Occurrence and morphology of pyrite in Bulgarian coals

Coals with different degrees of coalification (ranging from lignite to anthracite) from seven Bulgarian coal basins have been investigated. The forms of pyrite and their distribution have been established. The types found are: massive pyrite, represented by the homogeneous, cluster-like and microconcretionary varieties; framboidal pyrite, appearing in inorganic and bacterial forms; euhedral pyrite, which is either isolated or clustered; anhedral pyrite, in its infilling and replacement varieties; and infiltrational pyrite, as a replacement or infilling mineral.Most of the forms of the euhedral, framboidal and massive pyrite developed during peat deposition. The anhedral replacement pyrite formed in the peat bed during early diagenesis. Infiltrational pyrite filled fractures and cleats formed during the diagenesis, catagenesis and metagenesis.Both similarities and differences with respect to the distribution of the pyrite types have been determined between coals of different ranks from Bulgarian coal basins. These differences are due to: the presence of Fe and S in the rocks adjacent to ancient peat bogs; the activities of ground and surface waters which brought Fe and S into the peat bogs; the geochemical character (pH and Eh) of the peat bogs and the sulphur bacteria development; and the tectonic situation during diagenesis, catagenesis and metagenesis.     

Reduced sulfur species in a stratified seawater lake (Rogoznica Lake, Croatia); seasonal variations and argument for organic carriers of reactive sulfur

Over a period of a year, Hg⁰-reactive, total reduced sulfur species (RSS_T), as well as a non-volatile fraction that cannot be gas-stripped at pH ∼2 (RSS_NV), have been measured by voltammetry in a stratified, saline lake. In the hypolimnion, RSS_T is dominated by unusually high (up to 5 mM) dissolved divalent sulfur (S^−II), present as H₂S + HS⁻ and as inorganic polysulfides (H_xS_n^x−2). Less abundant RSS_NV is attributed to dissolved zero-valent sulfur (S⁰) in inorganic polysulfides. Assuming negligible contribution of organic S⁰ species in the hypolimnion, the equilibrium distribution of polysulfide ions is calculated; S₅²⁻ is found to predominate. In the epilimnion, all RSS_T consists of RSS_NV within analytical uncertainty. Through spring and summer, RSS_T and RSS_NV display little vertical or seasonal variation, but they increase dramatically when stratification breaks down in autumn. Based on decay rate, RSS during mixing events is attributed to dissolved S₈ from oxidation of sulfide and decomposition of inorganic polysulfides. This hypothesis quantitatively predicts precipitation of elemental sulfur in a year when colloidal sulfur was observed and predicts no precipitation in a year when it was not observed. Except during mixing events, the entire water column is undersaturated with respect to both rhombic sulfur and biologic sulfur, and the limited variations of RSS exclude hydrophobic and volatile aqueous S₈ as a major species. During such periods, RSS (typically 8 nM) may be associated with organic carbon, perhaps as adsorbed S₈ or as covalently bound polysulfanes or polysulfides. The hypolimnion is viewed as a zero-valent sulfur reactor that creates S⁰-containing, dissolved organic macromolecules during stable stratification periods. Some are sufficiently degradation-resistant and hydrophilic to be dispersed throughout the lake during mixing events, subsequently giving rise to ∼10⁻⁸ M RSS in the oxic water column. Voltammetrically determined RSS in oxic natural waters has often been described as “sulfide” or “metal complexed sulfide”, implying an oxidation state of S^−II; we argue that RSS in oxic Rogoznica Lake waters is mainly S⁰.     

Applying size segregation to relate the surrounding aerosol pollution to its source

Size segregated sampling of aerosol particles at the coal-fired power station Šoštanj, Slovenia was performed by a newly developed system. In addition, simultaneous sampling of particles was performed at two locations, Velenje and Veliki vrh, chosen on the basis of long term monitoring of SO₂ in the influential area of power plant. The signature of the power plant (e.g. characteristic size distributions of some typical trace elements) was identified. For elements, like As, Mo, Cd and Ga, which are typical for coal combustion, the highest concentrations were observed in the size range between 1 and 4 μm. For Se and sometimes for Ga two modes were identified, first between 0.1 and 0.5 μm and second between 1 and 4 μm. Ratios between the average concentrations of selected elements in fine and coarse particles collected at Veliki vrh (the most influenced location) and Velenje (usually not influenced by the thermo power station) were significantly higher than 1 in the case of Mo and Se for coarse and fine size range, while for As the ratio was higher than 1 for the coarse fraction. Consequently, Mo, Se and As were found as the most important tracers for the emissions from the investigated source. On the basis of the ratios between the concentrations of elements measured in particles at low and high SO₂ concentrations at Veliki vrh, Cd was shown to be a typical tracer as well. Our results definitely showed that size segregated measurements of particles at the source and in the influenced area give more precise information on the influence of source to the surrounding region. It was found that patterns of size distributions for typical trace elements observed at the source are found also in the influenced area, i.e. Veliki vrh.     

Mercury cycling during acid rain recovery at the forested Lesní potok catchment,Czech Republic

From 2011 to 2019, mercury (Hg) stores and fluxes were studied in the small forested catchment Lesní potok (LES) in the central Czech Republic using the watershed mass balance approach together with internal measurements. Mean input fluxes of Hg via open bulk deposition, beech throughfall and spruce throughfall during the periodwere 2.9, 3.9 and 7.6 μg m⁻² year⁻¹, respectively. These values were considerably lower than corresponding deposition Hg fluxes reported in the early years of the 21st century from catchments in Germany. Current bulk precipitation inputs at unimpacted Czech mountainous sites were lower than those in Germany. The largest Hg inputs to the catchment were via litterfall, averaging 22.6 and 17.8 μg m⁻² year⁻¹ for beech and spruce stands. The average Hg input, based on the sum of mean litterfall and throughfall deposition, was 23.0 μg m⁻² year⁻¹, compared to the estimated Hg output in runoff of 0.5 μg m⁻² year⁻¹, which is low compared to other reported values. Thus, only ~2% of Hg input is exported in stream runoff. Stream water Hg was only weakly related to dissolved organic carbon (DOC) but both concentrations were positively correlated with water temperature. The estimated total soil Hg pool averaged 47.5 mg m⁻², only 4% of which was in the O-horizon. Thus Hg in the O-horizon pool represents 72 years of deposition at the current input flux and 3800 years of export at the current runoff flux. Age-dating by ¹⁴C suggested that organic soil contains Hg from recent deposition, while mineral soil at 40–80 cm depth contained 4400-year old carbon, suggesting the soil had accumulated atmospheric Hg inputs through millennia to reach the highest soil Hg pool of the soil profile. These findings suggest that industrial era intensification of the Hg cycle is superimposed on a slower-paced Hg cycle during most of the Holocene.     

Origin of natural waters and gases within the Upper Carboniferous coal-bearing and autochthonous Miocene strata in South-Western part of the Upper Silesian Coal Basin,Poland

The molecular and stable isotope compositions of coalbed gases from the Upper Carboniferous strata and natural gases accumulated within the autochthonous Upper Miocene Skawina Formation of the D?bowiec-Simoradz gas deposit were determined, as well as the chemical and stable isotope compositions of waters from the Skawina Formation and waters at the top of the Upper Carboniferous strata of the Kaczyce Ridge (the abandoned “Morcinek” coal mine) in the South-Western part of the Upper Silesian Coal Basin. Two genetic types of natural gases within the Upper Carboniferous coal-bearing strata were identified: thermogenic (CH₄, small amounts of higher gaseous hydrocarbons, and CO₂) and microbial (CH₄, very small amounts of ethane, and CO₂). Thermogenic gases were generated during the bituminous stage of coalification and completed at the end of the Variscan orogeny. Degassing (desorption) of thermogenic gases began at the end of late Carboniferous until the late Miocene time-period and extended to the present-day. This process took place in the Upper Carboniferous strata up to a depth of about 550 m under the sealing Upper Miocene cover. A primary accumulation zone of indigenous, thermogenic gases is present below the degassing zone. Up to 200 m depth from the top of the Upper Carboniferous strata, within the weathered complex, an accumulation zone of secondary, microbial gas occurs. Waters within these strata are mainly of meteoric origin of the infiltration period just before the last sea transgression in the late Miocene and partly of marine origin having migrated from the Upper Miocene strata. Then, both methanogenic archaebacteria and their nutrients were transported by meteoric water into the near-surface Carboniferous strata where the generated microbial CH₄ saturated coal seams. Waters within the Miocene strata of the D?bowiec-Simoradz and Zab?ocie are of marine origin, and natural gases accumulated within autochthonous Miocene strata of the D?bowiec-Simoradz gas deposit were most probably generated by microbial processes of on organic matter dispersed within the strata, though some contribution of gases migrating from the Carboniferous coal-bearing strata cannot be excluded.     

Mercury capture by selected Bulgarian fly ashes: Influence of coal rank and fly ash carbon pore structure on capture efficiency

Mercury capture by fly ash C was investigated at five lignite- and subbituminous-coal-burning Bulgarian power plants (Republika, Bobov Dol, Maritza East 2, Maritza East 3, and Sliven). Although the C content of the ashes is low, never exceeding 1.6%, the Hg capture on a unit C basis demonstrates that the low-rank-coal-derived fly ash carbons are more efficient in capturing Hg than fly ash carbons from bituminous-fired power plants. While some low-C and low-Hg fly ashes do not reveal any trends of Hg versus C, the 2nd and, in particular, the 3rd electrostatic precipitator (ESP) rows at the Republika power plant do have sufficient fly ash C range and experience flue gas sufficiently cool to capture measurable amounts of Hg. The Republika 3rd ESP row exhibits an increase in Hg with increasing C, as observed in other power plants, for example, in Kentucky power plants burning Appalachian-sourced bituminous coals. Mercury/C decreases with an increase in fly ash C, suggesting that some of the C is isolated from the flue gas stream and does not contribute to Hg capture. Mercury capture increases with an increase in Brunauer-Emmett-Teller (BET) surface area and micropore surface area. The differences in Hg capture between the Bulgarian plants burning low-rank coal and high volatile bituminous-fed Kentucky power plants suggests that the variations in C forms resulting from the combustion of the different ranks also influence the efficiency of Hg capture.     

Properties and depositional environment of the Neogene Elhovo Lignite, Bulgaria

Several Mio-Pliocene aged lignite seams occur as part of a non-marine transgressive sequence in the Elhovo graben in south-eastern Bulgaria. The present study is focused on 45 samples collected from three boreholes in the eastern part of the basin. Petrographic data along with ash and sulphur contents were used in order to determine the lateral and vertical variations of the coal facies and depositional environment of the Elhovo lignite.The lignite seams accumulated in a rheotrophic, low-lying mire with high pH value and are characterized by high ash yields and sulphur contents. Despite of the neutral to weakly alkaline environment the bacterial activity was limited and the tissue preservation and gelification were mainly controlled by the redox conditions.Vegetation rich in decay resistant conifers dominated in the Elhovo basin together with mesophytic angiosperm species. The absence of algal remains and sapropelic coal indicated that open water areas were not present during peat accumulation. The latter processed in an environment, characterized by low subsidence rate, in which prior to the burial the woods were subjected to severe mechanical destruction. According to our interpretation, the enhanced impregnation of the tissues bacteria and fungi played only a secondary role in the process of humification. The lignite from borehole 122 and partly from BH 145 deposited in an environment characterized by relatively low (ground)water table, whereas to the south an area dominated by a flooded forest swamp (BH 104) formed. This is suggested by the better tissue preservation and gelification of the organic matter in BH 104. The vertical variation of the maceral composition in the studied lignite is interpreted as a consequence of vegetational changes, rather than to changes in the depositional environment. The low contents of inertinite macerals indicate that despite of the low water level the environment was relatively wet and the thermal and oxidative destruction of the tissues was limited.Peat accumulation was terminated by a major flooding event and a short term establishment of a lake. In contrast to the West Maritsa basin, no seam formed in the Elhovo basin during the filling stage of the lake.     

Late Cretaceous porphyry Cu and epithermal Cu–Au association in the Southern Panagyurishte District,Bulgaria: the paired Vlaykov Vruh and Elshitsa deposits

Vlaykov Vruh–Elshitsa represents the best example of paired porphyry Cu and epithermal Cu–Au deposits within the Late Cretaceous Apuseni–Banat–Timok–Srednogorie magmatic and metallogenic belt of Eastern Europe. The two deposits are part of the NW trending Panagyurishte magmato-tectonic corridor of central Bulgaria. The deposits were formed along the SW flank of the Elshitsa volcano-intrusive complex and are spatially associated with N110-120-trending hypabyssal and subvolcanic bodies of granodioritic composition. At Elshitsa, more than ten lenticular to columnar massive ore bodies are discordant with respect to the host rock and are structurally controlled. A particular feature of the mineralization is the overprinting of an early stage high-sulfidation mineral assemblage (pyrite ± enargite ± covellite ± goldfieldite) by an intermediate-sulfidation paragenesis with a characteristic Cu–Bi–Te–Pb–Zn signature forming the main economic parts of the ore bodies. The two stages of mineralization produced two compositionally different types of ores—massive pyrite and copper–pyrite bodies. Vlaykov Vruh shares features with typical porphyry Cu systems. Their common geological and structural setting, ore-forming processes, and paragenesis, as well as the observed alteration and geochemical lateral and vertical zonation, allow us to interpret the Elshitsa and Vlaykov Vruh deposits as the deep part of a high-sulfidation epithermal system and its spatially and genetically related porphyry Cu counterpart, respectively. The magmatic–hydrothermal system at Vlaykov Vruh–Elshitsa produced much smaller deposits than similar complexes in the northern part of the Panagyurishte district (Chelopech, Elatsite, Assarel). Magma chemistry and isotopic signature are some of the main differences between the northern and southern parts of the district. Major and trace element geochemistry of the Elshitsa magmatic complex are indicative for the medium- to high-K calc-alkaline character of the magmas. ⁸⁷Sr/⁸⁶Sr_(i) ratios of igneous rocks in the range of 0.70464 to 0.70612 and ¹⁴³Nd/¹⁴⁴Nd_(i) ratios in the range of 0.51241 to 0.51255 indicate mixed crustal–mantle components of the magmas dominated by mantellic signatures. The epsilon Hf composition of magmatic zircons (+6.2 to +9.6) also suggests mixed mantellic–crustal sources of the magmas. However, Pb isotopic signatures of whole rocks (²⁰⁶Pb/²⁰⁴Pb = 18.13–18.64, ²⁰⁷Pb/²⁰⁴Pb = 15.58–15.64, and ²⁰⁸Pb/²⁰⁴Pb = 37.69–38.56) along with common inheritance component detected in magmatic zircons also imply assimilation processes of pre-Variscan and Variscan basement at various scales. U–Pb zircon and rutile dating allowed determination of the timing of porphyry ore formation at Vlaykov Vruh (85.6 ± 0.9 Ma), which immediately followed the crystallization of the subvolcanic dacitic bodies at Elshitsa (86.11 ± 0.23 Ma) and the Elshitsa granite (86.62 ± 0.02 Ma). Strontium isotope analyses of hydrothermal sulfates and carbonates (⁸⁷Sr/⁸⁶Sr = 0.70581–0.70729) suggest large-scale interaction between mineralizing fluids and basement lithologies at Elshitsa–Vlaykov Vruh. Lead isotope compositions of hydrothermal sulfides (²⁰⁶Pb/²⁰⁴Pb = 18.432–18.534, ²⁰⁷Pb/²⁰⁴Pb = 15.608–15.647, and ²⁰⁸Pb/²⁰⁴Pb = 37.497–38.630) allow attribution of ore-formation in the porphyry and epithermal deposits in the Southern Panagyurishte district to a single metallogenic event with a common source of metals.