The Lokve Barite Deposit, Croatia: an Example of Early Diagenetic Sedimentary Ore Deposits

Syngenesis versus epigenesis in the Kupferschiefer genetic model is still a matter of controversy. The title of the article seems to be a paraphrase of a well-known paper by WEDEPOHL (1971), “Kupferschiefer as a prototype of syngenetic sedimentary ore deposits”. It is intended, however, more as a paradigm for the genesis of the hydrogen-sulphide geochemical barrier, an important ore formation episode prior to heavy metal accumulation, which shows the utility of RENFRO’s (1974) epigenetic model. Barite mineralization in Lokve is a stratabound ore deposit conformably situated at the Permian-Triassic boundary. It bears only two ore minerals, barite and pyrite exclusively, separated into two distinct, juxtaposed horizons stretching for tens of kilometers. The discovery of cryptalgal fabrics and other conspicious sedimentary features in underlying siliciclastics with massive pyrite and surmounting barite-bearing dolomites supports their affiliation to a tidal flat facies and sabkha environment. Barite and pyrite accumulation were formed by an early diagenetic, bacteriogenic sulphate reduction in a peritidal muddy environment, concommitant to a widespread process of evaporative dolomitization. The early diagenetic model is supported by an analysis of the sedimentary facies, trace element geochemistry and sulfur isotope distribution along two vertical profiles across the stratabound barite and pyrite mineralization

Lanthanide Geochemistry and Fluid Inclusion Peculiarities of the Fluorite from the Barite Deposits South of Kresevo (Bosnia and Herzegovina)

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

Heavy Metals in Liming Materials from NW Croatia: Possible Effect of Liming on Permissible Contents of Heavy Metals in Arable Soil

The evaluation of the heavy metal discharge from liming materials into the arable soil in NW Croatia is based upon the contents of Fe, Mn, Pb, Cu, Zn, Cd, Co and Hg in the studied carbonate raw materials, obtained under simulated conditions of the lowest presumed acidity (pH>3) which can occur in the agroecological environment. From the agroecological viewpoint, the heavy metal contents of the analyzed liming materials are much lower than the permissible levels. Only cadmium contents indicate that a certain amount of care should be taken into account. Because cadmium is bound in labile forms (pH>3 soluble fraction), it has to be considered quite mobile and biologically available in limed arable soils that are affected by drastic pH changes in the agroecological environment

Heavy Metals in Liming Materials from NW Croatia: Possible Effect of Liming on Permissible Contents of Heavy Metals in Arable Soil

The evaluation of the heavy metal discharge from liming materials into the arable soil in NW Croatia is based upon the contents of Fe, Mn, Pb, Cu, Zn, Cd, Co and Hg in the studied carbonate raw materials, obtained under simulated conditions of the lowest presumed acidity (pH>3) which can occur in the agroecological environment. From the agroecological viewpoint, the heavy metal contents of the analyzed liming materials are much lower than the permissible levels. Only cadmium contents indicate that a certain amount of care should be taken into account. Because cadmium is bound in labile forms (pH>3 soluble fraction), it has to be considered quite mobile and biologically available in limed arable soils that are affected by drastic pH changes in the agroecological environment

Origin of siderite mineralisation in Petrova and Trgovska Gora Mts., NW Dinarides

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 (100-230A degrees C). Finally, barite is precipitated from low salinity-low temperature solutions (3.7-15.8 wt % NaCl equ. and 115-145A degrees C). P-t conditions estimated via isochore construction yield formation temperatures between 180-250A degrees C for the quartz-sulphide stage and 160-180A degrees 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 +2.7aEuro degrees, 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)