Geochemical and stable isotopic variability within two rivers rising under the same mountain,but belonging to two distant watersheds

Complementary geochemical and stable isotope investigations of the Gorski Kotar karst aquifer system in western Croatia were obtained for the first time, to answer the question whether both studied rivers drain the same aquifer system or not. The two main rivers, the Kupa and the Rje?ina, rise under the same mountain range, but belong to two different watersheds (Black Sea and Adriatic Sea). The karst aquifer of Gorski Kotar is a potentially important source of drinking water for two neighboring countries, Croatia and Slovenia (Central and South Europe), and is strongly influenced by both Mediterranean and continental weather conditions. It is a part of the Dinaric karst, which is “locus typicus” for karst worldwide and one of the most typical karst areas in the world.     

Re–Os geochemistry and geochronology of the Ransko gabbro–peridotite massif, Bohemian Massif

The Ransko gabbro–peridotite massif in Eastern Bohemia is a strongly differentiated intrusive complex, which hosts low-grade Ni–Cu ores mainly developed close to the contact of olivine-rich rocks with gabbros, in troctolites, and to a much lesser extent in both pyroxene and olivine gabbros and plagioclase-rich peridotites. Gabbro, troctolite, peridotite and Ni–Cu ores from the Jezírka Ni–Cu (PGE) deposit, considered to be a typical example of the liquid segregation style of mineralization, were analyzed for Re–Os concentrations and isotopic ratios. Seven barren and mineralized samples from the Jezírka deposit yielded a Re–Os regression of 341.5?±?7.9 Ma (MSWD?=?69). Strongly mineralized peridotite with mantle-like initial ¹⁸⁷Os/¹⁸⁸Os ratio of 0.125 suggests that Os as well as other PGE present in the Ni–Cu mineralization are predominantly of mantle origin. On the other hand, barren and low-mineralized samples have radiogenic initial ¹⁸⁷Os/¹⁸⁸Os ratios of 0.14–0.16 suggesting some import of Re and/or radiogenic ¹⁸⁷Os most likely through contamination by continental crust during magma emplacement. The Re–Os age of the Ransko Massif is significantly younger than the previously suggested Lower Cambrian age, but it is similar to and/or younger than the age of metamorphism of the adjacent Kutná Hora crystalline complex and the Moldanubian unit. Therefore, it is likely that the emplacement of the Ransko massif and its Ni–Cu mineralization was closely connected with the late-stage evolution of the Kutná Hora crystalline complex.     

The unique environment of the most acidified permanently meromictic lake in the Czech Republic

Changes in the water properties and biological characteristics of the highly acidic Hromnice Lake (Western Bohemia) were investigated. This 110-year-old lake, formed as a consequence of the mining of pyritic shales, is permanently meromictic. Two chemoclines separate an extremely acidic (pH ～ 2.6) mixolimnion from a metal-rich anoxic monimolimnion. The absence of spring mixolimnetic turnover due to ice melting and very slow heat propagation through the chemocline with a 6-month delay were observed. Extreme mixolimnetic oxygen maxima (up to 31 mg l^?1) in phosphorus-rich lake (PO₄^3? up to 1.6 mg l^?1) well correlated with outbursts of phytoplankton. Phytoplankton consist of several acido-tolerant species of the genera Coccomyxa, Lepocinclis, Chlamydomonas and Chromulina. Surface phytoplankton biomass expressed as chlorophyll-a varies from 2 to 140 μg l^?1. Multicellular zooplankton are almost absent with the exception of Cephalodella acidophila, a small rotifer occurring in low numbers. Large red larvae of the midge Chironomus gr. plumosus were found at the bottom close to the shore, with larvulae in the open water. Developmental stages (protonemata) of a moss, resembling filamentous algae, dwell in the otherwise plant-free littoral zone.     

Constraining genesis and geotectonic setting of metavolcanic complexes: a multidisciplinary study of the Devonian Vrbno Group (Hrubý Jeseník Mts., Czech Republic)

The low-grade metavolcanic/volcanosedimentary complex of the Devonian Vrbno Group (Silesicum, NE Bohemian Massif, Czech Republic) occurs in two ~NE–SW trending belts, separated by tectonic slices of Cadomian metagranitic paraautochton. (1) The basic–intermediate lavas of the calc-alkaline Western Volcanic Belt came from a moderately depleted mantle $ \left( {\varepsilon_{\text{Nd}}^{370} \sim + 3} \right) $ . Rare rhyolites (374.0 ± 1.7 Ma: 2σ, LA–ICP–MS U–Pb Zrn) were derived most likely from immature crust or by extensive fractionation of primary basaltic melts. The rock association is interpreted as a vestige of a deeply dissected continental arc. (2) The Eastern Volcanic Belt consists mainly of (nearly) contemporaneous (371.0 ± 1.4 Ma) felsic alkaline lavas with high HFSE contents, as well as high Ga/Al and Fe/Mg ratios, typical of within-plate igneous setting. The petrology and Nd–Sr isotopic data point to a high-T anatexis of a young metagranitic crust, resembling the Cadomian (Brunovistulian) basement, in a back-arc setting. The attenuated Brunovistulian lithosphere could have partially melted by the heat provided by the upwelling asthenosphere and/or underplating basic magma. (3) Finally, the region was penetrated by numerous subalkaline, MORB/EMORB-like dolerite sheets—a hallmark of the considerable crustal thinning.     

A New Method for Low‐Temperature Decomposition of Chromites and Dichromium Trioxide using Bromic Acid Evaluated by Chromium Isotope Measurements

In recent years, routine application of the stable isotope determination of chromium (Cr) in environmental and health protection research has led to the search for simpler chromite decomposition techniques. As the range of Cr isotope abundance ratios in nature is very narrow, conventional chromite decomposition techniques are no longer suitable, due to the relatively high risk of contamination during laboratory procedures. We have developed a protocol for the decomposition of chromites based on oxidation by bromic acid at room temperature. The procedure takes 15 d and requires two doses of bromic acid during the reaction period (day 1 and 8), due to the limited stability of the reagent. Chromium extracted by alkaline oxidative fusion and by bromic acid decomposition yielded statistically indistinguishable δ⁵³Cr values, measured by multi‐collector inductively coupled plasma‐mass spectrometry following addition of a ⁵⁰Cr‐⁵⁴Cr double‐spike.     

The algal community at an ecocline of a cold sulphidic spring (Sovra artesian borehole,Slovenia)

The physicochemical parameters of the sulphide spring water from a 500?m deep artesian borehole in Sovra Valley (Slovenia) are stable, with very little variation: temperature, 9.2 ± 0.0 °C; pH 7.70 ± 0.11; specific electrical conductivity, 777 ± 8 μS/cm; and dissolved oxygen, 0.19 ± 0.11 mg/l. The water from the borehole is hard, rich in sulphates, and has a notable concentration of sulphide, while it is low in chlorides. Communities of phototrophs were analysed at the oxygenic ecocline at the outflow from the borehole, and from further downstream. Caloneis tenuis, Frustulla vulgaris, Gomphonema sp., Navicula radiosa, Oscillatoria sp., and Tribonema vulgare successfully thrive exclusively at the outflow from the borehole under sub-optimum conditions for the majority of phototrophs. Downstream from the borehole, where the hydrogen sulphide degasses, autotrophic biofilms were dominated by different diatoms. The Bray–Curtis similarity index confirms the distinctive phototrophic communities along the oxygenic ecocline downstream from the sulphidic spring. The sulphidic ecocline downstream from the spring is indicative of the composition of phototrophic communities, as some species appear only downstream from the spring. An ecocline downstream from the borehole of the sulphidic spring was reflected also in the bacterial indicator groups. This study brings novel insights to the limited knowledge in the field of oxygenic phototrophy related to sulphidic springs.     

Magnetic,geochemical and mineralogical properties of sediments from karstic and flysch rivers of Croatia and Slovenia

The aim of the present work was to investigate links between the low-field magnetic susceptibility (MS) and chemical and mineral composition of sediments from several Croatian and Slovenian rivers, as well as to determine possible anthropogenic influence on these sediments. MS measurements are a fast and simple method, which serves as a proxy for the estimation of pollution in different environmental systems. The investigated rivers are predominantly unpolluted rivers from Croatian and Slovenian karstic and flysch areas, which belong to the Adriatic or the Black Sea watersheds: the Dragonja, the Mirna, the Ra?a, the Ri?ana, the Reka, the Rak, the Cerkni?nica, the Unec and the Ljubljanica rivers. It was assumed that, due to their mostly unpolluted status, they could serve as a database for natural MS background values for this region. For comparison, several rivers and a lake from the Celje old metallurgic industrial area (Slovenia) were also investigated: the Savinja, the Hudinja, the Voglajna rivers and Slivni?ko Lake. They form a sub-basin of the Sava River drainage basin. Sediments of the clean karstic and flysch rivers showed extremely low MS values, with mass susceptibility values ranging from 0.58 × 10^?7 to 5.11 × 10^?7 m³/kg, and isothermal remanent magnetism (IRM) values ranging from 0.71 to 7.88 A/m. In the Celje industrial area, river sediments showed much higher MS values, with mass susceptibility values ranging from 1.31 × 10^?7 to 38.3 × 10^?7 m³/kg, and IRM values ranging from 0.91 to 100.42 A/m. The highest MS value was found in the Voglajna River at Teharje-?tore, a point which showed a significant number of anomalies of toxic metals in earlier investigations. Semiquantitative determination of relations between grain size and concentration of magnetite was performed using the Thompson-Oldfield method. X-ray diffraction (XRD) mineralogical analysis showed that sediments of the Celje area have mostly quartz as major mineral, with relatively small amount of carbonate minerals, while in sediments of karstic rivers carbonate minerals prevail. Statistically significant correlations were obtained between MS and Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd and Ba in the Slovenian karstic region and between MS and Cr, Fe, Co, Ni and Zn in flysch drainage basins. On the contrary, no correlation of MS and Hg content was obtained.     

Low permeability Neogene lithofacies in Northern Croatia as potential unconventional hydrocarbon reservoirs

We present two examples of describing low permeability Neogene clastic lithofacies to outline unconventional hydrocarbon lithofacies. Both examples were selected from the Drava Depression, the largest macrostructure of the Pannonian Basin System located in Croatia. The first example is the Beni?anci Field, the largest Croatian hydrocarbon reservoir discovered in Badenian coarse-grained clastics that consists mostly of breccia. The definition of low permeability lithofacies is related to the margins of the existing reservoir, where the reservoir lithology changed into a transitional one, which is mainly depicted by the marlitic sandstones. However, calculation of the POS (probability of success of new hydrocarbons) shows critical geological categories where probabilities are lower than those in the viable reservoir with proven reserves. Potential new hydrocarbon volumes are located in the structural margins, along the oil-water contact, with a POS of 9.375%. These potential reserves in those areas can be classified as probable. A second example was the Cremu?ina Structure, where a hydrocarbon reservoir was not proven, but where the entire structure has been transferred onto regional migration pathways. The Lower Pontian lithology is described from well logs as fine-grained sandstones with large sections of silty or marly clastics. As a result, the average porosity is low for conventional reservoir classification (10.57%). However, it is still an interesting case for consideration as a potentially unconventional reservoir, such as the ”tight” sandstones.     

Synthesis and characterization of high-pressure and high-temperature sphene (CaTiSiO5)

Sphene (CaTiSiO₅), a calcium titanosilicate ceramic has been prepared from a powder mixture of CaCO₃, TiO₂ and SiO₂ using vibro-milling for homogenization and activation of precursors. During the high-pressure and high-temperature synthesis (HPS) process at 4 GPa and 1,200 °C, sphene undergoes into phase transition, from room-temperature phase P2₁ /a to high-temperature phase A2/a. Evidence of that structural phase transition is given in this paper using infrared, Raman spectroscopy and X-ray powder diffraction. Rietveld refinement was employed to get the structural information of the synthesized powder. The most important structural change due to phase transition, the disappearance of the characteristic out-of-center distortion of the Ti atom and moving to the center of octahedra, was confirmed. HPS is an effective method for producing full-dense ceramics without any additives. Reduction of particle size occurred during high-pressure compaction. Microstructure and particle size of both phases were analyzed by scanning electron microscopy.     

Cold and warm air temperature spells during the winter and summer seasons and their impact on energy consumption in urban areas

The main objective of this study is to determine and analyze cold and warm air temperature spells in the last 6 years (2007–2012) and reveal their impact on electrical energy consumption in a small-sized city such as Sombor (Serbia) with less than 50,000 inhabitants. Hourly air temperature values and electrical energy consumption data have been used as database for all methods. Warm and cold temperature spells (during heat and cold waves) have had the increasing tendencies in the last 6 years and they reflect on additional electrical energy consumption. Detailed analysis showed that higher energy demands occur during workdays and daytime period. Monitoring of the amount of consumed energy showed a clear relationship during the winter cold temperature spells, when electrical energy demand was higher than 0.3 MW. In summer period, the relationship was weaker and consumption was higher than 0.15 MW only when temperature exceeded 30 °C. A small number of air condition devices in houses and companies and mainly one-store buildings with thick walls, which make a good insulation from the outside air temperatures, are probably the main reasons for the above-mentioned results in summer. This paper introduces a new method to resolve the problem of short-term load forecasting, based on the support vector machines (SVM) technology and particle swarm optimization that has been used to optimize the SVM parameters. Similar-day-based forecast has shown that similar days for training should be filtered also using classifier of temperature period (cooling degree-days or heating degree-days in a row). Forecasting error is smaller compared to solutions where similar days are found only on season and temperature.