Concentration of Organochlorine Pollutants in Surface Waters of the Central European Biosphere Reserve Krivoklatsko (8 pp)

Background, Aim and Scope The article is focused on dioxin, furan, PCB and organochlorine pesticide monitoring in the surface waters of the Central European, protected natural reserve Krivoklatsko, under the UNESCO programme Man and Biosphere. Persistent compounds are presently transported via different means throughout the entire world. This contamination varies significantly between sites. This raises the question of what constitutes the naturally occurring background levels of POPs in natural, unpolluted areas, but which are close to industrialised regions. Information of real background POP contamination can be of high value for risk assessment management of those sites evidently polluted and for the defining of de-contamination limits. Preserved areas should not be seen as isolated regions in which the impacts of human activities and natural factors are either unexpected or overlooked. Every ambient region, even those protected by a law or other means, are still closely connected to neighbouring human developed and impacted areas, and are therefore subject to this anthropogenic contamination. These areas adjacent to natural reserves are sources of diverse substances, via entry of air, water, soil and/or biota. After an extended period of industrial activities, organochlorine pollutants, even those emitted in trace concentrations have reached detectable levels. For future research and for the assessment of environmental changes, present levels of contamination would be of high importance. This work publishes data of the contamination with organochlorine pollutants of this natural region, where biodiversity and ecological functions are of the highest order. Materials and Methods: Semipermeable membrane devices (SPMDs) were utilised as the sampling system. SPMDs were deployed in two small creeks and one water reservoir selected in the central part of the Krivoklatsko Natural Reserve, where it could be expected that any possible contamination by POPs would be lowest. The exposed SPMDs were analysed both for chemical contents of POPs and for toxicity properties. The chemical analyses of dibenzo-dioxins, dibenzo-furans, PCBs and OCPs were analysed by GC/MS/MS on GCQ or PolarisQ (Thermoquest). Toxicity bioassays were performed on the alga Desmodesmus subspicatus, bacteria Vibrio fischeri and crustacean Daphnia magna. All toxicity data were expressed as the effective volume Vtox. Vtox is a toxicity parameter, the determination of which is independent of SPMD deployment time and pre-treatment dilution (unlike, for example, the EC50 of the SPMD extract). Results: The following chemical parameters were monitored: 1) tetra, penta, hexa and hepta dibenzo-p-dioxins and furans; 2) all those detectable from tri- through deca-polychloriated biphenyls (PCBs) and 3) a group of organochlorine pesticides: hexachlorobenzene and isomers of hexachlorocyclohexane, DDE, DDD and DDT. The concentrations of dioxins and furans on the assessed sites varied from under detection levels up to 7 pg.l-1; PCBs were detected in a sum concentration up to 2.8 ng.l-1; and organochlorine pesticides up to 346 pg.l-1. The responses of bioassays used were very low, with the values obtained for Vtox being under 0.03 l/d. Discussion: Toxicity testing showed no toxicity responses, demonstrating that the system used is in coherence with the ecological status of the assessed sites. Values of Vtox were under the critical value – showing no toxicity. The PCA of chemical analysis data and toxicity responses resulted in no correlations between these two groups of parameters. This demonstrated that the present level of contamination has had no direct adverse effects on the biota. Conclusions: The concentration values of six EPA-listed, toxic dioxins and sums of tetra-hepta dioxins; nine EPA toxic dibenzofurans and the sums of tetra-hepta bibenzofurans are presented together with all tri-deka PCBs and organochlorine pesticides (alfa-, beta-, gama-, delta-HCH, HCB, opDDE, ppDDE, opDDD, ppDDD, opDDT, ppDDT). These values represent possible current regional natural background values of these substances monitored within the Central European region, with no recorded adverse effects on the freshwater ecosystem (up until the present time). Recommendations and Perspectives: Assessment of dioxins, furans and other organochlorine compounds within natural reserves can be important for the monitoring of human-induced impacts on preserved areas. No systematic monitoring of these substances in areas not directly affected by industry has generally been realised. There is a paucity of data of the presence of any of these substances within natural regions. Further monitoring of contamination of both soil and biota by dioxins and furans in preserve regions is needed and can be used for future monitoring of man-made activities and/or accidents. Semipermeable membrane devices proved to be a very good sampling system for the monitoring of trace concentrations of ambient organochlorine compounds. Toxicity evaluation using the Vtox concept demonstrated that those localities assessed expressed no toxicity.     

Bioaccumulation of Metals in Fish of Salmonidae Family and the Impact on Fish Meat Quality

The study was aimed at determining the levels of metals in water samples and muscles of the fish caught in the Una River basin, located in the northwestern part of Bosnia and Herzegovina. For that purpose, three fish species: Brown Trout (Salmo trutta m. fario), Grayling (Thymallus thymallus) and Californian Trout (Salmo gairdneri), together with stem water samples, were analyzed for metal concentrations (Pb, Hg, Cd, As, Mn, Ni, Cu, Cr, Se, Co, Sn, Zn, Fe, Ca, P) during a 2-year period. The fish was captured using electric fishing, nets or fishing equipment. The capture was undertaken on three sites (the river source, the middle flow and the river mouth) of each of the five biggest rivers belonging to the Una River basin (Unac, Krušnica, Sana, Klokot, and Una). The concentrations of metals in each sample were determined via atomic absorption spectrophotometry. In the tested waters, the presence of Mn in concentrations higher than permitted (0.07 mg/l) had been detected. In the tested meat, the following average concentrations of metals (mg/kg) had been found: Pb (0.67), Cd (0.06), Mn (0.65), Ni (0.15), Cu (0.79), Cr (1.05), Se (0.03), Zn (8.92), Fe (5.40), Ca (14.68), and P (10.85). The correlation between Mn concentrations identified in the tested waters and those identified in the meat of Brown Trout was revealed to be statistically significant, which confirms that, over time, bioaccumulation of metals took place. Even though the results were not indicative of contamination, they strongly suggest that constant monitoring of the ecosystems in reference should be implemented.     

Modeling of policies for reduction of GHG emissions in energy sector using ANN: case study—Croatia (EU)

Environmental Science and Pollution Research - This study describes the development of tool for testing different policies for reduction of greenhouse gas (GHG) emissions in energy sector using...     

Synthesis of BiVO4/TiO2 composites and evaluation of their photocatalytic activity under indoor illumination

BiVO₄/TiO₂ composites with different weight ratios have been prepared by coprecipitation-based reactions followed by either thermal or hydrothermal treatment with the aim of evaluating the TiO₂ photosensitization by BiVO₄. The obtained materials present in all cases the desired monoclinic phase of BiVO₄ and anatase phase of TiO₂. Visible light absorption increased with increasing amount of bismuth vanadate. XPS results reveal the surface enrichment of Ti with respect to the bulk composition in samples characterised by a higher content of BiVO₄. The photocatalytic activity of the prepared materials was tested for the degradation of isopropanol in the gas phase under indoor illumination conditions. Although none of the composites was able to improve the activity of TiO₂, the low BiVO₄ containing samples appear as more suitable for further synthesis tuning.     

Environmental impacts of asphalt mixes with electric arc furnace steel slag

Electric arc furnace (EAF) steel slag can be used as an alternative high-quality material in road construction. Although asphalts with slag aggregates have been recognized as environmentally acceptable, there is a lack of data concerning the potential leaching of toxic Cr(VI) due to the highly alkaline media of EAF slag. Leaching of selected water extractable metals from slag indicated elevated concentrations of total chromium and Cr(VI). To estimate the environmental impacts of asphalt mixes with slag, leachability tests based on diffusion were performed using pure water and salt water as leaching agents. Compact and ground asphalt composites with natural aggregates, and asphalt composites in which the natural aggregates were completely replaced by slag were prepared. The concentrations of total chromium and Cr(VI) were determined in leachates over a time period of 6 mo. After 1 and 6 mo, the concentrations of some other metals were also determined in the leachates. The results indicated that chromium in leachates from asphalt composites with the addition of slag was present almost solely in its hexavalent form. However, the concentrations were very low (below 25 μg L) and did not represent an environmental burden. The leaching of other metals from asphalt composites with the addition of slag was negligible. Therefore, the investigated EAF slag can be considered as environmentally safe substitute for natural aggregates in asphalt mixes.     

The use of nondestructive methods to assess a physiological status and conservation perspectives of <Emphasis Type="Italic">Eryngium maritimum</Emphasis> L.

Eryngium maritimum is a perennial species growing exclusively in a coastal littoral zone both on sand dunes and shingle beach and indicated as declining in Northern Europe. The objective of the present study was to prove the use of nondestructive physiological measurement methods to access physiological status of endangered plants, using E. maritimum as a model species. Plants from two Latvian sites were studied in comparison with other populations in Northern Europe (Estonia, Lithuania, Poland, United Kingdom) to find out if local differences in environmental factors affect vitality of E. maritimum individuals. Noninvasive chlorophyll analysis and chlorophyll a fluorescence measurements were used as indicators of plant physiological status through characterization of various aspects of photochemistry of photosystem II activity. Dynamics and morphology of individuals were investigated for evaluation of clonal growth potential of E. maritimum in natural conditions. Highly fluctuating trend of dynamics of individuals (within 40 groups at two Latvian sites) was established for E. maritimum in natural conditions over a five-year period. Disturbance of individuals lead to formation of new shoots from nodal root meristems. An exponential regression between fluorescence parameters F_V/F_M and Performance Index and summary monthly precipitation was found indicating that E. maritimum plants had significant tolerance to water shortage together with susceptibility to increased precipitation. Negative correlation between leaf chlorophyll content and more northern localization of individuals was found (r = 0.95 and r = 0.94, for generative and vegetative shoots, respectively). Northern populations of E. maritimum are endangered by high precipitation in conditions of low air temperature, leading to decrease of photosynthetic productivity and overall physiological status. High developmental plasticity at the root level leads to clonal growth and an efficient survival and relatively long life span of E. maritimum individuals. Chlorophyll a fluorescence is a useful method to search for the effect of suboptimal conditions on physiological status of endangered plant species without elimination and disturbance of individuals.     

REP-LECOTOX: an example of FP 6 INCO project to strengthen ecotoxicological research in WBC (Western Balkan countries)

Background

In order to map exceedances of critical atmospheric deposition loads for nitrogen (N) surface data on the atmospheric deposition of N compounds to terrestrial ecosystems are needed. Across Europe such information is provided by the international European Monitoring and Evaluation Programme (EMEP) in a resolution of 50 km by 50 km, relying on both emission data and measurement data on atmospheric depositions. The objective of the article at hand is on the improvement of the spatial resolution of the EMEP maps by combining them with data on the N concentration in mosses provided by the International Cooperative Programme on Effects of Air Pollution on Natural Vegetation and Crops (ICP Vegetation) of the United Nations Economic Commission for Europe (UNECE) Long-range Transboundary Air Pollution (LTRAP) Convention.

Methods

The map on atmospheric depositions of total N as modelled by EMEP was intersected with geostatistical surface estimations on the N concentration in mosses at a resolution of 5 km by 5 km. The medians of the N estimations in mosses were then calculated for each 50 km by 50 km grid cell. Both medians of moss estimations and corresponding modelled deposition values were ln-transformed and their relationship investigated and modelled by linear regression analysis. The regression equations were applied on the moss kriging estimates of the N concentration in mosses. The respective residuals were projected onto the centres of the EMEP grid cells and were mapped using variogram analysis and kriging procedures. Finally, the residual and the regression map were summed up to the map of total N deposition in terrestrial ecosystems throughout Europe.

Results and discussion

The regression analysis of the estimated N concentrations in mosses and the modelled EMEP depositions resulted in clear linear regression patterns with coefficients of determination of r ² = 0.62 and Pearson correlations of r _p = 0.79 and Spearman correlations of r _s = 0.70, respectively. Regarding the German territory a nationwide mean of 18.1 kg/ha/a (standard deviation: 3.49 kg/ha/a) could be derived from the resulting map on total N deposition in a resolution of 5 km by 5 km. Recent updates of the modelled atmospheric deposition of N provided a similar estimate for Germany.

Conclusions

The linking of modelled EMEP data on the atmospheric depositions of total N and the accumulation of N in mosses allows to map the deposition of total N in a high resolution of 5 km by 5 km using empirical moss data. The mapping relies on the strong statistical relationship between both processes that are physically and chemically related to each other. The mapping approach thereby relies on available data that are both based on European wide harmonized methodologies. From an ecotoxicological point of view the linking of data on N depositions and those on N bioaccumulation can be considered a substantial progress.     

Numerical Modeling of Flow Fields and Dispersion of Passive Pollutants in the Vicinity of the Temelín Nuclear Power Plant

This study deals with numerical simulation of flow fields and dispersion of model passive admixtures in the planetary boundary layer in a 10 × 10 km square area, centered on the Czech Republic’s Temelín Nuclear Power Plant. Numerical calculations of three-dimensional flow fields with eight basic wind directions given for the inlet boundary of the computational domain are performed using the FLUENT CFD code with the standard k – ε turbulence model. The resultant modeling of the flow fields provides information as to probable local directions and velocities of flow vectors on a horizontal scale of 100 m, which are consistent with the data given for the boundaries of the calculation area in the framework of a scale of 10 km. The modeled flow fields generate the input data for related Lagrangian simulation of the ground concentration and deposition fields of passive particles assumedly emitted at the site of the Temelín plant. Simulated plumes describe eight cases of potential ground-level distribution of model passive admixtures in the area.