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.     

Removal and seasonal variability of selected analgesics/anti-inflammatory,anti-hypertensive/cardiovascular pharmaceuticals and UV filters in wastewater treatment plant

Seasonal removal efficiency of 16 pharmaceuticals and personal care products was monitored in a wastewater treatment plant in ?eské Budějovice, Czech Republic, over a period of 1 year (total amount of samples, n?=?272). The studied compounds included four UV filters, three analgesics/anti-inflammatory drugs and nine anti-hypertensive/cardiovascular drugs. In most cases, elimination of the substances was incomplete, and overall removal rates varied strongly from ?38 to 100 %. Therefore, it was difficult to establish a general trend for each therapeutic group. Based on the removal efficiencies (REs) over the year, three groups of target compounds were observed. A few compounds (benzophenon-1, valsartan, isradipine and furosemide) were not fully removed, but their REs were greater than 50 %. The second group of analytes, consisting of 2-phenylbenzimidazole-5-sulfonic acid, tramadol, sotalol, metoprolol, atenolol and diclofenac, showed a very low RE (lower than 50 %). The third group of compounds showed extremely variable RE (benzophenon-3 and benzophenon-4, codeine, verapamil, diltiazem and bisoprolol). There were significant seasonal trends in the observed REs, with reduced efficiencies in colder months.     

Root uptake of atenolol,sulfamethoxazole and carbamazepine,and their transformation in three soils and four plants

Soils can be contaminated by pharmaceuticals. The aim of this study was to evaluate the impact of soil conditions (influencing sorption and persistence of pharmaceuticals in soils) and plant type on the root uptake of selected pharmaceuticals and their transformation in plant-soil systems. Four plants (lamb’s lettuce, spinach, arugula, radish) planted in 3 soils were irrigated for 20 days (26) with water contaminated by one of 3 pharmaceuticals (carbamazepine, atenolol, sulfamethoxazole) or their mixture. The concentrations of pharmaceuticals and their metabolites in soils and plant tissues were evaluated after the harvest. Sulfamethoxazole and atenolol dissipated rapidly from soils. The larger concentrations of both compounds and an atenolol metabolite were found in roots than in leaves. Sulfamethoxazole metabolites were below the limits of quantifications. Carbamazepine was stable in soils, easily uptaken, accumulated, and metabolized in plant leaves. The efficiency of radish and arugula (both family Brassicaceae) in metabolizing was very low contrary to the high and moderate efficiencies of lamb’s lettuce and spinach, respectively. Compounds’ transformations mostly masked the soil impact on their accumulation in plant tissues. The negative relationships were found between the carbamazepine sorption coefficients and its concentrations in roots of radish, lamb’s lettuce, and spinach.

     

Investigation of PCDD/Fs and dl-PCBs in fish from the southern Baltic Sea during the 2002–2006 period

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dl-PCBs) in the southern Baltic herring (Clupea harengus), sprat (Sprattus sprattus), and salmon (Salmo salar) are reported.The significant interspecies and season-specific differences in PCDD/Fs and dl-PCBs concentrations were observed. The contribution of dl-PCBs to the total toxicity equivalents (TEQs) ranged between 50% and 70%, dependently on fish species. In all samples, concentrations of PCDF were higher in comparison with that of PCDD.The permissible limits of the content of PCDD/Fs and dl-PCBs (8 pg g⁻¹ fresh weight for the sum of PCDD/Fs and dl-PCBs, and 4 pg g⁻¹ fresh weight for the PCDD/Fs) were exceeded mainly in salmon samples (in 80% of salmon samples studied). The elevated levels of PCDD/F and dl-PCB were observed only in two of seventy two herring samples, and in ten of 62 sprat samples.The multiple regression analysis revealed that fish lipid content, and concentration of PCB 153, used simultaneously, might be useful in the prediction of TEQ values of fish samples. These two variables explained more than 80% of total variance. For all fish species studied, the correlation coefficients obtained with the multiple regression analysis were higher than that obtained with the regression analysis involving total TEQ values, and only one independent variable: fish lipid content.     

Interactions of bacteria and fungi on decomposing litter: differential extracellular enzyme activities

Fungi and bacteria are key agents in plant litter decomposition in freshwater ecosystems. However, the specific roles of these two groups and their interactions during the decomposition process are unclear. We compared the growth and patterns of degradative enzymes expressed by communities of bacteria and fungi grown separately and in coexistence on Phragmites leaves. The two groups displayed both synergistic and antagonistic interactions. Bacteria grew better together with fungi than alone. In addition, there was a negative effect of bacteria on fungi, which appeared to be caused by suppression of fungal growth and biomass accrual rather than specifically affecting enzyme activity. Fungi growing alone had a high capacity for the decomposition of plant polymers such as lignin, cellulose, and hemicellulose. In contrast, enzyme activities were in general low when bacteria grew alone, and the activity of key enzymes in the degradation of lignin and cellulose (phenol oxidase and cellobiohydrolase) was undetectable in the bacteria-only treatment. Still, biomass-specific activities of most enzymes were higher in bacteria than in fungi. The low total activity and growth of bacteria in the absence of fungi in spite of apparent high enzymatic efficiency during the degradation of many substrates suggest that fungi provide the bacteria with resources that the bacteria were not able to acquire on their own, most probably intermediate decomposition products released by fungi that could be used by bacteria.     

Fenton''s type reaction and chemical pretreatment of PCBs

This study evaluates the effects of Fenton's reagent (FR) on the rate and extent of the oxidative degradation of individual mono, di-, tri- and tetrachlorobiphenyls in the commercial mixture DELOR 103, equivalent to AROCLOR 1248. The oxidation effect of FR strongly increased with increasing the molar ratio of Fe²⁺/H₂O₂. The most effective oxidation of DELOR 103 (10 μg.ml⁻¹) was achieved in a solution containing 1M H₂O₂ and 1 mM Fe²⁺. The FR elimination rate constants of PCB congeners decrease with increasing number of chlorine substituents in the biphenyl molecule and show a good correlation with the values of molecular weights of the PCB congeners and their 1-octanol/water partition coefficients.     

Risk assessment of sensory irritants in indoor air--a case study in a French school

Exposure to airborne pollutants can result in adverse health effects. Acute symptoms can for instance comprise of irritation of the eyes or of the respiratory tract (called sensory irritation). In a recent case, health problems were reported in a French school and supposedly attributed to the presence of airborne irritant pollutants. Based on measured concentrations, the risk of developing the described health effects was assessed.Numerous airborne sensory irritants (aldehydes, organic acids, volatile organic compounds (VOCs), SO(2), NH(3)) were identified and quantified in the indoor air by using active and passive sampling and online monitoring techniques. Reference values based on toxicological properties of compounds (sensory irritants) were taken from the literature. If not available, tentative values were specially developed for this purpose. Concentrations of all sensory irritants remain below their corresponding guideline values and are comparable to literature data. It was concluded that the risk of developing sensory irritation due to the presence of the studied compounds is negligible. This holds both for individual compounds and for the mixture of studied compounds. Limitations of the employed sampling strategy, and of existing sampling and analytical techniques, which do not allow for analysing more reactive compounds-which are strong sensory irritants-may play a role. New sampling techniques need to be developed. Psychosocial factors (group behaviour, increased attention to sensory irritation) should also be taken into account when dealing with health complaints on sensory irritation.     

Presence of drug screening and employee assistance programs: Exclusive and inclusive human resource management practices

Drug screening and employee assistance programs (EAPs) are human resource management practices for addressing substance abuse among employees. The two practices reflect different human resource management strategies and lead to different outcomes for employees and applicants. Drug screening is designed to exclude drug users from the workplace whereas EAPs offer them ‘rehabilitation’. Characteristics of worksites and their surrounding labor market may influence the presence or absence of these personnel practices. The results suggest that, when controlling for number of employees, economic sector, industry, and union presence, worksites with low turnover and in areas with high unemployment rates are more likely to engage in pre-employment drug screening, while worksites with low turnover more often provide an EAP.     

Comparative Studies on the Usefulness of Seven Ecological Indices for the Marine Coastal Monitoring Close to the Shore on the Swedish East Coast

The simultaneous behaviour of seven ecological indices(Hurlberts, Margalefs, Menhinicks, Shannons,species number, Jaccards and saprobic index) wasstudied based on phytoplankton data close to the shoreon the East coast of Sweden during the summer 1998.The sampling stations had a similar eutrophicationlevel and were located in bays. Standard phytoplanktondatabases were used in calculating the indices, whichwere later compared using cluster analysis.Hurlberts, Margalefs, Menhinicks, Shannons andspecies number indices, as measure of communitydiversity, produced similar trends which oftendiffered from those based on Jaccards index ofsimilarity. However, the simultaneous use of theseindices was found meaningful as a possible part of themonitoring close to the shore. The application of asaprobic index lead to erroneous conclusions in thestudied case.     

Monitoring nekton as a bioindicator in shallow estuarine habitats

Long-term monitoring of estuarine nekton has many practical and ecological benefits but efforts are hampered by a lack of standardized sampling procedures. This study provides a rationale for monitoring nekton in shallow (<#60; 1 m), temperate, estuarine habitats and addresses some important issues that arise when developing monitoring protocols. Sampling in seagrass and salt marsh habitats is emphasized due to the susceptibility of each habitat to anthropogenic stress and to the abundant and rich nekton assemblages that each habitat supports. Extensive sampling with quantitative enclosure traps that estimate nekton density is suggested. These gears have a high capture efficiency in most habitats and are small enough (e.g., 1 m²) to permit sampling in specific microhabitats. Other aspects of nekton monitoring are discussed, including spatial and temporal sampling considerations, station selection, sample size estimation, and data collection and analysis. Developing and initiating long-term nekton monitoring programs will help evaluate natural and human-induced changes in estuarine nekton over time and advance our understanding of the interactions between nekton and the dynamic estuarine environment.