Experimental constraints on ultrapotassic magmatism from the Bohemian Massif (durbachite series, Czech Republic)

The equilibrium phase relations of a mafic durbachite (53 wt.% SiO₂) from the Třebíč pluton, representative of the Variscan ultrapotassic magmatism of the Bohemian Massif (338–335 Ma), have been determined as a function of temperature (900–1,100°C), pressure (100–200 MPa), and H₂O activity (1.1–6.1 wt.% H₂O in the melt). Two oxygen fugacity ranges were investigated: close to the Ni–NiO (NNO) buffer and 2.6 log unit above NNO buffer (∆NNO + 2.6). At 1,100°C, olivine is the liquidus phase and co-crystallized with phlogopite and augite at 1,000°C for the whole range of investigated pressure and water content in the melt. At 900°C, the mineral assemblage consists of augite and phlogopite, whereas olivine is not stable. The stability field of both alkali feldspar and plagioclase is restricted to low pressure (100 MPa) at nearly water-saturated conditions (<3–4 wt.% H₂O) and T < 900°C. A comparison between experimental products and natural minerals indicates that mafic durbachites have a near-liquidus assemblage of olivine, augite, Ti-rich phlogopite, apatite and zircon, followed by alkali feldspar and plagioclase, similar to the mineral assemblage of minette magma. Natural amphibole, diopside and orthopyroxene were not reproduced experimentally and probably result from sub-solidus reactions, whereas biotite re-equilibrated at low temperature. The crystallization sequence olivine followed by phlogopite and augite reproduces the sequence inferred in many mica-lamprophyre rocks. The similar fractionation trends observed for durbachites and minettes indicate that mafic durbachites are probably the plutonic equivalents of minettes and that K- and Mg-rich magmas in the Bohemian Massif may have been generated from partial melting of a phlogopite–clinopyroxene-bearing metasomatized peridotite. Experimental melt compositions also suggest that felsic durbachites can be generated by simple fractionation of a more mafic parent and mixing with mantle-derived components at mid crustal pressures.     

Sulfur isotope variations from orebody to hand-specimen scale at the Mežica lead–zinc deposit, Slovenia: a predominantly biogenic pattern

The Mississippi Valley-type (MVT) Pb–Zn ore district at Mežica is hosted by Middle to Upper Triassic platform carbonate rocks in the Northern Karavanke/Drau Range geotectonic units of the Eastern Alps, northeastern Slovenia. The mineralization at Mežica covers an area of 64 km² with more than 350 orebodies and numerous galena and sphalerite occurrences, which formed epigenetically, both conformable and discordant to bedding. While knowledge on the style of mineralization has grown considerably, the origin of discordant mineralization is still debated. Sulfur stable isotope analyses of 149 sulfide samples from the different types of orebodies provide new insights on the genesis of these mineralizations and their relationship. Over the whole mining district, sphalerite and galena have δ ³⁴ S values in the range of –24.7 to –1.5‰ VCDT (–13.5 ± 5.0‰) and –24.7 to –1.4‰ (–10.7 ± 5.9‰), respectively. These values are in the range of the main MVT deposits of the Drau Range. All sulfide δ ³⁴ S values are negative within a broad range, with δ ³⁴ S _pyrite <δ ³⁴ S _sphalerite <δ ³⁴ S _galena for both conformable and discordant orebodies, indicating isotopically heterogeneous H₂S in the ore-forming fluids and precipitation of the sulfides at thermodynamic disequilibrium. This clearly supports that the main sulfide sulfur originates from bacterially mediated reduction (BSR) of Middle to Upper Triassic seawater sulfate or evaporite sulfate. Thermochemical sulfate reduction (TSR) by organic compounds contributed a minor amount of ³⁴S-enriched H₂S to the ore fluid. The variations of δ ³⁴ S values of galena and coarse-grained sphalerite at orefield scale are generally larger than the differences observed in single hand specimens. The progressively more negative δ ³⁴ S values with time along the different sphalerite generations are consistent with mixing of different H₂S sources, with a decreasing contribution of H₂S from regional TSR, and an increase from a local H₂S reservoir produced by BSR (i.e., sedimentary biogenic pyrite, organo-sulfur compounds). Galena in discordant ore (–11.9 to –1.7‰; –7.0 ± 2.7‰, n = 12) tends to be depleted in ³⁴ S compared with conformable ore (–24.7 to –2.8‰, –11.7 ± 6.2‰, n = 39). A similar trend is observed from fine-crystalline sphalerite I to coarse open-space filling sphalerite II. Some variation of the sulfide δ ³⁴ S values is attributed to the inherent variability of bacterial sulfate reduction, including metabolic recycling in a locally partially closed system and contribution of H₂S from hydrolysis of biogenic pyrite and thermal cracking of organo-sulfur compounds. The results suggest that the conformable orebodies originated by mixing of hydrothermal saline metal-rich fluid with H₂S-rich pore waters during late burial diagenesis, while the discordant orebodies formed by mobilization of the earlier conformable mineralization.     

Re–Os age of non-mineralized black shale from the Kupferschiefer, Poland, and implications for metal enrichment

Six samples of non-mineralized black shale from a Kupferschiefer section in the northern part of the Polish Zechstein Basin (Zdrada IG-8 drill hole: 1026.16–1026.90 m) were studied for Re–Os isotopes and selected major and trace elements. These black shales, averaging 5.82 wt.% C_org and 1.69 wt.% S_tot, display very low base metal values (up to 106 ppb Cu, 792 ppb Pb, and 144 ppb Zn) and have abundances of 64–1376 ppb Re and 0.37–1.25 ppb Os, with a ¹⁸⁷Os/¹⁸⁸Os ratio of 6.95–22.5. The regression of all Re–Os data yields an age of 247 ± 20 Ma, which is within the range of uncertainties of previous Rb–Sr and K–Ar geochronological studies. The scatter in the Re–Os data can be explained in terms of fluctuations in sedimentary conditions, i.e., restricted basin with terrestrial influence.     

The upper cenozoic evolution of the Duero and Ebro fluvial systems (N-Spain): part I. paleogeography; part II. geomorphology

Lack of age dates in the terrigenous Cenozoic sediments of the Duero and the Ebro sedimentary basins has complicated tecto-stratic correlation across the two basins. We tentatively synthesize a range of existing studies and new data to construct a rough general paleogeography throughout Upper Cenozoic times. The more extensive erosion of the Ebro has been previously attributed to the earlier moment of opening. We tentatively analyse lithostratic data to conclude that the lower knick-point and different lithologies have also contributed to the deeper erosion in the Ebro Basin. We conclude from lithostratic data and field evidence that the W half of the Rioja was part of the Duero in earlier times and that the escarpment retreated westward through the Rioja in four subsequent episodes of erosion. The tilt of the NW Duero is a consequence of isostatic rebound to this erosion.     

Annual and seasonal variability of precipitation in Vojvodina,Serbia

Annual and seasonal variability of precipitation observed at 92 stations in Vojvodina (Serbia) were analyzed during the period 1946–2006. The rainfall series were examined by means of the empirical orthogonal functions (EOF). The first set of singular vectors explains from 68.8 % (in summer) to 81.8 % (in winter) of the total variance. The temporal variability of the time series associated with the main EOF configurations (the principal components, PCs) was examined using the Mann–Kendall test and the spectral analysis. The time series of PC1 revealed decreasing trend in the winter and spring precipitation and increasing trend in the autumn, summer, and annual precipitation. The relationships between the first PC and circulation patterns, such as the North Atlantic Oscillation (NAO), the East Atlantic (EA) pattern, and East Atlantic/West Russia pattern, were also investigated. The PC1, displaying temporal behavior of the first mode, demonstrated evident correspondence with the NAO index in analysis of the annual, winter, and autumn precipitation. Power spectra of the PC1 show statistically significant oscillations of about 3.3 years for the spring precipitation and about 8 and 15 years for the winter precipitation. Comparisons with spectral analysis of authors for some regions in Europe, most of them in the Mediterranean domain, show that similar periodicities are detected.     

Tertiary alkaline Roztoky Intrusive Complex, České středohoří Mts., Czech Republic: petrogenetic characteristics

The ?eské st?edoho?í Mts. is the dominant volcanic center of the Oh?e (Eger) rift zone. It hosts the Roztoky Intrusive Complex (RIC), which is made up of a caldera vent and intrusions of 33–28-Ma-old hypabyssal bodies of essexite–monzodiorite–sodalite syenite series accompanied by a radially oriented 30–25-Ma-old dike swarm comprising about 1,000 dikes. The hypabyssal rocks are mildly alkaline mostly foid-bearing types of mafic to intermediate compositions. The dike swarm consists of chemically mildly alkaline and rare strongly alkaline rocks (tinguaites). The geochemical signatures of the mildly alkaline hypabyssal and associated dike rocks of the RIC are consistent with HIMU mantle sources and contributions from lithospheric mantle. The compositional variations of essexite and monzodiorite can be best explained by fractional crystallization of parent magma without significant contributions of crustal material. On the other hand, the composition of monzosyenite, leuco-monzodiorite and sodalite syenite reflects fractional crystallization coupled with variable degrees of crustal assimilation. It is suggested that the parent magmas in the Oh?e rift were produced by an adiabatic decompression melting of ambient upper mantle in response to lithospheric extension associated with the Alpine Orogeny.     

2D geological–geophysical model of the Timok Complex (Serbia,SE Europe): a new perspective from aeromagnetic and gravity data

The study reports new aeromagnetic and gravity data for the northern part of the Timok Magmatic Complex (TMC), East Serbia. The TMC is part of the Tethyan Eurasian metallogenic zone well known for hosting large copper and gold deposits. The complex formed by continuous volcanic activity 90–78 Ma ago, that developed in roughly three phases: Turonian andesites, Santonian–Campanian andesites/basaltic andesites (both mostly volcanic) and Campanian latites/monzonites (mostly shallow intrusive). The aeromagnetic measurements included acquiring total magnetic intensity data that were corrected for diurnal variations, leveling, microleveling, calculated normal field values, calculated anomaly values of total magnetic field intensity and reduction to the pole. The gravity measurements were carried out in an irregular grid with relative gravity values obtained using a Worden gravity meter. 2D modeling reveals that the subsurface extension of the Campanian Valja Str? pluton is ten times larger than it is indicated by its surface outcrops. This implies that the area south and southeast from the pluton can be interesting in terms of finding new porphyry systems. The model indicates that this intrusive body should not be considered as a deeply dissected pluton. This sheds new light onto its potential with respect to epithermal gold mineralization, as well. The model also suggests that there are larger non-exposed bodies of Santonian–Campanian volcanics and near-surface hydrothermally altered rocks than it is inferred from geological maps. The results of our study suggest that further interdisciplinary investigations in the TMC, in particular those integrating geophysics and geology, may have potential of advancing the existing exploration models.     

A critical evaluation of using bulk sediment instead of fine fraction in environmental marine studies, investigated on example of Rijeka harbor, Croatia

This work tested the preferential use of fine (<63 μm) or bulk sediment (<2 mm) in environmental research of marine sediments in the Eastern Adriatic. Fine fraction sediment containing silt and clay (<63 μm), predominating in the studied area, was examined to evaluate past and present anthropogenic inputs and to test our hypothesis that investigation of bulk sediment should be preferred. Following aqua regia digestion, chemical analyses of 58 elements were performed by ICP/OES, ICP-MS and cold vapor AAS, and statistical analysis was performed. The concentrations of the majority of the analyzed elements increased with age of the sediment, except for Ag and Sn, which had higher concentrations in recent sediments. The previous main sources of metal contamination in Rijeka harbor were now abandoned municipal-sewage outflow and oil refinery, and continuing harbor activities and antifouling paint use. All activities except of antifouling paint use have been decreasing significantly. Anomalies of selected elements were determined by the box-plot method. More anomalies were found in the bulk sediment than in the fine fraction. Results of Q-modality clustering and factor analysis in the fine fraction almost correlate with that applied on bulk sediments. Thus, it can be said that the differences between the element distribution in the bulk and fine fraction are not statistically significant. Our conclusion is that analysis of bulk marine sediment gives a better insight into the state of pollution and supports previous recommendations to use bulk sediment as a chosen media for environmental studies.     

3D modeling and monitoring of karst system as a base for its evaluation and utilization: a case study from eastern Serbia

Beljanica Mountain in eastern Serbia is a part of the Carpathian Balkan arch (northern Alpine branch). It covers an area of about 300 km² and consists mostly of Jurassic and Cretaceous limestones. Numerous surface karst features, long caves and several large karstic springs located in Beljanica’s piedmont along the contact of karstic and non-karstic rocks are all indicators of an intense karstification. Currently, the large karstic water reserves of Beljanica Mountain are not properly utilized because of their distance from main consumers, the objection by national water managers that the springs lack a stable and sufficient discharge particularly during recession periods. Due to its unpolluted and high quality water, the area is a great prospect for future water supply, and provides an opportunity for artificial regulation and for the design and implementation of specific tapping structures. This paper includes an analysis of the created 3D ArcGIS model of karst interior and its correlation with historical and newly collected data of spring discharges and groundwater physico-chemical characteristics. The results of karst aquifer monitoring (both quantitative and qualitative) are linked with the results of extensive field geological and speleological survey of the upper non-saturated part of the karst (such as sinkholes, pits and caves) and with the investigation of the permanently saturated deeper part of the aquifer (including the diving methods). The model of karst interior is based on the data from the 69 caves, 15 sinks and 1,682 dolines (sinkholes) surveyed. The total length of the karst channels network, calculated using the GIS model and presented in a 3D environment, is 647 km. The catchment areas of five major springs that drain the areas are estimated to range from only 7 km² (Malo Vrelo Spring) to 124 km² (Vrelo Mlave Spring). The groundwater exploitable reserves of Beljanica karst aquifer are estimated to be over 4 m³/s. The waters are low mineralized, unpolluted and have a great potential for water supply.