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Epithermal Bicolor Black and White Calcite Spheres from Herja Ore Deposit, Baia Mare Neogene Ore District, Romania-Genetic Considerations

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Epithermal Bicolor Black and White Calcite Spheres from Herja Ore Deposit, Baia Mare Neogene Ore District, Romania-Genetic Considerations minerals Review Epithermal Bicolor Black and White Calcite Spheres from Herja Ore Deposit, Baia Mare Neogene Ore District, Romania-Genetic Considerations 1 1, 2 3 4,5 Ioan Mârza ,Călin Gabriel Tămas, * , Romulus Tetean , Alina Andreica , Ioan Denut, and Réka Kovács 1,4 1 Babe¸s-BolyaiUniversity, Faculty of Biology and Geology, Department of Geology, 1, M. Kogălniceanu str., Cluj-Napoca 400084, Romania; [email protected] (I.M.); [email protected] (R.K.) 2 Babe¸s-BolyaiUniversity, Faculty of Physics, 1, M. Kogălniceanu str., Cluj-Napoca 400084, Romania; [email protected] 3 Babe¸s-BolyaiUniversity, Faculty of European Studies, 1, Em. de Martonne, Cluj-Napoca 400090, Romania; [email protected] 4 County Museum of Mineralogy, Bulevardul Traian nr. 8, Baia Mare 430212, Romania; [email protected] 5 Technical University of Cluj-Napoca, North University Centre of Baia Mare, 62A, Dr. Victor Babes, str., Baia Mare 430083, Romania * Correspondence: [email protected] or [email protected]; Tel.: +40-264-405-300 (ext. 5216) Received: 24 April 2019; Accepted: 5 June 2019; Published: 8 June 2019 Abstract: White, black, or white and black calcite spheres were discovered during the 20th century within geodes from several Pb-Zn Au-Ag epithermal vein deposits from the Baia Mare ore district, ± Eastern Carpathians, Romania, with the Herja ore deposit being the maiden occurrence. The black or black and white calcite spheres are systematically accompanied by needle-like sulfosalts which are known by the local miners as “plumosite”. The genesis of epithermal spheres composed partly or entirely of black calcite is considered to be related to the deposition of calcite within voids filled by hydrothermal fluids that contain acicular crystals of sulfosalts, mostly jamesonite in suspension. The proposed genetic model involves gravitational concentration of sulfosalt acicular crystals towards the base of open spaces within paleochannels of epithermal fluid flow and the subsequent formation of calcite spheres by geochemical self organization of amorphous calcium carbonate that crystallized to calcite via vaterite. Keywords: calcite spheres; jamesonite; berthierite; gravitational concentration; Herja; Baia Mare; Romania 1. Introduction The Herja epithermal ore deposit, located in the Neogene Baia Mare ore district, Eastern Carpathians, Romania is known for the presence of fizélyite [1], but it is also renowned among mineral collectors for several mineralogy peculiarities, e.g., black calcite associated to jamesonite or siderite, marcasite pseudomorphs after pyrrhotite, tabular pyrrhotite, rosette-like semseyite crystal aggregates, ring-shaped jamesonite crystals, short prismatic stibnite crystals, loose siderite spheres with central hollow space, as well as white, black or bicolor white and black calcite spheres (Figure1a–c). The exquisite bicolor—approximately half black and half white—calcite sphere from Herja (Figure1c) hosted by the County Museum of Mineralogy “Victor Gorduza”, Baia Mare is indexed as a Romanian national patrimony mineral specimen. The specimen was stolen from its secure place during the night of January 25/26, 2014 and is still missing. Minerals 2019, 9, 352; doi:10.3390/min9060352 www.mdpi.com/journal/minerals Minerals 2019, 9, x FOR PEER REVIEW 2 of 20 MineralsRomanian2019 ,national9, 352 patrimony mineral specimen. The specimen was stolen from its secure place2 of 20 during the night of January 25/26, 2014 and is still missing. Figure 1.1. EpithermalEpithermal calcite calcite spheres spheres from from the the Herja Herja ore deposit hosted by County Museum of Mineralogy,Mineralogy „Victor Victor Gorduza”, Gorduza”, Baia Baia Mare; Mare; ( aa)) WhiteWhite dominateddominated calcitecalcite spheresphere (4.5(4.5 × 4.54.5 × 5 cm) with a × × minor blackblack calcitecalcite section section (not (not visible), visible), sample sample 177099; 177099; the spherethe sphere has apparently has apparently an inner an void inner hosting void solidhosting inclusions solid inclusions as indicated as indicated by the noise by that the occursnoise whenthat occurs the sample when is the joggled; sample (b) is Black joggled; calcite b) sphere Black (6calcite6 sphere(66 cm), formed × 6 × of6 rhombohedracm), formed of uprhombohedra to 10 mm long of edges;up to 10 A3 mm axis oflong each edges; rhombohedron A3 axis of seems each × × torhombohedron be parallel to theseems radius to ofbe theparallel sphere; to the the black radius calcite of isthe covered sphere; by the small-sized black calcite siderite is spherescovered andby apparentlysmall-sized marcasitesiderite spheres “dust”; and sample apparently 12990; (marcasitec) Bicolor calcite“dust”; sphere sample composed 12990; c) ofBicolor uneven calcite volumes sphere of whitecomposed and blackof uneven calcite. volumes The sample of white is classified and black as a Romaniancalcite. The national sample patrimony is classified specimen as a Romanian and was hostednational by patrimony the County specimen Museum ofand Mineralogy, was hosted Victor by Gorduza”,the County Baia Museum Mare until of January,Mineralogy 2014 when„Victor it wasGorduza”, stolen; Baia (a) and Mare (b) photosuntil Janu byary, Ioan 2014 Beres when, ,(c) photo it was by stolen; Valentin (a) Gantand, a.(b) photos by Ioan Bereș, (c) photo by Valentin Ganța. The research focuses on the occurrence of calcite/carbonate spheres from the Baia Mare ore district,The with research emphasis focuses on suchon the samples occurrence from Herjaof calc epithermalite/carbonate ore spheres deposit. from It updates the Baia the Mare available ore mineralogicaldistrict, with emphasis data and oonffers such information samples acquiredfrom Herj froma epithermal former geologists, ore deposit. miners It updates and other the sta availableff of the Herjamineralogical mine. Valuable data and data offers were information provided by acquired Victor Gorduza from former (1942–2014), geologists, founder miners of theand Mineralogical other staff of Collectionthe Herja mine. Baia Mare Valuable (1976–1992), data were and provided afterwards, by head Victor of theGorduza County (1942–2014), Museum of founder Mineralogy of the in BaiaMineralogical Mare (1992–2010). Collection This Baia information Mare (1976–1992), is important and forafterwards, at least two head reasons: of the (i)County the mine Museum has been of closedMineralogy since in 2006, Baia andMare (ii) (1992–2010). the former This staff informationof the mine is are important rapidly disappearingfor at least two without reasons: leaving i) the writtenmine has documents been closed for since future 2006, generations. and ii) the Theformer paper staff proposes of the mine a genetic are rapidly model disappearing for the formation without of carbonateleaving written bicolor documents spheres from for future Herja generations. and from other The orepaper deposits proposes in the a genetic Baia Mare model ore for district, the formation and, by extrapolation,of carbonate bicolor for similar spheres epithermal from Herja samples and from possibly other ore known deposits elsewhere in the Baia in the Mare world. ore district, and, by extrapolation, for similar epithermal samples possibly known elsewhere in the world. 2. Geological Setting 2. GeologicalThe Herja Setting Pb-Zn-Ag-Sb and subordinately Au ore deposit is located in the Baia Mare ore district fromThe Gut âHerjai Mountains, Pb-Zn-Ag-Sb Eastern and Carpathians, subordinately NW Au Romania ore deposit (Figure is 2located). The in deposit the Baia consists Mare of ore a conjugateddistrict from veins Gutâi system Mountains, striking Eastern generally Carpathians, ENE-WSW NW counting Romania over (Figure 250 vein2). The structures deposit consists [2]. At the of orea conjugated deposit scale veins 67 system veins were striking considered generally “principal” ENE-WSW [3 ],counting some of over them 250 being vein mined structures almost [2]. 1000 At the m onore strikedeposit and scale more 67 veins than 500were m considered on dip. Prior “princip to theal” mid [3], 1990s some Herjaof them was be unanimouslying mined almost considered 1000 m anon excellentstrike and example more than of a500 Pb-Zn m on mesothermal dip. Prior to the deposit mid 1990s according Herja to was Lindgren’s unanimously classification considered of ore an deposits.excellent Afterwards,example of thea Pb-Zn deposit mesothermal was described deposit as low according sulfidation to [2Lindgren’s]. classification of ore deposits.The oreAfterwards, deposit isthe related deposit to was the Neogenedescribed post-collisionalas low sulfidation volcanism [2]. that occurred due to the complex interaction among Alcapa and Tisia-Getia terranes with the south-western edge of the European plate during Neogene [5–7]. It was structurally controlled by Dragos, Vodă transform fault [8,9], etc., which contributed to the channeling of the hydrothermal fluids. Detailed geological and mineralogical data on the Herja ore deposit are given by [2], and a geological overview of the Herja ore deposit and its mineralogy was recently made by [10]. Additional information on mineralogy and geology of Herja area may be found in [11–32]. Minerals 2019, 9, 352 3 of 20 Minerals 2019, 9, x FOR PEER REVIEW 3 of 20 Figure 2. SimplifiedSimplified geology of the Baia Mare ore district,district, NW Romania with location of main ore deposits including Herja (modified(modified after [[4]).4]). TheZn, Pb,ore deposit Ag, Sb, is S related and minor to the Au Neogene were produced post-collisional
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