Bulletin Mineralogie Petrologie

Števko Martin, Sejkora Jiří, Súľovec Štefan

Ročník 25, číslo 2 (2017), strana 252-259

supergene minerals, libethenite, olivenite, olivenite-libethenite series, olivenite group, X-ray powder data, chemical composition, type locality, Podlipa deposit, Ľubietová, Slovak Republic

This paper is dealing with chemical composition of various morphological forms of libethenite from the type locality, Podlipa copper deposit near Ľubietová, Slovakia. The unit-cell parameters of different types of libethenite as well as relationships with other associated supergene minerals are also presented. Libethenite is one of the most common supergene minerals at the locality studied. It occurs mostly as developed dark green, olive green to pale green pseudo -octahedral to short prismatic crystals up to 9.5 mm in size, which are often grouped to aggregates, drusy coatings or crystalline crusts on fissures and cavities of quartz or host rocks. Other morphological forms of libethenite e.g., crystals with phantoms, hemispherical aggregates up to 11 mm with radial internal structure or olive green acicular crystals up to 5 mm in size were also observed, but are comparably rare. Libethenite is predominantly associated with pseudomala- chite (or its other polymorphs: reichenbachite and ludjibaite), Fe and Mn-oxides.  Its association with malachite is also possible, but is not so common. Observed paragenetic relationships of libethenite and minerals of pseudomalachite group indicate that prevalent amount of pseudomalachite group minerals is slightly older than libethenite and only minor amounts of them crystallized later (possibly the second generation?), hence the pseudomophoses of pseudomalachite after libethenite are very rare. Notable vertical difference in a distribution of libethenite and minerals of pseudomalachite group across the supergene zone in-situ, which is well uncovered at the Rainer mining field, was not confirmed. Libe- thenite from Ľubietová is mostly homogenous in BSE, only sporadically it shows strong oscillatory to irregular chemical zoning, which is caused by PAs_-1 isomorphism. Except of dominant Cu contents all morphological forms of libethenite has minor contents of Fe (up to 0.03 apfu) and Al (up to 0.01 apfu). Nearly all studied samples contained at least minor amounts of As, which are typically up to 0.02 apfu, but two samples of acicular crystals has elevated and very variable As content (from 0.01 to 0.58 apfu, with one spot already representing P-rich olivenite). Minor amounts of Si (up to 0.01 apfu) were also observed in several samples.

Abstrakt (PDF) - 211.59KB
Fulltext (PDF) - 2.14MB

Belik AA, Koo HJ, Whangbo MH, Tsujii N, Naumov P, Takayama-Muromachi E (2007) Magnetic properties of synthetic libethenite Cu₂PO₄OH: a new spin-gap system. Inorg Chem 46: 8684-8689

Belik AA, Naumov P, Kim J, Tsuda S (2011) Low-temperature phase transition in synthetic libethenite Cu₂PO₄OH. J Solid State Chem 184: 3128-3133

Bergemann C (1858) Bemerkungen ber phosphorsaures Kupferoxyd. Poggend Annal Phys Chem 4: 190-192

Bergfest A (1951) Baníctvo v Ľubietovej na medenú rudu. MS, archív Geofond, Bratislava, 1-42, 3668

Beudant FS (1823) Traité élémentaire de minéralogie 1-2. Verdière, Paris

Braithwaite RSW (1983) Infrared spectroscopic analysis of the olivenite-adamite series and of phosphate substitution in olivenite. Mineral Mag 47: 51-57

Breithaupt A (1823) Vollständige Charakteristik des Mineral-System´s. 1-358, Arnoldische Buchhandlung, Dresden und Leipzig

Burns PC, Hawthorne FC (1995) Rietveld refinement of the crystal structure of olivenite: A twinned monoclinic structure. Canad Mineral 33: 885-888

Cordsen A (1978) A crystal-structure refinement of libethenite. Canad Mineral: 16, 153-157

Crane MJ, Sharpe JL, Williams PA (2001) Formation of chrysocolla and secondary copper phosphates in the highly weathered supergene zones of some australian deposits. Records of the Australian Museum 53: 49-56

Čech F, Láznička P (1965) Cyanotrichit z ložiska měděných rud od Lubietové. Acta Univ Carol Geol: 3, 149-155

Effenberger H, Krause W, Belendorff K, Bernhardt HJ, Medenbach O, Hybler J, Petříček V (1994) Revision of the crystal structure of mrázekite, Bi₂Cu₃(OH)₂O₂(PO₄)₂·2H₂O. Canad Mineral 32: 365-372

Figuschová M (1977) Sekundárne minerály medi z Ľubietovej. In: Zborník referátov z konferencie Ložiskotvorné procesy Západných Karpát, Bratislava, 135-137

Hauerová J, Blaha M, Bartoň B, Linkešová M, Fodorová V, Makuša M, Pitoňák P, Spišiak J (1989) Ľubietová - Kolba, Záverečná správa úlohy: Surovina: Cu (Sb, Ag, Ni, Co, Bi, W), vyhľadávací prieskum, I. podetapa. MS, archív Geofond, Bratislava, 74660

Heritsch H (1940) Die Struktur des Libethenites Cu₂(OH)[PO₄]. Z Kristallogr 102: 1-12

Hyršl J (1991) Three polymorphs of Cu₅(PO₄)₂(OH)₄ from Ľubietová, Czechoslovakia. Neues Jb Miner Monat: 6, 281-287

Jonas J (1820) Ungerns Mineralreich orycto-geognostich un topographisch dargestellt. 1-414, Hartleben, Pesth

Keller P, Hess H, Zettler F (1979) Ladungsbilanzen an den verfeinerten Kristallstrukturen von Libethenit, Adamin und Co[OH/AsO₄] und ihre Wasserstoffbrückenbindungen. Neues Jb Miner Abh: 134, 147-159

Kühn OB (1844) Über einige natürliche phosphorsaure und arsensaure Kupfersalze. Ann Chem Pharm 51: 123-132

Lafuente B, Doens RT, Yang H, Stone N (2015) The power of databases: the RRUFF project. In: Armbruster T, Danisi RM, eds. (2015) Highlights in Mineralogical Crystallography. 1-30, W. De Gruyter, Berlin

Laugier J, Bochu B (2011) LMGP-Suite of Programs for the Interpretation of X-ray Experiments. http://www.ccp14.ac.uk/tutorial/lmgp

Leonhard CC (1812) Über das, in Ungarn entdecke, phosphorsaure Kupfer. Mineralogische Studien, Schrag, Nürnberg, 86-91

Li Ch, Yang H, Downs RT (2008) Redetermination of olivenite from an untwinned single-crystal. Acta Crystallogr E64: 60-61

Luptáková J, Milovská S, Biroň A, Jeleň S, Andráš P (2012) Study of secondary minerals of abandoned Cu deposit Ľubietová-Podlipa (Slovakia). Acta Mineralogica Petrographica, Abstract Series, 7, 80

Luptáková J, Milovská S, Jeleň S, Mikuš T, Milovský R, Biroň A (2016) Primary ore Cu mineralizitaion at the Ľubietová-Podlipa locality (Slovakia). AGEOS 8: 175-194

Majzlan J, Zittlau AH, Grevel KD, Schliesser J, Woodfield BF, Dachs E, Števko M, Chovan M, Plášil J, Sejkora J, Milovská S (2015) Thermodynamic properties and phase equilibria of the secondary copper minerals libethenite, olivenite, pseudomalachite, kröhnkite, cyanochroite, and devilline. Canad Mineral 53: 937-960

Michňová J, Ozdín D, Bačík P (2008) Štúdium fluidných inklúzií a chemického zloženia turmalínov z hydrotermálneho ložiska Ľubietová. Bull mineral-petrolog Odd Nár Muz (Praha) 16: 100-108

Milovská S, Luptáková J, Jeleň S, Biroň A, Lazor P, Polák Ľ (2014) Manganese oxides and oxyhydroxides from Banská Štiavnica, Ľubietová and Selce (Central Slovakia). In: Proceedings of the internatational symposium CEMC 2014 (Skalský Dvůr), 101-102

Polák M, Filo I, Havrila M, Bezák V, Kohút M, Kováč P, Vozár J, Mello J, Maglay J, Elečko M, Vozárová A, Olšavský M, Siman P, Buček S, Siráňová Z, Hók J, Rakús M, Lexa J, Šimon L, Pristaš J, Kubeš P, Zakovič M, Liščák P, Žáková E, Boorová D, Vaněková H (2003) Geologická mapa Starohorských vrchov, Čierťaže a severnej časti Zvolenskej kotliny. 1:50 000. Štátny geologický ústav Dionýza Štúra, Bratislava

Pouchou JL, Pichoir F (1985) “PAP” (φρZ) procedure for improved quantitative microanalysis. In: Microbeam Analysis (Armstrong JT, ed.). San Francisco Press, San Francisco, 104-106.

Povondra P, Řídkošil T (1980) Brochantit z Piesků a Lubietové u Banské Bystrice. Acta Univ Carol Geol 1-2: 1-8.

Řídkošil T, Povondra P (1982) The relation between posnjakite and langite. Neues Jb Miner Monat, 16-28

Řídkošil T, Šrein V, Fábry J, Hybler J, Maximov BA (1992) Mrázekite, Bi₂Cu₃(OH)₂O₂(PO₄)₂·2H₂O, a new mineral species and its crystal structure. Can Mineral 30: 215-224

Sejkora J, Ondruš P, Fikar M, Veselovský F, Mach Z, Gabašová A, Škoda R, Beran P (2006) Supergene minerals at the Huber stock and Schnöd stock deposits, Krásno ore district, the Slavkovský les area, Czech Republic. J Czech Geol Soc 51: 57-101

Slavkay M, Beňka J, Bezák V, Gargulák M, Hraško Ľ, Kováčik M, Petro M, Vozárová A, Hruškovič S, Knésl J, Knéslová A, Kusein M, Maťová V, Tulis J (2004) Ložiská nerastných surovín Slovenského rudohoria, Zväzok 2. 1-286, Štátny geologický ústav Dionýza Štúra, Bratislava

Súľovec Š (2015) Mineralogická charakteristika minerálov olivenitovej, pseudomalachitovej a adelitovej skupiny z lokalít Ľubietová-Podlipa a Poniky-Drienok. Diplomová práca, archív KMP PriF UK, Bratislava  

Števko M (2014) Mineralogická charakteristika supergénnych arzeničnanov medi z lokalít Novoveská Huta, Poniky a Špania Dolina. Dizertačná práca, archív KMP PriF UK, Bratislava, 1-134

Števko M, Sejkora J (2014) Contribution to chemical composition of chalcophyllite, pseudomalachite and olivenite group minerals from Špania Dolina-Piesky, Slovak Republic. Book of abstracts, CEMC 2014, 133-134

Števko M, Sejkora J, Malíková R (2016) Nové údaje o supergénnych mineráloch z banského poľa Rainer, ložisko Ľubietová-Podlipa (Slovenská republika). Bull mineral-petrolog Odd Nár Muz (Praha) 24: 1-12

Toman K (1977) The symmetry and crystal structure of olivenite. Acta Crystallogr B33: 2628-2631

Vlachovič J (1964) Slovenská meď v 16. a 17. storočí. 1-332, Vydavateľstvo Slovenskej akadémie vied, Bratislava

Vozárová A, Vozár J (1988) Late Paleozoic in the Western Carpathians. 1-314, Štátny geologický ústav Dionýza Štúra, Bratislava

Vrtiška L, Sejkora J, Malíková R (2016) Philipsburgit z Krásna u Horního Slavkova, Slavkovský les (Česká republika). Bull mineral-petrolog Odd Nár Muz (Praha) 24: 243-251

Walitzi EM (1963) Structure refinement of libethenite Cu₂(OH)(PO₄). Tscher Mineral Petrog 8: 614-624

Zema M, Tarantino SC, Callegari AM (2010) Thermal behaviour of libethenite from room temperature up to dehydration. Mineral Mag 74: 553-565

Zipser ChA (1817) Versuch eines topographisch-mineralogischen Handbuches von Ungern. 1-228, Wigand, Oedenburg