Origin and K-Ar age of the phreatomagmatic breccia at the Trepča Pb-Zn-Ag skarn deposit, Kosovo: Implications for ore-forming processes

The Trepča Pb-Zn-Ag skarn deposit in Kosovo is spatially and temporarily related to the phreatomagmatic breccia of Oligocene age (~23 Ma). The deposit shows features typical for skarn deposits worldwide, including a stage of isochemical metamorphism, a prograde stage of an anhydrous, low oxygen and low sulfur fugacity character and a retrograde stage characterized by an increase in the water activity as well as by an increase in oxygen and sulfur fugacities. The mineralization is hosted by the recrystallized Upper Triassic limestone. The prograde mineralization consists mainly of Ca-Fe-Mn±Mg pyroxenes. The host recrystallized limestone at the contact with the prograde (skarn) mineralization have the increased content of Fe, Mn, Mo, As, Au, Cs, Ga, REE and Y suggesting their transport by infiltrating magmatic fluids. The decreased  d13C and  d18O values reflect a contribution of magmatic CO2. The retrograde mineral assemblage comprises ilvaite, magnetite, arsenopyrite, pyrrhotite, marcasite, pyrite, Ca-Fe-Mn±Mg carbonates and quartz. Hydrothermal ore minerals, mostly galena, sphalerite and pyrite, were deposited contemporaneously with the retrograde stage of the skarn development. Syn-ore and post-ore carbonates reflect a diminishing influence of magmatic CO2. Syn-ore carbonates are enriched in Fe, Mg, Mn, many chalcophile elements, including Ag, As, Bi, Cd, Cu, Pb, Sb and Zn, as well as in Au, Y and REE. The post-ore stage accompanied the precipitation of significant amount of Ca-rich carbonates including the travertine deposits at the deposit surface. The phreatomagmatic breccia was developed along a NW dipping contact between the ore bearing recrystallized limestone and the overlying schist. It has an inverted cone shape with the vertical extension up to 800 m and diameter up to 150-m. The upper part of the diatreme (an underground segment of the phreatomagmatic breccia) is characterized by the presence of a hydrothermally altered rootless quartz-latite dike surrounded by an unsorted polymict breccia mantle. Despite the alteration processes, the dike has a preserved porphyritic texture. Partly preserved sanidine, accompanied with the mixture of muscovite and quartz, reflects a near-neutral to weakly acidic environment. The clasts of country rocks and skarn mineralization underwent intense milling and mixing due to repeated magmatic penetrations. Sericitization of the breccia matrix, locally accompanied with minor kaolinitization, point to an increased water activity under near-neutral to weakly acidic conditions. Large fragments originally composed of anhydrous skarn minerals (pyroxenes) are usually completely altered to a mixture of fibroradial magnetite, quartz and various amount of carbonates suggesting an increase in oxygen fugacity. Their pyrite rims reflect that the increase in oxygen fugacity was followed by an increase in sulfur fugacity. The clast predominantly composed of Fe-sulfides and minor Bi-sulfides point that the increase in sulfur fugacity was locally sufficient to complete sulfidation of hedenbergite to pyrrhotite and/or pyrite. Although the phreatomagmatic breccia at the Trepča Pb-Zn-Ag skarn deposit does not carry significant amounts of the ore mineralization, its formation was crucial for the ore deposition. Phreatomagmatic explosions and formation of the breccia turned the system from the lithostatic to hydrostatic regime and triggered the retrograde stage increasing the water activity and oxygen fugacity in the system. In addition, cooling and decompression of the system contributed to more effective degassing of magmatic sulfur increased the sulfur fugacity. </p

Groundwater responses to recharge in the Gacka Area, Croatia, as revealed by stable isotopes, tritium, CFCs and noble gases

Han L-F, Roller-Lutz Z, Hunjak T, Lutz HO, Matsumoto T, Aggarwal P. Groundwater responses to recharge in the Gacka Area, Croatia, as revealed by stable isotopes, tritium, CFCs and noble gases. GEOCHEMICAL JOURNAL. 2017;51(5):391-407.Due to their extreme anisotropy and heterogeneity, the hydrogeological characterization of karst terrains is notoriously difficult. Approximately 50% of Croatia consist of karst aquifers, in particular the touristically important region along the Adriatic coast. Being an important water reservoir for this area, we have chosen the Gacka area of Croatia as a typical example. We studied the mixing of groundwater and the responses to recharge in several karst springs by using environmental tracers, including stable isotopes in water (O-18, H-2), tritium (H-3), chlorofluorocarbons (CFCs) and noble gases (He-3, He-4, Ne, Ar, Kr, Xe). The variation of the stable isotopic signal (delta O-18 and delta H-2) in the spring discharges provides qualitative information on the mixing of waters with different transit time. Assuming piston flow in the system, the CFC and H-3 data indicate that the waters contain mainly post-1980 recharge. The CFC concentrations in the spring waters were found to be significantly different between wet and dry weather periods. The higher CFC values during the wet weather period indicate that the waters contained some water components that have relatively short mean residence times. An important finding of the study was that the sole application of tritium-helium methods does not permit an accurate age determination. This is due to mass exchange between liquid and gaseous phases occurring in karst aquifer systems particularly in dry weather periods. During such a dry weather period, more space in the karst groundwater system is not filled with water compared with a wet weather period. It is shown in this study, however, that the combined use of stable isotopes (O-18, H-2), tritium, CFCs and noble gases is able to account for groundwater mixing and responses to recharge in this specific scenario. Compared to single-tracer studies, multi-tracer techniques will allow a much better understanding and characterization of these systems. This information is vital for the assessment of resources and potential contamination of the groundwater in this special environment

Modern C, O, and H isotope composition of speleothem and dripwater from Modrič Cave, eastern Adriatic coast (Croatia)

Modrič Cave is a shallow horizontal cave situated in the middle of the eastern Adriatic coast (Croatia). The cave entrance is located 120 m from the coast at an altitude of 32 m above sea level, and due to its position on the SW slope of the Dinaridic mountain range, a Mediterranean climatic influence is dominant. Due to the stable environmental conditions [(15.6 ± 0.1) °C] Modrič Cave was recognized as a potential site for detailed palaeoclimatic studies. Isotope analyses of modern carbonate speleothems, rain and dripwater were conducted in order to evaluate the isotopic equilibrium conditions. The δ18O composition of rain and cave seepage waters shows an absence of kinetic isotopic fractionation within the epikarst zone, whereas the relation between δ13C and δ18O in modern carbonate samples and dripwater suggests the isotopic equilibrium conditions during the carbonate deposition. These results contribute to a better understanding of the present-day isotopic composition and provide a basis for interpretation of speleothem-derived palaeoclimatic records