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.     

PCDDs/PCDFs and PCBs in water samples from the Three Gorge Reservoir

The Three Gorge Reservoir (TGR) is the largest reservoir in China and its water quality is an important health concern, we have determined the concentrations of PCDDs/PCDFs and PCBs in the water samples collected at three seasons: August 2004, January 2005 and August 2005. The results showed that the average WHO-TEQ of total dioxins-like compounds (PCDDs/PCDFs+PCBs) was 0.06558 pg l(-1), ranged from 0.0008 to 0.32439 pg l(-1), which are much lower than other reported water sources. The main dioxins (PCDDs/PCDFs) are hepta- and octa-chlorinated dibenzo-p-dioxins (CDDs) and chlorinated dibenzofurans (CDFs). Since the levels of dioxins may change after the last water-store stage, the present study provides important data to compare the water quality in the TGR in the future.     

Air concentrations of PCDD/Fs, PCBs and PCNs using active and passive air samplers

The concentrations of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) were determined in air samples collected at four sampling sites located in two zones of Barcelona (Spain): near a municipal solid waste incinerator (MSWI) and a combined cycle power plant (3 sites), and at a background/control site. Samples were collected using high-volume active samplers. Moreover, 4 PUF passive samplers were deployed at the same sampling points during three months. For PCDD/Fs, total WHO-TEQ values were 27.3 and 10.9 fg WHO-TEQm(-3) at the urban/industrial and the background sites, respectively. The sum of 7 PCB congeners and the Sigma PCN levels were also higher at the industrial site than at the background site. In order to compare active and passive sampling, the accumulated amounts of PCDD/Fs, PCBs and PCNs in the four passive air samplers, as well as the total toxic equivalents in each sampling site were also determined. To assess the use of PUF passive samplers as a complementary tool for PCDD/F, PCB and PCN monitoring, sampling rates were calculated in accordance with the theory of passive air samplers. PUF disks allowed establishing differences among zones for the POP levels, showing that they can be a suitable method to determine POP concentrations in air in areas with various potential emission sources. Although both particle and gas phase were sorbed by the PUFs, data of gas phase congeners are more reproducible.     

Investigation of arsenic removal in batch wise water treatments by means of sequential hydride generation flow injection analysis

Arsenic water pollution is a big issue worldwide. Determination of inorganic arsenic in each oxidation state is important because As(III) is much more toxic than As(V). An automated arsenic measurement system was developed based on complete vaporization of As by a sequential procedure and collection/preconcentration of the vaporized AsH(3), which was subsequently measured by a flow analysis. The automated sensitive method was applied to monitoring As(III) and As(V) concentrations in contaminated water standing overnight. Behaviors of arsenics were investigated in different conditions, and unique time dependence profiles were obtained. For example, in the standing of anaerobic water samples, the As(III) concentration immediately began decreasing whereas dead time was observed in the removal of As(V). In normal groundwater conditions, most arsenic was removed from the water simply by standing overnight. To obtain more effective removal, the addition of oxidants and use of steel wools were investigated. Simple batch wise treatments of arsenic contaminated water were demonstrated, and detail of the transitional changes in As(III) and As(V) were investigated.     

Assessment of the potential of ecolabels to promote agrobiodiversity

We conducted a study to assess to what extent current ecolabels contain standards that stimulate conservation and sustainable use of on-farm biodiversity of agricultural landscapes (agrobiodiversity). First, we developed an agrobiodiversity management yardstick to assess and compare the labeling schemes of ecolabels for arable farming. Key characteristics of the yardstick are the five levels linking the abstract notion of agrobiodiversity management to concrete measures on a farm and its foundation upon expert judgment regarding the effect of farming practices on agrobiodiversity. Several environmental themes, among them agrobiodiversity management, are regulated through the standards of labeling schemes of ecolabels. With the aid of this yardstick, the labeling schemes were scrutinized and the number, average efficacy, and compulsory nature of relevant standards was determined for 10 categories of farm management. The results show that all examined ecolabels contain at least some standards that stimulate conservation and sustainable use of agrobiodiversity, but there are large differences between the labels. We consider the results of the five ecolabels to be insufficient to warrant their usefulness as a governance strategy that the Dutch government could refer to and depend on as part of a national agrobiodiversity policy to stimulate agrobiodiversity.     

Dioxin exposure in contaminated sawmill area: the use of molar teeth and bone of bank vole (Clethrionomys glareolus) and field vole (Microtus agrestis) as biomarkers

Developmental disorders of teeth are among the most sensitive targets of polychlorinated dibenzo-p-dioxin and -furan (PCDD/F) exposure. In rats, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) reduces dose-dependently the size of molars, most severely the third lower molars. Dioxins also have effects on developing bone, including altered bone mineral density as well as reduced bending breaking force and stiffness. The aim of this study was to evaluate the use of the third lower molar and long bones as biomarkers of PCDD/F exposure in two wild vole species, the bank vole (Clethrionomys glareolus) and the field vole (Microtus agrestis) collected from a PCDD/F contaminated former sawmill area. Survey of soil and biota of the sawmill area indicated a PCDD/F contamination with a congener profile characteristic for the chlorophenol wood preservative Ky-5. The PCDD/F concentration in the bank vole was notably higher than in the field vole. The third molar of the bank vole was significantly smaller in dioxin-exposed animals compared to control group, while there was no difference between these two groups in the field vole. No significant alterations were observed in bone density and strength in either species except for reduced bending strength of the femur neck in bank vole males exposed to dioxins. Even though the bone changes are among the sensitive endpoints of dioxin-exposure, high variability due to age, size and gender limits their use as biomarkers of wildlife exposure. In conclusion, the size of molar teeth seems to be a sensitive and robust biomarker for PCDD/F exposure in wild bank vole populations and thus worth of further studies.     

SIMULATED EFFECTS OF ALTERED SPILLWAY RELEASES ON THERMAL STRUCTURE AND KOKANEE GROWTH IN A COLORADO RESERVOIR1

ABSTRACT: In‐reservoir thermal and ecological effects of releasing some flows over the surface spillway at Blue Mesa Reservoir, Colorado, rather than routing all releases through the hypolimnetic outlet were evaluated using a calibrated and validated one‐dimensional thermal model (CE‐THERM) with a set of ecological models. Thermal model output indicated that surface water temperatures were influenced primarily by atmospheric conditions, but the release of warmer water over the spillway resulted in a thinner epilimnion and cooler metalimnetic water temperatures. Ecological model predictions indicated that spillway releases and associated temperatures resulted in lower growth rates for young‐of‐year (YOY) kokanee salmon (Oncorhynchus nerka) in the reservoir by up to 9 percent when compared with growth rates under baseline operations with no releases over the spillway. Kokanee growth rates were reduced under spillway release scenarios because lower temperatures not only affected metabolic rates, but limited the productivity of the zooplankton as well. Thus, altering the release regime with spillway discharges could have deleterious effects on Blue Mesa's YOY kokanee. However, in other reservoirs, distributing discharges among different elevations may provide managers with a mechanism to regulate temperatures to benefit species of concern that are facing challenges imposed by environmental conditions such as global warming.     

Behavior of potassium in bread by ion chromatography

Public attention was aroused when mutagenicity was found in potassium bromate (KBrO₃) which has been used as an oxidizing agent in baking bread. Ion chromatography was found to be very useful for analyzing bromide and bromate ions in food. The residual condition of potassium bromate added to bread in the baking process was clarified.It was found that the residual rate of bromate ions in bread was approximately 30% at the added level of 100 μg/g, but it decreased markedly when the added levels went down. At 40 μg/g no residue was detected.     

Growth, aboveground biomass, and nutrient concentration of young Scots pine and lodgepole pine in oil shale post-mining landscapes in Estonia

The investigation was carried out in 8-year-old Scots pine (Pinus sylvestris L.) and lodgepole pine (Pinus contorta var. latifolia Engelm.) plantations on post-mining area, Northeast Estonia. The aim of the study was to assess the suitability of lodgepole pine for restoration of degraded lands by comparing the growth, biomass, and nutrient concentration of studied species. The height growth of trees was greater in the Scots pine stand, but the tree aboveground biomass was slightly larger in the lodgepole pine stand. The aboveground biomass allocation to the compartments did not differ significantly between species. The vertical distribution of compartments showed that 43.2% of the Scots pine needles were located in the middle layer of the crown, while 58.5% of the lodgepole pine needles were in the lowest layer of the crown. The largest share of the shoots and stem of both species was allocated to the lowest layer of the crown. For both species, the highest NPK concentrations were found in the?needles and the lowest in the stems. On the basis of the present study results, it can be concluded that the early growth of Scots pine and lodgepole pine on oil shale post-mining landscapes is similar.