Rječina River sediments (Croatia): from captured spring to polluted prodelta

Surface sediments (fraction <63 μm) from the source to the mouth of the Rječina, short (18.3 km) karst allogenic river in Croatia, which is an important source of drinking water, were studied to investigate their mineral (by XRD) and chemical (by ICP-MS) composition to check possible anthropogenic influence at the lower course due to paper industry and mills, and in the prodelta area from untreated municipal sewage and the large harbor of Rijeka town. In all analyzed sediment samples and in the sandstone source, rock quartz is a major mineral, while feldspar and mica group minerals are less abundant. Chlorite is a minor or trace mineral in all samples. Calcite and dolomite are abundant in the river prodelta, reflecting changes in bedrock lithology from flysch to carbonates. In river sediments, Fe is the most abundantly analyzed element, while Ca is the most abundant in prodelta sediments. Concentrations of Al, Mn, Ni, Cr, Co, La and Nd decrease downstream, while Mg, S, Na, B, Pb, Zn, As, Sn, U, Mo, Hg and Ag have relatively higher concentration in prodelta sediments. The results are compared with sediments of other rivers in the area: Raša, Rižana and Dragonja, as well as with those of the Rosandra Creek (Italy). Sediments in the Raša River showed similar behavior as those in the Rječina, as the highest concentration of metals was found in the restricted upper part of the estuary, characterized by rapid deposition of clay particles and terrestrial sedimentary organic matter. The comparison also showed that the most contaminated were the sediments from the Rižana, followed by those from the Rječina and Rosandra Creek, which had similar results. Among the studied elements, As was present in all sediment samples at concentrations >6 ppm that might have the lowest toxic effects. At the lower Rječina and in prodelta sediments, Pb was also present at slightly elevated concentrations (>31 ppm) that could cause such effects. Concentrations of Zn in the prodelta correspond to those occurring in moderately polluted sediments (90–200 ppm). In the prodelta sediments, Hg is slightly below toxicity threshold (1 ppm), while Ag is present at toxicity threshold (0.5 ppm) or close to it. Rječina River could act as a good illustrative example for behavior of toxic metals in allogenic karstic rivers, in which accumulation of anthropogenically introduced pollutants usually occurs in their estuaries, as a result of transport and deposition of fine particles.     

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.     

Ab initio calculated electron densities for tetrahedral sheet [H2Si2O5]∞ in phyllosilicates

Periodic ab initio Hartree-Fock LCAO calculations have been carried out on the two dimensional sheet of SiO₄ tetrahedra, representing one of the basic constituting units of layer silicates, using Huzinaga's DZP basis sets. The influence of the basis set on the chemical bonding picture is characterized by Mulliken atomic charges and by electron density maps. Silicon atomic charges +1.6 ¦e¦ are more realistic than those +2.4 ¦e¦ reported for smaller basis sets. The silicon d orbital population is found to be 0.6 in close agreement with molecular data. Electron density maps indicate the absence of charge density in the center of the ditrigonal cavity. The charge buildup of nonbonding basal oxygen orbitals is directed mainly downwards perpendicular to the sheet plane.     

Cation exchange capacity of loess and overlying soil in the non-carbonate loess sections, North-Western Croatia

The adsorption properties in terms of cation exchange capacity and their relation to the soil and sediment constituents (clay minerals, Fe-, Mn-, and Al-oxyhydroxides, organic matter) were investigated in loess, soil-loess transition zone, and soil at four loess-soil sections in North-Western Croatia. Cation exchange capacity of the bulk samples, the samples after oxalate extraction of Fe, Mn and Al, and after removal of organic matter, as well as of the separated clay fraction, was determined using copper ethylenediamine. Cation exchange capacity (pH～7) of the bulk samples ranges from 5 to 12 cmol _c /kg in soil, from 7 to 15 cmol _c /kg in the soil-loess transition zone, and from 12 to 20 cmol _c /kg in loess. Generally, CEC values increase with depth. Oxalate extraction of Fe, Mn, and Al, and removal of organic matter cause a CEC decrease of 3–38% and 8–55%, respectively, proving a considerable influence of these constituents to the bulk CEC values. In the separated clay fraction (<2 μm) CEC values are up to several times higher relative to those in the bulk samples. The measured CEC values of the bulk samples generally correspond to the clay mineral content identified. Also, a slight increase in muscovite/illite content with depth and the vermiculite occurrence in the loess horizon are concomitant with the CEC increase in deeper horizons, irrespective of the sample pretreatment.     

Application of the photoacoustic method for characterization of natural galena (PbS)

Electron transport properties of single crystal and polycrystalline natural mineral galena (PbS) samples from the Trep?a mine, Yugoslavia, were determined using the photoacoustic frequency transmission technique. Their thermal diffusivity (D _T≈0.16 × 10^?5 m² s^?1), the coefficient of diffusion (D between 0.15×10^?2 0.16×10^?2 m² s^?1) and lifetime of the excess carrier (τ≈35 μs and the front and rear recombination velocity (s _g≈65.5 m s^?1 and s _b≈66.4 m s^?1, respectively), were calculated by comparing the experimental results and the theoretical photoacoustic amplitude and phase signals. The lattice parameter obtained by X-ray work was a?=5.936?Å. The free carrier concentration of these single-crystal samples was measured using the Hall method (N?=?3×10¹⁸ cm^?3). Measurements of the optical reflectivity of the same samples, as a function of wavelength, in the infrared and far infrared ranges, were performed. In the far infrared range a free electron plasma frequency was observed and numerically analyzed, using the least-squares fitting procedure. The values of optical parameters were calculated and the value of the free carrier concentration obtained by the Hall method was confirmed.     

Hydrogeochemical stratification of the unconfined Samobor aquifer (Zagreb,Croatia)

In the western part of the city of Zagreb, Croatia, hydrogeochemical and isotopic investigations of the Samobor aquifer were carried out with the aim of determining the differences in hydrogeochemical characteristics at increasing aquifer depths. The aquifer comprises 40-m thick gravelly–sandy deposits, with lenses and interlayers of silt and clay. The analyses have proven that with increasing aquifer depth, there are decreases in groundwater temperature and the values of electrical conductivity and increases in the sodium, iron and manganese concentrations. The δ¹³C distribution shows an evident increase in biogenic carbon concentrations with increasing aquifer depth. The measured specific ¹⁴C activities showed that the deeper part of the aquifer is characterized by slow water exchange, while the shallower part is influenced by current recharge, although the pumping wells located on the well-field downstream penetrate the aquifer fully. A direct exchange of water from the Sava River and groundwater occurs in the near vicinity of the river. This exchange weakens further away, while the difference in hydrogeochemical characteristics between the Sava River water and groundwater increases.     

Anthropogenic influence on trace element geochemistry of healing mud (peloid) from Makirina Cove (Croatia)

Due to their balneotherapeutic features, the organic-rich sediments in Makirina Cove are an important source of healing mud. An environmental geochemistry approach using normalization techniques was applied to evaluate the anthropogenic contribution of trace metals to sediments used as healing mud. Sediment geochemistry was found to be associated with land-use change and storm events, as well as with proximity of a road with heavy traffic in the summer months. Local valley topography preferentially channels lithogenic and pollutant transport to the cove. Concentrations and distribution of trace metals indicate lithogenic (Ni, Cr, Co) and anthropogenic (Pb, Cu, Zn and Se) contributions to the sediments. The calculation of enrichment factors indicates a moderate (EFs between 2–3.5) input of anthropogenic Cu and Pb in surficial sediments to a depth of 10 cm. Patients using the Makirina Cove sediments as healing mud could be to some extent exposed to enhanced uptake of metals from anthropogenic sources via dermal contact.     

Determination of ecological significance based on geostatistical assessment: a case study from the Slovak Natura 2000 protected area

The Sitno Natura 2000 Site covers an area of 935,56 hectares. The Sitno region is significant due to the number of rare and endangered species of plants, and as a result is considered a location of great importance to the maintenance of floral gene pools. The study area suffers human impacts in the form of tourism. The main purpose of this study is to the measure landscape elements, determine the ecological significance of habitats within the Sitno area, and from this data, organize the study area into conservation zones. The results of this landscape quantification are numerical values that can be used to interpret the quality of ongoing ecological processes within individual landscape types. Interpretation of this quantified data can be used to determine the ecological significance of landscapes in other study areas. This research examines the habitats of Natura 2000 Sites by a set of landscape metrics for habitat area, size, density, and shape, such as Number of patches (NP), Patch density (PD), Mean patch size (MPS), Patch size standard deviation (PSSD) and Mean shape index (MSI). The classification of land cover patches is based on the Annex Code system.     

Reduction of surface subsidence risk by fly ash exploitation as filling material in deep mining areas

The possibility of filling empty underground spaces, which exist owing to the extraction of mineral raw materials, with fly ash and cement fly ash mixes has been studied for the purpose of reducing the impact of deep mining on the surface. The method of physical modelling was used to study the behaviour of fly ash mixes deposited in extracted mine spaces. The models were constructed for two different geometries of underground extracted mine spaces: into cavities of the type of large slits created in the course of mining in steeply lode deposits without subsequently filling the empty space and in vertical shafts of rectangular or circular cross-section with horizontal side headings that have partly caved in due to mine shocks or other seismic events.     

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.