The Ljubija siderite deposits, hosted by a Carboniferous sedimentary complex within the Inner Dinarides, occur as stratabound replacement-type ore bodies in limestone blocks and as siderite–sulfides ...veins in shale. Three principal types of ore textures have been recognized including massive dark siderite and ankerite, siderite with zebra texture, and siderite veins. The ore and host rocks have been investigated by a combination of inorganic (major, trace, and rare earth element concentrations), organic (characterization of hydrocarbons including biomarkers), and stable isotope geochemical methods (isotope ratios of carbonates, sulfides, sulfates, kerogen, and individual hydrocarbons). New results indicate a marine origin of the host carbonates and a hydrothermal–metasomatic origin of the Fe mineralization. The differences in ore textures (e.g., massive siderite, zebra siderite) are attributed to physicochemical variations (e.g., changes in acidity, temperature, and/or salinity) of the mineralizing fluids and to the succession and intensity of replacement of host limestone. Vein siderite was formed by precipitation from hydrothermal fluids in the late stage of mineralization. The equilibrium fractionation of stable isotopes reveals higher formation temperatures for zebra siderites (around 245°C) then for siderite vein (around 185°C). Sulfur isotope ratios suggest Permian seawater or Permian evaporites as the main sulfur source. Fluid inclusion composition confirms a contribution of the Permian seawater to the mineralizing fluids and accord with a Permian mineralization age. Organic geochemistry data reflect mixing of hydrocarbons at the ore site and support the hydrothermal–metasomatic origin of the Ljubija iron deposits.
The epidote-bearing Čanište pegmatite and adjacent Upper Carboniferous granodiorites cut Precambrian gneises, at the western slopes of the Selečka Mts., the Eastern Pelagonian zone, FYRO Macedonia. ...The pegmatite exhibits zonal internal structure with the following sub-units: the wall zone (amazonite microcline ± biotite, quartz), the first intermediate zone (epidote + hematite + grossular + muscovite + quartz + almandine ± zircon, beryl, microcline, quartz), the second intermediate zone (albite + quartz ± microcline) and the core (massive quartz). According to the microprobe data epidote belongs to clinozoisite subgroup with formula (Ca 1.96-1.99 Mn 0.02-0.03 Fe 2+0.00-0.02 )(Al 2.17-2.46 Fe 3+0.51-0.82 Ti 0.00-0.01 )(Si 2 O 7 )(Si 0.99-1.00 Al 0.00-0.01 O 4 )O(OH). The occurrences of almandine and zircon with low U, Th and REE content, are indicative to weakly evolved granitic/granodioritic rocks. The absence of aplites suggests steady pressure condition during the course of pegmatite crystallization . Microthermometric data combined by the two-feldspar geothermometer gained pressure from 4.8 to 5.6 kbar for the second intermediate zone. The wall zone, composed of amazonite microcline, crystallized at temperature between 650 and 760. Dropping of melt temperature below 550°C, under the oxygen fugacity between 10 -22 and 10 -19.5 bar, was the principal trigger for deposition of minerals in the first intermediate zone. The residual fluid, depleted in Ca, Fe and K, and enriched in water, Na and Si, caused deposition of the second intermediate zone (albite + quartz) at temperature between 445 and 465°C. The massive quartz core crystallized in the very last stage of the pegmatite evolution (T ≈ 400-480°C) from melt residue enriched in silica, water and CO 2 content.
This paper presents the results of sampling surveys carried out in order to evaluate the environmental impact of the Rude and the Sv. Jakob historical mining sites, NW Croatia. The studied ...polymetallic ore deposits differ in their mineralogical and geochemical features as well as in the host rock lithology. The Rude Fe-Cu-Pb-Zn-Ba deposit is hosted by Permian siliciclastic sediments. Siderite, haematite, galena, sphalerite, chalcopyrite, pyrite, barite and gypsum are the major ore minerals. The Sv. Jakob Pb-Zn deposit occurs in the Middle Triassic dolostone. The most abundant ore minerals are galena, sphalerite and pyrite. Although the deposits represent potential sources of numerous toxic metals, no pollution of the drainage streams and associated stream sediments was recorded. The studied mining sites are characterized by high carbonate/sulfide ratios responsible for the alkaline character of the drainage streams (pH=7.3-8.7). Consequently, the mining sites have very low potential for both generation of acid mine drainage and for leaching of heavy metals into the drainage systems. Furthermore, the study revealed that the populated areas (stream waters with decreased redox potential, increased organic matter content, high NO super(-) sub(3), NH super(+) sub(4) and PO super(3)- sub(4) concentrations; stream sediments enriched in exchangeable Pb and Zn) and the Sava river alluvium (overflowing streams enriched in Hg) represent a greater environmental threat than the investigated polymetallic ore deposits.
Samoborska Gora Mts. is situated within the westernmost part of the Zagorje-Mid-Transdanubian zone of the Internal Dinarides. The Samoborska Gora Mts. predominantly consists of Permian ...unmetamorphosed siliciclastic sediments and evaporites, overlain by Lower Triassic sediments. Rude mineralisation is hosted by Permian siliciclastic sediments, below gypsum and anhydrite strata. The central part of the deposit consists of a 1.5 km long stratabound mineralisation, grading laterally into ferruginous sandstone and protruding vertically into a gypsum-anhydrite layer. Siderite-polysulphide-barite-quartz veins are located below the stratabound mineralisation. The stratiform part ofthe deposit is situated above the stratabound and consists of haematite layer with barite concretions and veinlets. Late stage galena-barite veins overprint earlier types of mineralisation. The Rude ore deposit was generated by predominantly NaCl±CaCl2-H2O solutions. Detrital quartz from stratiform mineralisation contains fluid inclusions with salinities between 7 and 11 wt. % NaCl equ., homogenizing between 150°C to 230°C. Stratabound/siderite-polysulphide-barite-quartz vein type mineralisation was derived from solutions with salinities between 5 and 19 wt. % NaCl equ., homogenizing between 60°C and 160°C, while late stage galena-barite veins were precipitated from solutions with salinities between 11 and 16 wt. % NaCl equ., homogenizing between 100°C to 140 °C. Fluid inclusion bulk leachate chemistry recorded Na+>Mg2+>K+>Ca2+>Li+ and Cl->SO42- ions. Sulphur isotope composition of barites and overlying gypsum stems from Permian seawater sulphate, supported by increased Br- content, which follows successively the seawater evaporation line. The sulphur isotopic composition of sulphides varies between -0.2 and +12.5 ‰, as a result of thermal reduction of Permian marine sulphate. Ore-forming fl uids were produced by hydrothermal convective cells (reflux brine model), and were derived primarily from Permian seawater, modified by evaporation and interaction with Permian sedimentary rocks. Rude deposits in Samoborska Gora Mts. may be declared as a prototype of the Permian siderite-polysulphide-barite deposits (products of rifting along the passive Gondwana margin), in the Inner Dinarides, and their equivalents extending northeastward into the Zagorje-Mid-Transdanubian Zone and the Gemerides, and southeastward to the Hellenide-Albanides.
The Darnó Unit within the Zagorje-Mid-Transdanubian Megaunit is an allochtonous part of Dinarides in NE-Hungary and represents a relict of the Neotethyan accretionary complex. It contains blocks of ...submarine basalts of Triassic age in turbiditic sediments (olistrostrome) of Jurassic age. The lava clogged in the lime mud at the original site of volcanism and developed closely packed pillow, pillow fragment hyaloclastite breccia, and peperite facies. Interaction between the lava and the sea water produced mostly chloritic alteration of basalt and precipitation of hydrothermal calcite in amygdales, feeding channels of lava lobes and hyaloclastite breccia cements. Calcite is associated with chlorite, epidote, hematite and pyrite. Fluid inclusions in calcite infillings record conditions of fluid/rock interaction. Salinities of fluid inclusions (3.2 – 5.6 wt.% NaCl equiv. wt.%.) are close to the salinity of recent sea water and their homogenization temperatures in the range of 80 – 150oC. Fluid inclusion data support interpretation that volcanic facies represent rapidly cooled distal zones away from the submarine volcanic centre. This is also confirmed by the comparison to the volcanic and hydrothermal alteration facies of the submarine basalt lava-flow complex and associated pillow lava formation of Triassic age in the Hruškovec quarry in the Kalnik Mts., NW-Croatia. The obtained data contribute to understanding of the early history of Neotethyan evolution, i.e. dilemma about rifting or oceanization in Triassic time and offer new aspects of correlation between units of Dinaridic origin which had been displaced from their original setting by large scale Tertiary tectonic processes.
The Petrova and Trgovska Gora Mts. (Gora=Mountain) are Variscan basement units incorporated into the northwestern Dinarides during the Alpine orogeny. They host numerous siderite-quartz-polysulphide, ...siderite-chalcopyrite, siderite-galena and barite veins, as well as stratabound hydrothermal-replacement ankerite bodies within carbonates in non-metamorphosed, flysch-like Permo-Carboniferous sequences. The deposits have been mined for Cu, Pb, Ag and Fe ores since Medieval times. Fluid inclusion studies of quartz from siderite-polysulphide-quartz and barite veins of both regions have shown the presence of primary aqueous NaCl−CaCl
2
±MgCl
2
−H
2
O±CO
2
inclusions. The quartz-sulphide stage of both regions show variable salinities; 2.7–26.2 wt% NaCl eq. for the Trgovska Gora region and 3.4–23.4 wt% NaCl eq. for the Petrova gora region, and similar homogenisation temperatures (100–230°C). Finally, barite is precipitated from low salinity-low temperature solutions (3.7–15.8 wt % NaCl equ. and 115–145°C). P-t conditions estimated via isochore construction yield formation temperatures between 180–250°C for the quartz-sulphide stage and 160–180°C for the barite stage, using a maximum lithostatic pressure of 1 kbar (cc. 3 km of overburden). The sulphur isotope composition of barite from both deposits indicates the involvement of Permian seawater in ore fluids. This is supported by the elevated bromium content of the fluid inclusion leachates (120–660 ppm in quartz, 420–960 ppm in barite) with respect to the seawater, indicating evaporated seawater as the major portion of the ore-forming fluids. Variable sulphur isotope compositions of galena, pyrite and chalcopyrite, between −3.2 and +2.7‰, are interpreted as a product of incomplete thermal reduction of the Permian marine sulphate mixed with organically- and pyrite-bound sulphur from the host sedimentary rocks. Ore-forming fluids are interpreted as deep-circulating fluids derived primarily from evaporated Permian seawater and later modified by interaction with the Variscan basement rocks.
40
Ar/
39
Ar data of the detrital mica from the host rocks yielded the Variscan age overprinted by an Early Permian tectonothermal event dated at 266–274 Ma. These ages are interpreted as those reflecting hydrothermal activity correlated with an incipient intracontinental rifting in the Tethyan domain. Nevertheless, 75 Ma recorded at a fine-grained sericite sample from the alteration zone is interpreted as a result of later resetting of white mica during Campanian opening/closure of the Sava back arc in the neighbouring Sava suture zone (Ustaszewski et al.
2008
).
Fellow of Croatian Academy of Sciences and Arts Ivan Jurkovic, professor emeritus of Economic geology (Ore petrology) and Ore microscopy at the Faculty of Mining-Geology-Petroleum engineering, and ...former Rector of University of Zagreb (1978-1982), passed away quietly in his home in Zagreb, on the 30 December, 2014. He was a founder of modern studies in the field of ore genesis and metallogeny in Croatia, and an outstanding lecturer, among the best teaching geology in Croatia. Academy of Sciences and Arts (former Yugoslav Academy of Arts). He was promoted to the position of Rector of Zagreb University for 1978-1982, and acted as the President of the Parliamentarian Council for education, science, culture and sport of Republic of Croatia between 1982 and 1984. He obtained the honored title of Professor emeritus of Zagreb University in 2000. Geological investigations of prof. Jurkovic covered, beside all republics of the former state, a vast global territory in Africa, Asia and South America. In the educational, social, and political domains, he undertook many high-ranking duties.
Strata-bound barite deposits occur in Devonian dolomites, situated in the Mid-Bosnian Palaeozoic Schist Mountains. These contain barite as the main ore mineral (5.9 wt% SrSO4 on average and d34S= ...+8.3‰) which comprises 90-99 wt% of the bulk ores. The subordinate components are calcite, fluorite, Hg-Sb-tetrahedrite, pyrite and quartz.
Analysis of REE by INAA revealed an extremely low content of lanthanides (1.584 ppm), negative Eu anomalies (Eu3+/Eu+ = 0.7398), and (Tb)N/(La)N = 6.2 indicating late-stage mineralization.
Primary fluid inclusions show a uniform number of infilling phases (L+V+S), and persistent volume ratio. This indicates homogeneity of the hydrothermal ore-forming fluids and an absence of boiling phenomena at the time of fluorite formation. Th is between 200° and 310°C, with a distinctive maximum at 250°C. Tfm -20.3°C predominates but careful examinations of the early melting behaviour of the inclusions warrants the existence of Tfm -51°C, and the presence of CaCl2. High salinity between 25 and 26 wt% eq. NaCl was determined from the hydrohalite melting temperature (Tmh). Some additional daughter minerals are also present. Fluorite, barite and calcite formed from the high saline waters probably originated by mixing of heated hydrothermal fluids with the highly evolved post-Variscan Upper Permian formation waters. This is supported by the study of the isotopic composition of the carbon, oxygen and sulphur of the paragenetic carbonates and sulphides.
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