Biomarker distributions as indicators for the depositional environment of lacustrine sediments in the Valjevo-Mionica basin (Serbia)

In this study, the molecular composition and biomarker distribution of lacustrine sediments from Val-1 drillhole in the central zone of the western part of the Valjevo-Mionica basin were investigated at depth interval of 0–400 m. Former investigations have shown that the core material can be separated into six depth intervals based on bulk geochemical, mineralogical and sedimentological characteristics. Concerning the quality of organic matter, presence of specific minerals, and high salinity and anoxicity, or alkalinity, three zones are of highest interest, defined at depth intervals of 15–75 m (A), 75–200 m (B) and 360–400 m (F). The first aim of the study was to identify which biomarkers characterize these specific intervals. The second aim, addressing the transitions zones of these intervals, was to extend the changes in the characteristics of the organic substance, to reflect the changes of conditions in the depositional environment as well as to define biomarker parameters which are the most sensitive sedimentological indicators.The sediments from the hypersaline anoxic and alkaline environment show high contribution of algal precursor biomass, what is in accordance with the good quality of organic substances in the sediments from these zones. High squalane content and low content of regular isoprenoid C₂₅ are typical for hypersaline anoxic environment, whereas sediments from alkaline environment have high regular isoprenoid C₂₅ content.Transition to specific sedimentation zones is characterized by change in total organic matter content, and of both free and pyrolysis-derived, and change in hydrogen index value. In the biomarker distributions, more significant changes were detected in distributions of n-alkanes and isoprenoids, compared to polycyclic alkanes. The most intensive changes in alkane distribution are reflected in changes in n-C₁₇ content compared to n-C₂₇, and phytane compared to n-C₁₈. In addition, significant sensitivity was seen in ratios between squalane and n-alkane C₂₆ (hypersaline depositional environment), or isoprenoid C₂₅ and n-alkane C₂₂ for high alkalinity environment.This study showed that Sq/n-C₂₆ ratio can be used to assess the quality of organic substance in immature lacustrine sediments.     

The Late Cretaceous Klepa basalts in Macedonia (FYROM)—Constraints on the final stage of Tethys closure in the Balkans

The waning stage(s) of the Tethyan ocean(s) in the Balkans are not well understood. Controversy centres on the origin and life‐span of the Cretaceous Sava Zone, which is allegedly a remnant of the last oceanic domain in the Balkan Peninsula, defining the youngest suture between Eurasia‐ and Adria‐derived plates. In order to investigate to what extent Late‐Cretaceous volcanism within the Sava Zone is consistent with this model we present new age data together with trace‐element and Sr–Nd–Pb isotope data for the Klepa basaltic lavas from the central Balkan Peninsula. Our new geochemical data show marked differences between the Cretaceous Klepa basalts (Sava Zone) and the rocks of other volcanic sequences from the Jurassic ophiolites of the Balkans. The Klepa basalts mostly have Sr–Nd–Pb isotopic and trace‐element signatures that resemble enriched within‐plate basalts substantially different from Jurassic ophiolite basalts with MORB, BAB and IAV affinities. Trace‐element modelling of the Klepa rocks indicates 2%–20% polybaric melting of a relatively homogeneously metasomatised mantle source that ranges in composition from garnet lherzolite to ilmenite+apatite bearing spinel–amphibole lherzolite. Thus, the residual mineralogy is characteristic of a continental rather than oceanic lithospheric mantle source, suggesting an intracontinental within‐plate origin for the Klepa basalts. Two alternative geodynamic models are internally consistent with our new findings: (1) if the Sava Zone represents remnants of the youngest Neotethyan Ocean, magmatism along this zone would be situated within the forearc region and triggered by ridge subduction; (2) if the Sava Zone delimits a diffuse tectonic boundary between Adria and Europe which had already collided in the Late Jurassic, the Klepa basalts together with a number of other magmatic centres represent volcanism related to transtensional tectonics.     

Modification of the subcontinental mantle beneath East Serbia: Evidence from orthopyroxene-rich xenoliths

Orthopyroxene-rich olivine websterite xenoliths (OWB₂) in Palaeogene basanites in East Serbia are mostly composed of tabular low-Al₂O₃ orthopyroxene (> 70 vol.%, Mg# 85–87) containing tiny Cr spinel inclusions. Orthopyroxene shows a slightly U-shaped primitive mantle-normalized trace element pattern with strong peaks at U and Pb, similar to that of orthopyroxene from normal regional peridotitic mantle. In between the orthopyroxenes are interstitial spaces composed of partially altered olivine (Mg# 85–87), clinopyroxene, Ti-rich spinel, Mg-bearing calcite, K-feldspar, apatite, ilmenite and relicts of a hydrous mineral. Clinopyroxene appears as selvages around orthopyroxene and as coarser euhedral crystals. Trace element patterns of the clinopyroxene selvages resemble those of adjacent orthopyroxene, whereas the coarser ones have flatter and more LREE- and LILE-enriched patterns, similar to that of metasomatic clinopyroxene. The OWB₂ xenoliths are interpreted as having formed in two stages. During Stage I orthopyroxene crystallized, along with some spinel, olivine and probably hydrous phase(s). This original OWB₂ lithology was a hydrous olivine-bearing orthopyroxenite that crystallised from subduction-related SiO₂-saturated, boninite-like magmas. During Stage II the interstitial minerals formed due to infiltration of a low-SiO₂, high-CaO and CO₂-rich external melt, accompanied by decomposition of original H₂O-bearing minerals. The calculated composition of the infiltrating liquid corresponds to a mafic alkaline melt similar to the basanitic host but more enriched in CO₂, LREE and LILE. Metasomatism is interpreted in terms of small degree melts related to the Palaeogene mafic alkaline magmatism.     

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.     

Cognate clinopyroxene from Paleogene mantle xenolith-bearing basanite lavas (East Serbia, SE Europe): the role of dissolution of mantle orthopyroxene

The study focuses on clinopyroxene from mantle xenolith-bearing East Serbian basanites and suggests that dissolution of mantle orthopyroxene played an important role in at least some stages of the crystallization of these alkaline magmas. Five compositional types of clinopyroxene are distinguished, some of them having different textural forms: megacrysts (Type-A), green/colourless-cored phenocrysts (Type-B), overgrowths and sieve-textured cores (Type-C), rims and matrix clinopyroxene (Type-D), and clinopyroxene from the reaction rims around orthopyroxene xenocrysts (Type-E). Type-A is high-Al diopside that probably crystallized at near-liquidus conditions either directly from the host basanite or from compositionally similar magmas in previous magmatic episodes. Type-B cores show high ^VIAl/^IVAl≥1 and low Mg# of mostly <75 and are interpreted as typical xenocrysts. Type-C, D and E are interpreted as typical cognate clinopyroxene. Type-D has Mg#<78, Al₂O₃?=?6–13?wt.%, TiO₂?=?1.5–4.5?wt.%, and Na₂O?=?0.4–0.8?wt.% and compositionally similar clinopyroxene is calculated by MELTS as a phase in equilibrium with the last 30?% of melt starting from the average host lava composition. Type-C has Mg#?=?72–89, Al₂O₃?=?4.5–9.5?wt.%, TiO₂?=?1–2.5?wt.%, Na₂O?=?0.35–1?wt.% and Cr₂O₃?=?0.1–1.5?wt.%. This clinopyroxene has some compositional similarities to Type-E occurring exclusively around mantle orthopyroxene. Cr/Al vs Al/Ti and Cr/Al vs Na/Ti plots revealed that Type-C clinopyroxene can crystallize from a mixture of the host basanite magma and 2–20?wt.% mantle orthopyroxene. Sieve-textured Type-C crystals show characteristics of experimentally produced skeletal clinopyroxene formed by orthopyroxene dissolution suggesting that crystallization of Type-C was both texturally and compositionally controlled by orthopyroxene breakdown. According to FeO/MgO^cpx/melt modelling the first clinopyroxene precipitating from the host basanite was Type-A (T?~?1250?°C, p?~?1.5?GPa). Dissolution of orthopyroxene produced decreasing FeO/MgO^melt and crystallization of Type-E and sieve-textured Type-C clinopyroxene (0.3–0.8?GPa and 1200–1050?°C). The melt composition gradually shifted towards higher FeO/MgO^melt ratios precipitating more evolved Type-C and Type-D approaching near-solidus conditions (<0.3?GPa; ~950?°C).     

Distribution of some elements in surface soil over the Kavadarci region,Republic of Macedonia

The results of a first systematic study of spatial distribution of different elements in surface soil over of the Kavadarci region, Republic of Macedonia, known for its nickel industrial activity are reported. The investigated region (360 km²) is covered by a sampling grid of 2 × 2 km²; whereas the sampling grid of 1 × 1 km² was applied in the urban zone and around the ferronickel smelter plant (117 km²). In total 344 soil samples from 172 locations were collected. At each sampling point soil samples were collected at two depths, topsoil (0–5 cm) and bottom soil (20–30 cm). Inductively coupled plasma-mass spectrometry (ICP-MS) was applied for the determination of 36 elements (Ag, Al, As, Au, B, Ba, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ga, Hg, K, La, Mn, Na, Mg, Mo, Ni, P, Pb, S, Sb, Sc, Se, Sr, Th, Tl, Ti, U, V, W and Zn). Data analysis and construction of maps were performed using the Paradox (ver. 9), Statistica (ver. 6.1), AutoDesk Map (ver. 2008) and Surfer (ver. 8.09) software. Four geogenic and three anthropogenic geochemical associations were established. Within the research, natural and anthropogenic enrichment with heavy metals was determined. Principally, the natural enrichment is related especially to Ni. Pollution by As, Cd, Co, Cr, Cu, Hg, Mo, Pb and Zn is basically insignificant.     

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.     

Occurrence of Sn-Bearing colusite in the ore-body “T” of the Bor copper deposit, Serbia

The ore body “T” is the newly discovered massive-pyrite type one which is located in the central part of the Bor copper mine. The main copper minerals are chalcocite-digenite, covellite and enargite. Small amounts of colusite are frequently present in the ore-body. It mostly occurs as the distinct exsolutions in digenite and, associating with enargite and covellite. Composition of the studied colusite shows enriched Sn content, giving an empirical formula from Cu_24.7V_1.8Fe_0.2As_5.1Sb_0.2Sn_0.8S₃₂ to Cu_26.7V_2.0Fe_0.3A_s3.0Sb_0.3Sn_3.5S₃₂. This colusite represents a solid solution between colusite and nekrasovite within a range of 14–54 mol % nekrasovite. Most of the analyses show content of <50 mol % nekrasovite corresponding to the Sn-bearing colusite variety, while one analysis shows content of 54 mol % nekrasovite corresponding to the As-bearing nekrasovite.