Some Examples of Lead-Zinc-Barite Depositions in Karstic Environments Giorgio Padalino, Salvatore Prettl, Sandro Tocco, and Maurizio Violo Forevvord Many occurrences of lead-zinc-barile deposits in karstic environments have been described by several authors, ali over the world, during the last years; e. g. Lel eu , 1966b; Bernard and Leleu, 1967; C ros s and Lagny, 1969; Lagny, 1969. Many other authors are listed in the above mentioned papers; they podnt out the advancements in this subject. Before starting to describe these occurrences we should like to point out that, in our opinion, ali the karst deposits are formed by similar genetic processes, although they display different characteristics in their texture, shape, mineral composition etc. Italy (Sardinia) The karstic ore deposits in South-Western Sardinia — described by several authors in these last years (Benz, 1964; Tamburrini and Violo, 1965; Tamburrini, 1966; Tamburrini and Zuf-f a r d i, 1967) — can be subdivided in three main types: 1. Thinly laminated beds, generally subhorizontal or slightly inclined along the crevice walls (Fig. 1), thus unconformably lying on the (Paleozoic) host roeks. This occurrence shows many varieties in the association both of ore and of gangue minerals. The ore minerals, vvhich may occur, are: pyrite (framboids), galena, sphalerite, barite; the gangue minerals are: carbonates (calcite, dolomite, siderite), quartz, iron hydrated oxides, clays. The types of deposits made by different associations of these minerals are mainly two: — The first one shows mainly thin altemances of barite and dark quartz beds, with minor galena and framboidal pyrite; sometimes carbonates and minor limonite and clay, cemented by quartz, are present. Not uncommonly, these deposits are covered by conglomerates and sandstones, whose cement, generally clayey and/or siliceous, is sometimes Fig. 1. S. Giovanni mine. "Ricchi Ag" stope. Sardinia (Italy). It is visible from right to left: — crevice wall made up by Cambrian carbonatic ročk (dark grey) — a large band of spathic calcite (whitish) — thin beds of sulphides-clay-carbonates rhythmic depositions. A gentle inclination of the beds is visible in this part of the karstic crevice. partially made by barite (Brusca, Pretti and Tamburrini, 1967). — The second one is characterized by the presence of sphalerite: the karst filling beds are thin, rather dark to black, made by sphalerite, galena, framboidal and euhedral pyrite, cemented by dolomite (Fig. 2). The most common type of karstic deposits is the first one, which is characterized by barite, carbonates, iron hydrated oxides, that is an association related to oxidizing environments (L e 1 e u , 1966a); the occur-rence of galena in these deposits may be due to different processes: either syngenetic galena related to horizons deposited in favourable Eh—pH conditions (Garrels, 1954), or (minor) galena formed when dispersed lead into the oxidized filling sediments was placed under reducing conditions and sulphurated during the normal evolution of the karsts. Only seldom the occurrence of other sulphides (second type) testifies the achievement of strong reducing conditions, which are typical of a late senility stage (Bernard and Leleu, 1967). Notwithstanding these characters, normally the described karsts are completely fossilized, thus they can be called holokarsts (C v i j i č , 1925; Llopis-Llado, 1953). Moreover the changing composition of the karst fillings testifies variable chemical-physical conditions, related to paleogeographical vari-ation during the deposition of residual materials. These types of karstic deposition are well developed mainly in the Cambrian carbonatic formation, especially where it is completely flattened by the post-Hercynian erosion. 2. Galena-barite-calcite cockades and stalactites. This kind of struc-tures, particularly well developed in the San Giovanni mine (Cambrian limestones, Iglesiente — SW Sardinia), (B r u s c a and D e s s a u , 1968), is related to meteoric water percolating into karstic cavities and leaving there the carried ions, which form the above mentioned minerals. This type of karstic deposition is quite similar, almost regarding to the macro-scopic appearance of the ore, to that of Sidi Bou Aouane, which will be described later. The cockades may have a Cambrian limestone fragment, as nucleus, surrounded by white calcite, silver-rich galena and quartz bands (Fig. 3); in other cases they are without any nucleus and included in large masses of spathic calcite (Fig. 4). Fig. 2. Gutturu Pala mine. Sardinia (Italy). Thin beds of galena, sphalerite and pyrite (very often with framboidal structure) cemented by dolomite and calcite. The clearer beds are richer of carbonates than the others. Small quartz veins (white) cut the bedding. Polished hand-specimen. Natural light. Fig. 3. S. Giovanni Mine. "Ricchi Ag" stope. Sardinia (Italy). Fragment of Cambrian carbonatic ročk surrounded by prevalent calcite (white) and quartz- -galena (grey to black). Fig. 4. S. Giovanni mine. "Ricchi Ag" stope. Sardinia (Italy). Cockades of galena (black), quartz and calcite included in spathic calcite (white). Fig. 5. Orcel Bialy mine. Bytom district. Poland, Sketch showing a typical mineralization in this mine. It is possible to observe from bottom to top: 1. Barren "Gogolin" limestone. 2. Fragments of "Gogolin" limestone included in "vitriol clay" passing to 3. A large band of "vitriol clay" which is a residual deposit due to karstic solution. 4. Bedded mineralization, where marcasite is prevalent in lower part and sphalerite content is gradually increasing upwards; small lenses of galena appear in the top part. 5. Ore-bearing dolomite. 3. Collapse breccias, characterized by limestone and dolomite boulders (coming from the Middle Cambrian "Metallifero" member) cemented with barite, calcite and "terra rossa" with a strongly anomalous geochemical lead-zinc content (M a r c e 11 o , 1969). This type of karst, which is probably younger than the others, is rarely related to economic ore deposits, excepted some clastic barite deposits. Pcland (Silesia — Cracovv) The well known Silesia-Cracow ore deposits have been the topic of many genetic interpretations. Recently Bogacz, Džulynski, H a -r a h c z y k described some karstic features in the ore-bearing Triassic ročk of this area; these authors imputed the sulphide deposition and the karst itself to hydrothermal-type ascendant streams. One of us had the possibility of studying the Bytom and Chanow mining districts, for some months, and the per descensum karstic deposition looked to play a main role in the sulphide genesis; in fact the ore-bearing horizon, which lies on the generally unmineralized G o gol in limestone, is made by an almost general sequence, which is, from bottom to top: vitriol clay, sphalerite-pyrite-marcasite beds (Fig. 5), which evolve upwards into collapse breccias made by boulders of ore-bearing dolomite cemented wit.h collophorm sphalerite or brunkite and galena veinlets (Fig. 6). In this čase, again, the karst evolved till reaching strong reducing conditions in its lower parts, while in the upper ones, where the reducing conditions were not so strong, large masses of "terra ros?a" with veinlets of rejuvenated galena are present, actually, in the ore-bearing horizon. This "terra rossa" and perhaps the galena are the recent weathering phenomena and they are mainly developed where the mineralizations are shallower (e. g., Matylda mine), nearer the surface. Fig. 6. Trzebionka mine. Chanow district. Poland. Collapse breccia made up by ore-bearing dolomite fragments, cemented with calcite (white) and galena. Sphalerite is rather uncommon in this type of deposit. Fig. 7. Sidi Bou Aouane mine. Tunisia. Cockades of galena, sphalerite and calcite. Galena may be present both in the core of the cockades and in the small veinlets and starlets in the cement. Sphalerite is present mainly in concentric bands with collophorm structure. Tunisia The important lead district of Djebel Hallouf-Sidi Bou Aouane, which is about 130 km NW of Tunis, holds, at least in some places, ore bodies of karstic origin. The cre bearing horizons, which occur mostly in massive Upper Cretaceous limestones at Djebel Hallouf and in Eocene marls at Sidi Bou Aouane, exhibit clear karstic features in some places. These karstic features may be grouped in two main types: 1. Cockades (Fig. 7) and stalactites (Fig. 8) made up by galena-sphalerite--jordanite and calcite. These structure are rather similar to those observed in S. Giovanni mine (Fig. 4). 2. Thin marly-sandy beds, impregnated by galena (Fig. 9): these beds, sub-horizontal or slightly inclined along the crevice walls, look like the described features in S. Giovanni mine from Sardinia (Fig. 1). Phenomena of this type, that is crevices filled by red clays, calcareous boulders and galena veinlets, have been observed also in other Tunisian mining districts (Djebel Hamra — Violo, 1965; Niccolini, 1970). Fig. 8. Sidi Bou Aouane mine. Tunisia. Stalactites of galena (black) and calcite (white) collected in the same mine of the preceeding photograph. Fig. 9. Sidi Bou Aouane mine. Tunisia. Thin marly beds impregnated by pre-valent galena. They show characters similar to those observed in S. Giovanni mine (see Fig. 1). England (Derbyshire) An example of karstic deposition of lead-barite beds in Carboniferous limestone has been described recently by Ford and King (1965) in the Golconda mine, Derbyshire. This occurrence, whose outcrops were visited by one of us, is very alike the first type of Sardinian ore bearing karsts, being made of thin galena-barite-dolomite beds which lie subhorizontally or slightly inclined near the walls of the karst cavity. The occurrence of collapse breccias confirms, once more, the supergenic, karstic nature of the cavities and their filling. Conclusions The few given examples show, even if roughly, the variety and spread of karstic mineral depositions; sometimes, e. g. in Sardinia and Silesia--Cracow, these karstic depositions may give rise, as regards both grades and tonnages, to exploitable ore accumulations. The different structures, visible in the different ore districts, are con-trolled by several factors and namely: mineralogical compositions of the roeks subjeeted to karstic phenomena, mineralogical composition of the karst filling sediments, morphological evolution and chemical-physical environment during karst processes. These parameters should be carefully investigated when studying and researching ore depositions in karstic environments. References Benz, J. P. 1964, Le gisement plombo-zincifere d'Arenas (Sardaigne). These Doct. Ing. 126 p. Nancy. Bernard, A.. Leleu, M. 1967, A propos de la concentration residuelle de la blende et de la galene. C. R. Acad. Sc. Pariš, t. 265, p. 729—732, Pariš. B o g a c z, K., Džulynski, S., Haranczyk, C. 1970, Ore-filled hydrothermal karst features in the Triassic roeks of the Cracow-Silesian region. Acta Geologica Polonica, Vol. XX, n« 2, p. 247—267. Warsaw. Brusca, C., Pretti, S., Tamburrini, D. 1967, Le mineralizzazioni baritose delle coperture di M.te Sa Bagattu (Iglesiente-Sardegna). Rend. Ass. Min. Sarda, n°. 7, p. 89—106. Brusca, C., Dessau, G. 1968, I giacimenti piombo-zinciferi di S. Gio-vanni (Iglesias) nel quadro della geologia del Cambrico sardo. Industria Mine-raria — anno XIX. Cross, P., Lagny, P h. 1969, Paleokarsts dans le Trias moyen et superieur des Dolomites et des Alpes Carniques occidentales. Importance strati-graphique et paleogeographique. Sc. de la Terre, t. XIV, n° 2, p. 139—195. Nancy. C v i j i č , J. 1925, Types morphologiques des terrains calcaires. Le Holo-karst. Comptes rendus des S. de l'Ac. de Sciences. Tour. 180, p, 592—594, CLXXX. Ford, T. D., King, R. J. 1965, Layered epigenetic galena-barite deposits in the Golconda Mine, Brassington, Derbyshire, England. Econ. Geol., vol. 60 n« 8. Garrrels, R. M. 1954, Mineral species as funetions of pH and oxidation-reduetion potentials, with special reference to the zone of oxidation and secon-dary enrichment of sulphide ore deposits. Geochim. Cosmochimica Acta, 5, n« 4, pp. 153—168. L a g n y , P h. 1969, Mineralisation plombo-zincifere triassique dans un paleokarst (gisement de Sala Fossa, province de Belluno, Italie). C. R. Acad. Sc. Pariš, t. 268, p. 1178—1181. Pariš. L e 1 e u , M. G. 1966a, Le karst et ses incidences metallogeniques, Sc. de la Terre, t. XI, n«. 4, p. 385—413, Nancy. Leleu, M. G. 1966b, Les gisements plombo-zinciferes du Laurium (Grece). Sc. de la Terre, t. XI, n« 3, pp. 293—343, Nancy. Llopis-Llado, N. 1953, Karst holofossile et merofossile. 1° Congres International de Speleologie. Tome II, p. 11—50, Pariš. M ar celi o, A. 1969, Deposition supergenique de galene: les examples de la Sardaigne. Meeting on Remobilization of Ores and Minerals. A. M. S., pp-293—303. Cagliari. N i c o 1 i n i, P. 1970, Gitologie des concentrations minerales stratiformes. pp. 479. Gauthier — Villars, Pariš. Tamburrini, D., Violo, M. 1965, Un esempio di deposizione super-genica di galena. Rend. Ass. Min. Sarda, n° 5, pp. 24—36. Tamburrini, D. 1966, Un esempio di deposizione supergenica di baritina. Period, di Mineral, n« 2, pp. 403—418. Tamburrini, D., Zuffardi, P. 1967, Ulteriori sviluppi delle cono-scenze e delle ipotesi sulla metallogenesi sarda. Giornata di studi geominerari. p. 19. Agordo. Violo, M. 1965, I giacimenti piombo-zinciferi di Ain Nouba e Dyebel Hamra (Tunisia). Notizie geo-giacimentologiche. Res. Ass. Min. Sarda, n° 8, parte I, pp. 41—91. SUMMARV In this paper, which is a preliminary report, we shall attempt to illustirate some examples of sulphide and barite depositions in karstic environments, whose description was made either by us or by other authors, from different ore districts. We describe briefly the shapes, the structures and the mineralogical associations of karstic ore deposits, trying to point out similarities and differences among some mining districts. DISCUSSION Emberger: D'une fagon generale, avez-vous des informations sur les teneurs en oligoelements des galenes encaissees dans des karsts? D'une fagon plus particuliere, quelles sont les teneurs en argent? Violo: Cest une question a laquelle je ne peux pas repondre. En e-ffet il y a une tres riche bibliographie sur les mineralisations de la zone de Cracovie. En ce qui concerne les mineralisations en Sardaigne, nous avons des analyses de la galene de la mine de San Giovanni. Elle contient 2 ou 3 kg a 6 kg d'argent par tonne de Pb, avec une moyene de 2,5 kg/t d'argent. Certaines galenes des cavites karstiques dans le calcaire cambrien peuvent contenir jusqu'a 10 kg d'argent par tonne de plomb. Lagny: Etes-vous certain que la terra rossa a veinules de galene que vous avez observe dans la breche d'effondrement soit contemporaine du remplissage sulfure de la base du gisement? II ne me semble pas que Bogacz, Džulynski et Haranczyk en fassent etat dans leur note. Si mes souvenirs sont bons, le remplissage de la breche d'effondre-ment est essentiellement constitue de sulfures a texture colloforme. Violo: Je crois que le remplissage de terra rossa avec des veinules de galene est plus recent que la formation massive des sulfures. En effet, la terra rossa est plus repandue dans la partie du Bytom ou les affleure-ments du Trias metallises sont plus voisins a la surface, par exemple, dans la mine de Matylda. On pourrait dire que peut etre une elaboration des eaux superficielles plus recente que la formation des sulfures massifs. Mais a Fechelle du gite il me semble qu'il existe une variation dans la composition mineralogique des couches mineralisees (par exemple dans le gite de Trzebionka ou Smolarska*a decrit deux couches mineralisees), c'est a dire (a part la blende qui est repandue dans tous les gites), pyrite-marcasite dans la partie inferieure et galene dans la partie su-perieure de 1'horizon mineralise. Amstutz: Regarding the breccia picture you sho