Biomonitoring of heavy metals in fish from the Danube River

The Croatian part of the Danube River extends over 188 km and comprises 58 % of the country’s overall area used for commercial freshwater fishing. To date, the heavy metal contamination of fish in the Croatian part of the Danube has not been studied. The main purpose of this study was to determine heavy metal levels in muscle tissue of sampled fish species and to analyze the measured values according to feeding habits of particular groups. Lead ranged from 0.015 μg^?1 dry weight in planktivorous to 0.039 μg^?1 dry weight in herbivorous fish, cadmium from 0.013 μg^?1 dry weight in herbivorous to 0.018 μg^?1 dry weight in piscivorous fish, mercury from 0.191 μg^?1 dry weight in omnivorous to 0.441 μg^?1 dry weight in planktivorous fish and arsenic from 0.018 μg^?1 dry weight in planktivorous to 0.039 μg^?1 dry weight in omnivorous fish. Among the analyzed metals in muscle tissue of sampled fish, only mercury exceeded the maximal level (0.5 mg kg^?1) permitted according to the national and EU regulations determining maximum levels for certain contaminants in foodstuffs, indicating a hazard for consumers of fish from the Danube River.     

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.     

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.     

The effect of thiacloprid formulation on DNA/chromosome damage and changes in GST activity in bovine peripheral lymphocytes

The potential genotoxic effect of thiacloprid formulation on bovine peripheral lymphocytes was evaluated using the comet assay and the cytogenetic endpoints: chromosome aberrations (CAs), sister chromatid exchanges (SCEs) and micronuclei (MNi). Whole blood cultures were treated with the insecticide at concentrations of 30, 60, 120, 240 and 480 μg mL^?1 for 24, 48 h and/or 2 h of incubation. A statistically significant increase in the frequency of DNA damage, as well as in unstable chromosome aberrations (% breaks) were found after exposure to the insecticide at concentrations ranging from 120 to 480 μg mL^?1 (P < 0.05, P < 0.01, P < 0.001). For the detection of stable structural chromosome aberrations (e.g., translocations) and numerical aberrations by the FISH method, three whole chromosome painting probes for bovine chromosomes 1, 5 and 7 (BTA1, BTA5 and BTA7) were used in our experiments. We observed numerical aberrations, but without any statistical significance. Regarding the sister chromatid exchanges, no significant elevation in the SCE frequencies was found after 24-h exposure to the insecticide. A dose-related response in the SCE induction was obtained in bovine cultures after the prolonged time of exposure (48 h) to thiacloprid formulation at concentrations ranging from 120 to 480 μg mL^?1 in each donor (P < 0.05, P < 0.01), which was associated with a reduction of the PI (P < 0.05, P < 0.01). The insecticide failed to produce MNi; however, a significant reduction of CBPI was observed. Using real-time PCR, a decrease in the expression of bovine glutathione S-transferase M3 (GSTM3) was detected at the lowest dose. The higher concentrations of thiacloprid formulation caused an increase in the mRNA expression.     

Alteration of cholinesterase activity as possible mechanism of silver nanoparticle toxicity

Due to their broad-spectrum antimicrobial activity, silver nanoparticles (AgNPs) have been used in a large number of commercial and medical products. Such proliferated AgNP production poses toxicological and environmental issues which need to be addressed. The present study aimed to investigate the effects of AgNPs on acetylcholinesterase (AChE) and butyrylcholinesterase (BChE), important enzymes in areas of neurobiology, toxicology and pharmacology. Three different AgNPs, prepared by the chemical reduction using trisodium citrate, hydroxylamine hydrochloride (Cl-AgNPs), and borohydride following stabilization with poly(vinyl alcohol), were purified and characterised with respect to their sizes, shapes and optical properties. Their inhibition potential on AChE and BChE was evaluated in vitro using an enzyme assay with o-nitrophenyl acetate or o-nitrophenyl butyrate as substrates, respectively. All three studied AgNPs were reversible inhibitors of ChEs. Among tested nanoparticles, Cl-AgNP was found to be the most potent inhibitor of both AChE and BChE. Although the detailed mechanism by which the AgNPs inhibit esterase activities remains unknown, structural perturbation of the enzyme may be the common mode of ChE inhibition by AgNPs.     

(210)Po and (210)Pb activity concentrations in Mytilus galloprovincialis from Croatian Adriatic coast with the related dose assessment to the coastal population

Activity concentrations of ²¹⁰Po and ²¹⁰Pb in the species Mytilus galloprovincialis from Croatian Adriatic coast were determined. The samples were collected in thirteen sampling places which are also a part of Croatian Mediterranean mussel watch project. The results of ²¹⁰Po and ²¹⁰Pb activity concentrations were found to vary between (22.1 ± 2.5)-(207 ± 21) Bq kg⁻¹ fresh weight and (2.8 ± 1.4)-(9.3 ± 0.7) Bq kg⁻¹ fresh weight, respectively. ²¹⁰Po/²¹⁰Pb ratio ranged between 6.2 and 30.7. The highest measured activities were found in the enclosed basins of the Neretva channel, where the majority of Croatian mussel cultivation is taking place. The estimated consequent average total annual effective ingestion dose due to ²¹⁰Po and ²¹⁰Pb from mussel consumption in Croatian coastal region is 202 ± 99 μSv with 96% contribution of ²¹⁰Po to the total effective dose.     

Accumulation of organochlorine contaminants in loggerhead sea turtles, Caretta caretta, from the eastern Adriatic Sea

We analyzed 15 polychlorinated biphenyls (PCBs) and five organochlorine pesticides (OCPs) in fat tissue of 27 loggerhead sea turtles (Caretta caretta) from eastern Adriatic Sea with the curved carapace length ranging from 25.0 to 84.5 cm. The PCB profile was dominated by hexa- and hepta-chlorinated congeners, with PCB-153 (median: 114.9 ng g⁻¹ wet mass), PCB-138 (80.0 ng g⁻¹ w.m.), and PCB-180 (26.7 ng g⁻¹ w.m.) detected with the highest levels. Toxic mono-ortho congeners PCB-118, PCB-105 and PCB-180 with dioxin-like toxicity were found in >70% samples. 4,4′-DDE (81.0 ng g⁻¹ w.m.) prevailed the OCP signature, accounting for 80% of the total DDTs. A significant increasing trend in accumulation with size was found for PCB-52 (r_s = 0.512, p < 0.01) and PCB-114 (r_s = 0.421, p < 0.05). Comparison of our results with organochlorine contaminant (OC) pattern in some prey taxa suggest that contamination occurs primarily through the food web, with biomagnification factors of 0.14-6.99 which were positively correlated with the octanol-water partition coefficient (log K_ow; p < 0.05). This study, based upon a fairly large sample size collected mostly from incidentally captured animals over a short time period (June 2001-November 2002), present a temporal snapshot of OC contamination in wild, free-ranging loggerheads from Adriatic feeding grounds and provide a baseline for monitoring the regional OC trends in this endangered species.     

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.     

Development of a nonlocal convective mixing scheme with varying upward mixing rates for use in air quality and chemical transport models

BACKGROUND, AIM, AND SCOPE: Asymmetrical convective non-local scheme (CON) with varying upward mixing rates is developed for simulation of vertical turbulent mixing in the convective boundary layer in air quality and chemical transport models. MATERIALS AND METHODS: The upward mixing rate form the surface layer is parameterized using the sensible heat flux and the friction and convective velocities. Upward mixing rates varying with height are scaled with an amount of turbulent kinetic energy in layer, while the downward mixing rates are derived from mass conservation. RESULTS: This scheme provides a less rapid mass transport out of surface layer into other layers than other asymmetrical convective mixing schemes. DISCUSSION: In this paper, we studied the performance of a nonlocal convective mixing scheme with varying upward mixing in the atmospheric boundary layer and its impact on the concentration of pollutants calculated with chemical and air-quality models. This scheme was additionally compared versus a local eddy-diffusivity scheme (KSC). Simulated concentrations of NO(2) and the nitrate wet deposition by the CON scheme are closer to the observations when compared to those obtained from using the KSC scheme. CONCLUSIONS: Concentrations calculated with the CON scheme are in general higher and closer to the observations than those obtained by the KSC scheme (of the order of 15-20%). Nitrate wet deposition calculated with the CON scheme are in general higher and closer to the observations than those obtained by the KSC scheme. RECOMMENDATIONS AND PERSPECTIVES: To examine the performance of the scheme, simulated and measured concentrations of a pollutant (NO(2)) and nitrate wet deposition was compared for the year 2002. The comparison was made for the whole domain used in simulations performed by the chemical European Monitoring and Evaluation Programme Unified model (version UNI-ACID, rv2.0) where schemes were incorporated.