Temporal and Seasonal Variations of Silicate Svratka River and Sediment Characterization, Czech Republic: Geochemical and Stable Isotopic Approach

This study investigated weathering and hydrobiogeochemical processes in a silicate dominated watershed (Svratka river) in the Czech Republic in comparison with nearby carbonate dominated catchments. Elemental and isotopic analysis of river waters, particulates and sediments provided a more holistic view of weathering contributions, anthropogenic contamination, biological activity and evasion or sinks of CO2 to the atmosphere. In water samples, we determined total alkalinity after Gran 1974, and cations and anions were determined with inductively coupled plasma-optical emission spectrometer and ion chromatograph. δ13CDIC in water samples was determined with isotope ratio mass spectrometer. pCO2 and saturation indexes of calcite and dolomite were calculated with PHREEQC speciation program. Evasion fuxes were calculated after Broecker, 1974. Isotopic composition of carbon and nitrogen in particulate matter and sediments were determined with isotope ratio mass spectrometer. Mineral composition of sediments was determined with XRD method and elements with XRF method. Further enrichment factors of elements were calculated. The Svratka river, which is the major tributary of the Dyje river, is dominated by Ca2+ > Na+ > Mg2+ > K+ and HCO3 MINUS SIGN (as total alkalinity). Partial pressure (pCO2) concentrations range from close to 0-572-fold of atmospheric pressure. Isotopic composition of carbon in dissolved inorganic carbon (δ13CDIC) value ranged fromMINUS SIGN 13.3 toMINUS SIGN 8.0%o refecting degradation of organic matter and exchange with the atmosphere. Bicarbonate weathering intensity for the Svratka river at its mouth is 11.8 mol/(lDOT OPERATOR  km2 DOT OPERATOR  s), more on par with silicate terrains and lower than nearby carbonate watersheds. Isotopic composition of carbon (δ13C) and isotopic composition of nitrogen (δ15N) values of river sediment refect soil and temperate plant (C3 plant) values, while higher δ15N values could be attributed to application of organic fertilizers in lower reaches. The river sediments, which came from weathering of crystalline rocks, are dominated by silt size, geochemically less mature quartz, feldspar and muscovite particles. All the stream sediments examined revealed slightly increased amounts of Zn, Cu and Pb. However, using Al as the normalization element to calculate enrichment factors, Zn, Cu and Pb are only elevated downstream, related to industrial contamination. This study is important for local and global level since it deals with contribution of weathering rates and contribution of CO2 to the atmosphere in silicate watershed.O

Mobility of selected trace elements bound in brown coal of the Most basin

Cílem studia bylo posoudit extrahovatelnost vybraných kovů obsažených ve vzorcích hnědého uhlí při odlišném pH. Na základě těchto údajů pak stanovit prvky, u kterých je nezbytné hodnotit spíše jejich formu výskytu než absolutní koncentraci.  Některé prvky vázané v uhlí, jsou potenciálně lehce mobilizovatelné, a představují riziko pro okolní ekosystém. Bylo studováno celkem 10 vzorků uhlí z hlavní sloje mostecké pánve pomocí sekvenční extrakční procedury. Podmínky extrakcí byly nastaveny tak, aby reprezentovaly reálné situace. Pro nejslaběji vázané, a tedy lehce mobilizovatelné prvky byla použita extrakce deionizovanou vodou, množství slabě adsorbovaných iontů na povrchu pevné matrice bylo extrahováno pomocí 1M roztoku octanu amonného při pH = 7. Pro frakci vázanou na uhličitany příp. extrahovatelnou za mírně kyselých podmínek bylo použito téhož činidla při pH = 5. U poloviny hodnocených vzorků se největší množství arsenu  extrahovalo v uhličitanové frakci, u druhé poloviny bylo nejvíce arsenu uvolněno již při extrakci deionizovanou vodou. Pozitivní korelace byla zjištěna mezi celkovým množstvím As a Ni. Při korelování dat z jednotlivých extraktů se ovšem vztah nepotvrdil. Množství uvolněného niklu ve všech extrakčních krocích bylo velmi nízké. Významné množství vanadu a chromu bylo extrahováno již za použití deionizované vody u poloviny vzorků. Velmi blízké chování chromu a vanadu potvrzuje i pozitivní korelace během všech kroků extrakce.Some of the trace elements bound in coal are potentially easily mobilizable and can represent a risk for an ecosystem. The aim of the study was to evaluate the extractability of selected metals from brown coal samples under surface conditions. Totally, 10 coal samples from the Main seam of Most Basin were studied using a sequential extraction procedure. Extraction conditions were set to represent real conditions on a dump. Extraction with deionized water was used for the most weakly bound and thus easily mobilizable elements, the amount of weakly adsorbed ions on the surface of the solid matrix was extracted with 1M ammonium acetate solution at pH = 7. For the carbonate-bound fraction, respectively the fraction extractable under mildly acidic conditions, the same reagent at pH = 5 was used. Highest extractable contents in case of arsenic were found in deionized water for samples 03–07, other samples exhibited the highest recovery with weakly acidic reagent (pH = 5) with concentration 1 mol/l. Nickel concentrations in the extracts were mostly low (hundredths to tenths μg/g). Exceptions are water extractable contents (single units of μg/g) in samples 01, 08 and 09. A positive correlation (r = 0.69) was found between the total content of As and Ni, however, the contents of As and Ni do not mutually correlate in each type of extract. Significant contents of vanadium (up to 0.844 μg/g) and chromium (up to 0.28 μg/g) were already extracted using deionized water. Very close behavior of chromium and vanadium was confi rmed by positive correlation in mobile water extractable (r = 0.95) and carbonate fraction (r = 0.85)

Applicability of portable x-ray fluorescence spectrometer in organomineral matrix analyses

The portable X-ray-fluorescence analyzer (Innov-X Systems, Inc.) is routinely used as screening tool in geochemical and environmental mapping. The applicability in organomineral matrices was not tested yet. The biogas is produced from maize silage, grass silage, beef and pig manure and slurry, sewage sludge, organic wastes from food industries, organic household waste. As the main result the digestate (anaerobic digestion residues) is manufactured. The digestate is used as fertilizer and/or fuel. In the presented study the three reference materials and three samples of the digestate were analyzed 50 times each. RFA analytical conditions for reference material and samples: Innov-X Systems, Inc., Delta, time measurement: 1. beam: energy 1–40 kV, time 140 s.; 2. Beam: energy 2–10 kV, time 140 s., analytical mode: geochem2. Statistical evaluation of the data set allowed comparison among accuracy and reproducibility for organomineral matrices. The results are in good correlation with data from standard elemental analyses. The presented results has proved very good or satisfactory reproducibility for fourteen elements (Al, S, K, Ca, Mn, Fe, Cu, Zn, Sr, Zr, Mo, Ag, Pb, Th ). The results for three elements (Al, S, Fe) in digestates have high reproducibility, for the Ag, Mn, Mo, Sr, Zr, Th have good reproducibility. The portable XRF is suitable for the mineral fraction characterization in the agricultural materials such as composts, digestates and silages.The portable X-ray-fluorescence analyzer (Innov-X Systems, Inc.) is routinely used as screening tool in geochemical and environmental mapping. The applicability in organomineral matrices was not tested yet. The biogas is produced from maize silage, grass silage, beef and pig manure and slurry, sewage sludge, organic wastes from food industries, organic household waste. As the main result the digestate (anaerobic digestion residues) is manufactured. The digestate is used as fertilizer and/or fuel. In the presented study the three reference materials and three samples of the digestate were analyzed 50 times each. RFA analytical conditions for reference material and samples: Innov-X Systems, Inc., Delta, time measurement: 1. beam: energy 1–40 kV, time 140 s.; 2. Beam: energy 2–10 kV, time 140 s., analytical mode: geochem2. Statistical evaluation of the data set allowed comparison among accuracy and reproducibility for organomineral matrices. The results are in good correlation with data from standard elemental analyses. The presented results has proved very good or satisfactory reproducibility for fourteen elements (Al, S, K, Ca, Mn, Fe, Cu, Zn, Sr, Zr, Mo, Ag, Pb, Th ). The results for three elements (Al, S, Fe) in digestates have high reproducibility, for the Ag, Mn, Mo, Sr, Zr, Th have good reproducibility. The portable XRF is suitable for the mineral fraction characterization in the agricultural materials such as composts, digestates and silages

Hydrocarbon-based parameters for the identification of oil contamination in an area with brown coal mining: Emphasis on pyrogenic index and alkylated PAHs

The aim of the study was to propose hydrocarbon-based parameters that can ben used to identify oil derived contamination in an area with a long-term load of coal mining industry. Aliphatic hydrocarbons and PAHs have been quantified for bottom sediments in the Bílina River, Czechia. Presented data demonstrate that all river sediments are highly contaminated with PAHs. The results showed that the distribution of PAHs was not possible to interpret by using the standard evaluation due to multisource long-term sedimentation of petroleum by-products, coal tars, and accidents of processing industry in the river system. The presence of petroleum derived hydrocarbons has been initially screened by the bulk parameter TEH and confirmed by the occurrence of steranes, hopanes and the unresolved complex mixture (UCM) in the chromatograms. The identification of the biomarkers 25-Norhopane and Gammacerane point out onsite microbial degradation of parent hydrocarbon compounds. The interpretation of the ratios Fl/Py, An/P, BaAn/Ch were not decisive to prove petrogenic origin of PAHs in the river sediments. However, using the combined evaluation of TEH together with the ratio of low molecular over high molecular weight PAHs, pyrogenic index and the presence of specific oil derived biomarkers allowed to prove the presence of petroleum contamination. Environmental implication: Due to oil spill accidents and intensive coal mining over the years, polycyclic aromatic hydrocarbons (PAHs) have been present in extreme amounts in bottom sediments of a tributary of the Elbe River, so called the Bílina River. Due to its hydrophobic and carcinogenic character, mutual understanding of the fate of alkylated PAHs homologues are usually overlooked within EPA PAHs 16 monitoring programme. This study pays attention to alkylated PAHs homologues and conventional diagnostic ratios when identifying oil derived contamination

Subcrustal CO2 flux measurement in the Hranice hydrothermal Karst, methodology and first results

Hranice Karst with Zbrašov aragonite caves is situated in the Teplice nad Bečvou district, 40 km SE from Olomouc. Hranice hydrothermal Karst is developed in the sequence of Paleozoic limestones as a result of deep influx of thermal water charged with subcrustal carbon dioxide (C02). Flux C02 (g.m-2.d-1) was measured in the soil and cave. Homogenisation chamber and pumping test were applied to evaluate C02 flux. The average soil C02 flux ranged from 74 to 125 g.m_2.d_1 reflecting venting of subcrustal C02 in the Hranice area. In the Zbrasovaragonite cave the C02 con- centration in the atmosphere varies from 0 to 85% with measured constant flux of 32894,45 g.m 2.d_1

Subcrustal CO2 flux measurement in the Hranice hydrothermal Karst, methodology and first results

Hranice Karst with Zbrašov aragonite caves is situated in the Teplice nad Bečvou district, 40 km SE from Olomouc. Hranice hydrothermal Karst is developed in the sequence of Paleozoic limestones as a result of deep influx of thermal water charged with subcrustal carbon dioxide (C02). Flux C02 (g.m-2.d-1) was measured in the soil and cave. Homogenisation chamber and pumping test were applied to evaluate C02 flux. The average soil C02 flux ranged from 74 to 125 g.m_2.d_1 reflecting venting of subcrustal C02 in the Hranice area. In the Zbrasovaragonite cave the C02 con- centration in the atmosphere varies from 0 to 85% with measured constant flux of 32894,45 g.m 2.d_1

The analytical approach of Drone use in radiation monitoring

During the traditional way of radiation field monitoring − walking measurements – is possible to encounter inaccessible or dangerous areas. For this case, the National Institute for Nuclear, Chemical and Biological Protection (SUJCHBO) has created the method of aerial measurement of ambient dose equivalent rate (ADER) using the drone equipped with gamma-spectrometer. This paper presents two methods on estimation of near-surface gamma radiation based on aerial measurements with Drone equipped with gamma-spectrometer D230A. The D230A was first tested in a room fitted with walls with a higher amount of natural radionuclides from uranium series. The aerial measurements were done at SUJCHBO’s Heliport at three altitudes (6, 11 and 16 m) and from the obtained data, the values of ADER for the altitude of 1 m were calculated and compared with the data measured in the altitude of 1 m. From the two proposed methods, the first one serves for evaluation of the whole measured area while the second method serves for evaluation of zones of interest. In the case of the first method, the highest difference between the calculated and measured data for the altitude of 1 m was 20% and, in case of the second method, the difference of −13.3% and −8.2% was achieved

Heat flow evolution, subsidence and erosion in Upper Silesian Coal Basin, Czech Republic

The deep boreholes in the Upper Silesian Coal Basin provide a valuable material to evaluate thermal maturity of the present Carboniferous units. 17 boreholes were used for evaluating expected paleothicknesses of the missing units and the maximum temperatures reached via 1D modelling. The models consider the geological evolution concepts accepted for the region. The reliability of the final thermal models was calibrated with vitrinite reflectance data. Vitrinite reflectance varies between 0.46 and 2.32% Rr indicating thermally early mature to over mature organic matter for the Ostrava Fm. and Karviná Fm. The coal rank increases from the east to the west. Based on the data from RockEval pyrolysis all samples from the Ostrava and Karviná Fms. belong to type III kerogen. The RE results show that the source potential of the Carboniferous sediments was not spent in full as part of the Variscan tectogen. Burial and thermal history on the Czech side of the Upper Silesian Coal Basin was reconstructed. The set of several 1D simulations proved that the thickness of the missing Palaeozoic molasses association is 2500 to 3400 m in the foreland and 1800 to 2000 m for the platform. The maximum burial is expected at the end of the Westphalian. The consequent sedimentation of the Carpathian Foredeep and nappe thrusting did not change the Palaeozoic thermal maturity pattern within the tested area of the USCB.Web of Science154-155423

Source rock potential of the Miocene sedimentary rocks in the Carpathian Foredeep of the Czech Republic

We determine the organic matter content, its thermal maturity, genetic type, and source rock potential of the Miocene sedimentary rocks in the Czech Carpathian Foredeep. In the Czech Republic the Carpathian Foredeep represents a peripheral foreland basin formed due to the tectonic emplacement and loading of the Alpine-Carpathian Thrust Wedge onto the passive margin of the Bohemian Massif. Random vitrinite/huminite reflectance measurements and maceral analyses were performed on 25 samples from the Carpathian Foredeep succession. Additionally, results of 135 TOC content measurements, 141 Rock-Eval pyrolysis analyses and 27 vitrinite reflectance measurements were used to evaluate the regional distribution and depth trends for the entire Carpathian Foredeep. The thermal maturity of organic matter is between the immature part and peak of the oil window (Tmax = 413–448°C). Beneath the Western Carpathian Thrust Belt, the thermal maturity reaches higher values (Rr = 0.43–0.58%, Tmax = 429–448°C). The hydrocarbon generation potential is poor or fair, even if the total organic carbon values indicate good or even very good source rock potential. This is mainly due to the prevailing gas-prone Type III kerogen. The best source rocks were observed in the Miocene strata of the southern and central segments of the area discussed

Late Carboniferous palaeodepositional changes recorded by inorganic proxies and REE data from the coal-bearing strata: An example on the Czech part of the Upper Silesian Coal basin (USCB)

In the Czech Republic, coal-bearing siliciclastic sediments have been deposited during the Serpukhovian and Bashkirian (Carboniferous). Until now, no attention has been paid to inorganic geochemical assessment of the coals and associated non-coal rocks from the mixed shallow-marine to continental sediments (Ostrava Formation), and continental non-marine settings (Karviná Formation). Samples were collected from a 750 m deep coal exploration borehole at the ČSM Mine. The bulk parameters, total organic carbon TOC, total inorganic carbon TIC, total sulphur TS, major elements, trace elements, and REEs were measured on these samples, and their mineral associations have been investigated using microscopy combined with the principal component analysis (PCA). Common redox proxies V/Cr, U/Th, Ni/Co, Mo/U, and the ratio S/TOC have been tested on the samples to investigate their usefulness for studying anoxia. Research concludes that redox proxies such as U/Th, Ni/Co and V/Cr have been strongly influenced by the clastic input and carbonates, which it hinders for them to be reliable indicators of anoxia. On the basis of Eu anomaly and REEs distribution, the primary source of detrital elements comes from the parent rock, being governed more by physical than redox processes.The Dominik Vöröš' Postdoctoral Fellowship at INCAR, Spain was financially supported by a grant (Project No. MSM100462001), provided by the Czech Academy of Science within the Research and Mobility Support of Starting Researchers Programme.Peer reviewe