New approach to common removal of dioxins and NOx as a contribution to environmental protection

Meeting environmental limits represents the most important issue in the field of waste processing. Our primary effort consists either in eliminating hazardous emissions or in prevention of their production. However, this is not feasible in most cases therefore the so called secondary methods have to be applied. Technologies based on adsorption of hazardous compounds using activated carbon, deNOx/deDiox technologies as well as technology of catalytic filtration using a special material REMEDIA^® proved itself to be very efficient. The latter technology consists in using a baghouse with bags manufactured from a special material (two layers – membrane from ePTFE and felt with bound in catalyst) called REMEDIA^® which has successfully been used for removal of PCDD/F during recent period. However, it has been found that this technology can partially remove NOx as well. Based on our experience from operation industrial incineration plants it has been proved that even after more than three years' operation the activity of filtration material was not decreased and efficiency of dioxins removal from flue gas ranges from 97 to 99% (Pa?ízek et al., 2008).Based on industrial experience and new findings it has been decided to focus continuing research and development on deNOx experiments by applying SCR using the above mentioned efficient filtration material. This type of material is primarily designed for reduction of PMs and PCDD/F. Experiments with this filtration material should test possibilities for simultaneous reduction of PMs, PCDD/F and NOx. Tests are performed in MSW incineration plant utilizing new experimental unit and under standard conditions. Waste processing capacity of the incineration plant amounts to 15 t/h. Tests result in evaluation of overall reduction efficiency and negative factors that might influence the efficiency. Catalytic filtration is further compared to other types of deNOx methods.Thus we have obtained qualitatively new knowledge about this method the value of which is emphasized by full scale industrial testing.     

Invasion costs,impacts, and human agency: response to Sagoff 2020

Article impact statement: In an era of profound biodiversity crisis, invasion costs, invader impacts, and human agency should not be dismissed.     

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.     

Importance of fish gender as a factor in environmental monitoring of mercury

Total mercury concentrations were determined in the gonadal tissues of 15 female and 10 male European perch (Perca fluviatilis) from one location of the stream “Jevanský potok” located about 30 km from Prague (Czech Republic). Tissue samples were frozen at ?26 °C in polypropylene containers until further processing, which was carried out using an Advance Mercury Analyser (single purpose atomic absorption spectrometer). Mercury concentrations were present in all analysed gonad samples, and ranged from 2.3 to 12.7 μg/kg wet weight. However, we determined a mean Hg concentration (9.45 μg/kg) in male gonads that was 2.4 times greater than that of female gonads (3.9 μg/kg). This is an important finding when taking into account fish sex in environmental pollution monitoring (especially for mercury contamination).     

Uranium uptake by hydroponically cultivated crop plants

Hydroponicaly cultivated plants were grown on medium containing uranium. The appropriate concentrations of uranium for the experiments were selected on the basis of a standard ecotoxicity test. The most sensitive plant species was determined to be Lactuca sativa with an EC₅₀ value about 0.1 mM. Cucumis sativa represented the most resistant plant to uranium (EC₅₀ = 0.71 mM). Therefore, we used the uranium in a concentration range from 0.1 to 1 mM.Twenty different plant species were tested in hydroponic solution supplemented by 0.1 mM or 0.5 mM uranium concentration. The uranium accumulation of these plants varied from 0.16 mg/g DW to 0.011 mg/g DW. The highest uranium uptake was determined for Zea mays and the lowest for Arabidopsis thaliana. The amount of accumulated uranium was strongly influenced by uranium concentration in the cultivation medium. Autoradiography showed that uranium is mainly localized in the root system of the plants tested. Additional experiments demonstrated the possibility of influencing the uranium uptake from the cultivation medium by amendments. Tartaric acid was able to increase uranium uptake by Brassica oleracea and Sinapis alba up to 2.8 times or 1.9 times, respectively. Phosphate deficiency increased uranium uptake up to 4.5 times or 3.9 times, respectively, by Brassica oleracea and S. alba. In the case of deficiency of iron or presence of cadmium ions we did not find any increase in uranium accumulation.     

Synthesis of zirconia-immobilized copper chelates for catalytic decomposition of hydrogen peroxide and the oxidation of polycyclic aromatic hydrocarbons

Chelating sorbents with diethylenetriaminepenta(methylene-phosphonic acid) (DTPMPA) and ethylenediaminetetraacetic acid ligands immobilized on zirconia matrix were prepared and subsequently saturated with Cu(II). All the Cu chelates catalyzed decomposition of H(2)O(2) yielding highly reactive hydroxyl radicals. All of them were also able to catalyze degradation of polycyclic aromatic hydrocarbons (anthracene, benzo[a]pyrene and benzo[b]fluoranthene). The most effective DTPMPA-based catalysts G-32 and G-35 (10 mg ml(-1) with 100 mmol H(2)O(2)) caused almost complete decomposition of 15 ppm anthracene and benzo[a]pyrene during a five day catalytic cycle at 30 degrees C. Anthracene-1,4-dione was the main product of anthracene oxidation by all catalysts. The catalysts were active in several cycles without regeneration.     

Possible effects of persistent organochlorinated pollutants cocktail on thyroid hormone levels and pituitary-thyroid interrelations

In polluted district of Michalovce in East Slovakia (POLL) and two districts with background pollution (BCGR) 2046 adults (834 males and 1212 females aged 20-75 years) were examined. Serum levels of thyrotropin (TSH), free thyroxine (FT4), total triiodothyronine (TT3) and antithyroperoxidase antibodies (TPOab) were estimated by electrochemiluminiscent assay and also these of 15 polychlorinated biphenyl congeners (PCBs), p,p'-DDE, p,p'-DDT, hexachlorobenzene (HCB) and hexachlorocyclohexane were measured by high resolution gas chromatography/mass spectrometry. In addition, also dioxins, furans, coplanar- and mono-ortho-PCBs as well as selected hydroxylated and methylsulphonated PCBs and DDE metabolites were measured by appropriate methods based on gas chromatography/mass spectrometry principle. In POLL significantly higher levels of all organochlorines were found than these in BCGR. When pooled values from both areas were stratified in terms of PCBs level and treated as continuous variables, positive association of PCBs with FT4 and TT3 was found, the latter two being also mutually associated. However, within the category of PCBs level <530 ng/glipid (n=232) the association between PCBs and both the FT4 (p<0.09) and TT3 (p<0.03) was negative and any association of these was not found within the category of PCBs level of 531-1000 ng/g (n=691). In contrast, in the category of 531-2000 ng/g (n=1307) positive association appeared between PCBs and FT4 (p<0.001) as well as TT3 (p<0.05). Highly significant association of PCBs with FT4 (p<0.001) was further found in the categories with PCBs level of 1001-101414 ng/g (n=1307) and 2001-101414 (n=1123), while significant association with TT3 was observed only in the category of 531-2000 ng/g. Such findings suggest possible threshold level in positive effect of PCBs on FT4 and TT3 level which seems to be individual and located somewhere around the PCBs level of 1000 ng/g. However, highly significant negative association of both FT4 and TT3 with TSH was found in each of above indicated PCBs categories. Considerable difference in FT4 and TT3 level between large groups of subjects with the same range of PCBs level was also found suggesting different individual susceptibility to the effects of organochlorines. Among a total of 26 cases from POLL with very low TSH level (<0.5 mU l(-1)) 13 cases showed very high level of PCBs, FT4 and TT3, thus supporting a hypothesis on a novel sporadic form of high PCBs related peripheral subclinical hyperthyroidism possibly resulting from the long-term disruption of equilibrium between bound and free thyroxine in plasma by high PCBs level followed by a striking inhibition of TSH release from the pituitary.     

Ice (photo)chemistry. Ice as a medium for long-term (photo)chemical transformations--environmental implications

This review accounts for the current knowledge about the distribution, accumulation, and chemical/photochemical transformations of persistent, bioaccumulative, and toxic compounds (PBTs) in water ice, especially in the connection with polar regions and atmospheric cloud particles. (Photo)reactions on/in ice are discussed in terms of photochemistry, photobiology, paleochemistry, as well as astrophysics. Authors propose a model, in which a significant amount of some PBTs are generated by (photo)chemistry of primary pollutants in ice, which may subsequently be released to the environment. It is argued that ice photochemistry might play an important role in the chemical transformations in cold ecosystems and in the upper atmosphere, particularly now when the ozone layer is partially depleted.     

Separating habitat invasibility by alien plants from the actual level of invasion

Habitats vary considerably in the level of invasion (number or proportion of alien plant species they contain), which depends on local habitat properties, propagule pressure, and climate. To determine the invasibility (susceptibility to invasions) of different habitats, it is necessary to factor out the effects of any confounding variables such as propagule pressure and climate on the level of invasion. We used 20 468 vegetation plots from 32 habitats in the Czech Republic to compare the invasibility of different habitats. Using regression trees, the proportion of alien plants, including archaeophytes (prehistoric to medieval invaders) and neophytes (recent invaders), was related to variables representing habitat properties, propagule pressure, and climate. The propagule pressure was expressed as the proportion of surrounding urban and industrial or agricultural land, human population density, distance from a river, and history of human colonization in the region. Urban and industrial land use had a positive effect on the proportion of both archaeophytes and neophytes. Agricultural land use, higher population density, and longer history of human impact positively affected the proportion of archaeophytes. Disturbed human-made habitats with herbaceous vegetation were most invaded by both groups of aliens. Neophytes were also relatively common in disturbed woody vegetation, such as broad-leaved plantations, forest clearings, and riverine scrub. These habitats also had the highest proportion of aliens after removing the effect of propagule pressure and climate, indicating that they are not only the most invaded, but also most invasible. These habitats experience recurrent disturbances and are rich, at least temporarily, in available nutrients, which supports the hypothesis that fluctuating resources are the major cause of habitat invasibility. The least invaded habitats were mires and alpine-subalpine grasslands and scrub. After removing the effect of propagule pressure and climate, some habitats actually invaded at an intermediate level had very low proportions of aliens. This indicates that these habitats (e.g., dry, wet, and saline grasslands, base-rich fens, and broad-leaved deciduous woodlands) are resistant to invasion.