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.     

Filamentous cyanophytes containing phycourobilin and in symbiosis with sponges and an ascidian of coral reefs

A study was made of the ultrastructure and pigment composition of filamentous cyanophytes living in symbiosis with several sponges and a colonial didemnid ascidian collected from the southern end of the Great Barrier Reef, Australia, between 1983 and 1986. The sponges were Dysidea herbacea Keller and several other encrusting sponges which have not been identified; the ascidian was Trididemnum miniatum Kott (1977). The cyanophyte Oscillatoria spongeliae (Shultz) Hauck was identified as the symbiont of several of the sponges, including D. herbacea. Two other unidentified Oscillatoria species were found in a bristly papillate sponge and in T. miniatum. Chlorophyll a, alone, was present in all the symbionts with the exception of T. miniatum, which contained the cosymbiont Prochloron and where chlorophyll b was also present. Two phycoerythrins were isolated by chromatography and chromatofocusing. Both resembled C-phycoerythrin, but one of the two carried the chromophore phycourobilin as well as phycoerythrobilin possibly on both the and subunits, which had apparent molecular masses of 18 and 20 kdaltons. No subunit was present. Ultrastructurally, the three Oscillatoria species were distinguished by an unusual type of parallel, longitudinal, thylakoid organisation; the arrangement was different in detail in each species.     

Sixteen priority polycyclic aromatic hydrocarbons in roadside soils at traffic light intersections (Bratislava,Slovakia): concentrations,sources and influencing factors

Environmental Geochemistry and Health - Combustion of fossil fuels is the most important source of polycyclic aromatic hydrocarbons (PAHs) in the environment. Cities are typical of many human...     

Sorption, desorption, and degradation of (4-chloro-2-methylphenoxy)acetic acid in representative soils of the Danubian Lowland, Slovakia

Herbicide leaching through soil into groundwater greatly depends upon sorption-desorption and degradation phenomena. Batch adsorption, desorption and degradation experiments were performed with acidic herbicide MCPA and three soil types collected from their respective soil horizons. MCPA was found to be weakly sorbed by the soils with Freundlich coefficient values ranging from 0.37 to 1.03 mg^1−1/n kg⁻¹ L^1/n. It was shown that MCPA sorption positively correlated with soil organic carbon content, humic and fulvic acid carbon contents, and negatively with soil pH. The importance of soil organic matter in MCPA sorption by soils was also confirmed by performing sorption experiments after soil organic matter removal. MCPA sorption in these treated soils decreased by 37-100% compared to the original soils. A relatively large part of the sorbed MCPA was released from soils into aqueous solution after four successive desorption steps, although some hysteresis occurred during desorption of MCPA from all soils. Both sorption and desorption were depth-dependent, the A soil horizons exhibited higher retention capacity of the herbicide than B or C soil horizons. Generally, MCPA sorption decreased in the presence of phosphate and low molecular weight organic acids. Degradation of MCPA was faster in the A soil horizons than the corresponding B or C soil horizons with half-life values ranging from 4.9 to 9.6 d in topsoils and from 11.6 to 23.4 d in subsoils.     

The potential impact of geological environment on health status of residents of the Slovak Republic

In order to assess the potential impact of the geological environment on the health of the population of the Slovak Republic, the geological environment was divided into eight major units: Paleozoic, Crystalline, Carbonatic Mesozoic and basal Paleogene, Carbonatic-silicate Mesozoic and Paleogene, Paleogene Flysch, Neovolcanics, Neogene and Quaternary sediments. Based on these geological units, the databases of environmental indicators (chemical elements/parameters in groundwater and soils) and health indicators (concerning health status and demographic development of the population) were compiled. The geological environment of the Neogene volcanics (andesites and basalts) has been clearly documented as having the least favourable impact on the health of Slovak population, while Paleogene Flysch geological environment (sandstones, shales, claystones) has the most favourable impact. The most significant differences between these two geological environments were observed, especially for the following health indicators: SMRI6364 (cerebral infarction and strokes) more than 70 %, SMRK (digestive system) 55 %, REI (circulatory system) and REE (endocrine and metabolic system) almost 40 % and REC (malignant neoplasms) more than 30 %. These results can likely be associated with deficit contents of Ca and Mg in groundwater from the Neogene volcanics that are only about half the level of Ca and Mg in groundwater of the Paleogene sediments.     

Evaluating the efficacy of adaptive management approaches: Is there a formula for success?

Within the field of natural-resources management, the application of adaptive management is appropriate for complex problems high in uncertainty. Adaptive management is becoming an increasingly popular management-decision tool within the scientific community and has developed into two primary schools of thought: the Resilience-Experimentalist School (with high emphasis on stakeholder involvement, resilience, and highly complex models) and the Decision-Theoretic School (which results in relatively simple models through emphasizing stakeholder involvement for identifying management objectives). Because of these differences, adaptive management plans implemented under each of these schools may yield varying levels of success. We evaluated peer-reviewed literature focused on incorporation of adaptive management to identify components of successful adaptive management plans. Our evaluation included adaptive management elements such as stakeholder involvement, definitions of management objectives and actions, use and complexity of predictive models, and the sequence in which these elements were applied. We also defined a scale of degrees of success to make comparisons between the two adaptive management schools of thought. Our results include the relationship between the adaptive management process documented in the reviewed literature and our defined continuum of successful outcomes. Our data suggest an increase in the number of published articles with substantive discussion of adaptive management from 2000 to 2009 at a mean rate of annual change of 0.92 (r2 = 0.56). Additionally, our examination of data for temporal patterns related to each school resulted in an increase in acknowledgement of the Decision-Theoretic School of thought at a mean annual rate of change of 0.02 (r2 = 0.6679) and a stable acknowledgement for the Resilience-Experimentalist School of thought (r2 = 0.0042; slope = 0.0013). Identifying the elements of successful adaptive management will be advantageous to natural-resources managers considering adaptive management as a decision tool.     

Input/output balance of estrogenic active compounds in a major municipal sewage plant in Germany

24 h samples of untreated and treated wastewater were taken in parallel from a modern municipal sewage plant in southern Germany in March and June 1998. After solid phase extraction, total estrogenic activity was quantitatively measured with a miniaturized E-screen assay and the levels of nine estrogenic phenolic chemicals analyzed by HRGC/LRMS. 17Beta-estradiol equivalent concentrations (EEQ) were 58 and 70 ng/l in the influent and 6 ng/l in the effluent, indicating that the load of estrogenic activity of the wastewater was reduced by about 90% in the sewage plant. Less than 3% of the estrogenic activity was found in the sludge. 4-t-octylphenol, 4-nonylphenol, bisphenol A, 2-hydroxybiphenyl, and 4-chloro-3-methylphenol were detected in the untreated wastewater at levels from 0.13 to 3.6 microg/l. 4-t-octylphenol, 4-nonylphenol, and bisphenol A were present in the effluent at concentrations from 0.16 to 0.36 microg/l, 2-hydroxybiphenyl and 4-chloro-3-methylphenol were not detectable. The contribution of the quantified levels of phenolic xenoestrogens to total estrogenic activity in the sewage was 0.7-4.3%.