Geochemical and mineralogical characterization of a neutral, low-sulfide/high-carbonate tailings impoundment, Markušovce, eastern Slovakia

Tailings deposits generated from mining activities represent a potential risk for the aquatic environment through the release of potentially toxic metals and metalloids occurring in a variety of minerals present in the tailings. Physicochemical and mineralogical characteristics of tailings such as total concentrations of chemical elements, pH, ratio of acid-producing to acid-neutralizing minerals, and primary and secondary mineral phases are very important factors that control the actual release of potentially toxic metals and metalloids from the tailings to the environment. The aims of this study are the determination of geochemical and mineralogical characteristics of tailings deposited in voluminous impoundment situated near the village of Marku?ovce (eastern Slovakia) and identification of the processes controlling the mobility of selected toxic metals (Cu, Hg) and metalloids (As, Sb). The studied tailings have unique features in comparison with the other tailings investigated previously because of the specific mineral assemblage primarily consisting of barite, siderite, quartz, and minor sulfides. To meet the aims, samples of the tailings were collected from 3 boreholes and 15 excavated pits and subjected to bulk geochemical analyses (i.e., determination of chemical composition, pH, Eh, acid generation, and neutralization potentials) combined with detailed mineralogical characterization using optical microscopy, X-ray diffraction (XRD), electron microprobe analysis (EMPA), and micro-X-ray diffraction (μ-XRD). Additionally, the geochemical and mineralogical factors controlling the transfer of potentially toxic elements from tailings to waters were also determined using short-term batch test (European norm EN 12457), sampling of drainage waters and speciation–equilibrium calculations performed with PHREEQC. The tailings mineral assemblage consists of siderite, barite, quartz, and dolomite. Sulfide minerals constitute only a minor proportion of the tailings mineral assemblage and their occurrence follows the order: chalcopyrite?>?pyrite?>?tetrahedrite?>?arsenopyrite. The mineralogical composition of the tailings corresponds well to the primary mineralization mined. The neutralization capacity of the tailings is high, as confirmed by the values of neutralization potential to acid generation potential ratio, ranging from 6.7 to 63.9, and neutral to slightly alkaline pH of the tailings (paste pH 7.16–8.12) and the waters (pH 7.00–8.52). This is explained by abundant occurrence of carbonate minerals in the tailings, which readily neutralize the acidity generated by sulfide oxidation. The total solid-phase concentrations of metal(loid)s decrease as Cu?>?Sb?>?Hg?>?As and reflect the proportions of sulfides present in the tailings. Sulfide oxidation generally extends to a depth of 2 m. μ-XRD and EMPA were used to study secondary products developed on the surface of sulfide minerals and within the tailings. The main secondary minerals identified are goethite and X-ray amorphous Fe oxyhydroxides and their occurrence decreases with increasing tailings depth. Secondary Fe phases are found as mineral coatings or individual grains and retain relatively high amounts of metal(loid)s (up to 57.6 wt% Cu, 1.60 wt% Hg, 23.8 wt% As, and 2.37 wt% Sb). Based on batch leaching tests and lysimeter results, the mobility of potentially toxic elements in the tailings is low. The limited mobility of metals and metalloids is due to their retention by Fe oxyhydroxides and low solubilities of metal(loid)-bearing sulfides. The observations are consistent with PHREEQC calculations, which predict the precipitation of Fe oxyhydroxides as the main solubility-controlling mineral phases for As, Cu, Hg, and Sb. Waters discharging from tailings impoundment are characterized by a neutral to slightly alkaline pH (7.52–7.96) and low concentrations of dissolved metal(loid)s (<5–7.0 μg/L Cu, <0.1–0.3 μg/L Hg, 5.0–16 μg/L As, and 5.0–43 μg/L Sb). Primary factors influencing aqueous chemistry at the site are mutual processes of sulfide oxidation and carbonate dissolution as well as precipitation reactions and sorption onto hydrous ferric oxides abundantly present at the discharge of the impoundment waters. The results of the study show that, presently, there are no threats of acid mine drainage formation at the site and significant contamination of natural aquatic ecosystem in the close vicinity of the tailings impoundment.     

Long-term investigations of post-Chernobyl radiocaesium in fallout and air in North Croatia

The long-term behaviour of (137)Cs activity concentrations in air and fallout has been studied in the city of Zagreb for the post-Chernobyl period (1986-2006) as a part of an extended monitoring program of radioactive contamination of human environment in Croatia. Annual mean (137)Cs activity concentrations in air and annual total deposition fluxes (wet plus dry) decreased from 2.8 x 10(-4) Bq m(-3) in September 1986 to 3.0 x 10(-6) Bq m(-3) in last quarter of 2006 and from 6,410 Bq m(-2) year(-1) in 1986 to 2 Bq m(-2) year(-1) in 2006 respectively. By fitting the measured (137)Cs activity concentrations to the theoretical curve the ecological half-lives of (137)Cs in air and fallout were estimated with respective values of 0.46 and 0.54 years for immediate post-Chernobyl period, increasing to 5.52 and 3.97 years afterwards. Using the data on (137)Cs activity concentrations in air and fallout total caesium deposition velocity of (3.34 +/- 3.13) x 10(-2) ms(-1) was estimated with median value being 2.13 x 10(-2) ms(-1). Such relatively high (137)Cs deposition velocities compared with pre-Chernobyl ones, are characteristic for the post-Chernobyl period and, according to Stokes' settling law, indicate that the diameters of aerosol particles associated with (137)Cs originated from the Chernobyl accident are pretty large, i.e. >1 microm. (134)Cs/(137)Cs activity ratio in fallout and in air has been found to be similar to the theoretically predicted values, initial value being about 0.5 and decreasing according to differential radioactive decay. The similar ratio has been observed in most of the other environmental samples.     

Uptake of Cd,Pb, U,and Zn by plants in floodplain pollution hotspots contributes to secondary contamination

Environmental Science and Pollution Research - Willows, woody plants of genus Salix common in floodplains of temperate regions, act as plant pumps and translocate the Cd and Zn in the soil profiles...     

A biochar-based medium in the biofiltration system: Removal efficiency,microorganism propagation,and the medium penetration modeling

Biofiltration is a method of biological treatment belonging to cleaner technologies because it does not produce secondary air pollutants, but helps to integrate natural processes in microorganisms for decomposing volatile air pollutants and solving odor problems. The birch wood biochar has been chosen as a principal material for biofilter bed medium. The experiments were conducted at the temperatures of 24, 28, and 32 °C, while the concentration of acetone, xylene, and ammonium reached 300 mg/m³ and the flow rate was 100 m³/hr. Before passing through the stage of the experimental research into the packing material inside biofilters, microorganisms were introduced. Four strains of microorganisms (including micromycetes Aspergillus versicolor BF-4 and Cladosporium herbarum 7KA, as well as yeast Exophiala sp. BF1 and bacterium Bacillus subtilis B20) were selected. At the inlet loading rate of 120 g/m³/hr, the highest elimination capacity of xylene in the biochar-based biofilter with the inoculated medium was 103 g/m³/hr, whereas that of ammonia was 102 g/m³/hr and that of acetone was 97 g/m³/hr, respectively. The maximum removal efficiency reached 86%, 85%, and 81%, respectively. The temperature condition (though characterized by some rapid changes) can hardly have a considerable influence on the biological effect (i.e., microbiological activity) of biofiltration; however, it can cause the changes in physical properties (e.g., solubility) of the investigated compounds.

Implications: The birch biochar can be successfully used in the biofiltration system for propagation of inoculated microorganisms, biodegrading acetone, xylene, and ammonia. At the inlet loading rate of 120 g/m³/hr, the highest elimination capacity of xylene was 103 g/m³/hr, that of ammonia was 102 g/m³/hr, and that of acetone was 97 g/m³/hr, respectively. The morphological structure of biochar can be affected by the aggressive air contaminants, causing the change in the medium specific surface area, which is one of the factors controlling the biofilter performance. Although biological effects in biofiltration are typically considered to be more important than physical effects, the former may be more important for compounds with high Henry’s Law coefficient values, and the biofilter design should thus provide conditions for better compound absorption.     

Influence of a nickel smelter plant on the mineralogical composition of attic dust in the Tikveš Valley, Republic of Macedonia

Mineral phases and their content were determined in attic dust samples collected from 27 houses in the Tikve? Valley, Republic of Macedonia. By using quantitative X-ray diffraction, the principal mineral phases were determined to be the serpentinite group (chrysotile, lizardite) and amphibole group of minerals (ribecite, tremolite, actinolite) present in the attic dust samples from this region which are not common constituents of urban dust. Strong correlations existed between these mineral phases in the dust and those in ores processed at a ferronickel smelter plant situated in this region. Spatial distributions of specific mineral phases were made and were consistent with wind directions and predicted deposition (60–70 %) of dust emitted from the metallurgical plant.     

Terrestrial Biodiversity Analyses in Dalmatia (Croatia): A Complementary Approach Using Diversity and Rarity

Here we present the methodology used for terrestrial biodiversity analysis and site selection in Phase B of the UNDP/GEF COAST project. The analysis was focused on the problem of biodiversity evaluation in four Croatian counties stretching from sea level to the highest mountain in Croatia. Data on habitats, vascular flora, and fauna (mammals, birds, reptiles, amphibians, butterflies, ground beetles, and underground invertebrates) were collected and analyzed for each of the four counties. Emphasis was given to the richness of endangered species and the rarity of endemic species. Based on the spatial analyses of habitat, fauna, and flora data, four to six areas were selected from each county and ranked according to their biodiversity importance. Overlap between areas important for richness and those important for rarity was highest for data on flora (65.5%) and lowest for data on fauna (16.7%). When different data sets were compared, the lowest overlap was between flora and fauna (17.1%) and largest between fauna and habitats (23.9%). Simultaneous overlap among all three data sets was found in just 6.5% of the overall selected areas. These results suggest that less specific data, with respect to taxa threat status, could better serve as surrogate data in estimating overall biodiversity. In summary, this analysis has demonstrated that Dalmatia is a region with a high overall biodiversity that is important in a broader European context.     

Air dispersion of heavy metals in the vicinity of the As-Sb-Tl abounded mine and responsiveness of moss as a biomonitoring media in small-scale investigations

A systematic study was carried out to investigate air deposition and to explore the natural distribution and enrichment (contamination) with trace elements in the small area (cca. 13 km²) of an antimony-arsenic-thallium mineralization outcrop at an abandoned mine “Allchar.” The mine is located on the northwestern part of Ko?uf Mount, Republic of Macedonia. The locality of Allchar is unique in its mineral composition; besides a very intriguing mineral, lorandite, there are 45 other minerals, some of which are rare. The distribution of 53 elements (with special attention to As, Sb, and Tl) were detected in 69 moss samples from eight various species collected from this area. Moss samples were analyzed following microwave digestion by inductively coupled plasma–mass spectrometry and inductively coupled plasma–atomic emission spectrometry. It was found that the atmospheric deposition for As in the moss samples on or around the Allchar mine is >6.5 times higher and for Tl is 19 times higher compared to values for the samples from the rest of the Allchar area. By the application of multivariate cluster and R-mode factor analyses (FA), five geochemical associations were determined. Cluster and R-mode FA were used to identify and characterize element associations, and five associations of elements were determined by the method of multivariate statistics. F1 (Co, Cr, Fe, Sc, Li, V, Ga, Y, Ni, Mn, Al, La-Lu, Cu, Ge, Be, Bi, and Hf); F2 (As, Tl, Sb, and Mg); F3 (Rb, Cs, and Mo); F4 (Sr, Ba, Hf, Zr, La-Lu, and Bi), and F5 (Cd, Zn, Ag, and Cu).     

Non-invasive prenatal testing (NIPT): Combination of copy number variant and gene analyses using an “in-house” target enrichment next generation sequencing—Solution for non-centralized NIPT laboratory?

Objective

Recent studies have integrated copy number variant (CNV) and gene analysis using target enrichment. Here, we transferred this concept to our routine genetics laboratory, which is not linked to centralized non-invasive prenatal testing (NIPT) facilities.

Method

From a cohort of 100 pregnant women, 22 were selected for the analysis of maternal genomic DNA (gDNA) along with fetal cell-free DNA. Using targeted enrichment, 135 genes were analyzed, combined with aberrations of chromosomes 21, 18, 13, X, and Y. The data were subjected to specificity and sensitivity analyses, and correlated with the results from invasive testing methods.

Results

The sensitivity/specificity was determined for the CNV analysis of chromosomes: 21 (80%/75%), 18 (-/82%), 13 (100%/67%), and Y (100%/100%). The gene detection was valid for maternal gDNA. However, for cell-free fetal DNA, it was not possible to determine the boundary between an artifact and a real sequence variant.

Conclusion

The target enrichment method combining CNV and gene detection seems feasible in a regular laboratory. However, this method can only be responsibly optimized with a sufficient number of controls and further validation on a strong bioinformatic background. The present results showed that NIPT should be performed in specialized centers, and that its introduction to isolated laboratories may not provide valid data.     

Catalytic gasification of tars from a dumping site

The work deals with catalytic gasification, pyrolysis and non-catalytic gasification of tar from an industrial dumping site. All experiments were carried out in a vertical stainless steel gasification reactor at 800 °C. Crushed calcined dolomite was used as the gasification catalyst. Parameters such as addition of water and air, and the influence of the catalyst in regard to the composition of the process gas were investigated. The catalytic gasification experiment in the steady state produced process gas with the composition: 56 % of H₂, 9 % of CO, 11 % of CH₄ and 12 % of CO₂ (mol.%). Concentration of the C₂ fraction was lower than 1 mol.%. Volume flow of air was later changed from 120 to 230 ml min^?1 reducing the amount of hydrogen to 51 mol.% and that of methane to 10 mol.%. Process gas created in a non-catalytic gasification process contained 26–30 mol.% of methane, 13–15 mol.% of carbon monoxide and 15–17 mol.% of the C₂ fraction and lower amounts of hydrogen (20 mol.%) and carbon dioxide (2–3 mol.%). The highest apparent conversion of tar was reached in the catalytic gasification processes. A higher rate of catalyst deactivation can be observed when water or air is not added.     

Fluxes and Loading of Heavy Metals, Benzo[a]pyrene and Oil Products in Vilnius City

The concentrations of heavy metals Pb, Cd, Cu, Zn and Hg, benzo[a]pyrene and oil products (C₁₅–C₂₈) in bulk (wet and dry) atmospheric deposition in Vilnius city in 2005–2006 were analysed. The highest flux to the ground surface of the city residential area, reaching 1,680 mg m^?2 year^?1, was determined for oil products, which in atmospheric bulk deposition was estimated to be mainly in the form of solid sediments. Among heavy metals, the highest flux was determined for Zn (113.5 mg m^?2 year^?1), while the lowest flux was determined for Hg (0.06 mg m^?2 year^?1). The flux of investigated pollutants ranges from a few times, or for some pollutants, up to one order of magnitude higher at the urban sampling site in comparison to residential or background sites. Some hundred tons of oil products, approximately 52 tons of zinc and a considerably lower amount of mercury, benzo[a]pyrene and cadmium deposit yearly to the ground and water surface of Vilnius city. Metallic constructions related to transport and buildings, automobile exhausts, spills of fuel and lubricants are suggested to be the factors which result in the accumulation of high amounts of heavy metals, oil products and other pollutants on the ground surface of the city.