeolite associations from the Balaton High- we paid special attention to the published experiences of land area. The only occurrence in Hungary was Bagókő Hill GUALTIERI et al. (1998). near Somoskő, Medves Hills. Offretite was found in small cavities in the Pliocene basaltic rock in association with Reference calcite, analcime, and clay minerals. Offretite forms colorless GUALTIERI, A., ARTIOLI, G., PASSAGLIA, E., BIGI, S., hexagonal needle shaped crystals up to ~1 mm in size. They VIANI, A. & HANSON, J. C. (1998). Amer. Mineral., cover the walls of cavities. We have identified offretite from 83: 590-606. this new occurrence using transmission electron microscopy,
Table 1: X-ray powder diffraction pattern of offretite from Karikás-tető quarry, Bazsi.
Offretite Offretite Karikás-tető, Bazsi JCPDS 22-0803 2*theta d(hkl) I(rel) d I(rel) hkl [deg] [Å] [%] [Å] [%] 7.68 11.5078 5.41 11.50 100 100 13.30 6.6561 2.10 6.64 20 110 15.42 5.7467 3.88 5.76 35 200 19.39 4.5772 2.11 4.58 4 201 20.44 4.3457 8.64 4.35 60 210 23.18 3.8365 8.09 3.84 45 300 23.62 3.7670 5.22 3.77 10 211 24.48 3.6363 3.06 3.60 4 102 24.98 3.5640 3.51 3.43 2 301 26.56 3.3561 1.31 3.32 20 220 27.99 3.1877 5.93 3.19 18 310 31.14 2.8718 5.45 2.88 65 400 33.35 2.6871 5.25 2.69 4 401 35.56 2.5245 14.78* 2.51 20 410 38.70 2.3265 2.42 2.30 6 500 40.57 2.2236 2.98 2.21 20 330 42.79 2.1133 24.66* 2.11 2 303 46.60 1.9490 7.54 1.96 2 502 47.84 1.9013 3.37 1.89 2 430
Reflections of accompanying minerals are omitted Other minerals also contributed to starred intensities
64 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
PLUTONIUM BEHAVIOR IN BRINES AFTER EQUILIBRATION WITH PERICLASE (MgO) BACKFILL
LU, N.1 & CONCA, J. L.2 1 Los Alamos National Laboratory, Los Alamos, NM 87545, USA. 2 Los Alamos National Laboratory, Carlsbad, NM 88220, USA. E-mail: [email protected]
Most radioactive waste disposal programs are considering to evaluate 1) stability of 239Pu(VI) in synthetic Brine G, the use of repository backfill materials to enhance the con- Brine E, 5M NaCl and 3.7M MgCl2 • 6H2O as a function of tainment of radioactive waste. The concepts include the use time, 2) behavior of 239Pu(VI) in the four brines after equili- of backfill to provide well-defined chemical conditions, brated with MgO backfill for 68 days at various water con- favorable hydraulic conductivity, and desirable physical tent, 3) release of 239Pu from of Pu-MgO-brine agglomerates characteristics within the disposal facility. The backfill ma- as a function of time, 4) characterization of 239Pu-loaded – terials have been classified into two groups according to their MgO-brine agglomerates. Equilibration experiments were primary properties: 1) chemical backfills such as cement, conducted at MgO-to-water ratios of 1:0.15, 1:0.25 and 1:10. iron, phosphates, and MgO, and 2) hydrological/physical Release of 239Pu from 239Pu-loaded MgO agglomerates was backfills such as clay, salt and cement. Magnesium oxide determined in the presence or absence of hypochlorite was proposed, and is being used, as a backfill material in a (OCl-), under agitated and non-agitated conditions. After the salt repository for transuranic waste in Carlsbad, New Mex- 239Pu(VI)-brines were equilibrated with MgO backfill for 68 ico. It was chosen for its capacity to control pH and carbon days, the solution pH and alkalinity changed dramatically, 239 dioxide (CO2) concentrations through specific reactions, with 99% to 100% of the Pu(VI) being removed from the maintaining the pH of the repository between 8.5 and 10, the brines (Figure 1). Only a small amount of 239Pu was subse- range in which many radionuclides exhibit their lowest solu- quently released from the 239Pu-loaded MgO-Brine G ag- bilities. In past years, most research has focused on the hy- glomerates after 110 days, but there was no 239Pu released dration and carbonation of MgO. A separate, but related from the 239Pu-loaded MgO-Brine E agglomerates. Our issue concerns the heterogeneity of the repository in terms of findings suggest that in NaCl-base brines such as Brine E, rewetting after closure and the formation of new minerals in the studied MgO material is an effective backfill to buffer the the backfill. Plutonium, with its multiplicity of oxidation pH to 9-10, which retards the release and migration of pluto- states, is one of the primary actinides of concern for long- nium. In MgCl2-base brines such as Brine G, the MgO is term disposal and storage of nuclear waste. The chemical slightly less effective because of buffering to a lower pH behavior of plutonium is influenced strongly by its oxidation (8.0-8.5). The MgO showed great affinity for Pu under re- state, which determines the strength of its complexation pository conditions and should perform well beyond its per- reactions, solubility, formation of colloids and sorption proc- formance predictions. esses. In this study, laboratory experiments were performed
120
100
99,8 100,0 99,9 100,0 99,2 99,9 80 99,9 99,9 100,0 100,0 Fig. 1: Percentage of 239Pu 15% removed from brines after 60 25% equilibrated with MgO 1000% backfill for 68 days. 40 %Pu-239 Removed
20
0 Brine G Brine E 5 M NaCl 3.7 M M gCl2.6H2O Brines
65 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MECHANISMS AND MICROSTRUCTURAL ELEMENTS OF THE EARLY, DUCTILE DEFORMATION PHASE IN LIMESTONES OF THE NE BÜKK MOUNTAINS, HUNGARY
MÁDAI, F.1 & NÉMETH, N.2 1 Department of Mineralogy and Petrology, University of Miskolc, H-3515 Miskolc-Egyetemváros, Hungary. E-mail: [email protected] 2 Department of Geology and Mineral Resources, University of Miskolc, H-3515 Miskolc-Egyetemváros, Hungary.
According to field investigations (e.g. CSONTOS, 1999), The intercrystalline boundaries of the fine-grained matrix the “main schistosity” in the NE Bükk is a generally recog- were predominantly serrate in specimens from hinge zones. nised feature. It constitutes the axial plane of the early folds On the other hand, the grains of the matrix of samples from formed by ductile deformation of the Late Palaeozoic- limbs had a fair proportion of straight (plain) boundaries. Triassic sequence. The ductile deformation elements are best Planar grain boundaries with polygonal texture dominated observable in beds where limestone alternates with seams or the sections cut parallel to shear direction, while they were lenses of materials with different competence, e.g. in cherty less frequent in the normal sections. limestone. According to inverse pole figures, the sample from a It was supposed that the early, ductile deformation took hinge zone had no CPO. Conversely, a weak but definite place during the Alpine low-grade metamorphism (ÁRKAI, CPO was detected on samples from the limb zones. They 1973, 1983). According to these investigations, the condi- showed a “c-axis fibre type” CPO (LEISS & ULLEMEYER tions of the peak metamorphism can be characterised by 300- 1999) having a simple c-axis maximum normal to the main 350 °C temperature and 200-300 MPa pressure. They already schistosity. The slight CPO and the predominance of straight pointed out that there is no correlation between the pressure boundaries in the matrix indicate that the limestones in limbs of metamorphism and the stratigraphic position (burial), the of the early phase folds could deformed by “superplastic metamorphic event is proved to have mainly a dynamother- creep” (SCHMID et al., 1977). mal character. The later deformation phases took place under The deformation twins within and the grain boundary lower temperature (DUNKL et al., 1994), where ductile zones around the large, pre-kinematic calcite crystals from deformation in the limestones cannot be formed. the intensively sheared limbs were dynamically recrystal- In the present paper different microstructural elements of lized: these elements were replaced by aggregates of small, limestones were studied which could have developed during isometric calcite grains with dominantly straight boundaries. the ductile deformation phase but were not overprinted by Conversely, the large calcite crystals from the hinge zones the later phases. The position of the samples in an early fold showed only serrated grain boundaries and straight, unde- was also considered: samples both from the hinge and limb formed twins. zones of folds were investigated. The following microstruc- These features indicate that the differential stress during tural elements were examined: the early, ductile phase was relatively weak (about 20 MPa) •grain shape preferred orientation (SPO) of the fine- in the hinge zones, the limestones here deformed by diffu- grained (10-20 µm) matrix, examined by quantitative sion mass transfer (pressure solution). The additional shear image analysis. stress on the limbs rose the differential stress (up to 35-60 •shape of the intercrystalline boundaries in the matrix. MPa) thus dynamic recrystallization and superplastic creep •crystallographic preferred orientation (CPO) by con- could take place. structing inverse pole figures. •formation and further deformation of calcite twins in References large (150-200 µm) pre-kinematic crystals. ÁRKAI, P. (1973). Acta Geologica Hung., 17(1-3): 67-83. No correlation was found between the stratigraphic posi- ÁRKAI, P. (1983). Acta Geologica Hung., 26(1-2): 83-101. tion and the occurrence and intensity of these microstructural CSONTOS, L. (1999). Földt. Közl., 129(4): 611-651. elements. Conversely, it was detected that they depend on the DUNKL, I., ÁRKAI, P., BALOGH, K., CSONTOS, L. & position of the sample relative to different fold elements NAGY, G. (1994). Földt. Közl., 124(1): 1-24. formed during the early deformation phase. LEISS, B. & ULLEMEYER, K. (1999). Z. dt. geol. Ges., The SPO of the matrix was weak in the hinge zones, 150(2): 259-274. while it was intensive on the limbs. The strongest SPO val- SCHMID, S. M., BOLAND, J. N. & PATERSON, M. S. ues were detected on samples from the limbs on sections cut (1977). Tectonophysics, 43: 257-291. normal to shear direction. The sections cut parallel to shear direction had more moderate SPO values.
66 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
THE ENVIRONMENTAL HAZARD OF THE GYÖNGYÖSOROSZI FLOTATION WASTE DUMP (MÁTRA MOUNTAINS, HUNGARY)
MÁDAI, V. Department of Mineralogy and Petrology, University of Miskolc, H-3515 Miskolc-Egyetemváros, Hungary. E-mail: [email protected]
Atmospheric effects can cause weathering of ore bodies. during the reconstruction of the plant a new job was estab- This is a natural phenomenon, which exists since millions of lished: the heavy suspension beneficiation. The used aggre- years ago. Originating low pH effluents, which contain gate was ferrosilicon (fersilicite). After flotation, waste was solved toxic metal ions surely cause a dramatic effect on the put on a flotation waste dump with a pipeline. The dump biota. Species living in surface waters may decrease in num- situated in the middle part of the Száraz Brook Valley. Since bers, and any biota will be necessarily poorer than before. A 1979, toxic heavy metal containing effluents were treated. new balance come into between the recreation capacity of the The produced high gypsum containing toxic sludge was nature and the pollution of the weathering of the waste. Low sampling in the Bence Valley. The mine was abandoned in pH and higher toxic metal concentration tolerant species may 1986 because of financial problems. spread in the polluted region. My task was to examin how hazardous the flotation waste ARD (Acid Rock Drainage) is generally regarded to be dump of Gyöngyösoroszi from the point of ARD using present if effluent pH is between 5-5.5 because in this pH chemical methods for the determination. range there is a negative impact on biota. The environmental hazard of the Gyöngyösoroszi flota- Gyöngyösoroszi is situated in the north east part of Hun- tion waste dump from the point of Acid Rock Drainage using gary in the county of Heves. The village, which is not far one of the most widely accepted static chemical test method from the former mine, lies in the south part of the Mátra is negligible. Mountains in the valley of Toka Brook. Gyöngyösoroszi Ore The NPR value: the ratio of NP (Neutralisation Potential) Mining Company was established in 1952. The mined ore to AP (Acid producing Potencial): was crushed, grinded and flotated on the spot. The products 274.25 : 39.8 ~ 7:1. were pyrite, sphalerite, galena, and galena with copper. Sphalerite, galena powder were smelted abroad. In 1962
67 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MONTICELLITE AND HYDROXYLELLESTADITE IN HIGH-TEMPERATURE SKARNS FROM ROMANIA
MARINCEA, Ş & DUMITRAŞ, D.-G. Geological Institute of Romania, Caransebeş 1, RO-78344 Bucharest, Romania. E-mail: [email protected]
The occurrences of high-temperature, gehlenite-bearing Hydroxylellestadite must occur as scattered at random skarns are quite exotic: fewer than forty such occurrences grains throughout the tinsleyite mass (at Cornet Hill), but were reported so far in the world. Four of them are known in also as sparingly, randomly oriented inclusions in gehlenite the Banatitic Magmatic and Metallogenetic Belt (BMMB) (at Oraviţa and Măgureaua Vaţei). In both cases, the mineral from Romania (BERZA et al., 1998). These occurrences are has an euhedral to subhedral, equant to short prismatic habit. those at Cornet Hill, Măgureaua Vaţei (Upper Cerboaia Val- Grains have an average diameter of 0.1 mm with a maximum ley), Ciclova (Ciclova and Ţiganilor valleys) and Oraviţa length of about 0.2 mm. No chemical or optical zoning was (Ogaşul Crişenilor). A very rich mineral association charac- observed. terizes the high-temperature skarn areas in Romania: The average chemical composition recorded for the gehlenite, wollastonite, calcic garnet, vesuvianite and locally tinsleyite-included hydroxylellestadite from the exoskarn spurrite and tilleyite are the most representative species zone from Cornet Hill (mean of 47 microprobe point analy- (MARINCEA & DUMITRAŞ, 2001; PASCAL et al., 2002; ses) leads to the crystal-chemical formula: 2+ MARINCEA et al., 2002). (Ca4.916Mg0.001Mn0.002Fe 0.004Na0.069K0.002)(Si1.492S1.354P0.154) Monticellite and hydroxylellestadite were also identified, [O12.180(OH)0.651F0.121Cl0.048]. but they are scarce. Due to their scarcity, their minute grain This formula does not differ essentially from that estab- size and the mixture with other mineral phases, very few data lished for the gehlenite-included hydroxylellestadite in the are available on these mineral species. The purpose of the inner skarn zone from Oraviţa, which is, as calculated for an present paper is to gain additional data on the chemistry, average composition taken as mean of 6 point analyses: 2+ physical and crystallographic parameters and mineral asso- (Ca4.975Mg0.004Mn0.001Fe 0.004Na0.057K0.005)(Si1.572S1.346P0.082) ciations of these mineral species. [O11.787(OH)1.164F0.031Cl0.018]. Monticellite occurs as accessory mineral in the endoskarn A P-rich, Si-poor hydroxylellestadite was identified in the zones from all the four occurrences, being characteristically inner skarn zone at Ciclova. It has the same morphology and included by the gehlenite mass. The crystals are subhedral, occurs in the same mineral association as the hydroxylell- with prismatic habit; they average 0.5 mm in length and have estadite from Oraviţa, being engulfed by vesuvianite or up to 0.2 mm in width. In all cases, the mineral does not gehlenite. The crystal-chemical formula, established for a show any significant chemical or optical zoning pattern. representative sample on the basis of 6 point analyses is: 2+ The scattering of the analytical points at the scale of the (Ca4.972Mg0.001Fe 0.005Na0.041)(Si0.786S1.253P0.961)[O12.464 same thin section is minor, so that the microprobe analyses (OH)0.297F0.213Cl0.026]. were averaged and taken as mean compositions. The mineral has average compositions ranging from 8.53 to 11.66 mol% References kirschsteinite and from 0.91 to 2.52 mol% glaucochroite in BERZA, T., CONSTANTINESCU, E. & VLAD, Ş. N. solid solution in the samples from Oraviţa, from 4.55 to (1998). Resource Geol. 48/4: 291-306. 10.86 mol% kirschsteinite and from 0.62 to 1.01 mol% glau- MARINCEA, Ş., BILAL, E., VERKAEREN, J., PASCAL, cochroite in the samples from Ciclova and from 13.01 to M.-L & FONTEILLES, M. (2001). Can. Mineral., 39/5: 13.29 mol% kirschsteinite and from 1.51 to 2.05 mol% glau- 1435-1453. cochroite in the samples from Măgureaua Vaţei. MARINCEA, Ş. & DUMITRAŞ, D. (2001). Rom. J. Miner. The refraction indices, measured and calculated densities Dep., 79, Suppl. 2, 66-67. and cell parameters, as measured for representative samples PASCAL, M.-L., FONTEILLES, M., VERKAEREN, J., from Oraviţa and Măgureaua Vaţei approaching the mean PIRET, R. & MARINCEA, Ş. (2001). Can. Mineral., compositions are listed in Table 1. 39/5: 1405-1434.
Table 1. (1) (2) (2) Occurrence α β γ Dmeas. Dx a (Å) b (Å) c (Å) Oraviţa 1.645(2) 1.653(2) 1.659(2) 3.17(2) 3.177 4.817(2) 10.948(5) 6.314(3) Măgureaua 1.646(2) 1.653(2) 1.661(2) 3.13(1) 3.127 4.822(2) 11.130(5) 6.384(3) 3 (1) calculated from the measured value of the optical angle (2Vα = 80°); (2) expressed in g/cm ; Dx calculated from the chemical composition and the cell volume for Z = 4 unit cells per formula.
68 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
THE ORIGIN OF AMPHIBOLES OCCURRING IN MAFIC AND ULTRAMAFIC ROCKS OF THE DITRĂU ALKALINE MASSIF (EASTERN CARPATHIANS, ROMANIA)
MÁRTON, I.1, PÁL-MOLNÁR, E.2 & LUFFI, P.3 1 S. C. Deva Gold S. A., Piata Unirii 9, RO-2700 Deva, Romania. E-mail: [email protected] 2 Department of Mineralogy, Geochemistry and Petrology, University of Szeged, P. O. Box 651, H-6701 Szeged, Hungary. 3 Department of Mineralogy, University of Bucharest, Bd. N. Baldescu 1, RO-70111 Bucharest, Romania.
The Ditrău Alkaline Massif, Middle Triassic to Lower bole forming reactions. The reaction equation indicates that Cretaceous in age (PÁL MOLNÁR & ÁRVA-SÓS, 1995; an infiltrating alkaline/syenitic metasomatic melts give rise DALLMEYER et al., 1997; KRÄUTNER & BINDEA, to continuous change in the composition of the origin ul- 1998; STRECKEISEN & HUNZIKER, 1974), intruded into tramafic rocks, and that the production of amphiboles was the pre-Alpine metamorphic rocks of the Bucovina Nappe in controlled by the original clinopyroxene-olivine (-spinel) several phases. This series are related to the Alpine exten- modal ratio. These “metasomatic amphiboles” have very sional tectonism, which began with the detachment of the similar compositions in all samples, indicating that the Getic-Bucovinian microplate from the margin of the Eura- chemical character of fluids below the amphibolitisation was sian platform (KRÄUTNER & BINDEA, 1998). still the same and only the proportion of component minerals The mafic and ultramafic rocks of the massif occur in a has changed. well-defined area (Tarnica Complex), interdigited, with The P-T conditions of formation of amphiboles are esti- gradual transitions or forming intercalations (PÁL MOL- mated to be in the interval of 1030–820 oC and 7–10 kbar. NÁR, 2000). MOROGAN et al. (2000) suggest that the ul- NIIDA & GREEN (1999) presented experimental results tramafic rocks (clinopyroxenites and olivine- defining the water-undersaturated solidus and the amphibole clinopyroxenites) are cumulates of mantle origin and they stability limits of MORB pyrolite compositions. In this terms have been carried to higher crustal levels by the first intru- the genesis of DAM ultramafites could be explained as fol- sion of dioritic-gabbroic magmas. lows: (1) among upper mantle - crustal limit conditions cli- The goal of our study is to describe samples from the ul- nopyroxenite cumulate containing no amphiboles was tramafic and mafic rocks, using detailed petrographic obser- formed in equilibrium with melt, (2) with the evolution of vations and mineral chemistry analyses, trying to express the processes (P-T change) from this melt the crystallization of characteristics of different rock types, focusing mostly on the amphiboles has started. These amphiboles on the one hand genesis of the most abundant rock-forming component, the were formed as new - nucleated crystals and on the other amphibole. hand because the melt has changed its composition by evo- Detailed petrographic study shows that the occurrence of lution, being to aggressive replacing and enclosing the pre- amphiboles varies in different rock types. In alkaline diorites existent minerals some other type (“metasomatised”) amphi- and hornblendites, with shape-preferred orientation, their boles were formed along the cleavage and contacts of clino- habitat is euhedral, prismatic indicating their primary mag- pyroxene (olivine, spinel) crystals. From this point of view matic origin. Amphiboles in clinopyroxenites and olivine the described metasomatism is suitable for the processes of clinopyroxenites display typical textural features: 1) small, the magmatic evolution, being a mechanism of it, appearing oriented crystals along clinopyroxene cleavages; 2) replacing on the microstructural scale of the rock. and enclosing clinopyroxenes which cause poikilitic-like textures; and 3) large amphiboles containing tiny relicts of References clinopyroxene. These textural features from type 1 to type 3 DALLMEYER, R. D., KRÄUTNER, H. G. & NEUBAUER, suggest a pro-grading amphibole metasomatism. Amphiboles F. (1997). Geol. Carpathica, 48: 347-352. are pargasites, kaersutites, ferro-kaersutites and magnesium- KRÄUTNER, H. G. & BINDEA, G. (1998). Slovak Geol. hastingsites. Amphiboles differ in their compositions with Mag., 4: 213-223. respect to their occurrence in different rock types. Amphi- MOROGAN, V., UPTON, B. G. & FITTON, J. G. (2000). boles in the hornblendites, with shape-preferred orientation, Miner. Petrol., 69: 227-265. display strong chemical zonation, with high Si, Ti, Fe, and K NIIDA, K. & GREEN, D. H. (1999). Contrib. Mineral. Pet- enrichment and Al, Mg, and Na depletion at the rims. rol., 135: 18-40. Compositional profiles through clinopyroxenes from cli- PÁL MOLNÁR, E. (2000). Hornblendites and diorites of the nopyroxenites suggest that infiltrated Na-Fe-K-Ti enriched Ditró syenite massif., Szeged, 172 p. fluids reacting along with clinopyroxene cleavages formed PÁL MOLNÁR, E. & ÁRVA-SÓS, E. (1995). Acta. Min- amphiboles. It is typical in some cases for clinopyroxenes in eral. Petrogr., Szeged, 36: 101-116. contact with amphiboles, that directly next to the amphibole SEN, C. & DUNN, T. (1994). Mineral. Petrol., 119: 422- they suddenly get depleted in mobile elements such as Na, 432. Fe, K and Ti, which may be related to the metasomatic “front STRECKEISEN, A. & HUNZIKER, I. C. (1974). Schweiz. effect”. Mineral. Petr. Mitt., 54: 59-77. The experimental results of SEN & DUNN (1994) for modal metasomatism were applied to constrain the amphi-
69 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
LIMESTONES FROM THE KRIVELJ QUARRY (EAST SERBIA) – PETROGRAPHIC STUDY
MATOVIĆ, V. & VASIĆ, N. Faculty of Mining and Geology, Belgrade University, Djušina 7, YU-11000 Belgrade, Yugoslavia. E-mail: [email protected]
The Lower Cretaceous shallow-marine carbonate sedi- crack-net filled by calcite, limonite and argillaceous material. ments in the East Serbia, belonging to the southwestern mar- That material filled also frequent sinusoidal stylolites with gin of the Carpathian Belt, have a large extent and thickness. throat of weld from 0.1mm to 2 mm and amplitude height to The investigated carbonate rocks of the Krivelj Kamen are 1 cm. Limestones are generally grayish in color but variable the part of the Kucaj-Tupiznica carbonate platform i.e. its amount of bituminous (organic) matter caused local change eastern margin composing mostly of thick-bedded and mas- of color from light to dark gray and black. Thin-sections sive reef limestone with remains of corals colonies, oo- study of samples extracted from the bottom to the top of the sparites etc. named Urgonian Limestones. These rocks ap- quarry revealed slightly sorted micritic limestones with dif- pear on the eastern margin of the Timok Magmatic Complex ferent amount of allochems. Among them the following making an area of about 2 km2. The Krivelj quarry (0.7 km2) microfacies can be distinguish: dismicrites, intrabiomicrites with four working benches, situated in the central part of it, to biomicrites. Some of them contain more than 10 % of represents a lens of Urgonian limestones thrusted over Upper marine macrofossiles (∼5 cm in size or larger) and defined as Cretaceous volcano-sedimentary rocks. Over them Albian biomicrudite. According to structure, beside micrite with glauconitic sandstones, shale and conglomerates are depos- stylolites, fenestral micrites (with spar–filled fenestraes i.e. ited. It mostly composed of limestones with number of va- birds-eye structure) are defined. Allochems are represented rieties (as for example, dolomitic limestone), marbles, marble by bioclasts and intraclasts (very often recrystallization proc- limestones, fault breccias etc. Transition between limestone esses preclude classification of allochems). Skeletal particles and marbles is gradual, but dominated rock types are are identified as molluscs (gastropods), corals, foraminifers limestones. Intrusions of quartz diorite during Laramian- (Miliolidae, Orbitolinae). Pyrenean orogene phase caused thermal metamorphic phe- The quarried material is characterized as pure limestone. nomena i.e. occurrences of marbles and marble limestones. It does not contain detrital grains, iron oxides-hydroxides or By the latest tectonic events the lens of Urgonian limestones clayey materials. The microfacies analysis revealed that was broken into five blocks along the transform faults. limestones of Krivelj quarry were deposited in nereitic facies The limestones from the quarry are homogenous, non- (shallow marine) of subtidal paleoenvironment during Lower bedded and intensively tectonized. The a-lineation marked Cretaceous. by argillaceous component deposited on fault planes is visi- ble on the small tectonic blocks. Rocks are affected by dense
70 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
THE TWINNING STRUCTURE OF TRIDYMITE FROM MIAROLITIC DACITE OF THE CHERNA MOUNTAIN (TRANSCARPATHIANS, UKRAINE)
MELNIKOV, V. S. Institute of Geochemistry, Mineralogy and Ore Formation, National Academy of Sciences, Palladine Avenue 34, Kyiv, Ukraine. E-mail: [email protected]
The alkali feldspars (sanidine, anorthoclase) and tridy- morph replacement of quartz by tridymite is an evidence that mite are the main high-temperature phases which crystallised tridymite crystallised above 867 ºC. It is known (CARPEN- in miarolitic dacites (KVASNITZA et al., 1987). Transparent TER et al., 1998), that tridymite structure undergoes phase tabular crystals of tridymite represented an excellent object transition (P6322 → C2221) below 353 ºC. It is suggested for X-ray (Laue and oscillation photographs) and light opti- that subsequent transformation into monoclinic structure (< cal investigation. On the basis of cell dimensions three types 180 ºC) also accompanied twinning. Then, the transforma- of tridymite crystals have been discovered: 1. a = 51.83 Å, tions at 353 ºC and < 180 ºC may be the reason of the pseu- b = 29.99 Å, c = 49.2 Å; 2. a = 25.83 Å, b = 5.0 Å, c = 49.2 dohexagonal and polysynthetic twinning. Below inversion Å; 3. a = 17.22 Å, b = 9.93 Å, c = 40.91 Å. The Laue photo- point the domain size was small, but during the subsequent graphs of the first type of crystals show 6/mmm diffraction rock cooling the enlargement of the twin structure occurred. symmetry. Three different optical domains are displayed. The following observations are the evidence of that. 1. The The symmetry of the twin domain is pseudo-orthorhombic. fraction of the large domains in domain size distribution is The cell dimensions of the twinned crystal correspond to the predominant. 2. The twin domain system is unbalanced be- superstructure based on the monoclinic cell of MC-tridymite cause only one of the three possible oriented domains is (TAGAI et al., 1977). The domain structure arises from predominant. 3. During domain enlargement, a reorientation pseudohexagonal twinning of the monoclinic cell. The twin of twin boundaries takes place. It should be noted that domains are related to each other by a 60º rotation about [– sanidine coexisting with tridymite is not only untwinned but 201]. When only one domain in the crystal exists, the super- does not even show indications of exsolution. This suggests structure along the b axis disappears. That is the second type that the enlargement of tridymite twin domains was not real- of tridymite crystals. The cell dimensions of the third type ised by a diffusion mechanism. crystals correspond to a pseudo-orthorhombic tridymite OP-5 (NIKUI & FLÖRKE, 1987). References Two different morphologic varieties of the domain CARPENTER, M.A., SALJE, E. K. H. & GRAEME- boundaries exist in twinned tridymite. 1. Serrated (or saw- BARBER, A. (1998). Eur. J. Mineral., 10: 621–691. like) boundaries are dominant. Their orientation in most KVASNITSA, V.N., MELNIKOV, V.S., et al. (1987). Min- cases conforms to {11-20} plane. The “teeth” of twin eral. Zhurnal, 9/5: 22–29. boundaries formed on the intersection of {10-10} and {11- NIKUI, A. & FLÖRKE, O. W. (1987). Amer. Mineral., 72: 20} planes. 2. The thin polysynthetic twins on serrated 167–169. boundaries are rarely observed. The straight and narrow twin TAGAI, T., SADANAGA, R., TAKEUCHI, Y., TAKEDA, domains originate from saw “teeth” and then rapidly disap- H. (1977). Mineral. J., 8/7: 382–398. pear when they move off from the boundary. The pseudo-
71 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
Cr-SPINELS FROM MESOZOIC VOLCANIC ROCKS FROM PODMANÍN (WESTERN CARPATHIANS, SLOVAKIA)
MIKUŠ, T. & SPIŠIAK, J. Geological Institute, Slovak Academy of Sciences, Severná 5, SK-974 01 Banská Bystrica, Slovak Republic. E-mail: [email protected]
Cr-spinels belong to the most important petrogenetic in- On the basis of Cr-spinels classification (KLEIN & HUL- dicators of ultramafic and mafic rocks. Cr-spinel composition BURT, 1985) both these types are close to spinel solid solu- was used to classify the source material (POBER & FAUPL, tion. 1988, etc.). Cr-spinel detritus in Mesozoic complexes of the We have compared the composition of studied Cr-spinels Western Carpathians has been identified in different rock with those from Mesozoic picrites from Poniky and from types (carbonates, sandstones and others) in central Western Mesozoic sediments of a wider area. With its chemical com- Carpathians, in the Klippen belts, Manín unit, Tatricum, position the first spinel type corresponds to the spinels from Fatricum and Hronicum. Mesozoic volcanics have been picrites from the area of Banská Bystrica (SPIŠIAK & HO- considered one of the possible sources of Cr-spinels and due VORKA, 2000). These rocks are ranked to the formation of to that we have focused on this rock type. Lower Cretaceous alkaline basalts-basanites. Cr-spinels from Podmanín were extracted from about 15 These are no equivalent for the 2nd spinel type among kg of the concentrate from hyaloclastites–hydroclastic vol- spinels from Mesozoic sequences of the close vicinity. Ow- canic breccias. Cr-spinel has been preserved as the only ing to the available data it can be compared to the 1st spinel primary mineral (from among olivine, pyroxene, amphibole type from serpentinite sandstones of the Šambron zone and Cr-spinels). Volcanics are part of the Manín unit and (SPIŠIAK et al., 2001). According to geochemical criteria were incorporated into Lower Cretaceous complex of strata. these spinels are likely to come from ultrabasites of Alpine Chemical composition of fresh volcanics corresponds to type. They show lherzolite affinity (derived from the Pen- primitive alkali volcanites (HOVORKA & SPIŠIAK, 1988). ninic Ocean?). In the present state of knowledge we are not Chemical composition of Cr- spinels was studied with JEOL able to say unambiguously whether the second spinel type SUPEPROBE 733 (GSDŠ Bratislava). The chemical compo- was brought from another source to volcanoclastics, or it was sition of Cr-spinels is presented in Table 1. On the basis of pulled off the host rocks during the ascent of volcanites. chemical composition we have determined two types. The On the basis of different discriminant diagrams, (e.g. first has low Cr and Fe contents and high Al and Mg contents JAN & WINDLEY, 1990) the Cr-spinels being studied and compared to the other type. The contents of Mn, N, Ti and compared are lying in the field of residual peridotites of Zn are low in both these types. Two different types can be ophiolite complexes. recognized also from histograms of Cr and Al distribution.
Table 1
Type I Type II 1 2 3 4 5 6 7 8 FeO 11.13 11.66 11.83 11.63 17.87 17.81 18.36 19 Al2O3 55.28 55.44 56.51 55.89 36.36 34.35 36.32 32.92 Cr2O3 12.43 11.31 11.22 11.09 27.81 29.14 27.63 30.56 MgO 20.46 21.13 20.71 20.75 17.77 17.06 17.61 17.27 TiO2 0 0 0 0 0.99 1.1 0.89 1 MnO 0.03 0.07 0.02 0 0.08 0.1 0.1 0.09 NiO 0 0.02 0 0 0 0 0 0 ZnO 0 0 0.01 0 0 0 0 0 Total 99.33 99.63 100.3 99.36 100.88 99.56 100.91 100.84 formula based on 4 oxygens Fe2+ 0.2 0.18 0.2 0.19 0.28 0.29 0.28 0.29 Fe3+ 0.04 0.07 0.05 0.06 0.14 0.13 0.15 0.16 Al 1.7 1.69 1.71 1.71 1.2 1.16 1.2 1.1 Cr 0.25 0.23 0.22 0.22 0.62 0.66 0.61 0.68 Mg 0.8 0.81 0.79 0.8 0.74 0.72 0.73 0.73 Ti 0 0 0 0 0.02 0.02 0.01 0.02
72 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
CHARACTERIZATION OF As-RICH IRON OCHRE PRECIPITATES FROM MINE DRAINAGE WATER OF KOLÁRSKY VRCH Sb (Au) DEPOSIT (MALÉ KARPATY MTS., SLOVAKIA)
MILOVSKÁ, S. Geological Institute, Slovak Academy of Sciences, Severná 5, SK-974 01 Banská Bystrica, Slovak Republic. E-mail: [email protected]
The natural arsenic-iron ochres formed from mine drain- = 1.84) and Sb (up to 1.64 wt%), whereas in yellow phase age waters in the abandoned Sb (Au) deposit (Kolársky vrch concentration of these elements is distinctively lower (hun- deposit, Malé Karpaty Mts., Slovakia) were studied. All of dreds ppm). them precipitate and accumulate at near-neutral to neutral Organic compounds were encountered in all samples, pH, whereby no distinct seasonal fluctuations in pH were contents of total organic C were up to 4.7 wt%. Also infrared recorded. Chemical compositions of water differed mostly in spectra clearly evidence its presence by the COO-band at 2- -1 concentrations of SO4 , As, and Sb. Concentration of As and 1387–1399 cm . 2- Sb, to a smaller extent Fe and SO4 , reflects seasonal The high contents of As in samples from tailing im- changes. These are best pronounced in the samples from poundment drainage pipe sediments is pronounced in IR tailing drainage pipe. spectra. Features at 812 cm-1 could be assigned to AsO3- or After removal of organic and mineral detritus and dis- AsO4- compounds (FARMER, 1974). Absorption bands of v1 2- -1 4 2- -1 solved salts, samples of ochreous precipitates were dried and (SO4 ) at 980 cm and v (SO4 ) at 610 cm are supressed digested in hydrochloric acid for the total element determi- probably due to increased As-contents (CARLSON & nation. Ratios of oxalate to dithionite-extractable iron (ex- BIGHAM, 1992). Unfortunately the present state of knowl- traction in ammonium oxalate, and sodium dithionite-citrate- edge does not allow for proper determination of As specia- bicarbonate solution, respectively) were used to assess the tion in oxyhydroxides. Infrared spectra of the samples from relative crystallinity of poorly ordered iron oxyhydroxides. two other localities (Budúcnosť and Sirková adits) indicate Mineral composition of fresh precipitates was determined presence of ferrihydrite. using X-ray powder diffraction and infrared absorption X-ray diffraction patterns show for poorly ordered mate- spectroscopy. Morphology of precipitates was studied by rial in all studied samples, diffractograms consist of one or means of transmission electron microscopy. exceptionally two very broad maxima at d-values typical for The iron ochre accumulations from the tailing drainage iron oxyhydroxides. pipe form accretion cone of intercalating red- and yellow- This study was financially supported by the Slovak Sci- coloured ochres, situated on the streambank and partially entific Agency (VEGA 2062). flooded by stream water. Except of newly precipitated ochres the accretion cone contains organic and mineral detritus. References Red-coloured ochres (?maturated) accumulate in the cen- CARLSON, L. & BIGHAM, J. M. (1992). V. M. Confer- tre of accreted cone and are overlain by the layer of yellow- ence, Reiton, VA. coloured younger precipitates. Chemical composition of FARMER, V. C. (1974): The infrared spectra of minerals. these two phases strongly differs: red precipitates are ex- Mineralogical Society, London. tremely enriched in As (up to 13.02 wt%, mole ratio Fetot/As
73 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
CONTACT METAMORPHIC PROCESSES ON METAMORPHIC XENOLITHS IN NEOGENE INTRUSIVE BODIES FROM SOUTHERN PART OF RODNA MOUNTAINS (EAST CARPATHIANS, ROMANIA)
MOSONYI, E. Department of Mineralogy, Babeş-Bolyai University, 1, Kogălniceanu Str, RO-3400 Cluj-Napoca, Romania. E-mail: [email protected]
The Rodna Mountains consist of orogenic metamorphic fabrics, disequilibrium testifying reaction coronas around rocks, dynamic metamorphosed rocks (associated to the Pre- porphyroblasts; relic foliated structures, mimetic overgrowth Alpine and Alpine shear zones), post-tectonic sedimentary of relic foliation by neoblastic phyllosilicates and general rocks and Neogene intrusive rocks. tendency to obliterate oriented fabrics. The composition of intrusive bodies ranges between dio- The gneissic relict mineral assemblages were generated ritic and granodioritic. They are employed in Eocene sedi- in garnet-amphibolite facies conditions (peak conditions) of mentary rocks and metamorphics, too. The metamorphic host orogenic metamorphism and retrogression in greenschist rocks underwent slight, locally developed transformations facies conditions (T ~ 400 °C, P ~ 2.5–3 kbar; in MOSONYI, under chlorite-, biotite- and garnet zone conditions (green- 1992) were suffered. In gneissic xenoliths contact metamor- schist facies) at the contact zone, while xenoliths enclosed in phic transformation and conditions were deduced from min- magma suffered higher grade processes. eral reaction coronas and petrogenetic grid: Tmax = 400 °C + The main purpose of our research was to decipher the ∆T/2 ~ 770 °C and P ≤ 4 kbar conditions in the opaque zone, contact and orogenic metamorphic processes in metamorphic while into the central zone of xenoliths the lowered tem- xenoliths and to establish their PT-path. peratures (530–600 °C) determined recrystallized zone (relic The observed characteristics of metamorphic xenoliths biotite, garnet recrystallization and structural-textural reset- are the followings: the degree of contact metamorphic ting ) and newly crystallized mineral zone (cordierite + an- changes is directly related to the primary composition of dalusite + biotite; andalusite + biotite; staurolite + cordierite xenoliths; the most impressive mineralogical changes have + andalusite + garnet + hercynite). After these conditions the been observed in gneissic and pelitic xenoliths; zonal andalusite Æ sillimanite (“fibrolite”) transformation resulted changes in gneissic xenoliths could be detected (from contact and due to the temperature decreasing phyllosilicate to the inner zone of xenoliths: opaque mineral zone; recrys- (“pinite”) were formed. tallized zone: biotite, garnet, feldspar, amphibole; neoblas- thesis zone: garnet, staurolite, spinel, andalusite, cordierite, sillimanite (“fibrolite”) and chlorite); granoblastic, massive
74 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
NACARENIOBSITE IN PHONOLITES IN THE MECSEK MTS. (HUNGARY) – SECOND OCCURRENCE IN THE WORLD?
NAGY, G. Research Centre for Earth Sciences, Laboratory for Geochemical Research, Hungarian Academy of Sciences, Budaörsi út 45, H-1112 Budapest, Hungary. E-mail: [email protected]
Phonolites are highly differentiated members of the Cre- Nacareniobsite compositions measured by EMPA taceous submarine volcanic/subvolcanic alkaline rock suite in Mecsek Mts. (PANTÓ, 1980; DOBOSI, 1987; HARANGI 1) From PETERSEN et al. (1989) (average of 10 analyses) et al., 1996). They are enriched in light rare earth elements 2) In phonolite from Kövestető, Mecsek Mts. (average of 5 (REE) that are hosted mainly by accessory minerals analyses) (PANTÓ, 1980). By means of electron microprobe analysis (EMPA) the following accessory REE minerals have been 1) 2) found in the phonolites: britholite [(Ce,Ca)5(SiO4,PO4)3 SiO2 29.63 29.78 (OH,F)]; cheralite [(Ce,Th,Ca)(P,Si)O4]; nacareniobsite TiO2 2.79 1.26 [NbNa3Ca3REE(Si2O7)2OF3]; rarely bastnäsite [Ce(CO3)F]. Nb2O5 11.61 14.92 Nacareniobsite was described by PETERSEN et al. Ta O 0.34 0.00 (1989) from nepheline syenite in South Greenland. It is 2 5 Na2O 10.01 8.34 monoclinic, P21/a, “forms ruler-shaped crystals”. It “belongs CaO 19.92 20.54 to the same group of minerals as rinkite*, johnstrupite* and SrO 0.27 0.40 rinkolite*” (ibid.) (*Recently all three minerals are taken as Y2O3 0.78 0.66 synonyms or variants of mosandrite, see JONES et al., La O 4.09 4.72 1996). Their published analyses show deficiency in sodium 2 3 Ce2O3 10.32 9.21 and, in lower extent, calcium, which was attributed to leach- Pr O 1.42 0.83 ing. Since 1989 no other occurrence of this mineral has been 2 3 Nd2O3 4.19 2.41 mentioned. Sm O 0.81 0.36 Microscopic grains (with up to 140 µm lengths and 10-15 2 3 Eu2O3 n.a. 0.10 µm widths) of nacareniobsite were found in all of the phono- Gd2O3 n.a. 0.39 lite occurrences of the Mecsek Mts. They are often idiomor- Dy2O3 0.05 0.18 phic or hypidiomorphic, associated with albite and alkali ThO2 n.a. 0.71 feldspar, sometimes with pyroxene. Their energy dispersive F 6.87 6.23 X-ray spectra (EDS) and compositions unequivocally iden- Total 103.10 101.03 tify them. Based on the REE evolution model established by F=O 2.89 2.62 PANTÓ (1980), this mineral (as well as britholite and cher- Total* 100.21 98.40 alite) may have crystallized from the residual melt of the differentiated alkali magma. This work was supported by the Hungarian Scientific Re- search Fund (OTKA) program no. T032198, conducted by EDS spectrum of nacareniobsite Gy. Pantó.
References DOBOSI, G. (1987). N. Jb. Miner. Abh., 156: 281-301. HARANGI, Sz., SZABÓ, Cs., JÓZSA, S., SZOLDÁN, Zs., ÁRVA-SÓS, E., BALLA, Z. & KUBOVICS, I. (1996). Internat. Geol. Rev., 38: 336-360. JONES, A. P., WALL, F. & WILLIAMS, C. T. (1996): Rare Earth Minerals, 1-372. PANTÓ, Gy. (1980). Doctoral thesis, 1-152. PETERSEN, O. V., RONSBO, J. G. & LEONARDSEN, E. S. (1989). N. Jb. Miner. Mh., 84-86.
75 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
PROBLEMS OF MONAZITE DATING BY EMPA
NAGY, G. Research Centre for Earth Sciences, Laboratory for Geochemical Research, Hungarian Academy of Sciences, Budaörsi út 45, H-1112 Budapest, Hungary. E-mail: [email protected]
Theory Evaluation Monazite is suitable for age determination due to the 1) Isochron method according to SUZUKI et al. (1991) following properties: 1) It can incorporate Th and U (up to starting from the fact that in the Th*–Pb plane the isochrons >10%). 2) It is stable even at high P-T conditions. 3) Due to are straight lines. A line is fitted to the data points by least the low diffusion rate the emerging Pb does not escape. squares method, the ages are calculated from the slope and The radiogenic lead emeging during t time is: the uncertainties from the confidence intervals. This method Pbrad(t) = Th ·k1 ·(exp{λTh ·t}-1) + U ·[k2 can be used only if the Th* values fall in a wide range. 2) Method of MONTEL et al. (1996). Accepted that ·(exp{λ238U ·t}-1)+k3 ·(exp{λ235U ·t}-1)] non-radiogenic Pb in monazite is negligible, each Th-U-Pb data set is evaluated individually and weighted average is If t<400Ma it can be approximated linearly: formed. They described also a statistical method by which -5 Pbrad(t) ≈ 4.46 ·Th* ·10 ·t[Ma] where Th* multiple events can be discriminated. = Th + 3.2 ·U 3) More recent method of COCHERIE & ALBAREDE (2001) approaches the data by a straight line in the plane of By electron microprobe analysis (EMPA) the local Th, U Th/Pb – U/Pb quotients. The ages are calculated from axis and Pb contents can be determined so that even small and intercepts. This method can be applied only for relatively U- inhomogeneous monazite grains can be dated. rich monazites.
Analytical problems and conditions Results The amount of radiogenic Pb is usually small, near to In metamorphic rocks of Sopron Hills (Eastern Alps) two monazite generations were found, giving ages of ca. 300 the detection limit. (If Th* = 10%, t = 200Ma, Pb ≈ 0.09%; Ma and ca. 75 Ma (NAGY et al., 2002). The method has the background intensity is equivalent with 0.2% Pb con- been applied to Hungarian and Iberian granitoids and Vepo- tent.) Pb Mα line was used for analysis, which is relatively ric migmatites, too. free of overlaps, however due to numerous high-order and The present work is supported by the Hungarian Na- satellite lines it was difficult to find the proper spectrometer tional Research Fund (OTKA) pogamme no. T032198. positions for background determination. The analyses were performed at 20 kV, 80 nA, with fo- cussed electron beam; counting times 100 s on peaks, 50 s on References COCHERIE, A. & ALBAREDE, F. (2001). Geochim. Cos- both background positions. Mα lines measured on PET crys- tals were used for all three elements. Differential discrimi- mochim. Acta, 65: 4509-4522. nator was applied to decrease Pb background. Lead was MONTEL, J-M., FORET, S., VESCHAMBRE, M., NICOLLET, C. & PROVOST, A. (1996). Chem. Geol., measured twice in each point and has been corrected for Y L γ 131: 37-53. overlap. On standards and applied ZAF correction factors see NAGY, G., DRAGANITS, E., DEMÉNY, A., PANTÓ, Gy. NAGY et al. (2002). The standard deviation for individual & ÁRKAI, P. (2002). Chem. Geol., 191: 25-46. Pb analyses obtained from 200 duplicates: σ = 0.014wt-%, Pb SUZUKI, K., ADACHI, M. & TANAKA, T. (1991). Tecto- the statistical limit is ≈ 0.012%. nophysics, 235: 277-292.
76 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
CONDITIONS OF FORMATION OF THE GOLD-BEARING STOCKWORK-TYPE BODIES OF THE BEREGOVE ORE FIELD (TRANSCARPATHIANS, UKRAINE)
NAUMKO, I., KOVALYSHYN, Z. & MATVIISHYN, Z. Institute of Geology and Geochemistry of Combustible Minerals of the Ukrainian Academy of Sciences and National Joint- Stock Company “Naftogaz of Ukraine”, Naukova st. 3a, UA-79053 Lviv, Ukraine. E-mail: [email protected]
The search and estimation of new gold-bearing ore bodies bodies (bends of joints; superposition of various age gold- are acquiring great significance for the Beregove ore region bearing fluids; zones of brecciation; increased content of the in the Ukrainian Transcarpathians where famous gold depos- main associated elements of native gold (As, Sb, Ag, Ba, its of industrial importance are known. They are the most Mo)). perspective within the limits of the north zone of the (s.s) The generalisation of the results of investigations of par- Muzhieve deposit (Kuklia ore occurrence), in its southern ageneses with minerals of native gold, their typomorphism, and eastern flanks, and in zones of transition from quartz especially of fluid inclusions, follows. The solutions in the vein (lower horizons) to stockwork-type (upper horizons) period of forming of gold-bearing stockwork-type bodies formations. Here stockwork-type ore bodies developed were characterised by sulfate–bicarbonate salt composition where Au is found as quartz-clay gold ores. with the predominance of calcium and magnesium ions. The The deposits of this type in the Ukrainian Transcarpathi- gaseous phase of inclusions in minerals is enriched by nitro- ans belong, together with the similar deposits of Hungary, gen (64.5–41.4 vol%) compared to CO2 (24.0–12.5 vol%). Slovakia and especially Romania, to a single metallogenic The optimal temperature interval of ore (gold) forming province of epithermal gold-polymetallic mineralization. comes to 250–170 ºC. The ore bodies were formed when the There is a need for the investigation of the genetic peculiari- gold-bearing hydrothermal systems intensively boiled and ties of these ore-bearing parageneses. fluids of different origin (deep-seated and surface) mixed in Thermometrical and geochemical fluid inclusion research zones of mineral forming. The movement of mineral forming was carried out on minerals of one of the typical stockwork fluids from a depth in the direction from northwest to south- ore bodies. This formed the basis of specific criteria for the east was traced in a prevalent increase of temperatures of estimation of the perspective of their gold content. These homogenisation of fluid inclusions in the same direction. The data are supplemented by data from geological-structural precise regional temperature zonality with predominance of analysis (with our participation) which showed that several lateral over vertical is observed. additional factors can be used in the localisation of such ore
77 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MINERAL MICROINCLUSIONS HOSTED IN SULFIDES OF MAIN NEOGENE PORPHYRY COPPER AND EPITHERMAL ORE DEPOSITS OF THE SOUTH APUSENI MOUNTAINS, ROMANIA
NEDELCU, L., ROSU, E. & COSTEA, C. Geological Institute of Romania, Caransebeş 1, RO-78344 Bucharest, Romania. E-mail: [email protected]
The Neogene porphyry copper and epithermal ore depos- 1. Mineral microinclusions mainly appear as daughter its of the South Apuseni Mountains are related to calc- phases trapped within fluid inclusion cavities during fluid alkaline intermediate volcano-plutonic complex structures evolution from magmatic to hydrothermal stage. closely connected with extensional deep-seated faults. These 2. Chloride and silicate glass microinclusions from por- structures contain a large variety of ore deposit types, but phyry systems studied fill up to 50–90 vol% of fluid inclu- with a strong specialization for Cu-Au that would involve a sion cavities, especially that of potassic zone, suggesting that unique source (ROSU et al., 2000). they could be considered as really salt melt and silicate melt The sulfides of main porphyry copper and epithermal ore inclusions as in paragenetic quartz (PINTEA, 1997). deposits of this region contain a lot of mineral microinclu- 3. The ubiquity of the chloride and sulfide microinclu- sions. In order to establish the role of these solid microinclu- sions hosted in pyrite and sphalerite of all porphyry copper sions in the magmatic-hydrothermal fluid evolution the aim and epithermal ore deposits studied reveals the role played of our study is to determine, using SEM/EDAX analyses, by Cl and S as complexing ligand components during the their chemical composition. magmatic-hydrothermal fluid evolution. This one could in- The SEM/EDAX analyses were performed in open cavi- volve a metal fractionation between the coexisting fluids ties by splitting of pyrite and sphalerite crystals from differ- (HEINRICH et al., 1999). According to DRUMMOND & ent ore deposit types: porphyry copper, base metal/gold brec- OHMOTO (1985) Cl mainly fractionates into the saline cia pipe and low/high-sulfidation epithermal deposits. The liquid (see the chloride microinclusions), whereas S usually chemical composition of the mineral microinclusions was fractionates into the vapour phase (see the sulfide microin- determined using a PHILIPS electron microscope (METAV- clusions). Therefore the liquid-partitioning elements proba- Bucharest Laboratory) and a REMMA 202 electron micro- bly include in our case Na, K, Fe, Zn, (P, Th?) and also low probe (IGR Laboratory) both equipped with EDAX analyzer. contents of Cu and Au, especially as complex chlorides in The operating conditions were an accelerating voltage of 30 porphyry copper and epithermal ore deposits. As regards the kV and a counting time of 50 s. vapour-partitioning elements these could include, to a certain Thus, based on about 170 SEM/EDAX analyses, the fol- extent, Au, Cu (Valea Morii, Voia and Rosia Poieni por- lowing mineral microinclusions have been determined: phyry copper deposits) and Au, As, Sb, Cu (Baia de Aries • chlorides: halite, sylvite, CaCl2 gold breccia pipe deposit). • complex chlorides: (Na,K)Cl; (K,Fe)Cl; 4. Anhydrite microinclusions suggest that magmatic- (K,Fe,Cu)Cl; (K,Fe,Zn)Cl; (K,Fe,Au)Cl; (K, Zn, Au)Cl hydrothermal fluids operated under oxidizing conditions, • sulfides: chalcopyrite, bornite, molybdenite, also supported by magnetite presence. sphalerite, galena, pyrite, pyrrhotite, marcasite • oxides: hematite, rutile, zircon, spinel, quartz References • sulfates: anhydrite, gypsum DRUMMOND, S. E. & OHMOTO, N. (1985). Econ. Geol., • phosphates: apatite, chlorapatite±Th±Cu 80: 126-147. • carbonates: calcite, dolomite, siderite, HEINRICH, C. A., GUNTER, D., AUDETAT, A., ULRICH, ankerite I. & FRISCHNECHT, R. (1999). Geology, 27: 755-758. PINTEA, I. (1997). ECROFI XIVth, Nancy, Abstracts: 266- • phyllosilicates: illite, sericite 267. • silicates: Al, Ca silicates ROSU, E., NEDELCU, L., UDUBASA, G., PINTEA, I. & • silicate glass IVASCANU, P. M. (2000). ABCD-GEODE 2000 All mentioned data lead us to some conclusions, as fol- WORKSHOP Borovets, Bulgaria, Sofia, May 2000, Ab- lows: stracts: 72.
78 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MINERALS OF THE CARPATHIANS: FIRST UPDATE
ONAC, B. P. Babeş-Bolyai University & “Emil Racoviţă” Institute of Speleology, 1, Kogalniceanu Str, RO-3400 Cluj-Napoca, Romania. E-mail: [email protected]
This abstract presents an update to the Minerals of the gates (3 to 50 mm in diameter) and earthy masses in the Carpathians book (SZAKÁLL, 2002). The entries listed lower part of the fresh guano that that overlies the argilla- below largely consist of new species of minerals described ceous floor deposits from Măgurici Cave (ONAC & VEREŞ, from various caves in Romania and few other minerals that 2003). are in course of publication (both from caves and old mining Glaukosphaerite - (Cu,Ni)2(CO3)(OH)2 occurs in Water galleries). Chemical and mineralogical characterization of Cave from Codreanu mine (Băiţa) as thin coatings of deep these minerals was undertaken by XRD, XRF, energy- green color in association with malachite and rosasite. 2+ dispersive, atomic absorption, and infrared spectrometry, Jokokuite - Mn SO4 • 5H2O forms pale pink, rosette-like thermal and electron-microprobe analyses, optical and scan- aggregates (2-3 cm in length) intimately associated with ning electron microscope observations. The specimens are rozenite. The jokokuite crystals have vitreous luster and deposited in the Mineralogical Museum of the “Babeş- show no cleavage (ONAC et al., unpublished). Bolyai” University and at the “Emil Racoviţă” Institute of Lansfordite - MgCO3 • 5H2O was first described as a Speleology in Cluj-Napoca and Bucharest, Romania. cave mineral from Valea Rea Cave (Bihor Mts.) were it ap- pears as white fine powdery masses associated with hydro- Minerals discovered before 2002 magnesite (ONAC & FEIER, 2003). 3+ Monohydrocalcite - CaCO3 • H2O, was reported to occurs Leucophosphite - KFe2 (PO4)2(OH) • 2H2O forms thin in the composition of white hydrated moonmilk in Humpleu pale yellowish-brown crusts (less than 1 mm thick) within and Lucia Mică caves (Bihor Mts.) (ONAC & GHERGARI, white taranakite veins in a section below the Bivouac Room, 1993). Cioclovina Cave (ONAC et al., 2002). Darapskite - Na3(SO4)(NO3) • H2O and nitratine - Norsethite - BaMg(CO3)2 appears as well crystallized NaNO3 were found closely associated within the sediments white nodular aggregates on the walls of two skarn-hosted accumulated on the floor of Şălitrari Cave (Cerna Mts.) (DI- caves (Crystal and Surprise) in the Băiţa metallogenic district ACONU & LASCU, 1999). (ONAC, 2002). Phosphammite - (NH4)2HPO4 occurs as sparse, colorless, Mineral species described in caves and old mine galleries and transparent anhedral crystals (0.5 mm in size) in the from the Romanian Carpathians in 2002 tower part of the guano deposit hosted by the Măgurici Cave Berlinite - AlPO4 was found as grayish or colorless fine (ONAC & VEREŞ, 2003). crystals growing along cracks in well-cemented clay or im- Tinsleyite - KAl2(PO4)(OH) • 2H2O appears in small pregnating the body of this clay in Cioclovina Cave, Şureanu quantities, as composite aggregates, early diagenetic mineral Mts. (ONAC et al., 2002). in the bat guano deposit from Cioclovina Cave (MARINCEA Burbankite - (Na,Ca)3(Sr,Ba,Ce)3(CO3)5 appears as a thin et al., 2002). crust composed of sub-millimeter yellow grayish anhedral crystals. This rare anhydrous carbonate was found in asso- References ciation with colorless or milky white needle-like brushite and DIACONU, G. & LASCU, C. (1999). Theor. Appl. Karstol., gypsum crystals in Cioclovina Cave (ONAC et al., 2002). 11-12: 47-52. Cesanite - Na3Ca2(SO4)3(OH) was found closely associ- MARINCEA, Ş., DUMITRAŞ, D. & GIBERT, R. (2002). ated with hydroxylapatite in ochre to red-brown crusts along Eur. J. Mineral., 14: 157-164. the walls in Măgurici Cave (Someş Plateau) (ONAC & ONAC, B. P. (2002). Can. Mineral., 40: 1551-1561. VEREŞ, 2003). ONAC, B. P., BREBAN, R., KEARNS, J. & TĂMAŞ, T. 2+ Collinsite - Ca2(Mg,Fe )(PO4)2 • 2H2O appears as trans- (2002). Theor. Appl. Karstol., 15: 27-34. lucent millimeter thin-walled balloons lining dissolution ONAC, B. P. & FEIER, N. (2003). Studia Univ. Babeş- cavities within a thick hydroxylapatite crusts collected from Bolyai, Geologia, XLVIII/1. Cioclovina Cave (ONAC et al., 2002). ONAC, B. P. & GHERGARI, L. (1993). Cave Science, 20/3: Foggite - CaAl(PO4)(OH)2 • H2O was identified within a 107-111. black earthy-mass aggregates collected from below brown- ONAC. B. P. & VEREŞ, D. Ş. (2003). Eur. J. Mineral., in reddish crandallite-rich clays in Cioclovina Cave (ONAC et press. al., 2002). SZAKÁLL, S. (ed.) (2002): Minerals of the Carpathians. 3+ Francoanellite - H6(K, Na)3(Al, Fe )5(PO4)8 • 13H2O Granit, Prague, 480 p. forms soft and unctuous to the touch, white nodular aggre-
79 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
DEPOSITIONAL ENVIRONMENT OF SECONDARY PHOSPHATE MINERALS IN MĂGURICI CAVE (ROMANIA)
ONAC, B. P. & VEREŞ, D. Ş. Babeş-Bolyai University & “Emil Racoviţă” Institute of Speleology, 1, Kogalniceanu Str, RO-3400 Cluj-Napoca, Romania. E-mail: [email protected]
The Măgurici Cave is located in northwestern Romania, a decrease in the water vapour partial pressure (phenomenon approximately 100 km north of the town of Cluj, in the north restricted to certain locations within the cave), and (b) a central part of the Someş Plateau. The floor of the Entrance sequence of Ca-rich phosphate minerals formed when guano Passage comprises boulders and rubble fallen from the roof reacts with limestone bedrock or fallen blocks. In the second and walls. Throughout the rest of the cave the floor com- situation, four main mineral assemblages were documented prises argillaceous sediments of unknown thickness. The (Fig. 1). We interpreted their precipitation as a response to main guano deposits are at the far end of the cave, reached changes in the pH and relative humidity of the environment, through several tight clefts and low passages. Isolated bat along with a progressive increase of the Ca/P ratio (Fig. 1). colonies have formed small guano deposits along the Bat In addition, an interesting observation is that all Ca-rich Gallery and Clay Passage. Dry powdery guano covers the phosphate minerals appear in paragenesis with different cave floor, limestone blocks and parts of the walls except in sulphates, each of them strengthens the physico-chemical the Guano Gallery, where most of the organic sediment is conditions of the depositional environment. fresh and damp. Throughout the sampled part of the cave, the The coexistence of the described minerals within the relative humidity ranges from 85 and 100% while the mean phosphate aureole gives information about genetic environ- temperature remains constant year-round in the range of 9- ments. Brushite and taranakite form under damp conditions 10.2 °C (Borda, pers. comm.). A temperature increase (in from solution with a pH lower than 6. Partial or total dehy- average with 5–6 °C higher) was measured within both fresh dration under the same acidic pH results in the precipitation and fossil guano deposits. of francoanellite and monetite, respectively. Although arde- alite may form over a wide range of relative humidity values, its field of nucleation lies between pH 6.2 and 7. The presence of hydroxylapatite indicates a slightly alkaline environment, which precipi-tates and is stable under such conditions (POSNER et al., 1984). Its abundance when comparing to the other phosphates in this cave clearly suggests that the depositional environment throughout much of the cave extent is slightly alkaline, being acidic or neutral only in the vicinity of guano accumulations. In addition, the present study presents the second worldwide reported occurrence of phosphammite discovered in a cave environment. This rare mineral occurs as small transparent crystals within the guano deposit, precipi- Fig. 1: Mineral paragenesis sequences in Măgurici Cave. tated in an early stage from the liquid fraction of guano.
Reference The mineral assemblages investigated in Măgurici Cave POSNER, A. S., BLUMENTHAL, N. C. & BETTS, F. are diverse. The phosphatization of argillaceous sediments (1984). Chemistry and structure of precipitated and limestone leads to the generation of a complex suite of hydroxylapatites. in Nriagu, J. O. & Moore, P. B. (Eds.): phosphate minerals. Two tendencies were observed: (a) in Phosphate minerals, Springer-Verlag, Berlin, 330-350. the presence of excess alkali, the mineral formed initially is taranakite, which partially dehydrates to francoanellite due to
80 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
SECONDARY MINERALS FOUND IN OLD MINE GALLERIES FROM ROŞIA MONTANĂ, ROMANIA
ONAC, B. P.1, VEREŞ, D. Ş.1, KEARNS, J.2, CHIRIENCO, M.3, MINUŢ, A.4 & BREBAN, R.4 1 Babeş-Bolyai University & “Emil Racoviţă” Institute of Speleology, 1, Kogalniceanu Str, RO-3400 Cluj-Napoca, Romania. E-mail: [email protected] 2 Pennsylvania State University, USA. 3 Department of Mineralogy, Babeş-Bolyai University, 1, Kogalniceanu Str, RO-3400 Cluj-Napoca, Romania. 4 S. C. Roşia Montană Gold Corporation S. A., Roşia Montană, Romania.
Recent investigations carried out on some secondary on metamorphic or igneous rocks (RĂDULESCU & DIMI- minerals formed along old mining galleries in the Cârnic TRESCU, 1966). 2+ 2+ district (Roşia Montană) enabled us to characterize eight Dietrichite - (Zn,Fe ,Mn )Al2(SO4)4 • 22H2O forms minerals, out of which, according to a recently published tufted aggregates of acicular crystals and efflorescences inventory (SZAKÁLL, 2002), one (jokokuite) is for the first along galleries’ ceiling. The color is dirty yellow or some- time mentioned in the Carpathians. Another mineral (apjoh- times greenish. The type locality for this mineral is Baia nite) seems to represent a new occurrence in Romania as it Sprie (Maramureş, Romania) whereas Roşia Montană repre- was neither mentioned on UDUBAŞA’s (1999) checklist nor sents its second occurrence in Romania. in SZAKÁLL (2002). The precipitation of the minerals de- 2+ Halotrichite - Fe Al2(SO4)4 • 22H2O was observed as scribed below is largely controlled by changes in temperature yellowish-brown mammillary aggregates with vitreous lus- and water vapor partial pressure of the galleries microenvi- ter. It was also found as hair-like efflorescences. ronment, and also by the cation substitutions. All the miner- Kalinite - KAl(SO ) 11H O is rather abundant in the als described were identified by routine X-ray powder dif- 4 2 • 2 fraction analyses, being subsequently investigated by means gallery we investigated and appears as delicate, tiny fibers of energy-dispersive spectrometry, electron-microprobe overlying halotrichite aggregates. Crystals are translucent analyses, optical and scanning electron microscope observa- and if removed from the gallery environment will decompose tions. The specimens are deposited in the Mineralogical within minutes into a white milky powder. 2+ Museum of the “Babeş-Bolyai” University in Cluj-Napoca, Melanterite - Fe SO4 • 7H2O forms colorless to translu- Romania. cent, sometimes slightly green fibrous aggregates (up to 4 2+ cm) having vitreous luster. Upon exposure to dry air crystals Jokokuite - Mn SO4 • 5H2O forms pale pink, rosette-like aggregates up to 2-3 cm in length on the walls of an old become white-yellowish and opaque. mining gallery at horizon +958 m, intimately associated with Pickeringite - MgAl2(SO4)4 • 22H2O was first identified rozenite. The jokokuite crystals have vitreous luster, no in Romania in Diana Cave, Băile Herculane (DIACONU & cleavage and are easily soluble in water. The average cell MEDEŞAN, 1973). In our investigated occurrence at Roşia parameters obtained on the basis of 29 powder reflections are Montană the mineral forms shining white to silky thin crys- a = 6.38(2) Å, b = 10.70(1) Å, c = 6.22(2) Å, α = 97.619(5)°, tals (3-5 mm in length) covering apjohnite crusts. 2+ β = 110.493(8)°, γ = 75.88(9)°. The c cell parameter is Rozenite - Fe SO4 • 5H2O is the main component of the smaller than the reported value in the ICDD file 31-836, rosette-like aggregates found on the ceiling of abandoned which may reflect the substitution of Mn2+ with Fe2+. adits of the gold deposit at Roşia Montană. The white or 2+ colorless fibrous aggregates of rozenite form directly on Apjohnite - Mn Al2(SO4)4 • 22H2O. Found in several samples collected from either floor or walls of old adits. It highly weathered dacites and can reach 3 to 5 cm in length. forms white to yellowish brown or greenish crusts or fibrous and needle-like crystals (up to few centimeters). The unit cell References of a representative sample (#1538) as refined by least squares DIACONU, G. & MEDEŞAN, A. (1973). Trav. Inst. Spéol. of 48 reflections were found to be a = 6.266(5) Å, b = „Emile Racovitza”, XII: 303-309. 24.502(2) Å, c = 21.281(3) Å, and β = 98.692(8)°. In sample RĂDULESCU, D. & DIMITRESCU, R. (1966). Mineralo- #1541 it appears associated with pickeringite. gia topografică a României. Ed. Academiei Române, Bu- cureşti, 376 p. Alunogen - Al (SO ) 17H O appears in association 2 4 3 • 2 SZAKÁLL, S. (ed.) (2002). Minerals of the Carpathians. with pickeringite as efflorescences on dietrichite botryoidal Granit, Prague, 480 p. aggregates. The prismatic crystals of alunogen are up to 2 UDUBAŞA, G. (1999). Rom. J. Mineralogy, 79: 3-30. mm in length and are extremely thin (<0.5 mm). Up to now, this mineral was mentioned to occur only as efflorescences
81 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
ROCK-FORMING MINERALS OF BATTONYA AND CSONGRÁD UNIT GRANITOIDS
PÁL-MOLNÁR, E., BATKI, A. & KÓBOR, B. Department of Mineralogy, Geochemistry and Petrology, University of Szeged, P. O. Box 651, H-6701 Szeged, Hungary. E-mail: [email protected]
The crystalline mass of the Tisia Composite Terrane is are albite-oligoclase in composition, the plagioclases of PB characterised by granitoid ranges and anticline wings of High granitoid rocks are albite-andesine (Fig. 1). middle and high grade metamorphites. This paper presents The biotites of PB and ADMF High granitoids are rich in the results of a mineralogical analyses on the granitoid rocks Fe (Fig. 2). Besides, biotites can also be considered as petro- originating from characteristic uplifts of the basement (Al- genetic indicators for early stage granite genesis, since their győ-Deszk-Ferencszállás-Makó - [ADFM] High and Pusz- Mg content reflects the grade of magma fractionation taföldvár-Battonya - [PB] High) of the Békésia Terrane, (HECHT, 1993). Parallel to proceeding magma fractionation Tisia Composite Terrane. the Mg content of biotites decreases while the AlVI content The granitoid samples of PB High are mainly of light remains constant, i.e. its value varies between 0.54 and 0.93. grey, greenish grey colour. Most of them have a holocrystal- Thus, based on the composition of biotites ADMF granites line, inequigranular texture, however, some samples are of are more fractioned than PB granitoids (Fig. 3). According to equigranular texture. The colour of ADMF High granitoid the Mg vs Altot ratio in biotites, the granites proved to be rocks is mainly light grey, subordinately pale rose-colour. calc-alkaline. Their texture is mostly holocrystalline, medium-grained Or inequigranular and equigranular. Based on the orientation of Fig.1. Feldspars from PB (z) mica, in some places the studied rocks are characterised by a and ADMF ()granitoids. preferred orientation in terms of their texture. Concerning the
e in id mineral composition and texture of the rocks, significant n a differences cannot be detected, thus they can be considered S of similar character (PÁL-MOLNÁR et al., 2002a, b). The major rock forming minerals are quartz, K-feldspar, plagio- clase feldspar and mica (biotite, muscovite). The usual size Anorthoclase Oligoclase of minerals falls between 1-3 mm, however microcline por- Albite Andesine Labradorite Bytownite Anorthite phyroblasts of 2-3 cm are not rare either. Accessory compo- Ab An nents are apatite, zircon, monazite, less frequently garnet and titanite. Secondary components are chlorite, sericite, carbon- 1,4 3,0 ate, epidote, limonite and opaque minerals. Eastonite Siderophyllite 1,2 2,8 Rock forming and accessory minerals were investigated 1,0 2,6 0,8
with electron microprobe analysis. Representative results on Al(VI)
Al(IV) 2,4 0,6 the minerals are presented in Table 1. 2,2 0,4 Phlogopite Annite 2,0 0,2 Table 1. Representative microprobe analyses of minerals from granites of Battonya- and Csongrád Unit 0 0,2 0,4 0,6 0,8 0,0 0,5 1,0 1,5 2,0 2,5 3,0 Sample 1610 13151315 1318 1241 1318 1214 1241 1214 Fe /(Fe +Mg) Mg Mineral biotite muscovite feldspar apatite monazite rim core SiO2 36,8 37,3 35,6 35,9 45,7 47,7 68,2 65,9 65,0 0,38 0,17 SiO2 0,83 TiO2 2,99 3,08 2,91 3,19 1,28 0,46 - 0,06 0,07 0,02 nd CaO 1,45 IV VI Al2O3 17,4 17,2 16,6 16,4 31,8 34,5 19,8 21,3 18,4 0,23 0,06 P2O5 28,9 Fig. 2. Al vs. Fe/(Fe+Mg) ratio in Fig. 3. Mg vs. Al of FeO* 17,6 16,8 20,48 20,2 3,3 1,6 0,06 0,07 0 0,11 nd La2O3 13,5 MnO 0,22 0,3 0,59 0,48 0,04 0,04 - 0,03 0,06 0,12 0,02 Ce2O3 28,0 biotites from PB (z) and ADMF biotites from PB (z) and MgO 9,5 8,8 8,2 8,4 0,7 0,7 - 0,04 nd 0,03 nd Pr2O3 2,02 CaO 0,16 0,12 0,11 0.05 nd 0 0,87 2,59 0,04 52,6 52,7 Nd2O3 9,95 () granitoids. ADMF () granitoids. Na2O 0,23 0,150 0,22 0,14 0,30 0,39 11,42 10,3 0,89 nd 0,51 ThO2 8,88 K2O 9,24 7,33 9,13 9,00 9,49 9,64 0,09 0,08 15,98 0,28 nd P2O5 nd nd nd nd nd nd - - nd 40,6 41,3 Total 94,19 91,05 93,89 93,85 92,59 94,89 100,45 94,38 94,71 93,73 Cations to Cations to Cations to 22 oxygens Cations to 8oxygens 12 oxygens 4oxygens Acknowledgements Si 5,62 5,79 5,56 5,58 6,30 6,33 2,99 2,89 2,99 0,03 0,01 Si 0,034 Al 3,14 3,15 3,05 3,02 5,17 5,41 1,02 1,10 1,00 0,02 0 Ca 0,064 The financial background of this work was ensured by AlIV 2,39 2,22 2,44 2,42 ------P 1,001 AlVI 0,75 0,92 0,61 0,60 ------La 0,204 Ti 0,34 0,36 0,34 0,37 0,13 0,05 - 0 0 0 - Ce 0,419 the Hungarian National Science Found (OTKA) (Grant No. Fet 2,24 2,19 2,67 2,63 0,38 0,18 0 0 0 0 - Pr 0,030 Mn 0,03 0,04 0,08 0,06 0,01 0,01 - 0 0 0 0 Nd0,145 F/029061) and the János Bolyai Research Grant. Mg 2,16 2,03 1,91 1,94 0,15 0,14 - 0 - 0 - Th 0,083 Ca 0,03 0,02 0,02 0,01 - 0 0,04 0,12 0 4,70 4,68 Na 0,07 0,05 0,07 0,04 0,08 0,10 0,97 0,87 0,08 - 0,08 K 1,80 1,45 1,82 1,79 1,67 1,63 0 0 0,94 0,03 - P ------2,872,90 References nd - not detected element; FeO* - as total iron HECHT, L. (1993). Münchener Geol Hefte, 10, 221. PÁL-MOLNÁR, E., KOVÁCS, G. & BATKI, A. (2002a). The dominant mineral assemblages are feldspars and mi- Acta Mineralogica-Petrographica, Szeged, 42: 21-31. cas. K-feldspar and microcline are abundant in the studied PÁL-MOLNÁR, E., KOVÁCS, G. & BATKI, A. (2002b). granites, and orthoclase is generally present as well. The Acta Mineralogica-Petrographica, Szeged, 42: 51-58. often zoned plagioclase feldspars of ADMF High granitoids
82 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
ORIGIN OF GRANITOID ROCKS OF THE DITRĂU ALKALINE MASSIF, TRANSYLVANIA, ROMANIA
PÁL-MOLNÁR, E.1, KOVÁCS, G.2 & BENŐ, É.3 1 Department of Mineralogy, Geochemistry and Petrology, University of Szeged, P.O. Box: 651, H-6071 Szeged, Hungary. 2 Environmental Protection Inspectorate of Lower Tisza Region, Felső-Tisza part 17, H-6721 Szeged, Hungary. E-mail: [email protected] 3 Dipartimento di Scienze Mineralogiche e Petrologiche, Università degli Studi di Torino, Via Valperga Caluso 35, I-10125 Torino, Italy.
Recent analyses of the granitoid rocks of the Ditrău Al- 32.3, indicating heterogenites. Besides, it refers to the frac- kaline Massif (DAM) have shown that the massif is more tionation and differentiation trend as well. complex than it was suggested earlier. The modal analyses The morphology of zircons shows that they were crystal- enabled the identification of nine different rock types from lised under a high temperature (800–850 °C), in a hyperalka- an area that was handled as a homogenous granite body be- line environment, which also proves the mantle derivation of fore. The most abundant accessory minerals are apatite, zir- the magma. con, sphene and allanite, suggesting that the granites of the Applying geothermobarometry on quartz inclusions (Th DAM were formed by magmatic differentiation processes and salinity data) the trapping temperature and pressure of (BROSKA & UHER, 1991). fluid inclusions were also estimated: T = 620–680 °C, P = On the basis of ASI, varying between 0.92-1.06 (mean = 6.2–10.2 kbar. These results show that the crystallization of 1.01), most of the samples are peraluminous. When consid- quartz took place in the upper crust. ering their geochemical character, two groups, namely subal- K/Ar radiometric dating of the examined granitoid rocks kaline and alkaline can be identified. Rocks of higher SiO2 suggests that they have magmagenetic relationship with content are subalkaline, while those of lower SiO2 content hornblendites and nepheline syenites (PÁL-MOLNÁR, are alkaline (e.g. COX et al., 1979). A magmatic evolution- 2000). The rocks represent a Middle Triassic-Lower Jurassic ary differentiation and fractionation relationship can also be comagmatic suite which can be separated from younger detected among the examined rocks. The most fractionated diorites and syenites of DAM on the basis of dating. Geo- samples are those oversaturated rocks (granites) which repre- chronology also confirms that these granitoids are end- sent the subalkaline branch of the magmatic trend. The other products of the magmatic differentiation of mantle derived branch is alkaline, and involves Qtz-monzonites, Qtz- ultramafic rocks. syenites, syenites and probably nepheline syenites (PÁL- Considering the results above, it is possible that the MOLNÁR, 2000; MOROGAN et al., 2000). source of the examined rocks were mantle derivatives formed Based on the comparison of major and trace elements in an extensional, within-plate tectonic environment and found in some characteristic samples, the granitoid rocks of subsequently modified by differentiation and crustal con- DAM have higher Al2O3, Na2O, K2O, Rb, Sr, Nb, Zr, Ga and tamination. lower MgO, CaO, Ba, Pb, Y, Ni contents. These data suggest that the examined rocks belong to A-type granites, which is References also supported by discrimination diagrams. The examined BROSKA, I. & UHER, P. (1991). Geol. Carpath., 42/5: 271- rocks plot to the A1 subgroup. The Harker variation dia- 277. grams for major, trace and REE elements show that the sam- COX, K. G., BELL, J. D. & PANKHURST R. J. (1979): The ples are representatives of the evolutionary trend character- Interpretation of Igneous Rocks. George Allen & Unwin, ising magmatic differentiation. The value of (Eu/Eu*)ch indi- London. cates different degree of fractionation in terms of the exam- MOROGAN, V., UPTON, B. G. J. & FITTON, J. G. (2000). ined samples. The lowest value (0.10) represents the most Mineralogy and Petrology, 69: 227-265. fractionated sample which is monzogranite, while the highest PÁL-MOLNÁR, E. (2000). Hornblendites and diorites of the value (0.48) refers to a slightly differentiated Qtz-monzonite Ditró Syenite Massif. Ed. Department of Mineralogy, sample. The Nb/Ta ratio varies in a wide range: 13.2 and Geochemistry and Petrology, University of Szeged, Szeged, 172p.
83 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
A SEARCHABLE DATABASE OF MINERAL LOCALITY NAMES OF THE CARPATHIAN REGION
PAPP, G. Department of Mineralogy and Petrology, Hungarian Natural History Museum, Pf.: 137, H-1431 Budapest, Hungary. E-mail: [email protected]
After twenty years of collection practice and science his- (from the 1913 Official Gazetteer of Hungary). An auxiliary tory research one can conclude that the locality names of the record on the same screen lists all spelling variants to be Carpathian Region may cause much trouble even to an expe- found in the database corresponding to the given entry. rienced “aboriginal”. For a better orientation in this jungle of The original gazetteer was compiled with the financial names the manuscript Gazetteer of the mineral locality support of the OTKA (Hungarian National Research Fund) names of the Carpathian Basin (PAPP, 1996) was developed grant F18007. The editorial work was helped by many local into a searchable database. At present the database contains experts. The database was developed with the financial sup- some 11,800 variants of 4300 locality names of the area. port of the Pro Renovanda Cultura Hungariae Foundation These variants were collected from topographical and de- with the kind assistance of M. RAJCZY (Dept. of Botany, scriptive mineralogies published since the XVIIIth century. Hungarian Natural History Musem). The resulting records (one screen per record) of a given Development plans include geographical broadening (to query contain the present name corresponding to the input, the external areas of the Carpathians) and facilitating of the the type of the named feature (populated place, stream, min- access (a web searchable version). ing area etc.), the country and the administrative unit where it belongs to and other data (geographical co-ordinates or rela- Reference tive position) helping the localisation of the name. Name of PAPP, G. (1996). Acta Mineral.-Petrogr. (Szeged), 37 the relevant historical region (if any) and the last official (Suppl.): 89. Hungarian name and administrative subdivision is also given
84 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MICROMINERALOGICAL AND CLAY MINERALOGICAL STUDY OF THE EPLÉNY LIMESTONE FORMATION, ÚRKÚT, HUNGARY
PEKKER, P.1, WEISZBURG, T. G.1 & POLGÁRI, M.2 1 Department of Mineralogy, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary. E-mail: [email protected] 2 Laboratory of Geochemical Research, Research Centre of Earth Sciences, Hungarian Academy of Sciences, Budaörsi út 45, H-1112 Budapest, Hungary.
This presentation reports on the mineralogical study of The third type, a hard, grey, silicic limestone is charac- the Eplény Limestone Formation (Dogger) overlying the terised by high silica content, an almost complete lack of Úrkút Manganese Ore Formation in the Bakony Mts., Hun- sheet silicates, randomly oriented Bositra shells and many gary. (not pyritic) radiolarians and sponge spicules. The sequence consists of three types of sedimentary rocks All three types have a high carbonate content (27–40 appearing as thin and apparently randomly alternating beds. wt%), apatitic fish fossils, quartz grains, muscovite, a little The three types can easily be distinguished both on the walls biotite and a small amount of fine-grained pyrite aggregates. in the adits and in the laboratory, during density and grain It can be seen that the differences between the beds show up size separations, in thin sections, X-ray powder diffracto- mainly in the extent of diagenetic silicification-opal forma- grams, chemical and electron microanalytical investigations. tion and pyritisation and in clay mineral content. The soft, greenish type of layers has low silica content. It The results of the study include the description of pyritic consists of lamellae of Bositra shells and small amounts of fossils, the relation between Bositra shells and opal forma- siliceous radiolarians and sponge spicules in a micritic– tion and the identification of apatite grains as fish fossils. clayey matrix. These results serve as a basis for further research that may In the lamellar, harder, greenish grey transitional type provide a better characterisation of this marine succession layers the lamellae of Bositra shells are cemented by opal. and supplement new data for the better understanding of They alternate with micritic–clayey lamellae similar to the chemical and biological processes on the sea floor. material of the previously described type, containing large This work was supported by the OTKA (Hungarian Sci- numbers of both siliceous and pyritic radiolarians and sponge ence Foundation) grant #T032140 and T25873. spicules.
Fig. 1: Schematic comparative drawings of thin sections of the three different rock types described. The height of the picture is about 3 mm. The black parts represent the fine grained clayey matrix, the thin white strips the Bositra shells, while the larger white areas refer to silica precipitation. The differences among the three rock types are mainly in the size and orientation of the Bositra shells and in the intensity of silica precipitation. The soft greenish rock (samples U1/98 etc.) contains smaller and oriented shells, a larger amount of fish fossils (white spots on the left side figure) and no trace of silica precipitation can be observed. For the lamellar, harder rock type (U3/98 etc.) larger shells in less oriented position are typical. The shells are cemented by silica (opal). Pyritic and sili- ceous radiolarians and sponge spicules (small white dots on the middle figure) are frequent. The hard, grey rock type contains larger blocks of opal (a syndiagenetic precipitate) and larger shells. No trace of (diagenetic) pyritisation of the radiolarians and sponge spicules (small white dots on the right side figure) can be observed.
85 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
ROŞIA MONTANĂ, ROMANIA: FROM MUSEUM SAMPLES TO THE IMPLICATIONS OF A NEW “GOLD RUSH”
POP, D.1, URECHE, I.2 & BEDELEAN, H.3 1 Mineralogical Museum, Babeş-Bolyai University, 1, Kogălniceanu Str, RO-3400 Cluj-Napoca, Romania. E-mail: [email protected] 2 Geological Institute of Romania, Cluj Branch, P.O. Box 181, RO-3400 Cluj-Napoca, Romania. 3 Department of Geology and Palaeontology, Babeş-Bolyai University, 1, Kogălniceanu Str, RO-3400 Cluj-Napoca, Romania.
Since prehistoric times, gold has been a mineral with a mining was a private business, then in parallel it became special status, influencing the complex development of cer- partly state-owned. A huge network of surface and under- tain areas of the world. In Europe, the most famous gold area ground works was created. Several successive state-owned was traditionally considered the Golden Quadrilateral in the companies were operating in RM starting with 1948; in 1970 Western Carpathians, with the mining center at Roşia Mon- the largest open cast mine for gold in Romania was opened tană (RM). RM is located in the NErn part of the Metallifer- here. ous Mountains, in the neighborhood of the towns Abrud and The actual economic politics promoted by the Romanian Câmpeni. The long lasting mining activity in the region re- government (The Mining Law, 1998) encouraged privatiza- sulted, among others, in famous museum samples that can be tion in the field on mining. The mining area RM was con- found today in several Romanian museums, as well as in ceded by the Canadian company Gabriel Resources Ltd., and most of the important mineralogical collections all around lately the mixed Romanian-Canadian company Roşia Mon- the world. The paper starts with a brief overview and evalua- tană Gold Corporation S.A. (RMGC) was given the exploi- tion of the gold collection at the Mineralogical Museum of tation license. The current mining project concerns the explo- the Department of Mineralogy, Babeş-Bolyai University in ration, large-scale surface mining, and processing of the Cluj-Napoca (MMBBU) mainly focusing on the samples gold-silver ores from several perimeters (Cetate, Cârnic, from RM. Then a historical presentation of the mining activ- Orlea, and Jig) in RM area. ity in the area follows, including the current status of the According to the data presented by RMGC a total reserve gold mining project. of 225,740,000 tons of ore was estimated, with an average In Romania, The Gold Museum from Brad owns the most metal content of 1.7 g/t gold and 9.1 g/t silver. The mining representative collection, with specimens especially origi- activities are planned to start in 2005 and based on the esti- nating from the local mines; MMBBU hosts the second most mated reserves, the duration of the exploitation would be of valuable collection in the country. The gold collection con- 17 years. The Au-Ag ore from the opencast mines would be sists at present of about 500 samples from Romania and from crushed and milled by using conventional methods, and then abroad. Among them 31 % are from Roşia Montană, 41 % processed with open cyanide (“carbon-in-leach” type). from about 20 other localities in the Western Carpathians, 6 RMGC planned to build a cyanide destroyer unit, where the % from other Romanian occurrences, 9 % from abroad and concentration would be reduced to 1 ppm prior to the storage 13 % have an unknown occurrence. Accordingly, it can be of the waste into the tailing pond that would be located on said that the RM samples represent the core of the collection. the present-day location of Corna village. Museum gold samples are considered to have an intrinsic The current mining project was the target of an intense high value due to their content of precious metal, as well as public debate. Representatives of various local NGOs, and of to the interest they present for the public. Still, there are internationally recognized official bodies evidenced the im- mineralogical and museological criteria that can be used plications that could arise from the implementation of the when evaluating such individual samples or collections, project. Among them, long-term social and environmental among which: form of crystallization, mineral assemblage, impacts, such as the resettlement and relocation of 1800 genesis, status of the occurrence (closed mines etc.). These people (affecting 38 % of the RM commune surface), possi- criteria were applied for evaluating the RM samples in our ble failure of structures and dams leading to cyanide leaking collection. into the soil, ground water, river and air pollution not only Besides its fame and richness in gold, another fact that with cyanide but also with other metals (As, Pb, U, Hg, Fe, makes RM unique is the long history of the mining activity. Ni, Cd, etc.) Proofs of alluvial gold panning as well as surface and under- The impressive cultural heritage values concentrated here ground mining by Geto-Dacians were revealed by historians. give an additional weight to the final process of decision- The best-preserved antique mining works go back to the making. Archaeologists and historians from all around the Roman times (106-273 a. D.). Between 1786-1855 50 world underlined the importance of the conservation of this “waxed plates” dating from the period 131-167 a. D. were archaeological site that could be declared as “archaeological identified in the region; one of them (plate no. XVIII, from park of an European interest”. the 6th of February, 131 a. D.) contained the name of RM in that times (Alburnus Maior). Prior to the XVIIIth century
86 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
COMPLEX APPLICATION OF THE METHODS OF PRACTICAL THERMOBAROCHEMIS- TRY AND GEOINDICATION: DECYPHERING OF AERIAL COSMIC PRODUCTION IN THE STUDY ORE GENERATING SYSTEMS
POPIVNYAK, I., KOLODIY, O., LYAKHOV, Y., EKHIVANOV, V., NIKOLENKO, A., NIKOLENKO, P., PAVLYUK, T., KOVALEVSKY, V., MARUSYAK, V., OLIYNIK, T. & TSIKHON’, S. Lviv National University, Hrushevskiy 4, UA-79005 Lviv, Ukraine. E-mail: [email protected]
In the Baley ore region of the Transbaikalian area, during volcano-plutonic structures at a certain distance from the the studying of the gold deposits the methods of practical central stocks. thermobarochemistry were used in conjunction with geoindi- Complex assessment made possible to correct exploration cational decoding of aerial cosmic production. works and to establish new gold-bearing bodies (Kolodiy). Two types of ore-mineralisation were established: pneu- In Ukraine, in the limits of the Kirovograd block the matolytic-hydrothermal (moderate-sulphide medium-depth domed radial-circular structure with the diameter about 150 formation; 470–60 °C, 120–40 MPa) and proper hydrother- km was discovered by decoding of aerial cosmic production mal (low sulphidation low-depth formation; 310–50 °C, 3– and by morphotectonic analysis. Gold mineralisation spa- 4 MPa; data of Lyakhov et al.). tially coincides with certain parts of the structure. The condi- The mineralisation is genetically connected to the series tions of gold mineralisation in the western and eastern parts of the observed, radial-circular volcano-plutonic structures of are similar. In both of them the process of mineral formation the central type with a diameter up to 20 km. Among them is characterised by cyclic penetration of fluids into the zones the domed and depressive forms are singled out (Kolodiy). of ore localisation during five stages. Gold deposition took The mineralisation of medium-depth formation is also con- place at 270–225 °C (the eastern part; Nikolenko, Popiv- nected to the domed forms, and low-depth mineralisation is nyak) and 280–220 °C (western zone; Popivnyak, Karamys- connected with the volcano-depressive forms. Known are the heva, Kovalevsky) in the intensively boiling fluids. Complex zones combined with the fractures. Topographic mineralogi- approach made it possible to outline the areas perspective for cal analysis (Popivnyak) showed that the high temperature gold. mineral associations change into the low temperature ones We must note that in the coal-bearing seams of the Don- from the centre of the structure to the peripheral areas. bas the gold mineralisation is also connected with the forma- Temperature gradients are about 20 °C per 100 m from tion of the radial-circular structure (Ekhivanov). the deep horizons to the surface, and 5–7 °C per 100 m later- Analogous complex approach made it possible to deter- ally. Spatial directivity of paleotemperature vectors is under mine the Beregove ore field of the Transcarpathians as a the control of radial faults and is focused on the central volcanic radial-circular structure, leading to the discoveries stocks. of new ore zones (Kolodiy). Gold occurrences formed in the average temperature range (300–200 °C) and are localised in the middle part of
87 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
STRUCTURE, COMPOSITION, AND MAGNETIC PROPERTIES OF MINERALS IN MAGNETOTACTIC BACTERIA
PÓSFAI, M.1, ARATÓ, B.1, DUNIN-BORKOWSKI, R. E.2, FRANKEL, R. B.3 & BUSECK, P. R. 4 1 Department of Earth and Environmental Sciences, University of Veszprém, P. O. Box 158, H-8200 Veszprém, Hungary. E-mail: [email protected] 2 Department of Materials Science and Metallurgy, University of Cambridge, Pembroke Street, Cambridge CB2 3QZ, UK. 3 Department of Physics, California Polytechnic State University, San Luis Obispo, California, USA. 4 Department of Geological Sciences and Chemistry/Biochemistry, Arizona State University, Tempe, Arizona, USA.
Magnetotactic bacteria form chains of nanometer-scale, of biologically-controlled mineralization of iron oxides and magnetic iron oxides or sulfides (magnetite and greigite, sulfides, and to define criteria that could be used to distin- respectively) inside their cells. The bacterium uses the chains guish bacterial from inorganically formed minerals in geo- of magnetic minerals as an internal compass for orienting logical specimens. itself in its aquatic environment, following geomagnetic field Our transmission electron microscope (TEM) observa- lines in order to reach an optimal position in a chemically tions showed that ferrimagnetic greigite in magnetotactic non-uniform medium (water or sediment) (BAZYLINSKI & bacteria forms from nonmagnetic mackinawite (tetragonal MOSKOWITZ, 1997). In order to assess the impact of mag- FeS) and possibly cubic FeS. Greigite crystals typically con- netotactic bacteria on sediment and rock magnetism, it is tain defects and show uneven, blotchy contrast in TEM im- necessary to characterize mineral species within contempo- ages. In contrast, we found no precursor mineral for magnet- rary bacteria and to compare them with magnetic minerals in ite from magnetotactic bacteria. We also used electron holog- geological specimens. Since magnetotactic bacteria produce raphy in the TEM to study magnetic domain structures, mag- single-domain magnetic crystals that have specific mor- netocrystalline and shape anisotropies, and magnetostatic phologies and sizes, such crystals could have practical appli- interactions between oriented, nano-scale magnetic particles. cations in fields such as medicine or magnetic recording; it is Crystal size distributions (CSDs) convey information thus important to obtain a better knowledge of biological about the growth histories of crystal populations (EBERL et control over crystal growth. Nanometer-scale magnetite al., 1998). We found that magnetite from magnetotactic crystals from the geological environment have also been bacteria typically produces asymmetric, negatively-skewed interpreted as “magnetofossils” signatures of former life. The CSDs, whereas greigite from the MMP has a Gaussian CSD. most notable among the reports of biogenic magnetite are Since inorganically-formed crystals commonly have lognor- studies that claim to have identified relics of former life on mal distributions, the statistical analysis of crystal sizes pro- Mars in the form of “prismatic” magnetite crystals in Martian vides a tool for identifying biogenic iron minerals in both meteorite ALH84001 (MCKAY et al., 1996). However, it is terrestrial and extraterrestrial geological specimens. difficult to distinguish with confidence the biogenic or inor- ganic origins of these minerals. A knowledge of the magnetic References microstructures of biogenic iron minerals is also important BAZYLINSKI, D. A. & MOSKOWITZ, B. M. (1997). Rev. for a better understanding of their paleomagnetic contribu- Mineral., 35: 181-223. tions. DELONG, E. F., FRANKEL, R. B. & BAZYLINSKI, D. A. We studied the sizes, morphologies, microstructures and (1996). Science, 259: 803-806. compositions of magnetite from several morphological types EBERL, D. D. DRITS, V. A. & SRODON, J. (1998). Amer. of magnetotactic bacteria, from both cultured and “wild” J. Sci., 298: 499-533. strains, collected from lakes and streams in Hungary. The MCKAY, D. S., GIBSON, E. K., Jr., THOMAS-KEPRTA, widespread occurrence of magnetotactic species indicates K. L., VALI, H., ROMANEK, C. S., CLEMETT, S. J., that they are significant contributors to the magnetic mineral CHILLIER, X. D. F., MAECHLING, C. R. & ZARE, R. content of freshwater sediments. We also studied iron sul- N. (1996). Science, 273: 924-930. fides from a marine organism that was earlier described as a “multicellular magnetotactic prokaryote” (MMP) (DELONG et al., 1996). Our goals were to better understand the process
88 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
ZIRCON IN MIGMATIC ROCKS OF THE SOUTH CARPATHIANS (ROMANIA)
ROBU, I. N. & ROBU, L. Geological Institute of Romania, Caransebeş 1, RO-78344 Bucharest-32, Romania. E-mail: [email protected]
Migmatic rocks are spread in a large area of the South In the northern part of the Sebes Mountains, S is the ex- Carpathians, occurring in the western part (Semenic Moun- clusive morphological type and G and P types accompany it tains) to the central (Sebes-Lotru and Fagaras Mountains) in migmatites from the rest of the South Carpathians. and eastern ones (Iezer-Papusa Mountains). The most spread subtypes, found in the majority of in- They are enclosed in different metamorphic series or vestigated samples, are S16 – S17. tectonic units, their genesis being considered in connection The proportion of S, G and P types is variable from west with different geological events and phenomena, so that there to east, the S type decreasing from the Sebes Mountains to are no an unitary opinion about their origin. the Iezer-Papusa Mts. They are considered to be either: (i) metasomatic (Faga- The same variations have been emphasized by the optical ras Mountains), (ii) generated by magmatic and metamorphic properties: the majority of crystals is light-dark pink, with a events, (iii) formed in tectonic conditions (ductile-brittle good and very good transparency; the light-dark brown regime), having a granitoid protolith (Sebes Mountains), (iv) crystals and those translucent ones are fewer in the western upper zone (cupola zone) of an anatectic granitoid body part of South Carpathians, but their number is increasing to developed in lower parts of the crust (Fagaras Mountains). the east, so that such kind of crystals is much more numerous Zircon, through its characteristics could help to elucidate in the migmatic rocks from the Iezer-Papusa Mountains. some problems connected to the origin of the rocks, taken Zoned or/and overgrown crystals are few and they are ab- into account its well-known resistance to chemical and me- sent in the North Sebes migmatites. chanical weathering. Petrogenetically, the properties of zircons correspond Study of zircons from migmatites of South Carpathians, mainly to crustal type, especially for zircons of the North with special attention to their morphological and optical Sebes migmatites, and this character decreases from West to properties, tried to solve the origin of this type of rocks. East, so that in the Iezer-Papusa migmatites the mantle or Morphologically, they mainly belong to the same type (S mainly mantle component becomes predominant. type), but a large variety of subtypes, each of them with very specific concentrations, have been observed.
89 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
CRYSTALLOCHEMISTRY OF CHLORITES ASSOCIATED WITH ULTRAMAFIC BODIES FROM SOUTH CARPATHIANS (ROMANIA)
ROBU, L. & ROBU, I. N. Geological Institute of Romania, Caransebeş 1, RO-78344 Bucharest-32, Romania. E-mail: [email protected]
Chlorites are one of the most widespread mineral groups rites investigated from ultramafites from Banat (Tisovita–Iuti of the phyllosilicates, associated with the ultramafic rocks occurrence). from the South Carpathians. The octahedral sheets, in the majority of chlorites, are oc- They have been observed in ultramafic bodies enclosed in cupied mainly by Mg and octahedral interlayer ones are both major tectonic units of the South Carpathians (Danubian filled by Mg and others, respectively Al, Ti, Fe3+, Fe2+, Mn, and Getic) with similar morphological, physical and optical Cr and Ni. characteristics: pale-dark green microscopic or large flakes, The substitutions in the octahedral sheets determined a grouped in geometrical packets, randomly distributed in the few changes of the magnesian character of clinochlore; in mass of the ultramafic rocks, in veins crossing the bodies, or some occurrences clinochlore has a ferric/ferrous character in the marginal zones of them. (Sebes-Cibin Lotru, Semenic and Almaj Mountains), it is Chemical investigations have emphasized the presence of less aluminous in the chlorites from Semenic Mountains and specific cations [Mg (mainly) Al, Fe3+, Fe2+, Mn, Cr, Ni, in it contains Cr - Ni cations in chlorites collected from Cibin, variable proportions] for clinochlore, with some obvious Sebes, Semenic and Almaj Mountains. substitutions in tetrahedral and octahedral sheets. The variations of the reticular cell parameters reflect all The structure of clinochlore belongs to the trioctahedral Mg substitutions, but they are similar to those mentioned in type (2:1:1), determined by the entire filling of the octahedral the literature: a = 5.322–5.329 Å; b = 9.233–9.249 Å; c = positions in both of its sheets, octahedral and octahedral 14.100–14.267 Å. interlayer ones. The lack of difference between Danubian and Getic chlo- As an exception one has to mention the Tisovita-Iuti oc- rites pointed out the similar conditions of their crystalliza- currence, where have been found a tri-dioctahedral chlorite. tion, the emphasized differences being determined by local The most frequent substitution in the tetrahedral sheets is variation of the chemistry of crystallization environment. between Si and Al, more obviously in the Getic chlorites; sometimes Fe3+ is present in the tetrahedral positions in chlo-
90 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MAPPING MINERALS IN OBSIDIAN GLASSES BY USING MICRO-PIXE TECHNIQUE
RÓZSA, P.1, ELEKES, Z.2, SZÖŐR, Gy.1, SIMON, A.2, UZONYI, I.2, KISS, Á. Z.2 & SIMULÁK, J.1 1 Department of Mineralogy & Geology, University of Debrecen, P. O. Box 4, H-4010 Debrecen, Hungary. 2 Institute of Nuclear Research of the Hungarian Academy of Sciences [ATOMKI], P. O. Box 51, H-4001 Debrecen, Hungary. E-mail: [email protected]
The subject of the current paper is to map minerals in equilibrium, while Ca-rich pyroxene crystals of obsidians mainly in Carpathian obsidian glasses by nuclear microprobe from Melos and Giali (Greece) may be in equilibrium with based Particle Induced X-ray Emission (PIXE) method pro- the residual glass. Therefore, it is possible that these crystals viding analytical data on them for the first time. The samples cannot be regarded as xenocrysts. However, Ca-rich plagio- were basically collected in order to study the glassy material clase feldspars detected in samples from Viničky (Slovakia) from archaeometrical and geochemical point of view and Melos (Greece) have probably been incorporated in the (ELEKES et al., 2000; RÓZSA et al., 2000). Most of the glass. Anhydrite-chalcopyrite and pyrrhotite-pyrite-chalco- analysed obsidian specimens containing different pheno- pyrite assemblages in obsidians from Aragats Mountain crysts come from the Tokaj Mountains. These mountains (Armenia) and Viničky (Slovakia) were formed by hy- (NE Hungary, Borsod-Abaúj-Zemplén County) form the drothermal activity. However, it is questionable whether the southern part of the Tokaj−Prešov Tertiary volcanic range. solid obsidian rocks suffered the hydrothermal activity or Some samples from Armenia, Greece are also involved to these crystals were incorporated by the rhyolitic melts. It is make a comparison with the Carpathian specimens. also possible that sulphur was stored in a coexisting fluid Although the routine analysis of mineral phases is usually phase; in this case these minerals could be regarded as pri- carried out by electron microprobe (EPMA) technique, the mary ones. applications of nuclear microprobes (NMP) with the use of well-established proton induced X-ray emission (PIXE) Acknowledgments method have become more and more common and accepted This work has been supported by the Hungarian National during the last decade (RYAN, 1995). Concerning elemental Science Research Foundation (OTKA) under Res. Contracts analysis, NMPs have approximately similar resolution (1x1 No. A 080, T 025771, T 019516, by the National Committee m2) as EPMAs but NMPs provide superior detection limits for Technological Development under Res. Contract No. 97- that can be especially advantageous when minor and trace 20-MU-0030 and by the Project for Higher Educational Re- elements are to be measured. search and Development (FKFP) under Res. Contract No. The following minerals are identified and analysed: pyr- 0135/1999. rhotite, chalcopyrite, pyrite, zircon, pyroxene, biotite, plagio- clase feldspar, and anhydrite. Although our main goal is to report on the above minerals, on the basis of rock-forming References silicate minerals, some petrologic processes are outlined, as ELEKES, Z., UZONYI, I., GRATUZE, B., RÓZSA, P., well. Moreover, with the identification of accessory minerals KISS, Á. Z. & SZÖŐR, Gy. (2000). Nuclear Instruments (such as anhydrite, pyrrhotite, chalcopyrite, pyrite), some and Methods in Physics Research B, 161-163: 836–841. geological conclusions are also drawn. RÓZSA, P., SZÖŐR, Gy., SIMULÁK, J., GRATUZE, B., On the basis of the study of phenocrysts observed in the ELEKES, Z. & BESZEDA, I. (2000): Applied Mineral- obsidian glasses some petrologic conclusions can be drawn. ogy, 1, Rotterdam: Balkema, 217–220. Hf contents of zircon crystals in obsidian samples from two RYAN, C. G. (1995). Nuclear Instruments and Methods in localities of the Tokaj Mts. (Sima in Hungary and Viničky in Physics Research B, 104/1-4: 377–395. Slovakia) show definite differences. It seems that Ca-poor orthopyroxene crystal in the sample from Sima (Hungary) is
91 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
A NEW LOVERINGITE OCCURRENCE: ORIENTED RODS IN GARNET FROM THE FOLTEA LHERZOLITE, SOUTH CARPATHIANS, ROMANIA
SĂBĂU, G.1 & ALBERICO, A.2 1 Geological Institute of Romania, 1 Caransebeş St., RO-78344 Bucharest 32, Romania. E-mail: [email protected] 2 Dipartimento di Scienze Mineralogiche e Petrologiche, Università di Torino, Via Valperga Caluso 35, I-10125 Torino, Italy.
Loveringite - (Ca, REE)(Ti, Fe, Cr,...)21O38 is a relatively WD microprobe analyses is given in Tab. 1 (average of 3 rare mineral, belonging to the crichtonite group, identified so analyses). far in a number of occurrences related to layered mafic intru- Loveringite, together with associated microinclusions in sions and their metamorphosed equivalents. TARKIAN & garnet indicates metasomatic processes in the mantle frag- MUTANEN (1974) suggested that it could be more wide- ment where the Foltea ultrabasite was sampled from. In par- spread than actually recognised, being overlooked due to its ticular, metasomatism is responsible for HFSE-enrichment small grain size and optical properties similar to those of recorded by the oxide microinclusions hosted by garnet. The other oxide minerals. The material described as lunar Cr-, topotactic relationships with host garnet most presumably Ca-, Zr-, Nb- armalcolite (HAGGERTY, 1973) (CCZNA) resulted from epitaxial co-precipitation, a mechanism that displays strikingly similar chemical composition and optical has to be considered also in other instances in which garnet properties (e. g. LÉVY et al., 1972), implying that the first contains oriented oxide or silicate rods, usually deemed as discovery of loveringite precedes by a few years its official exsolution features. An interpretative option between co- recognition as a new mineral species by GATEHOUSE et al. precipitation vs. exsolution has to be supported in particular (1978), though in a completely different setting. A remark- cases by concurrent evidence, given its paramount conse- able occurrence was described by WANG et al. (1999) in the quences on the interpretation of the rock geodynamic history. Garnet Ridge (Arizona) kimberlite pipe, where loveringite is cited together with other oxides (rutile, crichtonite, srilankite, References carmichaelite) as oriented rod-like inclusions in garnet crys- GATEHOUSE, B. M., GREY, I. E., CAMPBELL, I. H. & tals. KELLY, P. R. (1978). Amer. Mineral., 63: 28-36. The Foltea garnet lherzolite is an isolated ultramafic body GRÉGOIRE, M., LORAND, J. P., O’REILLY, S. Y. & enclosed in upper crustal metapelitic and gneissic rocks of COTTIN, Y. (2000). Geochim. Cosmochim. Acta, 64(4): the polymetamorphic basement (the Lotru Metamorphic 673-694. Suite) of the Getic Nappe in the South Carpathians. Pyrope- HAGGERTY, S. E. (1973). Proc. 4th Lunar Sci. Conf., Geo- rich garnet is a common component in the rock itself or in chim. Cosmochim. Acta, Suppl. 4(1): 777-797. garnet-clinopyroxenite veins and nests, hosting a variety of LÉVY, C., CHRISTOPHE-MICHEL-LÉVY, M., PICOT, P. oxide, silicate, sulfide and carbonate-rich inclusions. Oxide & CAYE, R. (1972). Proc. 3rd Lunar Sci. Conf., Geo- inclusions usually occur as a net of µm-sized rods and blades chim. Cosmochim. Acta, Suppl. 3(1): 1115-1120. oriented along four directions consistent with <111> of host LORAND, J. P., COTTIN, J. Y. & PARODI, G. C. (1987). garnet, and consist chiefly of rutile and loveringite. Can. Mineral., 25: 683-693. Loveringite appears as rods up to 5 µm thick and 300 µm SCHULZE, D. J. (1990). Amer. Mineral., 75: 97-104. long, blades up to 300 µm and rare elongated grains bordered TARKIAN, M. & MUTANEN, T. (1987). Mineral. Petrol., by crystal faces, all oriented with respect to the host garnet. It 37: 37-50. is almost opaque, being however translucent in deep olive- WANG, L., ESSENE, E. J. & ZHANG, Y. (1999). Contrib. green shades in very thin grains. SAED patterns are consis- Mineral. Petrol., 135: 164-178. tent with a loveringite cell (trigonal symmetry, aH = 10.34 Å, cH = 20.68 Å). The chemical composition recalculated after
Table 1: Chemical composition of loveringite from the Foltea ultrabasite.
Na2OK2O CaO SrO MgO FeO NiO MnO Fe2O3 Cr2O3 Al2O3 TiO2 ZrO2 SiO2 VO2 Σ 0.23 0.15 2.59 0.45 4.05 9.40 0.08 0.14 1.35 0.94 5.04 70.28 3.36 0.08 0.39 98.52 KNaSrCaΣ Mn Fe2+ Ni Mg Fe3+ Cr Al V Ti Zr Si Σ O 0.05 0.12 0.07 0.76 1.00 0.03 2.15 0.02 1.65 0.28 0.20 1.63 0.08 14.48 0.45 0.02 21.00 38.00
92 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
PETROGRAPHIC AND GEOCHEMICAL STUDIES ON A TRAVERTINE CONE IN SOUTH VÉRTES MTS. (HUNGARY): EVIDENCE FOR MAGMATIC FLUID INFLUENCE?
SIKLÓSY, Z.1, GÁL-SÓLYMOS, K.1, KORPÁS, L.2 & SZABÓ, Cs.1 1 Lithosphere Fluid Research Lab, Department of Petrology and Geochemistry, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary. E-mail: [email protected] 2 Geological Institute of Hungary, Stefánia út 14, H-1143 Budapest, Hungary.
Introduction travertine fabric and consists of alternating massive, layered Spectacular reddish brown carbonate cone was found in and porous calcite. the southern part of Vértes Mts. (Transdanubian Central Range), close to NW of village Gánt (PEREGI & KORPÁS, Results and conclusions 2002). Some red calcite dikes were already described from Samples are composed of mostly calcite crystals that can other parts of the Transdanubian Central Range (HAAS et grow up to 0.5 mm. The calcite crystals mostly banded due al., 1984; DEMÉNY et al., 1997). These dikes are mostly to the zonation of Fe-oxide layers. Based on petrographic situated in Upper Triassic carbonates and never cut Tertiary study, the carbonate cone can be described as a travertine rocks. There are two localities where their Upper Cretaceous deposit. Electron microprobe and scanning electron micro- age could be stratigraphically determined. The origin of these scope techniques and neutron activation analyses were also red calcite formations is different from the other calcite veins used to determine the accessories minerals of sitting in the that can be found in almost all Mesozoic and Tertiary car- carbonate material. Xenomorphic zircon, xenotime and bonates. A detailed stable isotope and fluid inclusion study monazite were found as small grains (up to 10 µm). Based on of DEMÉNY et al. (1997) suggested that percolation of the textural features, only monazite and xenotime can be magmatic fluids played a significant role during the forma- considered as autochthon minerals. The carbonate cone is tion of the red calcite dikes. PEREGI & KORPÁS (2002) relatively enriched in light rare earth elements (La, Ce, etc.) postulated a travertine spring cone origin for the Gánt occur- particularly samples collected close to the hypothetical vent rence and we have carried out a careful petrographic and facies. Also, each sample has a positive U anomaly (up to geochemical study to determine its relation to the red calcite 3.73 ppm). The presented geochemical data are partially dikes. characteristic and similar to the Quaternary thermal Buda travertine as indicated by KORPÁS et al. (2003). In our case a generic relation to the Late Cretaceous lamprophyres oc- curring in the northern part of the Transdanubian Central Range (SZABÓ et al., 1993) can be considered.
References DEMÉNY, A., GATTER, I., & KÁZMÉR, M. (1997). Geologica Carpathica, 48: 315-323. HAAS, J., JOCHÁNÉ EDELÉNYI, E., GIDAI, L., KAISER, M., KRETZOI, M., & ORAVECZ, J. (1984). Geologica Hungarica Series Geologica, 20: 353 p. KORPÁS, L., KOVÁCS-PÁLFFY, P., LANTOS, M., Fig. 1: The studied carbonate cone in the Vértes Mts. FÖLDVÁRI, M., KORDOS, L., KROLOPP, E., STÜBEN, D., & BERNER, Zs. (2003). Quaternary Re- search (submitted) Structure of the carbonate cone PEREGI, Zs., & KORPÁS, L. (2002). Földtani Közlöny, The isometric and elliptical carbonate cone is 40 to 50 m 132: 477-480. long and 7 to 8 m high. It has a ring structure likened to a SZABÓ, Cs., KUBOVICS, I. & MOLNÁR, Zs. (1993). willow-tree that differs totally from the surrounding Upper Mineralogy and Petrology, 47: 127-148. Triassic Hauptdolomite (Fig. 1). The middle part of the cone is vertically bedded, whereas at the rim the beddings turn to less steep: 10-50°. The carbonate material itself has a typical
93 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
ADSORPTION OF LEAD ON A LUVISOL PROFILE FROM THE CSERHÁT MTS., NE HUNGARY
SIPOS, P.1, NÉMETH, T.1, MOHAI, I.2 & DÓDONY, I.3 1 Laboratory for Geochemical Research, Hungarian Academy of Sciences, Budaörsi út 45, H-1112 Budapest, Hungary. E-mail: [email protected] 2 Research Laboratory of Material and Environmental Chemistry, Chemical Research Center, Hungarian Academy of Sci- ences, Pusztaszeri út 59-67, H-1025 Budapest, Hungary. 3 Department of Mineralogy, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary.
Geochemical analyses using sequential extraction and organic matter free variant. The different soil horizons method, lead adsorption and analytical TEM studies were adsorb lead to different extent depending on their organic carried out in order to characterize the distribution and ad- matter, clay mineral and carbonate content, and the minera- sorption behaviour of lead on each genetic horizon of a Luvi- logical features of soil clays significantly affect their lead sol profile. This soil was developed on schlier, and it is char- adsorption capacity. The clay fraction adsorbs 25% more acterized by clay illuviation as the most important pedogenic lead than the whole soil, while in the calcareous subsoil the process. Clay minerals are presented in the profile by lead precipitated due to the high pH. 10% and 5% of ad- “chloritized” vermiculite species with increasing chlorite sorbed Pb can be leached with distilled water in the organic component downward. The amount of carbonate minerals matter and clay mineral dominated soil horizons, respec- strongly increases in the lower part of the profile resulting tively. abrupt rise in soil pH within small distance (from 5.66 to Samples treated with the highest amount of lead contain- 8.41). ing solution (2000 mg/l) were studied by analytical TEM. The average Pb concentration of this soil is at the level of The results show that among mineral phases the most im- natural geochemical background in Hungary (14 ppm), and portant lead adsorbing ones are the vermiculite and the chlo- its amount decreases with depth suggesting the binding of Pb rite. The amount of adsorbed lead increases with the in- to soil organic matter (27 ppm at 5 cm, 15 ppm at 35 cm, 4 creasing iron content of this phases. The lead also adsorb on ppm at 65 cm). According to the sequential extraction analy- Fe oxides in smaller extent, but lead adsorption on carbon- sis the organic matter is an important sink of lead: with de- ates was not found. creasing organic matter content the amount of lead bound to These results suggest that the soil organic matter plays it decreases, but its proportion increases. The distribution of decisive role in the adsorption of Pb, but the fixation by clay lead among soil constituents varies especially in the function minerals is stronger. The carbonate phases plays role in lead of the carbonate content of soil, as well. These effects vary in adsorption through their pH buffering capacity. the different soil horizons. Lead adsorption experiments were carried out on whole soil samples, soil clay fractions, as well as on their carbonate
94 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
SELECTED MINING DUMPS IN SLANSKÉ VRCHY MTS. (SLOVAKIA): GEOCHEMICAL CONDITIONS AND THEIR INFLUENCE OF VEGETATION
SITÁŠOVÁ, E. Eastern Slovakian Museum, Hviezdoslavova 3, SK-041 36 Košice, Slovak Republic. E-mail: [email protected]
Mining dumps are specific anthropogenic habitats after and we can record certain similarity at certain types of mining of raw materials. According to the presence of ore dumps. In plants the content of Hg, As exceed the values of minerals in dumps and their chemical composition in soils ash. It is exhibited the most strikingly in the case of bent developed on dumps, we supposed higher concentration of grass (Agrostis capillaris). In another species there is a high some elements (arsenic, copper, mercury, lead, antimony). concentration of Hg from each locality (SITÁŠOVÁ, 2001). Dumps in the Slanské vrchy Mts. have different soil con- It is deduced from the results that the contamination by tamination by observed heavy metals. The most contami- heavy metals is caused not only by mining activity but nated are the soils with high content of As, Hg and Sb. It mainly by weathering of hydrothermally altered rocks with relates to their increased content in substratum, which can be sulphide content. caused by natural and anthropogenic factors. Increased mer- Considering already ascertained facts about the types and cury content relates to the battering and processing activity amount of heavy metals at observed dumps and their nega- and increased mineralisation of soil horizon by components tive influence on the other components of environment or containing structurally bound mercury. their contamination (SITÁŠOVÁ, 2001) we suggest: Chemical analyses of leaking mining waters and waters – to ensure the dumps in a way that can eliminate adverse running over observed mining dumps in the Slanské vrchy influences on the environment; Mts. and in Merník demonstrate by documents that: – we do not recommend, considering the high toxicity of – at Dubník in the Slávik exploratory gallery even after materials in some dumps, to use this material for surfacing total flooding very acidic mineralising waters still develop, roads in forests, fixture of road communications or as a which then leak onto the surface and join the Jedľovec building material, because uncontrollable diffusion of heavy Brook. This brook farther runs over peat marshes at the metals into the natural environment occurs; dump of Jozef gallery at Dubník. These waters preserve their – it is necessary to recultivate the dumps and cover them acidic pH value in the interval 2.30–2.47. with soil and plant trees or another plants for building in this From a scientific viewpoint the results confirm the mi- area to the immediate surroundings. gration of heavy metals and their accumulation in the envi- ronment. Our aim was to observe the natural succession of References plants at dumps, their development and stand conditions at SITÁŠOVÁ, E. (2001). Natura Carpatica, 42: 55–64. individual localities. We discovered some differences be- SITÁŠOVÁ, E. (2001). Natura Carpatica, 42: 177–182. tween the growth of young and old dumps. Colonisation of dumps by vegetation took place and still takes place slowly
95 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
GLAUCONY IN THE LOWER JURASSIC DEPOSITS OF THE KRIŽNA UNIT (TATRA MTS., POLAND)
STARZEC, K. & JACH, R. Institute of Geological Sciences, Jagiellonian University, ul. Oleandry 2a, PL-30-063 Cracow, Poland. E-mail: [email protected]
The Lower Jurassic glaucony-bearing deposits crop out in netic alteration (ODIN & MATTER, 1981; IRELAND et al., the Długa Valley of the Križna Unit (Western Tatra Mts., 1983). In spite of very high potassium content the XRD pat- Poland). They occur locally above limestone/marl alternated tern show that the grains do not represent well-ordered glau- complex, covered with phosphatic stromatolites up to 3 cm conite phase. They are at an evolved stage of glauconitiza- thick. The complex is probably Toarcian in age. The glau- tion. Some amount of calcite was also found in these grains cony-bearing deposits are, in turn, covered with a condensed (it is because calcite fills the cracks). section of red nodular limestones. The glaucony-bearing The above mineralogical and geochemical evidences deposits developed as dark green marlstones, up to 20 cm show that discussed glaucony represents autochthonous type thick. They contain abundant crinoidal ossicles, belemnite (see AMOROSI, 1997). Facies geometry and their lateral guards, and relatively high amount of fish teeth. In thin sec- variation suggest that described deposits represent the crest tion they display wackestone texture. The crinoidal ossicles or the slope of pelagic carbonate platform. Sedimentological are poorly rounded and sorted. Their internal pores are and palaeontological characteristic of glaucony-bearing de- mostly impregnated by green material. posits confirm the above interpretation and prove that the The collected rocks were disaggregated, submitted to deposits in question originated during periods of very low magnetic separation and hand-picking. Physical properties rate of deposition. and chemical composition of green grains were determined The research is partly financed by the Polish State Com- by applying optical microscope, scanning electron micro- mittee for Scientific Research grant no 3PO4D 017 22. R.J. scope with energy dispersive spectrometry (SEM-EDS) and is also supported by the Polish Geological Society in frame X-ray diffraction (XRD) of oriented powder samples. of the Beres Scholarship in 2003. The grains are mainly 0.1– 0.4 mm in size and medium to dark green in colour. Mostly sub-rounded, irregular shapes References are present, rarely tabular or well-rounded ovoidal shapes AMOROSI, A. (1997). Sediment. Geol., 109: 135-151. were observed. The most important elements shown by EDS IRELAND, B. J., CURTIS, C. D. & WHITEMAN, J. A. point analysis are Si, Al, Fe, Mg, K, with some minor ad- (1983). Sediment., 30: 769-786. mixtures of Ti. Thus the green grains are rich in K ODIN, G. S. & MATTER, A. (1981). Sediment., 28: 611- (K2O>7%) but reveal relatively small amount of Fe2O3 (up to 641. 19%) and high content of Al2O3 (from 13% to 20%). Al-rich glaucony has been interpreted to reflect the results of diage-
96 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
GRANITIZATION PHENOMENA IN THE GILĂU MOUNTAINS (ROMANIA). A GEOCHEMICAL APPROACH
STUMBEA, D. University “Al. I. Cuza”, 20A Carol I. Bvd., RO-6600 Iaşi, Romania. E-mail: [email protected]
The Gilău Mountains represents a morphological subdivi- metamorphic rocks; plagioclase + microcline-bearing peg- sion of the Apuseni Mountains. The later unit is localized in matite, hosted by metamorphic rocks/granite of Muntele the western part of the Romanian territory and considered as Mare (the words wrote in italic characters represent the terms one of the three units of Romanian Carpathians. presumed as arising by means of granitization process). In The geological background of Gilău Mountains is pro- the following scheme, our main results are exhibited: vided by the medium-grade metamorphic series of Someş, built up mainly by mig- PM pegmatite Micaschist → matites, leptynites, gneiss, micaschists in metamorphic rocks with almandine, disthene, staurolite and ↓ sillimanite. The geology of the area is → Granite gneiss → Granite completed by the granite body of Mun- tele Mare that penetrates the metamor- PMm pegmatite Paragneiss → phic formations and by numerous peg- in metamorphic rocks matite bodies hosted both by granite and metamorphic rocks. Our last studies carried out on pegma- tites (STUMBEA, 2000) seem to confirm MÂRZA’s (1980) This scheme shows that granite gneiss can arise as a re- hypothesis, which attach to these rocks a metamorphic gene- sult of micaschist granitization and it reveals also that PM sis (metamorphic differentiation or even anatexis). pegmatites, PMm pegmatites (both hosted by metamorphic Granitization phenomena in the Gilău Mountains have rocks) and granite can be generated by the granitization phe- been reported almost forty years ago. In the span of time of a nomenon of gneiss. But the most interesting conclusion re- decade, STOICOVICI & TRIF (1961), TRIF (1961), TRIF & vealed by the geochemical balance and pictured in the STOICOVICI (1963), TRIF (1968) lead research works – scheme above is the granitization-like feature of the balance mostly field works followed by both macroscopic and micro- between PM pegmatite and granite. Though the granite body scopic observations; the outline of their conclusions consist of Muntele Mare is much younger than the metamorphic in a spatial superposition of granitization phenomena on the rocks of Someş series and it can’t be the result of their most intense metamorphic phenomena (metamorphic differ- anatexis, the result could represent a geochemical proof of entiation and/or anatexis). the possibility of granite engendering through this way. The geochemical approach of the granitization phenom- ena consist in establishing the geochemical balance between References the rocks arisen by means of granitization and those pre- MÂRZA, I.. (1980). Anuarul I. G. G., Bucureşti, 57: 423- sumed not being affected by this process; in this respect, the 432. standard cell of these two types of rocks has been deter- STOICOVICI, E. & TRIF, A. (1961). Studia Univ. “Babeş- mined. The results of the geochemical balance have been Bolyai”, Cluj, I: 71-82. compared to the theoretical modeling of input and output in STUMBEA, D. (2000). Publishing House of “Al. I. Cuza” the rocks during the granitization process (Si, Al, K input University, Iaşi, 264p. and Ti, Fe, Mg, Mn output). TRIF, A. (1961). Studia Univ. “Babeş-Bolyai”, Cluj, I: 47- Taking into account the above mentioned hypothesis we 70. have been able to identify features of granitization-like proc- TRIF, A. (1968). Studia Univ. “Babeş-Bolyai”, Cluj, I: 59- ess regarding the following pairs of rocks: micaschist/granite 70. gneiss; paragneiss/ granite gneiss; granite gneiss/ plagioclase TRIF, A. & STOICOVICI, E. (1963). Studia Univ. “Babeş- + microcline-bearing pegmatite (PM pegmatite), hosted by Bolyai”, Cluj, I: 7-28. metamorphic rocks; granite gneiss/ plagioclase + microcline + muscovite-bearing pegmatite (PMm pegmatite), hosted by
97 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
COMPOSITION AND EVOLUTION OF LITHOSPHERIC MANTLE BENEATH THE PANNONIAN BASIN: A PETROGRAPHIC AND GEOCHEMICAL REVIEW
SZABÓ, Cs., FALUS, Gy., BALI, E., KOVÁCS, I., ZAJACZ, Z. & HIDAS, K. Lithosphere Fluid Research Lab, Department of Petrology and Geochemistry, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary. E-mail: [email protected]
Introduction deformed xenoliths are enriched in strongly incompatible Knowledge of the lithosphere beneath the Carpathian- trace elements (e.g. light rare earths elements). Pannonian Region (CPR) have been greatly improved by Chemical composition of the pyroxenite xenoliths shows petrologic, geochemical and isotopic studies of upper mantle enrichment in basaltic and light rare earths elements. These xenoliths hosted in Plio-Pleistocene alkali basalts of Styrian rock fragments represent mafic melts crystallized as pyrox- Basin, Little Hungarian Plain, Bakony-Balaton Highland, enite dykes or cumulate bodies in the lithospheric mantle. Nógrád–Gömör and East Transylvanian Basin (EMBEY- Hydrous phases, pargasitic and kearsutitic amphiboles ISZTIN et al., 1989; DOWNES et al., 1992; SZABÓ & and phlogopitic micas occur as evidence of modal metaso- TAYLOR, 1994; VASELLI et al., 1995, 1996). The CPR matism in both peridotite and pyroxenite xenoliths. Amphi- mantle xenoliths are mostly spinel lherzolites, however sub- boles, occurring as interstitial phases, veins and selvages, are ordinate pyroxenites, websterites, wehrlites, harzburgites and more common than phlogopites. A portion of both hydrous dunites are also present. Garnet-bearing mantle fragments phases is texturally and chemically in equilibrium with the have not been reported, however breakdown products of anhydrous mantle minerals in the peridotites. However, am- garnet were recognized in some mantle xenoliths (TÖRÖK, phiboles frequently in veins and pyroxenites show enrich- 1995; FALUS et al., 2000). ment in K, Fe and light rare earth elements. Existence of carbonate-bearing melt pockets and veins Textural features related to melting of amphiboles and clinopyroxenes, and The peridotite (basically spinel lherzolite) xenoliths, rep- existence of silicate melts, sulfide and CO2 inclusions, resenting residual material of the mantle with complex his- trapped in the anhydrous mantle minerals, indicates the pres- tory, show variable textural features. In order of increasing ence and migration of melts and/or fluids, which caused deformation, protogranular, porphyroclastic and equigranular metasomatic interactions at different time and under different textures can be distinguished. Also, minor secondary recrys- PT conditions (BALI et al., 2002). The source of the meta- tallized xenoliths have been found as a result of mantle re- somatic melts/fluids might have related to subduction, oc- laxation. The lithospheric mantle is more deformed in the curred beneath the CPR during the late Tertiary times. central part of the CPR than towards the western and eastern edges. The deformation could have been associated with References asthenospheric upwelling and extension in the late Tertiary BALI, E., SZABÓ, Cs., VASELLI, O. & TÖRÖK, K. affected strongly the central part of the subcontinental litho- (2002). Lithos, 61: 79-102. sphere of the CPR. DOWNES, H., EMBEY-ISZTIN, A. & THIRLWALL, M. F. The pyroxenite xenoliths, composed of mostly clinopy- (1992). Contrib. Miner. Petrol., 107: 340-345. roxene, are also widespread in the CPR but in low number. EMBEY-ISZTIN, A., SCHARBERT, H. G., DIETRICH, H. Textures of these xenoliths are slightly variable: coarse- & POULTIDIS, H. (1989). J. Petrol., 30: 79-106. grained igneous textural features can be observed; sign of FALUS, Gy., SZABÓ, Cs. & VASELLI, O. (2000). Terra recrystallization and deformation is not common. Nova, 12: 295-302. SZABÓ, Cs. & TAYLOR, L. A. (1994). Inter. Geol. Rev., Geochemical features 36: 328-358. The peridotite xenoliths have a bulk compositions rang- TÖRÖK, K. (1995). Acta Vulcanol., 7: 285-290. ing from 36 to 46 wt% MgO, 0.5 to 4.0 wt% CaO and 1.0 to VASELLI, O., DOWNES, H., THIRLWAAL, M. F., DO- 4.5 wt% Al2O3. There are no significant chemical differences BOSI, G., CORADOSSI, N., SEGHEDI, I., SZAKÁCS, among the xenoliths of the major localities. Nevertheless, A. & VANNUCCI, R. (1995). J. Petrol., 36: 23-53. mineral composition, particularly in case of clinopyroxene, VASELLI, O., DOWNES, H., THIRLWAAL, M. F., VAN- varies according to the xenolith textures. Less deformed NUCCI, R. & CORADOSSI, N. (1996). Mineral. Petrol., xenoliths have clinopyroxene with higher content of basaltic 57: 23-50. major elements (Al, Ti, Na and Fe) compared to the more deformed samples. However, clinopyroxenes in the more
98 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
NEOGENE-QUATERNARY VOLCANISM OF THE CARPATHIAN-PANNONIAN REGION. A VOLCANOLOGICAL PERSPECTIVE
SZAKÁCS, A. Institute of Geodynamics, Romanian Academy, 19-21 Jean Louis Calderon str., RO-70201 Bucharest, Romania. E-mail: [email protected]
The Carpathian-Pannonian Region (CPR) records a ca. 20 and related specific evolution patterns – are due to features of Ma old volcanic activity closely related to the geodynamic the overriding plates, unlike most modern analogues world- evolution of the area. Eruption styles are different for the wide. Eruptions occurred at a large number of centers, most three main compositional groups of the feeding magmas – of them being composite volcanoes with variable size and felsic calc-alkaline, intermediate calc-alkaline and alkali- complexity, located in various paleogeographic environ- basaltic. The time-space evolution of volcanism, inferred ments. Some of them evolved until large caldera systems using K-Ar geochronology, shows that volcanism started including post-caldera resurgence stages or even multiple with felsic magmas and ended with alkali-basaltic magmas in caldera-forming events. Edifice instability led to sector col- most of CPR. lapse and generation of large-volume debris avalanche de- Felsic calc-alkaline magmas, sometimes with alkaline af- posits at a few volcanoes. Spatial distribution of volcanic finity, mostly produced large-volume explosive eruptions centers shows close spacing of edifices in most areas, leading generating welded and non-welded ash-flow deposits as well to complicated patterns of merging, interfingering and over- as their reworked counterparts deposited both on land and lapping of various volcanic facies at neighboring volcanoes. under water. Since most of their occurrences are buried be- Interaction between large volcanic edifices and their base- neath younger sediments, their respective eruptive centers are ment including low yield-strength rocks have been observed difficult to identify. However, a few centers have tentatively at some volcanoes in the East Carpathians. been localized – e.g. as buried calderas in the central part of Alkali-basaltic volcanism is clustered in a number of the Pannonian Basin. Felsic and intermediate calc-alkaline rather well-localized areas, corresponding to narrow-section volcanics are closely related in both space and time in vari- mantle plumes. They form fields of small-sized monogenetic ous areas of CPR. volcanoes, including maar structures, Strombolian cinder Andesite-dominated intermediate calc-alkaline magmas – cones and lava fields. The size of the fields, number of cen- traditionally thought as being subduction-related – generated ters included and duration of volcanism are variable. volcanics with an obvious geochemical signature, however, The most recent volcanic activity in CPR occurred ca. coeval subduction is very unlikely for most of the areas in 35–42 Ka ago in the Ciomadul Massif at the southeastern CPR, since most of the volcanism is postcollisional. This end of the East Carpathian volcanic arc, and ca. 0.1 Ma ago volcanism first developed in the western part of CPR with an in the Central Slovakian Volcanic Field. Further eruptions areal-type spatial distribution. An obvious magmatic arc with cannot be ruled out in these areas and volcanic hazard should a definable volcanic front has been active after ca. 14 Ma be considered for the unforeseeable future. from Eastern Moravia to the Calimani and Gurghiu Mts. in the East Carpathians, until ca. 8 Ma ago. Arc segmentation –
99 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
SYNCHYSITE-(Ce) FROM THE KOMLÓ COAL DEPOSIT, MECSEK MTS., SOUTH HUNGARY
SZAKÁLL, S.1, NAGY, G.2 & SAJÓ, I. E.3 1 Department of Mineralogy and Petrology, University of Miskolc, H-3515 Miskolc-Egyetemváros, Hungary. E-mail: [email protected] 2 Research Centre for Earth Sciences, Laboratory for Geochemical Research, Hungarian Academy of Sciences, Budaörsi út 45, H-1112 Budapest, Hungary. 3 Chemical Research Centre, Hungarian Academy of Sciences, Pusztaszeri út 59-67, H-1025 Budapest, Hungary.
A REE-bearing mineral, synchysite-(Ce), was identified Ce and Nd content are very similar, but the ionic number is from the Komló coal deposit, Mecsek Mts. Its appearance Ce = 1.85; Nd = 1.74. was probably influenced by the surrounding phonolite area. The chemical formula, which was calculated from EPMA Some REE (such as lanthanum, yttrium) were earlier is as follows: Ca(Ce0.38Nd0.37La0.08Pr0.07Sm0.05Ga0.02Eu0.01) identified by complex trace element studies in the coal de- (CO3)2F0.57. posit (CSALAGOVITS & VIGHNÉ FEJES, 1969), but REE- The X-ray diffraction data support the results of the bearing minerals have not been found. In the close geological chemical analyses, the d values show good correlation with environment of the coal deposit (partly in the coal seams the bibliographic data of synchysite-(Ce), but the intensity of too), submarine volcanic/subvolcanic alkaline rocks, espe- the reflections are different, assumable due to the high Nd- cially phonolite occur in some outcrops. Electron microprobe content. The most important d values are the following (the analyses proved the presence of some accessory REE miner- data of JCPDS 18-284 file are in the brackets): 9.07 (9.1), als like britholite, bastnäsite, nacareniobsite and joaquinite in 4.54 (4.53), 3.54 (3.55), 2.79 (2.80), 2.04 (2.06), 1.91 (1.87). the phonolite (PANTÓ, 1980; NAGY, 2003; SZAKÁLL, Unit cell data are: a = 7.082 Å, c = 54.565 Å. It shows tran- unpublished). sitional values between synchysite-(Ce) (a = 7.126 Å, c = A mineral-rich paragenesis was identified in the septarian 55.08 Å; ICDD PDF2 # 44-1438) and synchysite-(Nd) (a = fissures of pelosideritic concretions at Zobák shaft, Komló in 6.984 Å, c = 54.27 Å; ICDD PDF2 # 35-0589). The Ca : the last few years. The main fissure fillings are: quartz, cal- REE ratio is near 1 : 1 (4.7822 : 4.8118), this is also an evi- cite, siderite, pyrite, marcasite and kaolinite. The rare acces- dence for synchysite. TEM study, however, signed some sory minerals are: barite, galena, sphalerite, millerite, etc. inhomogenities in the synchysite; in these places both pa- The synchysite-(Ce) was shown as pale rose, prismatic risite and röntgenite may appear. crystals (up to 1.5 mm) in close association with quartz and The appearance of synchysite-(Ce) can be in connection calcite. The crystals always have pseudohexagonal habits. with the REE-enrichment of the magmatic environment. The The prism is always strongly striated because of its oscillat- REE was mobilized by post-magmatic processes, together ing development. with other elements. The close paragenesis of synchysite- The synchysite at Komló proved to be rich in cerium and (Ce) demonstrate definitely hydrothermal conditions. neodymium by electron microprobe analyses. The result of Investigated synchysite-(Ce) sample from Komló is pre- EPMA (average of five analyses in weight %): CaO 16.80, served in the mineral collection of Herman Ottó Museum Y2O3 0.26, La2O3 4.21, Ce2O3 18.82, Pr2O3 3.67, Nd2O3 (Miskolc, Hungary) under catalogue number 18590. 18.95, Sm2O3 2.79, Eu2O3 0.37, Gd2O3 0.96, Tb2O3 0.00, Dy2O3 0.01, Ho2O3 0.01, Er2O3 0.00, F 3.24, Σ 70.08. The References minerals in the synchysite-subgroup of bastnäsite-synchysite- CSALAGOVITS, I. & VIGHNÉ FEJES, M. (1969). MÁFI parisite group are distinguished according to the dominant Évk., 51: 520–591. REE as synchysite-(Ce), synchysite-(Nd) and synchysite-(Y) FLEISCHER, M. (1978). Can. Mineral., 16: 361–363. (FLEISCHER, 1978). Considering the EPMA, the Komló NAGY, G. (2003). Acta Mineral- Petrogr., this volume synchysite can be identified as synchysite-(Ce) because the PANTÓ, Gy. (1980). Doctoral thesis, 1–152.
100 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
EUHEDRAL CALCITE IN CARBONATIC CONCRETIONS FROM QUATERNARY PALEOSOL ENVIRONMENT, GYÖNGYÖSVISONTA, HUNGARY
SZILÁGYI, V.1, SZINGER, B.1, WEISZBURG, T. G. 1, HORVÁTH, Z.2 & MINDSZENTY, A.2 1 Department of Mineralogy, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary. E-mail: [email protected] 2 Department of Applied and Environmental Geology, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary.
Carbonate concretions, including grown up, fine, euhe- the concretions, 2) the root zone and 3) the coronal zone of dral crystals of calcite were discovered in the open cast lig- the euhedral calcite crystals. The results can be interpreted as nite mine at Gyöngyösvisonta, in the southern foreland of the the euhedral crystals precipitated in a closed system inside Mátra Mountains, Hungary. The concretions are embedded the concretions. There is no data indicating any elevated in a thick (8–10 m) paleosol (red clay) sequence sedimented temperature (hydrothermal) formation condition. on Pannonian age strata. They attracted our attention because The closed system crystallization raises the question on such calcite crystals are very common in hydrothermal envi- the origin of the growth zoning of calcite. In an open system ronments, but seemed to be unusual in a soil-related envi- chemical changes of the fluid could be assumed, in a closed ronment. system physical environmental parameters, in our case Our aim was to describe the morphological appearance of mainly temperature and maybe temperature related biological the crystalline calcite in the concretions and to obtain infor- activity could be responsible for the entrance of manganese mation about their formation. in the calcite lattice. In order to get morphological data we applied stereomi- For a better understanding of the genetic conditions we croscopy, scanning electron microscopy and two-circle re- studied also the black, mm sized nodules to be found both in flecting goniometer measurements. Two main morphological the paleosol (red clay) environment of the concretions and types of calcite were found. The rhombohedral type is built encapsulated in the micritic wall of the concretions them- up of the combination different rhombohedra, while the sca- selves. Based on X-ray diffractometry and optical emission lenohedral type is built up of the combination of rhombohe- spectroscopy they turned out to be mixtures of (detrital) dra and scalenohedra. quartz and poorly crystallized oxides and oxy-hydroxides of X-ray powder diffraction patterns showed two types of iron (goethite and hematite). Their manganese content is in calcite. The micritic wall of the concretions and the root zone the 1000–10000 ppm range. There was no significant differ- of the euhedral crystals consisted of pure calcite. In the coro- ence between the nodules separated from the micritic wall nal zone of the crystals, beside the pure calcite, another, and from the red clay, thus we consider the former ones as sligtly substituted calcite of shorter lattice parameter relicts of the red clay environment in the concretions. (d104 = 2.98 A) can also be detected. Based on our data we reconstruct the formation of the That substituted calcite region was studied in detail by concretions as follows: cathode luminescent microscopy and by SEM+EDX. We In the first phase loose, calcareous concretions formed in found growth zoning of calcite in that part of the samples. the red clay sequence. In a second step volume changes, The width of the individual zones varies between 50 and coming from alternation of dry and humid climatic periods 150 µm. The zoning is caused by chemical substitution. In caused cracks in the concretions within the soil. In these the cathode luminescent microscope an unusually strong cracks calcite growth started, resulting both the thickening of luminescence of these zones (in “pure” calcite) could be the wall of the concretions and, simultaneously or subse- seen. Back scattered electron images showed the presence of quently, the precipitation of the root zone of the euhedral cation(s) of larger average atomic number than calcium in crystals. Concretions became thick-walled, at most 35–40 cm the luminescent zones. Based on EDX measurements the in diameter, bodies due to subsequent solutions and final substituting element is manganese (3–6 cation%). Pure cal- desiccation. Inside the concretions, in the closed cavities cite and manganese bearing calcite are separated by sharp crystallization of euhedral calcite continued, resulting bigger boundaries. The oscillatory precipitation of the two phases and bigger crystals towards the inside of the concretions. resulted in the formation of several, sometimes many tens, We hope that our results contribute not only to the better manganese free and manganese containing zones. understanding of the formation of concretions, but also to Carbon and oxygen stable isotope analysis was carried that of the development of the whole soil environment. out on a set of samples representing 1) the micritic wall of
101 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
HYDRONIUM JAROSITE FROM IZA CAVE (RODNEI MTS., ROMANIA)
TAMAS, T.1 & GHERGARI, L.2 1 Department of Mineralogy, Babeş-Bolyai University & “Emil Racoviţă” Institute of Speleology, 1, Kogalniceanu Str, RO-3400 Cluj-Napoca, Romania. E-mail: [email protected] 2 Department of Mineralogy, Babeş-Bolyai University, 1, Kogalniceanu Str, RO-3400 Cluj-Napoca, Romania.
Several secondary deposits consisting of crusts and flow- small amounts of alunite (5.1%), quartz (4.97%), and kao- stones have been investigated in Iza Cave (Rodnei Moun- linite (0.67%). tains, Maramureş county, Romania). The cave is formed at The thermal analysis on the sulfate sample shows a the contact between Eocene limestones and conglomerates weight loss of 5.79% until 163 °C, which was assigned to the and crystalline rocks (sericite-chlorite schists and crystalline loss of H3O. The following weight losses, totaling 9.75%, limestones). were assigned to the decomposition of OH from the jarosite Previous studies carried out in Iza Cave reported a large structure, which was theoretically calculated at 9,77%. clay-like deposit, consisting of muscovite, illite, kaolinite, Both goethite and hydronium jarosite formed through the dickite, quartz and possibly rutile, formed by subaerial action of percolating water over pyrite that is present as ac- weathering of schists in the cave environment (VIEHMANN cessory mineral in the crystalline schists. et al., 1979, 1981). We found that the heavy fraction of the Minerals from the jarosite group are rarely present in weathered schists is composed mainly of quartz and pyrite, caves; a survey of the known records around the world evidenced by XRD and SEM - EDAX. shows very peculiar depositional conditions (HILL & The secondary deposits studied consist of hydronium FORTI, 1997). Iza Cave is the first known occurrence of jarosite [(H3O,K)Fe3(SO4)2(OH)6] deposited over goethite hydronium jarosite in Romania. Moreover, this mineral has flowstone. Hydronium jarosite forms millimeter to centime- not been previously reported from the cave environment. ter–sized orange crusty nodules, composed of small (1–3 µm), relatively isometric rhombohedral crystals. References The X-ray diffraction pattern shows the major participa- HILL, C. & FORTI, P. (1997). Cave minerals of the world. tion of hydronium jarosite, associated with small amounts of 2nd ed. NSS, Huntsville, 463p. alunite (most intense reflections, partially covered by hydro- VIEHMANN, I., DEMETER, I., LUNGU, V. & nium jarosite lines), and quartz (the peak at 3.34) and kao- SARKADY, P. (1981). Trav. Inst. Speol. “E. Racovitza”, linite (peak corresponding at 7.2), the latter two as impuri- XX: 213-215. ties. VIEHMANN, I., SILVESTRU, E. & FABIAN, C. (1979). The normative calculus based on the EDAX analysis al- Trav. Inst. Speol. “E. Racovitza”, XVIII: 201-207. lowed us to determine the participation of hydronium jaro- site, which is the main mineral (87.50%), associated with
102 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
A DOS PROGRAM FOR SUPPORTING MODAL ANALYSIS OF ROCKS (MOD_EL v. 2.12)
TÓTH, S.1, CSÁMER, Á.2 & RÓZSA, P.2 1 Darabos u. 10, H-4026 Debrecen, Hungary. 2 Department of Mineralogy and Geology, University of Debrecen, P.O. Box 4, H-4010 Debrecen, Hungary. E-mail: [email protected]
Modal analysis is a basic petrographic method for deter- XLS (MS-Excel) file formats, and to evaluate these data mination of mineralogical composition and grain-size distri- statistically. It gives the minimal measuring length for the bution of rocks. Two types of data series can be obtained by required accuracy, and compiles tables and graphs for repre- this method: (1) relative quantity of rock forming minerals, senting the results of the measurement. Minimal hardware and (2) grain-size distribution of the studied rock. Moreover, and software requirements are to run the software: AT 386 using an appropriate method, grain-size distribution of the compatible computer with (4 MB RAM, 20 MB hard disk main mineral components can be also determined. This way, space, monochromatic monitor, MS-DOS 5.5 operation sys- further petrological conclusions (such as classification of the tem. Of course, MOD_EL v. 2.12 runs on Windows OS texture, distinction of rock varieties and facies, etc.) can be (Windows 9x/NT/2000), too. Both English and Hungarian drawn. Any method of the modal analysis should satisfy versions are available. As a final result, the program lists the three principal requirements: (1) appropriate accuracy, (2) grain-size and mineral components data in a summarized simplicity, and (3) speed. table, and makes grain-size distribution curves (Fig. 1). Amongst methods of modal analysis (CHAYES, 1956) the authors regard the classic Rosiwal’s method (ROSIWAL, Acknowledgement 1898) − measuring along the line − as the most efficient. This work was supported by the OTKA Grant T-029058. First, this method does not require special equipment, and second, relative quantity of the rock forming minerals as well References as grain-size distribution can be simultaneously determined. CHAYES, F. (1956): Petrographic Modal Analysis. John Moreover, in the case of necessary measurements its accu- Wiley and Sons Inc., New York. 113 pp. racy is acceptable (JÁRAI et al., 1997). However, a rela- JÁRAI, A., KOZÁK, M. & RÓZSA, P. (1997). Math. Geol., tively long line has to be measured, and large amount of data 29/8: 977–991. has to be evaluated to obtain precise results. ROSIWAL, A. (1898). Verh. der k. k. Geol. Reichanstalt, MOD_EL v. 2.12 software package introduced by this Wien, 5–6: 143–175. paper is able to use data recorded in simple text and special
Fig. 1: Grain-size distribution curves drawn by MOD_EL v. 2.12 program.
103 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
HISTORICAL-MUSEOLOGICAL DATA OF THE METEORITE OF KISGYŐR (BORSOD-ABAÚJ-ZEMPLÉN COUNTY, HUNGARY)
TÓTH-SZABÓ, T. Department of Mineralogy, Herman Ottó Museum, Kossuth u. 13, H-3525 Miskolc, Hungary. E-mail: [email protected]
Meteors (falling stars) and their parts falling on Earth, as the handover in the 1950s. It is mentioned under log number well as meteorites are exciting the curiosity of mankind. If “b 121” here. Its weight is determined to be 3,61 grams. If only we consider the history of mankind, which is neglect- the latter version is valid, than the only question is: what has able in time compared to that of Earth, than we find that the happened to the other 4 particles, for according to the data, as number of them is quite significant. I have previously mentioned, there were 5 parts recorded in There have been impacts recorded in Hungary as well, the Borsod–Miskolc Museum, while there is only one in the both recently and in past times. Considering the historical meteorite catalogue. However if those were a part of a new background one of the oldest meteorite falls was that of collection enlargement it is also worth to examine their fur- Diósgyőr in 1559 (1449? or 1560?). Furthermore, not far ther destiny. Where are they? Are they still on storage? If from Miskolc, at Kisgyőr a meteorite has also been docu- not, what has happened to them? Later the Hey’s meteorite mented in 1901, centuries later. Examining the arriving catalogue (HEY, 1906) mentions them, though on the basis agenda of the natural history collection of the predecessor of of the letter of Viktor Zsivny they are considered to be ques- Herman Ottó Museum, the Borsod–Miskolc Museum, I have tioned, questionable meteorites. However, according to found the particles of the Kisgyőr materials entered under MTM, that part was also destroyed in the destruction reach- register number 180. According to that there were 5 parts of ing most of the mineral collection in 1956. The fact that the the meteorite presented to the museum’s fossil and mineral catalogue of Csaba Ravasz, prepared in 1969, mentions only collection by SámuelNagy. The notes only describe that the two sites, the ones at Ófehértó and Zsadány, seems to sup- parts touched down near Miskolc, at Kisgyőr — as it was port that. The collection shows the circumstances after the known before — on 23rd May 1901. Some collection infor- tragic conflagration of 1956. Though it is still not clear for mation could be found in the 1902 catalogue of the Borsod– me, whether that destruction reached only the part mentioned Miskolc Museum. According to those the listed parts were in the catalogue in 1951, or the parts from Miskolc were also put on exhibition in section “A” and “E” of the main hall on included. the ground floor. The list contained the meteorites of Kisgyőr under the numbers “120”, “121”, “122”, “123”, “124”. That References may mean that the parts arrived to the museum not long after BUDAI, J. (1902) in: Molnár, J. (ed.): Borsod-Miskolci their impact. From 1905 the fossil and mineral collection did Múzeum ismertető katalógusa (Information Catalogue of not form a separate part, but was handled together with the Borsod–Miskolc Museum), Szelényi és Társa, similar collections under the name of “natural history collec- Miskolc. tion”, which makes the processing of the collection agenda HEY, M. H. (1906): Catalogue of Meteorites (Trustees of the harder. They have probably been in museum property for British Museum), London. many decades. Their time of destruction is supposed to be RAVASZ, Cs. (1969): Catalogue of Meteorites of the Hun- the 50s, when the natural history collection was eliminated. garian Natural History Museum. Fragm. Miner. Paleon. The geological material became part of the natural science TOKODY, L. & DUDICH-VENDL, M. (1951): Magyaror- collection of the National Museum. After all these the ques- szág meteoritgyűjteményei (Meteorite collections of tion is whether the meteorite found in the meteorite catalogue Hungary). Akadémiai Kiadó, Budapest. of TOKODY & DUDICH-VENDL (1951) and kept at the latter place derives directly from Kisgyőr or is a remainder of
104 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MINERAL FORMATION PROCESSES IN KARST CAVE SYSTEMS OF THE MIDDLE MIOCENE BADENIAN GYPSUM (CARPATHIAN FOREDEEP, WEST UKRAINE)
TURCHINOV, I. I. Lviv Geological Survey Expedition, Turgeneva 33, UA-79018 Lviv, Ukraine. E-mail: [email protected]
Giant labyrinth cavern systems (largest of them – Opti- - crystallization from free flowing water after mistic Cave – has a length more than 210 km) are a result of carbon dioxide loss (calcite, rhodochrosite); deep karst processes in the middle Miocene Badenian gyp- - crystallization in clay filling of cavities (gyp- sum in the outer part of Carpathian Foredeep. These systems sum); are characterized as lateral labyrinth networks of karst cavi- - crystallization from water in joints (gypsum, ties. Air temperature in the caves is +8,2–10,5 °C, air hu- calcite); midity 96–100%, CO2 concentration 0,1–4,8%, radon con- - crystallization from aerosol (gypsum); centration up to 23700 Bq/m3. Original geological, physical - subaqueous crystallization (calcite); and chemical conditions have determined a wide develop- - crystallization from gels (chalcedony); ment of mineral formation processes here. - biochemical precipitation (iron and manganese Minerals originated in karst cavern systems of the Mio- oxides and hydroxides); cene gypsum belong to classes of sulphates (gypsum, celes- - freezing crystallization (ice). tine), carbonates (calcite, rhodochrosite), silicates (chalced- Processes of mineral formation in the karst cave systems ony), oxides and hydroxides (minerals of iron and manga- of the Miocene gypsum are low-temperature. Minerals origi- nese, ice). Formation of minerals is determined by following nated as a result of these processes occur in the form of spe- processes: cific aggregates – speleothems (crusts, stalactites, helictites, - crystallization after evaporation of thin film of etc.). Subaerially-formed speleothems predominate, and their water (gypsum, celestite, calcite); growth is controlled by air currents in the cavities. - crystallization after evaporation of seeping in- terstitial water (gypsum);
105 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
OUTSTANDING MINERAL OCCURRENCES IN ROMANIA: WHAT’S NEW?
UDUBAŞA, G. Geological Institute of Romania, Caransebeş Street No. 1, RO-78344 Bucharest-32, Romania. E-mail: [email protected]
To date some 900 mineral species are known in Romania, 4. Ocna de Fier / Moravicza / Vaskő / Eisenstein: 100 m.s; much more than UDUBAŞA (1999) reported, i.e. about one 2xTL. Also many pyrite crystal forms have their TL quarter of the minerals in the world. The increase of number here. of mineral species is considerable as compared to about 450 5. Ditrău / Ditró: 60m.s.; a new Bi-Pb sulphotelluride. in 1966. An attempt was also made to identify the most 6. Răzoare/Macskamező: 70m.s.; many rarities! “productive” occurrences (“sacred monsters”) (see table) 7. Roşia Montană / Verespatak: 50 m.s.; twin law of high both as concerns the total number of mineral species and quartz. some unusual crystal forms or intergrowths (UDUBAŞA, 8. Uroiu/Arany/Aranyerberg: 20 m.s.; TL of pseudo- 1994). brookite. Among the “sacred monsters” the hydrothermal and 9. Bistriţa Mts (Iacobeni, Dadu, Tolovanu, Oiţa deposits, skarn deposits are by far dominating. In addition to the old etc): some 300 mineral species and varieties discovered skarn deposits quoted in the table, the high temperature skarn in the last 10 years (HARTOPANU, 2002 and the paper occurrences at Măgureaua Vaţei near Brad (Cornet Hill and in this volume). Cerboaia Valley localities) have proved to contain also nu- 10. Bihor Mts caves: mineral rarities: taranakite, merous other high–T calcium silicates as well as the rare metatyuyamunite, norsethite, glaucosphaerite, scawtite, chlorosulphide, djerfisherite, and hydroxylellestadite (PAS- etc. (ONAC & DAMM, 2000; ONAC et al., in press). CAL et al., 2001; MARINCEA et al., 2001). Nevertheless 11. Cioclovina Cave: TL of ardealite; also brushite, crandal- the caves and the stratiform Mn-Fe ores show a greater min- lite, tinsleyite, etc. (MARINCEA et al., 2002) eral diversity after recent careful investigations by ONAC & 12. Măgureaua Vaţei: high T skarns with scawtite, tilleyite, DAMM (2002), ONAC et al. (2000), MARINCEA et al. spurrite, gehlenite and many other Ca silicates, as well as (2002) and HARTOPANU (2002), respectively. Metatyuya- hydroxylellestadite, djerfisherite etc. (PASCAL et al., munite, wittichenite, scawtite, tinsleyite, taranakite, nor- 2001; MARINCEA et al., 2001). sethite etc were thus identified in different caves. The whole series of the manganhumites, some silicates-arsenates, nam- References bulite, bannisterite etc are only few among the 300 mineral HARTOPANU, P. (2002). Ph.D. Thesis, Univ. of Bucharest species and varieties discovered in the Mn-Fe ores in the MARINCEA, Şt., BILAL, E., VERKAEREN, J., PASCAL, Bistriţa Mts. (HARTOPANU, 2002 and this volume). It is M. L. & FONTEILLES, M. (2001). Canadian Mineralo- expected that the Ditrău “monster” will produce soon many gist, 39: 1435-1453. novelties as about one quarter of the proposals for new min- MARINCEA, Şt., DUMITRAS, D. & GIBERT, R. (2002). erals submitted to CNMMN is delivered by alkaline massifs. Eur. J. Mineral., 14: 157-164. ONAC, B. P. & DAMM, P. (2002). Studia Univ. Babes- Table Bolyai, Geologia, XLVII: 93-104. “Sacred monsters” of mineral occurrences in Romania ONAC, B. P., KEARNS, J., DAMM, P., WHITE, W. B. & (1 to 8 acc. to UDUBASA, 1994). MATYASI, S. (2000). Rom. J. Mineralogy, 80: 5-10. PASCAL, M. L., FONTEILLES, M., VERKAEREN, J., 1. Săcărâmb / Nagyág: 120 mineral species, 6 times type PIRET, R. & MARINCEA, Şt. (2001) Canadian Miner- locality. alogist, 39: 1405-1434. 2. Baia Sprie / Felsőbánya: 80 m.s.; 6xTL; Felsőbánya UDUBAŞA, G. (1994). Anal. Univ. Bucuresti, XLIII, habit of “adularia”. Suppl.: 34-35. 3. Băiţa Bihor / Rézbánya: 120 m.s.; 5xTL. UDUBAŞA, G. (1999). Rom. J. Mineralogy, 79: 3-30.
106 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MAGMATIC DIFFERENTIATION PROCESSES DURING EVOLUTION OF NEOGENE CALC-ALKALINE MAGMATITES OF THE SUBVOLCANIC ZONE IN THE EAST- CARPATHIANS
URECHE, I.1, PAPP, D. C.1 & NIŢOI, E.2 1 Geological Institute of Romania, Cluj-Napoca Branch, C. P. 181, RO-3400 Cluj-Napoca, Romania. E-mail: [email protected] 2 Geological Institute of Romania, 1, Caransebeş str, RO-78344 Bucharest-32, Romania.
This paper evaluates Neogene calc-alkaline magmatism sites, andesites and microdiorites. It trends towards the high- from Rodna-Bârgău Mts. based on new data on mineral K domain. compositions, and new major and trace element data for The major elements host rocks TiO2, FeO, MgO, and estimating specific chemical and P-T conditions of the dif- CaO variation with SiO2 content shows trends of negative ferent magmatic structures. Great variety of petrographic correlation, whereas K2O and Na2O increase with increasing types (from basaltic andesites to rhyolites), preponderance of SiO2. These trends are consistent with fractional crystalliza- intermediary and basic rocks which form more extended tion starting from basic magmas. Rb, Nb, Pb, Sr, Zr, Y show intrusive structures compared with acid ones, as well as pres- a scattered variation with SiO2. This indicates diverse condi- ence of cognate xenoliths only in the intermediary facies, tions of magma generation for different magmatic structures. deal with conjugate processes of assimilation, fractional LIL and LREE enrichment as compared to primitive mantle crystallization, and repeatedly refilled magma chambers. deal with crustal assimilation processes. Amphiboles are the main mafic mineral within the mag- Using Al content in hornblende as geobarometer and am- matic rocks in the Rodna–Bârgău area. Most of the amphi- phiboles-plagioclase geothermometer, we obtained a tem- bole phenocrysts, especially those found in the andesites and perature range from 798 to 936 °C, and a more significant microdiorites, as well as the amphiboles in mafic cognate pressure variation from 6201 bars to 8886 bars. Generally, xenoliths hosted by these rock types can be defined as mag- the cognate xenoliths display slightly lower P-T values com- nesiohastingsites. The amphiboles belonging to more acidic pared with their host rocks. The pressure estimates for host facies (dacites, quartz andesites) are represented by tscher- rocks and cognate xenoliths suggest mid-crustal depths of makite. The chemical composition of the amphiboles in cog- approximately 15–25 km, which probably represent the nate xenoliths is also relatively heterogeneous; it corresponds depth of intermediate chambers where mixing-mingling to various species such as magnesiohastingsite, magnesio- processes took place. hornblende, and pargasite. Each intrusive structure encountered specific magmatic Pyroxenes are present only in the more basic petrographi- evolution processes, which have been controlled by absence cal types, quantitatively subordinated to the amphiboles. or presence of an intermediate magmatic chamber and its They are also found in a number of cognate xenoliths. Within depth, by magma volume, and by refilling of magma cham- the cognate xenoliths the Ca-rich pyroxenes (diopside) is ber. The acidic rocks from the medium to low-K series form present, while in the host-rocks the Mg and Fe-rich variety much smaller structures, and the petrographic and geochemi- (augite). cal characteristics are not consistent with the existence of In most of the petrographic types the plagioclase feld- intermediate magmatic chambers. The presence of primary spars (oligoclase to bytownite) show normal zoning, and magmatic garnets and the absence of cognate xenoliths indi- oscillatory normal zoning. The normal oscillatory zoning cate rapid ascent toward the surface. indicates modification of the crystallization conditions (i.e. The evolution of the rocks from high-K series was more magma chamber refilling and/or rapid cooling during the complex; thus, the presence of intermediate large magma emplacement of the intrusive body). Potassic feldspars (or- chambers situated in the upper crust where AFC processes thoclase, sanidine) are present in very small amounts, mostly took place is to be considered. These rocks are well crystal- in the cognate xenoliths. lized, have high K and Sr content. The garnets are present only in the quartz andesites and Within this chamber different process type could occur: dacites (1–2 wt% of the rock volume). The analyzed garnet complex magma mixing and crustal assimilation. Beside the crystals are almandine (over 55%). Garnets are fresh, with no assimilation process of the middle crust, an additional proc- inclusions and reaction zones. ess of repeated fed of magma chamber could explained the Discrimination between two series of rocks is better evi- abundance of cognate xenoliths, including pyroxenites, and denced in the K2O–SiO2 diagram. The first series comprises the low SiO2 content of these rocks. Such processes could andesites, dacite, and rhyolite. It characterizes the medium- also explain the chemical and isotopic heterogeneity of the to low-K domain. The second series contains basaltic ande- cognate xenoliths found in these units.
107 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
COMPUTER SIMULATION BY ENERGY MINIMISATION ON FIBROUS ZEOLITE STRUCTURES
VÁCZI, T.1 & WARREN, M. C.2 1 Department of Mineralogy, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary. E-mail: [email protected] 2 Department of Earth Sciences, University of Manchester, Manchester M13 9PL, UK.
There is an extensive set of papers dealing with fibrous duction of Ca + H2O for Na substitution was more problem- zeolites in past and recent literature, focussing largely on atic. Static lattice calculations represent shared or partial order–disorder issues. The hottest debate concerns the ques- occupancies by calculating appropriate weighted potentials. tion of tetragonal species sharing natrolite topology, i.e. the This approach is invalid in the case of fibrous zeolites be- validity of and distinction between gonnardite and tetrana- cause in the shared/partial occupancy model each hybrid trolite (e.g. ALBERTI et al., 1995; ARTIOLI & GALLI, secondary cation is paired with a “partial” H2O molecule 1999; EVANS et al., 2000). The aim of this presentation is to whereas the water molecule W2 should only be present in report the first results of computer simulation on structures conjunction with Ca. If in the (Na, Ca) positions there are with natrolite topology. “hybrid” atoms (e.g. 0.75 Na and 0.25 Ca), W2 in the re- Two input structures were analysed in depth, a reportedly sulting configuration behaves differently from what is ex- completely ordered natrolite (ARTIOLI et al., 1984) and a pected. completely disordered gonnardite structure (ARTIOLI & To correct the problem, the structure was rebuilt with P1 TORRES SALVADOR, 1991). The method chosen was to symmetry, i.e. all positions symmetrically inequivalent (160 calculate the lattice energy of the structures with the GULP atoms per unit cell altogether). This allows looking at hypo- code (GALE, 1997). This method has previously been used thetical substitution configurations, in such a way that the to locate extraframework species in zeolite A by HIGGINS complete but long range disorder is not taken into account et al. (2002), and the interatomic potentials used in that work and “pure” channel contents are present with an occupancy were applied. The structure and unit cell of each phase were of 1. (However, the shared occupancy of the T positions was optimised by energy minimisation whenever possible. Initial retained for simplicity.) The calculations have shown that the atomic coordinates were directly taken from the neutron split W2 positions in ARTIOLI & TORRES SALVADOR diffraction data of ARTIOLI et al. (1984) in the case of na- (1991) cannot be optimised in static simulation runs. After trolite and occupancies were all set to 1. In the case of gon- “probing” several W2 positions, a structure with one Ca and nardite (sample no. 3 in ARTIOLI & TORRES SALVA- one adjacent H2O in the average of the two W2 positions, DOR, 1991, Rietveld refinement from X-ray powder data), H however, was found to achieve optimisation. Another simu- positions were added to the data set and T1 and T2 positions lation run on a structure with 2 Ca + 2 H2O(W2) in the unit were given shared occupancies by Si and Al. cell was also optimised when all the channel contents were In all successful calculations on all cell contents, cell pa- allowed to move (the framework was held fixed in position). rameters a and b are slightly smaller than experimental ones. In unsuccessful calculations the reason for failure was mostly References the unreasonable displacement of channel contents, espe- ALBERTI, A., CRUCIANI, G. & DAURU, I. (1995). Eur. J. cially H2O. Water molecules are well known to be difficult to Mineral., 7: 501–508. model empirically and further development of the potentials ARTIOLI, G. & GALLI, E. (1999). Am. Mineral., 84: 1445– may be advantageous. 1450. Simulation runs on the natrolite structure were unsuccess- ARTIOLI, G. & TORRES SALVADOR, M. R. (1991). Ma- ful. With symmetry constraints on, the structure could not be ter. Sci. Forum, 79–82: 845–850. optimised. With symmetry off, the non-primitive cell first ARTIOLI, G., SMITH, J. V. & KVICK, Å. (1984). Acta distorted (β the most, i.e. through monoclinic) and then the Cryst., C40: 1658–1662. calculations failed completely, the distortion did not stabilise EVANS, H.T., KONNERT, J. A. & ROSS, M. (2000). Am. the structure. The reasons are yet unknown, could be that the Mineral., 85: 1808–1815. potentials used were derived for a different system. GALE, J. D. (1997). J. Chem. Soc. Faraday Trans., 93: 629– The first few tentative simulation runs on the tetragonal 637. structure were simplified to the level of using only Na as HIGGINS, F. M., DE LEEUW, N. H. & PARKER, S. C. secondary cation and omitting W2’s (additional H2O not (2002). J. Mater. Chem., 12: 124–131. present in natrolite) completely. These configurations were successfully optimised with symmetry constraints. The intro-
108 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MAJOR ELEMENT MODELING OF THE BRNJICA GRANITOIDS (EASTERN SERBIA)
VASKOVIC, N.1, KORONEOS, A.2, CHRISTOFIDES, G.2, SRECKOVIĆ-BATOCANIN, D.1 & MILOVANOVIĆ, D.1 1 Faculty of Mining and Geology, University of Belgrade, Djušina 7, YU-11000 Belgrade, Yugoslavia. E-mail: [email protected] 2 Department of Mineralogy, Petrology and Economic Geology, Aristotle University of Thessaloniki, GR-54124 Thessaloniki, Greece.
The Brnjica granitoid pluton has an exposed area of ca. requires 50% crystallization (F=0.5) of the mineral assem- 2 27 km intruding Proterozoic gneisses (subordinate mi- blage Qz24.9Pl52.3Bt18.2Zrn0.1Ap1.5Mgt1.7Ttn1.2 to give the caschist and amphibolite) and Ripheo-Cambrian meta- daughter magma (BRJ-231). A model using the most evolved volcanosedimentary series with a variety of green rocks. The TON (BRJ-223L) as parental for the evolution of GRD failed Brnjica granitoids occur in the Kučaj terrane (KRSTIĆ & to give reliable results. The TON could originate in the crust KARAMATA, 1992), the oldest rocks of which are the Pro- by melting of amphibolites and basalts under various P-T terozoic Osanica metamorphic rocks, followed by the late conditions, which gives melts having 61-67 wt% silica. The Proterozoic to early Cambrian “Green Complex”. During the GRD could also originate in the crust by melting of amphi- Variscan magmatism the Brnjica pluton intruded the above bolites, basalts and pelites, which gives melts with 64-70 rock formations, as a late- to post-kinematic intrusion, caus- wt% silica. Lastly, the source of the granites could be crustal ing an extensive thermal metamorphic phenomena melts produced by melting of amphibolites, gneisses, gray- (KARAMATA & KRSTIC 1996; VASKOVIC & MATO- wackes and pelites. VIC,1997). The Brnjica pluton, comprising tonalite (TON), granodio- References rite (GRD), two-mica granite (TMG) and leucogranite (LG), BATCHELOR, R. A. & BOWDEN, P. (1985). Chem. Geol., has Fe-biotite and magnesiohornblende, as main mafic min- 48: 43-55. eral constituents. Muscovite occurs subordinately. Plagio- BEARD, J. S. & LOFGREN, G. E. (1991). J. Petrol., 32: clase is of oligoclase-andesine composition. Pressure of 2.3 365-401. to 4.1 kb and temperatures from 626 to 813 °C were calcu- BEARD, J. S. et al. (1994). J. Geoph. Res., 99: 21591- lated for TON, using hornblende and co-existing hornblende 21603. and plagioclase compositions respectively. SiO2 in TON and GARDIEN, V. et al. (1995). J. Geophys. Res., 100: 15581- GRD ranges from 64.2 to 68.25 wt.% and from 67.7 to 72.5 15591. wt.% while in TMG is 73.8 wt.% and in LG 75.7 to 75.9 HOLLAND, T. & BLUNDY, J. (1994). Contrib. Mineral. wt.%. Most of the oxides (TiO2, Al2O3, Fe2O3t, MgO and Petrol., 116: 433-447. CaO) in TON and GRD form well-correlated trends. In TMG HOLTZ, F. & JOHANNES, W. (1991). J. Petrol., 32: 935- and LG most of the elements (TiO2, Fe2O3, MgO, CaO, 958. Na2O, K2O and total alkalies) follow the general trend of KARAMATA, S. & KRSTIC, B. (1996): In “Terranes of GRD. All samples analyzed are slightly peraluminous with Serbia and neighbouring areas” 25-40. A/CNK=1.0-1.3. Based on the R1-R2 diagram, the TON and MONTEL, J. M. & VIELZEUF, D. (1997). Contrib. Mineral. most of the GRD plot in the pre-plate collision granites Petrol., 128: 176-196. (VAG). The granites and the most evolved GRD plot in the PICKERING, J. M. & JOHNSTON, D. (1998). J. Petrol., 39: syn-collision granite field or around it. Combined mineral 1787-1804. and rock major element chemistry suggests the involvement RAPP, R. P. & WATSON, E. B. (1995). J. Petrol., 36: 891- of fractional crystallization for the evolution of the Brnjica 931. rocks. Major element modeling, using the less evolved (BRJ- RAPP, R. P. et al. (1991). Precambrian Res., 51: 1-25. 208) and the most evolved (BRJ-223L) samples as parental SCHMIDT, M. W. (1992). Contrib. Mineral. Petrol., 110: and daughter magma respectively, requires 24% (F=0.76) 304-310. crystallization of the assemblage Pl55.5Kfs8.4Bt9.8Hbl21.1Ap0.3 SKJERLIE, K. P. & JOHNSTON, D. A. (1993). J. Petrol., Mgt2.1Ttn2.9 for the evolution of the TON. In the model for 34: 785-815. the GRD evolution the less evolved sample BRJ-227 and the VASKOVIC, N. & MATOVIC, V. (1997). Proc. Intern. most evolved sample BRJ-231 were used as the parental Symp. “Geology in the Danube Gorges”, 130-141. magma and as the daughter magma respectively. The model
109 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
GENERAL TRENDS IN THE EUROPEAN HIGHER EDUCATION AND THEIR EFFECTS ON THE TEACHING OF MINERAL SCIENCES.
WEISZBURG, T.G., BUDA, GY., LOVAS, GY.A., (Eötvös Loránd University, Pázmány Péter sétány, Budapest, H-1117), BENEA, M., POP, D. (Babeş-Bolyai University, str. Kogalniceanu, Cluj-Napoca, RO-3400), CHRISTOFIDES, G., KORO- NEOS, A. (Aristotle University, Panepistimioupolis, Thessaloniki, GR-54124), COMPAGNIONI, R., FERRARIS, G. (Uni- versity of Turin, via Valperga Caluso, Torino, I-10125), EFFENBERGER, H.S., TILLMANNS, E. (University of Vienna, Althanstrasse, Wien, A-1090), GEIGER, C.A. (Christian-Albrechts University, Olshausenstrasse, Kiel, D-24098), MERLINO, S., PASERO, M. (University of Pisa, Via S. Maria, Pisa, I-56126), MÜLLER, W.F. (Technical University of Darmstadt, Karolinenplatz, Darmstadt, D-64289), PÓSFAI, M. (University of Veszprém, Egyetem utca, Veszprém, H-8200) & VAUGHAN, D.J. (Manchester University, Oxford Road, Manchester, M13 9PL, U.K.) E-mail: [email protected]
In Europe, the general landmarks for modern higher edu- environmental science and material science became very cation were established by a series of agreements signed by important in the last few decades. governmental representatives from more than 30 countries That multidisciplinary character and the expensive appa- (Sorbonne Declaration, 1998; Bologna Declaration, 1999; ratuses needed for proper teaching of MS in addition to the Prague Communiqué, 2001). relatively limited number of students in MS resulted in the The Bologna Declaration introduced the concept of a step-by-step loss of the position of these disciplines within European Higher Education Area (EHEA; to be established the different curricula and within the university structures, by 2010) based on the compatibility of the degree structure too.Accordingly, teaching of MS had to follow the trends, (two main cycles: undergraduate and graduate studies), the and to reformulate its topics, goals and targets and to fit that credit system (ECTS and compatible), the promotion of stu- renewed content in the new EHEA. dent and staff mobility, the quality assurance, and the pro- A break-out point from the present situation could be a motion of the European dimensions in higher education. harmonised teaching of MS in the first cycle at home univer- The introduction of the first cycle (undergraduate, sities, which would give a solid base for a recognised Euro- “bachelor-type” degree, of a minimum length of 3 years) + pean joint degree system (EuroMaster in Mineral Sciences) second cycle (graduate, “master-type” degree) structure aims in the second cycle. Between 1998–2001 a group of 10 at creating convergence only, and is explicitly “not a path European universities gathered their efforts in preparing a towards the ‘standardisation’ or ‘uniformisation’ of European “Co-ordinated European Core Curriculum in MS” (for the higher education”. Concerning the European dimensions the first cycle, undergraduate level) in the frame of a SOCRA- Prague Communiqué emphasizes the importance of “the TES/ERASMUS CDI project sponsored by the EC. These development of modules, courses and curricula at all levels activities led to a proposal for the minimum mineral science with ‘European’ content, orientation and organisation”, in- related content and structure of the first cycle degrees (=input cluding the preparation of “degree curricula offered in part- level of the second cycle; see figure). From the academic nership by institutions from different countries and leading to year 2002/03, as a continuation, work has started on the a recognised joint degree”. second cycle (CDA, graduate) part. This part will be com- Mineral Sciences (MS), a group of sciences dealing with pleted in the academic year 2004/05. The project is open in natural and analogous solid substances, have been tradition- two ways for universities not partners in the consortium: 1) ally taught in geoscience-centred curricula in Europe, though the results of the project are freely available for local adapta- their century long connection to physics and chemistry re- tion at any university, 2) by the summer of 2003 further mained unchanged and their interactions with new fields, like universities can officially join the third year of the project.
Eurobachelor Eurobachelor Eurobachelor in Mineral in in Applied Sciences Geosciences Mineralogy
Basics of Basics of Basics of other Mathematics, Applied Geosciences Physics, Mineralogy (Mineralogy Chemistry (Environmental applied to (Fundamental and Technical year (level 3); Geosciences) rd ORIENTATION (FIRST CYCLE) research) Mineralogy) 3 year (level 1&2);
nd Environ- Material (FIRST CYCLE) INTRODUCTION Earth mental Sciences & & 2
st Mineralogy (Mineral Sciences) Geology Sciences Sciences Engineering 1
110 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
CHEMISTRY-BASED NOMENCLATURES VERSUS DISCRIMINATING ANALYTICAL METHODS (FTIR, XPD) IN THE CELADONITE-GLAUCONITE FAMILY
WEISZBURG, T. G.1, POP, D.2 & TÓTH, E.1 1 Department of Mineralogy, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary. E-mail: [email protected] 2 Mineralogical Museum, Babeş-Bolyai University, Kogălniceanu St. 1, RO-3400 Cluj-Napoca, Romania.
Celadonite and glauconite are VIFe3+-rich dioctahedral donites and glauconites can have similar tetrahedral Al sub- mica-type layer silicates. In the last 20 years three chemistry- stitution, similar VIR2+ / VIR3+ ratio and consequently, similar based nomenclature proposals were published for them by grade of ordering in the octahedral sheet and similar infrared the IMA-CNMMN (RIEDER et al., 1998) and the AIPEA pattern shapes. (BAILEY, 1980; 1986). In practice, infrared spectroscopy Based on numerous XPD data (BUCKLEY et al., 1978), (IR) and X-ray powder diffraction (XPD) were found to be an almost linear relationship is supposed between the VIFe3+- useful distinguishing tools between the two green layer sili- content of the phyllosilicate and the d060 spacing. It is sug- cates (BUCKLEY et al. 1978), and these methods became gested that the phyllosilicate is celadonite if the d060 < 1.51 Å incorporated into the first AIPEA nomenclature (BAILEY, and glauconite if d060 > 1.51 Å. As mentioned earlier, the 1980), too. This work tries to compare the three chemistry- 1.51 Å d060 value was adopted as a discriminating value by based classification schemes and evaluate their relationship the AIPEA nomenclature (BAILEY, 1980) though VIFe3+- with the two distinguishing analytical methods. content is not a distinguishing criterion in none of the classi- The three classification schemes are partly overlapping, fication schemes. The IMA nomenclature (RIEDER et al., partly divergent. Based on the three possible cation positions 1998) does not deal with the applicability of any simple and in these minerals, a positive charge diagram xT–xO–xIL was practical XPD parameter for that discrimination, moreover it designed for the interpretation of the species definitions. In is clear that the IL occupancy (i.e. the distinguishing feature the diagram, the following charge ranges were plotted (using between the two minerals) should not be in direct relation- a formula unit based on 11 oxygen atoms): 0–1 for the ship with the d060 spacing in the mica structure. interlayer charge, 5–6 for the octahedral layer charge and 15– It seems that only in the case of the AIPEA nomencla- 16 for the tetrahedral layer charge, respectively. tures (BAILEY, 1980, 1986) can we expect simple IR and In the IMA terminology celadonite is described in terms XPD criteria for discriminating between celadonite and glau- of four true mica end-members while glauconite represents a conite. Except for the complete chemical analysis itself there series of interlayer-deficient micas. The decisive discrimina- is no other – simple – analytical method that could be used tion between celadonite and glauconite is the interlayer for the application of the IMA nomenclature. Even the for- charge, with the dividing value of 0.85 per formula unit. In mation conditions, used frequently by geologists (glauconite the AIPEA nomenclature of 1980, discriminative is the tetra- – clearly sedimentary environment, celadonite –always influ- hedral layer charge with a value of 15.8 (this corresponds to enced by some kind of hydrothermal activity) may be mis- 0.2 IVAl per formula unit). The 1986 recommendation used leading, as we know “classical” sedimentary glaucony grains however, the octahedral layer charge, and the discriminative of IL charge > 0.85 and celadonite can also be present in value was this time 5.3 per formula unit. seemingly “normal” sediments (WEISZBURG et al., 2003) Celadonite and glauconite have thus been distinguished This work was supported by the OTKA grant #T25873. by the charge values of all the three possible cation positions. Concerning IR spectroscopy, both minerals have absorp- References tion bands at similar wave numbers, but celadonite has sharp BAILEY, S. W. (1980). Clays Clay Miner., 28: 73–78. and distinct peaks in the OH-stretching region (3400– BAILEY, S. W. (1986). Suppl. to AIPEA Newsletter 22. 3700 cm–1) while glauconite is characterized by less BUCKLEY, H. A., BEVAN, J. C., BROWN, K. M., JOHN- pronounced, broader peaks. The sharpness of the absorption SON, L. R. & FARMER, V. C. (1978). Mineralogical bands in the OH-stretching region is dependent on the cation Magazine, 42: 373–382. ordering in the octahedral sheet. This is influenced by both ODIN, G. S. (ed., 1988). Green marine clays. Development the chemistry of the octahedral sheet and the tetrahedral Al in sedimentology, 45. Elsevier, Amsterdam. substitution. The 1980 AIPEA nomenclature (BAILEY, RIEDER, M., CAVAZZINI, G., D’YAKONOV, Y. S., 1980) defines the border between the two minerals upon the FRANK-KAMENETSKII, V. A., GOTTARDI, G., tetrahedral Al substitution, the 1986 AIPEA nomenclature GUGGENHEIM, S., KOVAL, P. V., MÜLLER, G., (BAILEY, 1986) mainly upon the charge of the octahedral NEIVA, A. M. R., RADOSLOVICH, E. W., ROBERT, sheet, thus the AIPEA nomenclatures are somehow coherent J., SASSI, F. P., TAKEDA, H., WEISS, Z. & WONES, with the infrared spectroscopic data of the literature (e.g. D. R. (1998). Canadian Mineralogist, 36: 905–912. BUCKLEY et al., 1978; ODIN, 1988). The IMA WEISZBURG, T. G., TÓTH, E. & BERAN, A. (2003). Acta nomenclature (RIEDER et al., 1998), on the other side, Mineralogica-Petrographica, Szeged, 44: (accepted) differentiates between the two minerals upon the interlayer content, suggesting that celadonites and glauconites can have
111 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
NEW MINERALS FROM PICRITE SILL IN MIĘDZYRZECZE, POLISH CARPATHIANS (TYPE AREA OF THE TESCHENITE-PICRITE ASSOCIATION)
WŁODYKA, R. & KARWOWSKI, Ł. Department of Geochemistry and Petrology, University of Silesia, ul. Będzińska 60, PL-41-200 Sosnowiec, Poland. E-mail: [email protected]
Evidence of the Mesozoic volcanic activity can be found the presence of sector zoning. We suppose that the dominant in all the main West Carpathian geotectonic zones. The west- factor controlling the forming of complex megacrysts were ern part of the External Carpathians is a classic area of the polybaric conditions. The chrome-diopside cores can be teschenite-picrite association occurrence. The Cretaceous interpreted as xenocrysts, derived from disaggregation of the volcanism extends from Nowy Jičin (NE Moravia, Czech mantle xenoliths which became unstable during ascent and Republic) to Cieszyn and Bielsko Biała (Poland) for over were resorbed in great parts. These partly resorbed xeno- 100 km. Its geochemical pattern close to the interplate alkali crysts thereafter acted as nucleation sites for subsequent rim rocks (SPIŠIAK, 2002). crystallization when the magma had reached the crustal lev- The Międzyrzecze sill belongs to the most interesting els. ones in the western part of Polish Flysch Carpathians. That In the Międzyrzecze sill spinels occur in two size classes. small 12 m thick sill was emplaced into the Cieszyn Upper The first type includes anhedral, large grains (0.15 to 1.12 Jurassic (Tithonian) limestones. It shows division into two mm). They display concentric zoning; the core is reddish- main parts. The wall effect played a significant role in devel- brown (zone A), while the mantle is opaque (zone B). This opment of olivine-free, up to 1.5 m thick external parts of the narrow (from 0.02 to 0.15 mm) opaque rim contains very sill. Migration of the olivine towards the centre of the sill tiny (about 1µm), trapped solid inclusions, most likely py- resulted in formation of a central plug of phenocrysts (up to 9 roxenes. The core of the chromium spinel is optically homo- m thick). The high amount of olivine (up to 30 vol%) and geneous and it has a sharp and embayed contact with the lower amount of diopside (below 20 vol%) in the central part titanomagnetite rim. The second type of spinel with titano- and the very elevated content of diopside (up to 60 vol%) in magnetite composition consists of small subhedral to anhe- the olivine-free parts with trace of olivine shows the differ- dral grains (up to 0.08 mm), forming up to 6 vol% of the ences between the main parts of the sill. Textural relations rock. The central part (A) is rich in Cr, Al and Mg, poor in Ti among minerals indicate that diopside began to crystallize and low in Fe, with wide range of the Cr/Cr+Al ratio. Its from homogeneous silicate melt when the intrusive flow composition is very similar to Al-rich spinels from Alpine- ceased, but prior to the crystallization of phlogopite. The type peridotite bodies or peridotite nodules from basaltic olivine and chromium spinels were the first minerals crystal- volcanic rocks. The opaque rim (B) is rich in Fe and Ti, poor lized before the emplacement of the sill. The amount of in Mg and Al whereas Cr content gradually decreases to- phlogopite makes up to about 30 vol% in both parts of the wards the grain margins through the sharp chemical bound- Międzyrzecze sill. Spinels, apatite and perovskite belong to ary between zones A and B. Recalculation of total iron to the minor phases. Fe2+ and Fe3+ shows a contrast between a low state of oxida- Mafic alkaline rocks often contain clinopyroxenes of dif- tion in the deep crust or upper mantle (zone A) and higher ferent origin providing information about the evolution of the oxygen fugacity in the near-surface environments (zone B host magmas. Megacrysts of clinopyroxenes have been and groundmass spinels). found in the Międzyrzecze sill. They are composed of col- Perovskite occurs in both zones of the Międzyrzecze sill ourless cores and pale brown rims. The cores are rounded or filling the interstices between silicate minerals (diopside and embayed indicating resorption prior to the rims formation. phlogopite). The perovskite grains range in size from 0.07 to Occasionally the core of megacrysts encloses poikilitically 0.6 mm forming up to 2 vol%. The perovskite encloses nu- euhedral olivine and Cr-spinels. The cores of megacrysts are merous trapped melt inclusions with a diameter below 1 µm. chrome-diopsides. Their mg-number ranges between 0.88 Perovskite studied is almost pure CaTiO3 (perovskite sensu VI IV and 0.92 while the Al /Al values fall within the field of stricto) with low level of REE (2.60–4.20 wt% REE2O3), Nb “granulites and inclusions in basalts” (AOKI & SHIBA, (2.40–3.60 wt% Nb2O3), Fe (0.40–1.20 wt% Fe2O3) and Na 1973). The TiO2 content is very low, below 0.9 wt%, (0.80–1.10 wt% Na2O). whereas Cr2O3 ranges from 0.74 to 1.57 wt%. The rims are composed of diopsides with mg-numbers from 0.71 to 0.83, References while TiO2 and Al2O3 contents vary between 1.67–5.11 and AOKI, K. & SHIBA, I. (1973). Lithos, 6: 41-51. 3.34–7.53 wt%, respectively. Their AlVI/AlIV values fall SPIŠIAK, J. (2002). Geol. Carpathica, 53: 183-185. within the field of “igneous rocks” on diagram of Aoki and Shiba. The wide range of the rim compositions result from
112 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
CENOMANIAN–TURONIAN BOUNDARY EVENTS IN POLISH PART OF THE PIENINY KLIPPEN BELT IN THE LIGHT OF GEOCHEMICAL DATA
WÓJCIK-TABOL, P. Institute of Geological Sciences, Jagiellonian University, Oleandry 2a, PL-30-063 Cracow, Poland. E-mail: [email protected]
Geological setting particular elements are as follows: Ag, Cd > 10; Cu, Zn, V > The Pieniny Klippen Belt (PKB) represents a long and 5. V/V + Ni > 0.7 and V/Cr < 2 are associated with negligi- narrow arch-like structure situated in the Paleo-Alpine Ac- ble low Mn content. Black shales, unlike the Sn. Mb, where cretionary wedge, between the Inner and the Outer Carpathi- they occur as thin intercalation, in the Mg. Mb. comprise ans (cf. BIRKENMAJER, 1986; MISIK, 1997). prevailing sediments.
Samples Conclusions The Cenomanian–Turonian Boundary Events (CTBE) in Rock-Eval pyrolysis data indicate that organic matter in the Pieniny rock formations is marked as the grey and the Mg Mb samples are represented by mature, gas prone IV brownish black layers in marls of the Jaworki Formation. type kerogen. The Sn Mb. consist of II and III type kerogen. The Magierowa Member (Mg. Mb.) represents dark sedi- Maturation degree corresponds to the oil-window stage. ments in the Pieniny Succession. It consists of alternating Abnormally low value of PSk might be explained by the beds of laminated black shales and bioturbated green mud- impregnation of heavy hydrocarbons or asphaltens resulting stones. The Sneżnica Member (Sn. Mb.) is equivalent of from oil migration (ESPITALIE, 1993). Magierowa Mb. in the Niedzica Succession. Grey marls with Trace metal analyses for the Sn. Mb. suggest that this se- occasional intercalations of turbiditic calcarenites are domi- quence was deposited in an alternating oxic-anoxic environ- nant (GASIŃSKI, 1988; BIRKENMAJER & GASIŃSKI, ment. High trace element contents for the Mg. Mb. seem to 1992). show its deposition under increasing reductive conditions (anoxic-euxinic) (ALBERDI-GENOLET & TOCCO, 1999) Methods Total organic carbon (TOC) content, HI/OI ratio and Tmax Acknowledgements were determined the Rock–Eval pyrolysis and LECO com- This work has been financially supported by Grant no 3 bustion – infrared instrumentation. PO4 D 027 22 (State Committee for scientific research). The major and trace element concentrations were ana- lyzed by INNA and ICP-OES. References ALBERDI-GENOLET, M. & TOCCO, R. (1999). Chem. Results Geol., 160: 19-38. The Mg Mb. samples have a hydrogen index (HI) ranging BIRKENMAJER, K. (1986). Stud. Geol. Pol., 88: 7-32. from 27 to 52 mg HC/g TOC, oxygen index (OI) varies be- BIRKENMAJER, K. & GASIŃSKI, M. A. (1992). Creta- tween 33 and 97 mg CO2 /g TOC. The temperatures of ceous Research, 13: 479-485. maximum pyrolysis (Tmax) values pass 465 °C. In the Sn Mb. ESPITALIE, J. (1993). In: M. L. Bordenave (Editor), Ap- HI and OI values are between 36 and 104, and between 9 and plied Petroleum Geochemistry. Technip, Paris, 524 pp. 190, respectively. T values exceed 430 °C except one sam- GASIŃSKI, M. A. (1988). Cretaceous Research, 9: 217-247. ple, PSk, with Tmax below 400 °C, at around 360 °C. MISIK, M. (1997). Geol. Carpathica, 48/4: 209-220. Significant metal enrichment is correlative with high or- ganic carbon content within black sediments and diminish in adjacent, organic-poor layers. The enrichment factors for
113 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
REMEDIATION OF GROUNDWATER CONTAMINATED WITH Zn, Pb AND Cd USING APATITE II
WRIGHT, J. V.1 & CONCA, J. L.2 1 PIMS NW Inc., Carlsbad, NM 88220, USA. 2 Los Alamos National Laboratory, Carlsbad, NM 88220, USA. E-mail: [email protected]
Phosphate-Induced Metal Stabilization (PIMS) using nated soil was also greatly reduced using Apatite II even Apatite II stabilizes a wide range of metals (Pb, Cd, Zn, Cu, when the metal was not in an apatite phase. Pb precipitated U, Pu) in situ or ex situ, by chemically binding them into as pyromorphite while Zn and Cd both sorbed onto particles new stable phosphate minerals and other low-solubility min- and precipitated as hopeite, zincite, hydrocerussite, and ota- erals that are stable over geologic time. The concept resulted vite. As a result of these tests, a PRB of Apatite II was em- from paleochemical oceanographic studies, in the 1970s and placed between the Success Mine Tailings pile and Nine 1980s, of phosphatic sedimentary materials from the Cam- Mile Creek and has been operating for over two years. It is a brian period (570 my ago) to the Present (WRIGHT et al., 13.5-ft high, 15-ft wide and 50-ft long baffled vault filled 1987). These studies showed that apatite hard parts of marine with 100 tons of Apatite II that reaches down to bedrock and animals, and even abiotic phosphorite deposits, developed is designed to capture most of the subsurface drainage from identical trace metal signatures of the seawater with which the 500,000-ton tailings pile. The concentrations of metals they were in contact, but with concentrations enriched by six entering the barrier averages 500 ppb Cd, 1,000 ppb Pb and or seven orders of magnitude. The chemical reactions were 100,000 ppb Zn. The pH has been between 4.5 and 5.0. The relatively fast and the chemical signatures were retained over average concentrations of metals leaving the barrier has been geologic time, even after burial, lithification, heating, and < 2 ppb Cd, < 5 ppb Pb and about 100 ppb Zn. The exiting weathering. Recent laboratory and field studies have demon- pH has been between 6.5 and 7.0. Flow rates are seasonal strated the applicability of apatite towards remediation of and vary between 1 gpm and 50 gpm. Based on periodic metal-contaminated waters and soil. Some form of mineral daily metal-loading averages over the 2.2 years since it was apatite is necessary for efficient metal remediation under emplaced, the Apatite II barrier has sequestered over 75 lbs environmental conditions. A special form of biogenic apatite, of Cd (both sorbed onto the Apatite II as well as precipitated Apatite II, has been developed that, unlike any other apatite, as CdS), over 125 lbs of Pb (precipitated as pyromorphite), has the optimal structural and chemical characteristics for and over 6,000 lbs of Zn (both sorbed onto the Apatite II as metal and radionuclide remediation: 1) no substituted fluo- well as precipitated as ZnS). The second half of the barrier is rine, 2) a high degree of substituted carbonate ion, 3) low anaerobic and supports a robust Entercocci population that initial trace metal concentrations, 4) extremely poor crystal- also reduces Zn to ZnS. This results from the residual or- linity (basically amorphous) coupled with random nanocrys- ganics on the Apatite II, the small amount of P released, and tallites, and 5) high microporosity. The driving force for the the buffering capacity of the Apatite II. The effluent is able robust performance of reactive phosphate is the extreme to be released back into the river with no further treatment. stability of metal-phosphate phases, e.g., pyromorphites Performance was successfully predicted using MINTEQ-A2, [Pb5(PO4)3(OH,Cl); logKsp = -76.5] and autunites a thermodynamic speciation model. This barrier is estimated [Ca(UO2)2(PO4)2 • 10H2O; logKsp = -49.0]. Non-apatite phos- to last over thirty years for Cd and Pb, but Zn should begin to phate will not perform as well, if at all, under environmental breakthrough in a few years based upon the feasibility re- conditions. The apatite can be emplaced as a permeable re- sults. Either the Apatite II can be replaced, or a second bar- active barrier (PRB) to capture groundwater or seeps, mixed rier can be emplaced behind the first one, allowing the first into contaminated soil or waste, used as a disposal liner, or one to continue to sequester Cd and Pb and condition the pH emplaced by any method that brings the soluble metal into while the second captures Zn as it begins to breakthrough the contact with the apatite surface. first barrier. The cost of the Apatite II was about $350/ton for A PRB was emplaced in the field at the Success Mine site the approximately 100 tons used in this barrier. Emplacement in Idaho State to treat groundwater contaminated with Zn, used traditional backhoe and earth-moving equipment to Pb, Cd and Cu up to concentrations of 250 ppm, 10 ppm, 1 trench the vault. The Apatite II was gravel-sized for easy ppm and 20 ppm, respectively. Various reactive media were flow. This technology should work for most acid mine drain- investigated to determine which would be most effective at age problems with most metals under most field conditions. this site for removing Pb, Cd and Zn. Materials included zeolites (clinoptilolite and chabazite), compost, various References polymers, iron filings and oxides, and apatites [cowbone, CHEN, X.-B., WRIGHT, J., CONCA, J. L. & PEURRUNG, phosphate rock, and three different formulations of Apatite L. M. (1997). Water, Air and Soil Pollution, 98: 57-78. II]. Apatite II performed best with respect to stabilization of WRIGHT, J., SCHRADER, H. & HOLSER, W. T. (1987). these three metals, sequestering almost 20% of its weight in Geoch. Cosmoch. Acta, 51: 631-644. Pb, and about 5% of its weight in Zn and Cd (CHEN et al., 1997). The bioavailability of the metals from the contami-
114 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MINERAL COMPOSITION OF THE PELITIC FRACTION OF THE DNISTER RIVER BOTTOM SEDIMENTS (UKRAINE): DATA OF SEMI-QUANTITATIVE ANALYSIS
YAREMCHUK, Ya., SKUL’S’KA, L. & KOSHIL’, M. Institute of Geology and Geochemistry of Combustible Minerals of the National Academy of Sciences of Ukraine and National Joint-Stock Company “Naftogaz of Ukraine”, St. Naukova, 3а, UA-79053 Lviv, Ukraine. E-mail: [email protected]
Investigation of the mineralogy of the pelitic component mentary clay minerals of the Dnister river bottom sediments of the riverbed sediments is an integral part of the environ- (KOSHIL’, 2000). Quartz, calcite, feldspar and gypsum are mental–geochemical studies of the hydroecosystem as a among the non-clay minerals. whole, as fine-dispersed muds possess increased sorption Average clay mineral contents are the following: hydro- ability (in comparison with sands), and can accumulate mica 27%, montmorillonite-chlorite 15%, kaolinite 4%, and plenty of mineral salts and heavy metals. The sorption ca- chlorite 3%. On the basis of the observed data the allocation pacity of the pelitic fraction increases in the presence of sheet of clay minerals was carried out on the Dnister catchment silicates (e.g. kaolinite and montmorillonite). area. Hydromica, chlorite, montmorillonite and montmoril- The quantitative phase identification was carried out with lonite-chlorite content increases from upstream to down- the methodology developed in the Karpynskyi`s Geological stream Dnister. In this direction some “refining” clay com- Research Institute, which is based on the dependence of the ponent from terrigenous impurities (feldspars, quartz, gyp- intensity of diffraction peaks of a crystalline phase on its sum) is noted. It is interesting to note that kaolinite content is relative quantity in a powdered sample (PONOMARIOV et practically the same on the entire investigated territory. Cal- al., 1980). cite content sharply increases from west to east. The diffractograms were recorded on an ADP-2 auto- The results have demonstrated the expediency of apply- mated powder diffractometer with cobalt radiation and iron ing semi-quantitative X-ray phase analysis for a more de- filter (40 kV, 10–15 mА). tailed analysis of the mineral composition of the pelitic frac- Oriented samples from the fraction ~0,005 mm were pre- tion and established laws of allocation of basic sedimentary pared. The mineral composition, with the identification of minerals. different varieties of illites and chlorites, was studied in de- tail. References It was proved by semi-quantitative of analysis that hy- КOSHIL’, М. (2000). Miner. Zbirnyk, 50/2: 106–109. dromica (illite) (reflections 10 Å, 4.9–5.0 Å, 3.32–3.34 Å, PONOMARIOV, V. et al. (1980). Methodic recommenda- 2.5 Å), montmorillonite-chlorite (14.2–15.5 Å), kaolinite tion on quantitative analyses of the mineral content of the (7.0–7.1 Å, 3.52–3.57 Å, 2.38 Å), chlorite (13.8–14.0 Å, clay rocks by using X-ray diffractometry. Moscow: 7.0–7.1 Å, 4.7 Å, 3.52 Å, 2.87–2.89 Å) and illite- VSEGINGEO, (in Russian), 38. montmorillonite (rectorite) (11.0–11.2 Å) are the basic sedi-
115 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MINERALOGY OF THE CAVE No. 4 FROM RUNCULUI HILL (METALIFERI MTS., ROMANIA)
ZAHARIA, L.1, SUCIU-KRAUSZ, E.1 & TAMAS, T.2 1 Babeş-Bolyai University, 1, Kogălniceanu St., RO-3400 Cluj-Napoca, Romania. E-mail: [email protected] 2 Babeş-Bolyai University & “Emil Racoviţă” Institute of Speleology, 1, Kogalniceanu Str, RO-3400 Cluj-Napoca, Romania.
Trestia-Baita is a metallogenetic region located in the documented only from two other occurrences in the area of central part of the Metaliferi Mountains (South Eastern the Carpathians (Hungary and Slovakia, SZAKÁLL, 2002). Apuseni Mts.), characterized by a complex geological set- ting: Tithonic reef limestone blocks are disposed over an Table 1: Minerals found in Cave No. 4 and in the mine Early Jurassic ophiolitic basement. Both limestones and passage ophiolites are part of Capalnas-Techereu Nappe (BALINTONI, 1997), affected by the Neogene volcanic Occurrence Mineral activity (andesitic pyroclastic deposits and lava flows). The Mineral name (1-cave, group hydrothermal activity associated to the Neogene volcanism 2-mine gallery) resulted in the formation of several sulfide veins, emplaced Calcite 1, 2 both within limestones and basalts. Carbonates Aragonite 2 Cave No. 4 (D = 127.4 m, H = 10 m), discovered in Cerussite 1 2002, is the largest cave in the Trestia-Baita karst area. One Gypsum 1, 2 of the cave passages connects with a 13 m long mine gallery Sulfates Barite 1, 2 with collapsed entrance, which ends in a hydrothermal vein. Serpierite 2 Thirteen samples taken from the cave and from the old Galena 1 Sulfides mine gallery were analyzed by means of X-ray powder dif- Pyrite 1, 2 fraction, optical and scanning electron microscopy (including Oxides, Quartz 1, 2 EDX), electron microprobe, infrared and Raman spectros- hydroxides Goethite 1 copy. Apart from calcite, aragonite and gypsum – the most Kaolinite 1, 2 common minerals in limestone caves – in Cave No. 4 an Silicates Montmorillonite 2 interesting range of other minerals were reported from both Muscovite 2 cave and mine gallery. These minerals are sulfates: barite - BaSO4, serpierite - Ca(Cu,Zn)4(OH)6(SO4)2 • 3H2O; sulfides: galena - PbS, pyrite - FeS2; carbonates: cerussite - PbCO3, References smithsonite - ZnCO3; quartz and goethite. Along with these BALINTONI, I. (1997). Geologia terenurilor metamorfice minerals some silicates such as kaolinite, montmorillonite din Romania, Carpatica, Cluj-Napoca. and muscovite form a consistent clay layer covering the floor SZAKÁLL, S. (ed.). (2002). Minerals of the Carpathians, and partially the walls of the cave (Table 1). Granit, Prague, 480 p. It is worth mentioning that cerussite has not been previ- ously reported from a Romanian cave environment, whereas serpierite is also the first known occurrence in Romania. Furthermore, serpierite is a relatively rare mineral that was
116 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MINERALOGICAL STUDIES ON HUNGARIAN GEOLOGICAL PROFILES CROSSING THE PERMIAN/TRIASSIC BOUNDARY
ZAJZON, N. Department of Mineralogy, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary. E-mail: [email protected]
In the frame of a multidisciplinary research we are The samples from the section usually contain few mag- studying the Permian/Triassic (P/Tr) boundary, to understand netic spherules. In the “Basal Bedset” their amount is re- better the dramatic and abrupt ecological change in this pe- duced, there are usually none or only a few of them present. riod. At the P/Tr boundary about 90% of the marine species The uppermost bed of the Nagyvisnyó Limestone contains a become extinct (SEPKOSKI, 1996). very high amount of spherules (88 pieces/kg). Previous The current presentation is a preliminary report of some measurements support that the material of the spherules is of the mineralogical data on Hungarian geological sections magnetite. crossing this border. This project was sponsored by the research grant OTKA Having sampled several P/Tr sections we started with the #T037966. detailed mineralogical study of the two most promising sets of samples. The first set is from the borehole Gá-1a from References Gárdony, Hungary (about 40 km SW of Budapest). In that HAAS, J. (ed.) (2001). Geology of Hungary. Eötvös Univer- borehole the Upper Permian cyclic lagoonal dolomitic facies sity Press, Budapest. p. 317. changes, probably due to a eustatic sea level rise, into an HIPS, K. & PELIKÁN, P. (2002). Geologica Carpathica, Early Triassic shallow marine limestone facies containing 53/6: 351–367. more or less terrigenous material as well (HAAS, 2001). Our SEPKOSKI, J. J., Jr. (1996). Patterns of Phanerozoic extinc- results show that the dominating clay mineral in the bound- tion: A perspective from global databases. - In: Wallisier, ary zone (both in the limestone and in the earlier reported 20 O. H. (ed.): Global events and the event stratigraphy in cm thick clay bed) is illite. The micromineralogical descrip- the Phanerozoic. Springer, Berlin, pp. 35–51. tion of the profile is still in progress. Our second, main, section is located close to the top of the Bálvány Hill in the Bükk Mountains (about 120 km NE of Budapest). This is a composite section, exposed in two BE 27 outcrops in a distance of a few hundred meters from each BE 26 other. The outcrop containing the lower part, is on the north- BE 12 ern slope of the hill (“Bálvány North”). The upper part is BE 25 located on the eastern side of the hill (“Bálvány East”). The BE 11 section contains the top of the black, thick bedded Nagyvis- BE 10 nyó Limestone Formation (NLF; samples #BE1–7, Fig. 1) BE 24 and the lower part of the Gerennavár Limestone Formation BE 23 (GLF). The GLF starts with the fine siliciclastic “Basal Bed- BE 22 set” (BBS; #8–11 and #18–25, Fig. 1) followed by the thin BE 21 >63 µm BE 20 bedded “Transitional Bedset” (TBS; #12, 26–27, Fig. 1) < 63 µm (HIPS & PELIKÁN, 2002). BE 19 Going upward in the Nagyvisnyó Limestone the marl BE 9 Carbonate component increases (from 2 to 40%, see Fig. 1). The marl of BE 18 the BBS is very homogeneous with an average carbonate BE 8 content of 26%, except for a 2 cm thick limestone and a 3 cm BE 7 thick sandstone bed. The thin bedded TBS contains BE 6 limestones, interlayered by marls and clay horizons. BE 5 Through the section, the terrigenous grains are rare, ex- BE 4 cept in the above mentioned sandstone layer in the BBS. BE 3 Beside the dominating actinolite there are about 20 more BE 2 minerals to be found, from strongly resistant to easily weath- BE 1 ering species. In the upper part of the TBS the resistant min- 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100% erals are missing. The sandstone layer in the BBS contains a much (two magnitude) higher amount of terrigenous grains. This population is mature. Zircon represents most of the Fig. 1: Composition (wt%) of the Bálvány North section, grains. The rest is tourmaline and rutile, some actinolite is showing the acid soluble (carbonate) and the non-soluble also present. fractions. The latter is divided into two size fractions. For the identification of the samples see the text.
117 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
MINERALOGICAL PECULIARITIES AND FORMING CONDITIONS OF VEINLET MINERALISATION IN THE PALAEOZOIC SEDIMENTARY SERIES OF CARPATHIAN FORELAND
ZINCHUK, I., KALYUZHNYI, V. & NAUMKO, I. Institute of Geology and Geochemistry of Combustible Minerals of the Ukrainian Academy of Sciences and National Joint- Stock Company “Naftogaz of Ukraine”, Naukova st. 3a, UA-79053 Lviv, Ukraine. E-mail: [email protected]
The forehand of Ukrainian Carpathians, called L’viv Pa- The age of the veinlets ranges from Carboniferous for leozoic depression, developed on the southwest margin of the katagenetic formations to post-Carboniferous–pre- Ukrainian Shield and it is represented by a trough subparallel Cretaceous for hydrothermal ones. to the main structures of the Carpathians. The Lower Palaeo- According to the structural and mineralogical features zoic sedimentary series of this depression are considered there are about three stages of vein formation connected both lately as perspective for hydrocarbon prospecting. Significant with katagenetic and hydrothermal processes. Distinguishing amounts of veinlet katagenetic and hydrothermal mineralisa- between katagenetic and hydrothermal veins is difficult. Vein tion of various ages within the sedimentary complexes are mineralisation in tectonic fractures coincident with definite detected. These veins often contain bitumen and oil filled disjunctive structures is regarded as hydrothermal. Hy- openings. Quartz and calcite, the main minerals of the vein- drothermal veins consist mainly of calcite with 2–3 genera- lets often contain numerous, essentially water or hydrocarbon tions of the mineral. The veins also contain quartz crystals, fluid inclusions. Investigations of these inclusions can give and accessory barite, celestite, sphalerite. well-grounded information about the conditions of post- Quartz and calcite contain numerous primary coexisting sedimentation transformations of rocks, as well as informa- inclusions of water solution and hydrocarbon fluid. This is an tion about the composition and migration behaviour of hy- evidence for the heterogeneous two-phase state of the min- drocarbon-bearing fluid palaeosystems. But the lack of eral forming system. The salt concentration of water solution knowledge about mineralogy and formation stages of vein amounts to 0.9–9.0 wt%, rarely 10–12 wt%. The main dis- formations in rocks makes interpretation of fluid inclusion solved components are NaCl, CaCl2, Na2SO4.The volatile data difficult. components of hydrocarbon inclusions consist of CH4 (81– Mineralogical peculiarities are investigated and previous 99 vol%), CnH2n+2 (up to 15 vol%) with admixtures of CO2 paragenetic scheme of the stages of veinlet mineral genesis and N2. in the rocks of the region is proposed. During the post- As derived from microthermometrical data for oil and sedimentary history of the trough the following stages water inclusions, the minerals precipitated at 220–140 ºC for formed: 1 – carbonate concretions and septarian calcite quartz and 200–110 ºC for calcite. A clear lateral zonation veinlets in them with admixtures of crystals of brown siderite was established by inclusion composition. From the north- or ankerite, dickite, sometimes quartz and pyrite; 2 – calcite western to the southeastern part of the depression the organic and quartz–calcite nests and veinlets, zones of recrystallisa- part of heterogeneous fluids changes from light oils to sub- tion, dolomitisation, silicification of limestones connected stantially methane fluid. This information could be used as with katagenic processes; 3 – post-katagenetic hydrothermal the basis of oil and gas prospecting. vein formation in fractured zones; 4 – late marcasite–calcite mineralisation in coal beds in surrounding rocks.
118 Acta Mineralogica-Petrographica, Abstract Series 1, Szeged, 2003
PHYSICAL CHARACTERISTICS OF COAL DEPOSITS DETERMINED FROM BOREHOLE LOGS. APPLICATION IN THE SUBCARPATHIAN ZONE OF MUNTENIA, ROMANIA
ZUGRĂVESCU, D., POLONIC, G. & NEGOIŢĂ, V. Institute of Geodynamics, Romanian Academy, 19-21 Jean Louis Calderon str., RO-70201 Bucharest, Romania. E-mail: [email protected]
The geology of Romania is dominated by the formation The search for potential mining exploitation required a of the Carpathian mountain belt during the Alpine orogeny. better knowledge of coal seam physical parameters and with The arc reflects the complex suturing of microplates (in- this aim in view we started a program of quantitative evalua- cluding the Moesian and Apulian terrains) onto the European tion of coal deposits on the basis of well logs recorded in plate margin during the Tethyan Ocean closure. more than 300 boreholes. Complete well log suites including The Carpathians may be divided into the Overthrust Belt electric, radioactive, acoustic, etc., are available without any (Carpathian Flysch) and the molass basins of the Carpatian extra cost in the petroleum data banks. An adequate method- Foredeep which includes our study area, the so-called Mun- ology for log processing and quantitative evaluation was also tenia’s Miopliocene subzone. elaborated using linear equations and specific plots. The Pliocene present in this Carpathian subzone is situ- The final results were expressed as relative amounts of ated below the pebbles, conglomerates, sands and marls carbon, ash and moisture of rock bulk volume, together with belonging to Quaternary fluviatile facies. coal bed thickness, qualification index and elastic moduli for The geological formations involved in this study belong surroundings rocks-dynamic competence estimation. to the Levantine and Dacian lacustrine facies and consist of The graphical representations, maps, tables and other sands, silts, marls and lignite deposits. illustrating documents related to our study are presented in Throughout the study area, soft brown coal (lignite ac- the form of posters. cording to ASTM coal class) have been met by numerous boreholes crossing the Levantine and Dacian coal seams References before reaching their deeper oil and gas-exploitation targets. NEGOIŢĂ, V (1973). Erdoel – Erdgas Zeitschrift., 5: 174- Nowadays 7 mining exploitations are actve in Muntenia's 180. area in which the coal rank parameters related to organic NEGOIŢĂ, V (1980). Rev. Roumaine de Geologie et matter maturation takes the following average values: 3 – for Géophysique. Serie Geoph., 24/2: 307-321. level of organic metamorphism and a little less than 0.3% for the vitrinite reflectance.
119 AUTHOR INDEX
Aigner-Torres, M. 53 Frankel, R. B. 88 Alberico, A. 92 Fulín, M. 32 Andráš, P. 3, 4, 5, 57, 58 Füri, J. 33 Arató, B. 88 Gajić, B. 34 Babić, D. 6, 7 Gál-Sólymos, K. 9, 93 Bajnóczi, B. 8 Gawęda, A. 35, 36 Bali, E. 98 Geiger, C. A. 110 Barabás, A. 9 Geiger, J. 52 Batki, A. 82 Georgiţă, M. 37 Bedelean, H. 86 Ghergari, L. 38, 39, 102 Benea, M. 10, 110 Gorea, M. 10 Benkó, Zs. 11 Gorie, J. 13 Benő, É. 83 Gorovaya, N. 40 Berbeleac, I. 12 Gorovoy, A. 40 Besutiu, L. 13 Gorshkov, A. A. 41 Bilal, E. 28 Háber, M. 41, 49 Bilonizhka, P. 14 Hidas, K. 42, 98 Blazhko, V. 62 Hîrtopanu, P. 43, 44 Breban, R. 81 Höck, V. 45, 47 Breitner, D. 9 Horváth, P. 54 Broska, I. 15 Horváth, Z. 101 Buda, Gy. 110 Hryniv, S. P. 61 Bükös, M. Cs. 16 Il’chenko, K. O. 46, 61 Burda, J. 17 Ionescu, C. 38, 39, 45, 47 Burján, Zs. 9 Jach, R. 96 Burke, E. A. J. 18 Jáger, V. 48 Buseck, P. R. 88 Jeleň, S. 41, 49 Chirienco, M. 81 Kalyuzhnyi, V. 118 Chovan, M. 3, 4, 19 Karwowski, Ł. 50, 112 Christofides, G. 109, 110 Kasztovszky, Zs. 33 Cocić, S. 20 Kearns, J. 81 Compagnioni, R. 110 Kele, S. 51 Conca, J. L. 65, 114 Kępińska, B. 35 Constantina, C. 21 Kiss, Á. Z. 91 Costea, C. 78 Kóbor, B. 52, 82 Csámer, Á. 22, 103 Kodĕra, P. 49 Damian, F. 23, 24, 25 Koller, F. 53 Damian, Gh. 23, 24, 25 Kolodiy, O. 87 Danáková, A. 57 Koroneos, A. 109, 110 Diaconu, G. 28 Korpás, L. 93 Dluholucká, L. 58 Koshil’, M. 115 Dódony, I. 16, 26, 94 Kotulová, J. 5 Dordea, D. 13 Kovács, G. 54, 83 Dorofeev, V. 40 Kovács, I. 98 Ďuďa, R. 27 Kovács-Pálffy, P. 55 Dumitraş, D.-G. 28, 68 Kovalevsky, V. 87 Dunin-Borkowski, R. E. 88 Kovalyshyn, Z. 77 Edelstein, O. 29 Král, J. 4 Effenberger, H. S. 110 Kristály, F. 56 Ekhivanov, V. 87 Križáni, I. 57, 58 Elekes, Z. 91 Kulchytska, G. 59 Erić, S. 20 Kulibaba, V. 62 Falus, Gy. 42, 98 Kvasnytsya, I. V. 60, 61 Fehér, B. 30 Kvasnytsya, V. M. 61 Fekete, J. 31 Lazar, C. 38 Ferraris, G. 110 Lazarenko, H. 62
120 Leél-Őssy, Sz. 63 Săbău, G. 92 Lexa, J. 49 Sajó, I. E. 100 Lóránth, Cs. 64 Schroll, E. 4 Lovas, Gy. A. 26, 110 Scott, P. 43, 44 Lu, N. 65 Seres-Hartai, É. 8 Luffi, P. 69 Shkolnik, E. L. 41 Luptáková, J. 5 Siklósy, Z. 93 Lyakhov, Y. 87 Simon, A. 91 Mádai, F. 66 Simulák, J. 91 Mádai, V. 67 Sipos, P. 94 Marincea, Ş. 28, 68 Sitášová, E. 95 Márton, I. 69 Skul’s’ka, L. 115 Marusyak, V. 87 Spišiak, J. 72 Marynowski, L. 35 Srecković-Batocanin, D. 20, 109 Matović, V. 70 Starzec, K. 96 Matviishyn, Z. 77 Stremtan, C. 56 Melnikov, V. S. 71 Stumbea, D. 97 Merlino, S. 110 Suciu-Krausz, E. 116 Mikuš, T. 72 Surányi, G. 63 Milovanović, D. 109 Szabó, Cs. 9, 42, 51, 93, 98 Milovská, S. 73 Szakács, A. 99 Mindszenty, A. 101 Szakáll, S. 8, 30, 100 Minuţ, A. 81 Szakmány, Gy. 33 Mohai, I. 94 Szilágyi, V. 101 Molnár, F. 11, 48 Szinger, B. 101 Molnár, Zs. 9 Szöőr, Gy. 91 Mosonyi, E. 74 T. Bíró, K. 33 Müller, W. F. 110 Tamas, T. 102, 116 Nagy, G. 30, 75, 76, 100 Thamó-Bozsó, E. 55 Nagy-Balogh, J. 9 Tillmanns, E. 110 Naumko, I. 77, 118 Topa, D. 47 Nedelcu, L. 78 Tóth, A. 56 Negoiţă, V. 119 Tóth, E. 31, 111 Neiva, A. M. R. 4 Tóth, S. 103 Németh, N. 66 Tóth-Szabó, T. 104 Németh, T. 94 Tsikhon’, S. 87 Nikolenko, A. 87 Turchinov, I. I. 105 Nikolenko, P. 87 Udubaşa, G. 44, 106 Niţoi, E. 107 Ureche, I. 86, 107 Oliynik, T. 87 Uzonyi, I. 91 Onac, B. P. 79, 80, 81 Váczi, T. 108 Ozdín, D. 3, 19 Vaselli, O. 51 Pál-Molnár, E. 52, 69, 82, 83 Vasić, N. 70 Papp, D. C. 107 Vasković, N. 34, 109 Papp, G. 84 Vaughan, D. J. 110 Pasero, M. 110 Vereş, D. Ş. 80, 81 Pavlyshyn, V. 59 Voznyak, D. K. 61 Pavlyuk, T. 87 Warren, M. C. 108 Pekker, P. 85 Weiszburg, T. G. 31, 85, 101, 110, 111 Pieczka, A. 36 Włodyka, R. 50, 112 Polgári, M. 85 Wójcik-Tabol, P. 113 Polonic, G. 119 Wright, J. V. 114 Pop, D. 21, 86, 110, 111 Yaremchuk, Ya. 115 Popivnyak, I. 87 Zachariáš, J. 4 Pósfai, M. 88, 110 Zaharia, L. 116 Raucsik, B. 54 Zajacz, Z. 98 Robu, I. N. 89, 90 Zajzon, N. 117 Robu, L. 89, 90 Zhegallo, E. A. 41 Rosu, E. 78 Zinchuk, I. 118 Rózsa, P. 91, 103 Zugrăvescu, D. 119 Rusu-Bolindet, V. 39
121 Notes
122 Notes
123 Notes
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