Post-war levels of persistent organic pollutants (POPs) in air from Serbia determined by active and passive sampling methods

For the duration of the war accident in former Yugoslavia, several industrial and military targets were burnt and damaged, resulting in a significant release of persistent organic pollutants. Locations heavily targeted in the attacks were later defined by UNEP as four “hot spots”: Kragujevac, Novi Sad, Pancevo and Bor. We analyzed concentration levels of pollutants collected in 2004 and 2005 in air samples from the city of Kragujevac, Serbia, following the war accident of 1999. Pollutants included polycyclic aromatic hydrocarbons (PAHs), hexachlorocyclohexane (HCH), dichloro-diphenyl-trichloroethane (DDT), dichloro-diphenyl-dichloroethylene (DDE), dichloro-diphenyl-dichloroethane (DDD) and polychlorinated biphenyls (PCBs). We present results obtained during air sampling campaign conducted in July 2004 by the active sampling method; and during September 2004–June 2005 by the passive sampling method. Our findings show the occurrence of residual quantities of DDT, HCH, PCBs and PAHs in air samples. High levels of PCBs are probably due to the destruction of transformers during the war accident.     

Toxicity of mancozeb,chlorothalonil, captan,fluopyram, boscalid,and difenoconazole to Didymella applanata isolates from Serbia

Field isolates of Didymella applanata, the causal agent of spur blight of raspberry, were evaluated in vitro for their sensitivity to mancozeb, chlorothalonil, captan, fluopyram, boscalid and difenoconazole. A total of 10 isolates, collected during 2013 at five localities in the major raspberry growing region in Serbia, and characterized as copper hydroxide, dithianon, and tebuconazole (sensitive), pyraclostrobin (sensitive or highly resistant) and fluazinam (sensitive or moderately resistant), were used in this study. The EC₅₀ values for the isolates ranged from 1.33 to 2.88 mg L^?1 for mancozeb, from 3.18 to 6.65 mg L^?1 for chlorothalonil, from 15.75 to 24.69 mg L^?1 for captan and from 1.80 to 8.20 mg L^?1 for fluopyram. The narrowest range of EC₅₀ values was recorded for difenoconazole (0.23–0.49 mg L^?1), whereas the widest range was obtained for boscalid (4.49–49.25 mg L^?1). The calculated resistance factors showed that all D. applanata isolates were sensitive to mancozeb, chlorothalonil, captan, and difenoconazole. Four isolates were moderately resistant to boscalid, while three of them were also moderately resistant to fluopyram. This finding of moderately resistant isolates to these SDHI fungicides indicates a possible cross-resistance which should be clarified in further investigations.     

Monitoring of DNA damage in haemocytes of freshwater mussel Sinanodonta woodiana sampled from the Velika Morava River in Serbia with the comet assay

This study was undertaken to investigate the potential of the freshwater mussel Sinanodonta woodiana for detection of genotoxic pollution of the environment. Study was performed at two sites in the Velika Morava River, from May 2010 to February 2011. The alkaline comet assay on haemocytes was used, and the olive tail moment (OTM) was chosen as a measure of DNA damage. The specimens held on acclimation under controlled laboratory conditions for 10 d were used as a control. Chemical analysis revealed the presence of phosphates and increased concentrations of zinc, copper and nickel at both sites during the entire sampling period. The values of OTM in mussels collected from the environment, significantly correlated with the concentration of zinc (r = 0.6248), temperature (r = 0.7006) and dissolved oxygen (r = 0.7738). Seasonal variations in genotoxic response were observed, with the highest OTM values obtained during summer months. Preliminary results of the in vitro study indicated the effect of water temperature on genotoxic response to zinc and cadmium in S. woodiana suggesting that the presence of genotoxic pollutants during months with lower temperature could be under-estimated. Obtained results indicate that S. woodiana could be a valuable tool for active biomonitoring of aquatic environments and emphasizes the importance of seasonal genotoxic monitoring with this organism.     

Cancer risk assessment after exposure from natural radionuclides in soil using Monte Carlo techniques

Purpose  

The purpose of this paper is to assess fatal cancer risk after external and internal (inhalation and ingestion) exposure from natural radionuclides in soil like ²³⁸U, ²³²Th, ⁴⁰K, and ²²⁶Ra on the territory of Bela Crkva, Serbia. Although receiving doses are low from sources like natural radionuclides in soil, because of stochastic effects of ionizing radiation, risk for developing cancer exists and can be quantified.     

The Quality of Water in the Buško Blato Reservoir

The article presents the results of chemical andmicrobiological measurements of the water quality in theBuko Blato reservoir, the largest in Europe, in the period 1989 to 1998.The aim was to observe possiblechanges in water quality during the past decade and itsinfluence on the downstream section of the Cetina River andits numerous tributaries and reservoirs, where there are twolarge regional water supply systems. This reservoir wasbuilt in order to exploit the high hydro-electric potentialof small streamflows in the karst fields of south-westernBosnia. It has strongly influenced the hydrologicconditions of the downstream section of the Cetina River.Buko Blato is a relatively shallow reservoir with the meandepth of 5 m. It covers an area of 57 km². The waterexchange in the reservoir is slow, occurring from one toseveral years. When the water inflow exceeds the hydroelectric plant demands the excess water is delivered by a reversible channel and pre-pumped into the Buko Blato reservoir. The total and carbonate water hardness in thereservoir is lower than in the Cetina River and in typicalkarst streamflows, since the water in this reservoir comesmainly from surface sources including numerous springs withhigh capacity oscillations, torrents and rainfall.Measurements, carried out during the past years, showed asignificant increase in nitrate content as well as in thecoli bacteria and a less significant increase in totalphosphorus content. The water quality was evaluated asmezotrophic according to the total phosphorus content basedon the Carlson index of trophic level, a lower quality thanin the Perua reservoir, upstream on the Cetina River. Thelatter contains a smaller phosphorus content and wasclassed between oligotrophic and mezotrophic. According tothese data, employing the Vollenweider equation, the totalphosphorus content in this water should not exceed the meanof 20 mg m^-3 P. The results indicate that the water inthe Buko Blato reservoir did not deteriorate the waterquality on the downstream section of the Cetina River.     

Development of a fast instrumental method for the analysis of pharmaceuticals in environmental and wastewaters based on ultra high performance liquid chromatography (UHPLC)-tandem mass spectrometry (MS/MS)

This work describes the development, optimization and validation of an analytical method for the simultaneous detection and identification of 74 pharmaceutically active compounds (PhACs), from various therapeutic groups, in both environmental (ground and surface water) and wastewaters (WW). The method is based on the simultaneous extraction of all target compounds by solid phase extraction (SPE), using a hydrophilic-lipophilic balanced polymer followed by ultra high performance liquid chromatography (UHPLC) tandem mass spectrometry (MS/MS). Two selected reaction monitoring (SRM) transitions have been monitored per compound in order to fulfil the EC guidelines, as well as to ensure an accurate identification of target compounds in the samples. Quantification is performed by internal standard approach, applying 24 specific isotopically labeled compounds. The main advantages of the developed method, besides the selectivity and reliability of the results, is its high throughput. All compounds are extracted in a single step and the instrumental analysis lasts 5 min (NI mode) + 8 min (PI mode), allowing fast throughput of samples. The limits of detection range from 0.01 to 50 ng L⁻¹, depending on the matrix, for most of the compounds. Finally, the method developed has been applied to the analysis of pharmaceuticals in the Ebro river basin (NE Spain).     

Ex situ bioremediation of a soil contaminated by mazut (heavy residual fuel oil)--a field experiment

Mazut (heavy residual fuel oil)-polluted soil was exposed to bioremediation in an ex situ field-scale (600 m(3)) study. Re-inoculation was performed periodically with biomasses of microbial consortia isolated from the mazut-contaminated soil. Biostimulation was conducted by adding nutritional elements (N, P and K). The biopile (depth 0.4m) was comprised of mechanically mixed polluted soil with softwood sawdust and crude river sand. Aeration was improved by systematic mixing. The biopile was protected from direct external influences by a polyethylene cover. Part (10 m(3)) of the material prepared for bioremediation was set aside uninoculated, and maintained as an untreated control pile (CP). Biostimulation and re-inoculation with zymogenous microorganisms increased the number of hydrocarbon degraders after 50 d by more than 20 times in the treated soil. During the 5 months, the total petroleum hydrocarbon (TPH) content of the contaminated soil was reduced to 6% of the initial value, from 5.2 to 0.3 g kg(-1) dry matter, while TPH reduced to only 90% of the initial value in the CP. After 150 d there were 96%, 97% and 83% reductions for the aliphatic, aromatic, and nitrogen-sulphur-oxygen and asphaltene fractions, respectively. The isoprenoids, pristane and phytane, were more than 55% biodegraded, which indicated that they are not suitable biomarkers for following bioremediation. According to the available data, this is the first field-scale study of the bioremediation of mazut and mazut sediment-polluted soil, and the efficiency achieved was far above that described in the literature to date for heavy fuel oil.     

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.     

The Adsorption of Formaldehyde on Suspended Particles investigated on model systems

Our laboratory investigation aimed at assessing to what extent suspended particles could adsorb formaldehyde, allowing it, when inhaled, to penetrate deeper into the lung. We used two types of pure soot, N-220 and N-660 (the former being a highly active oil furnace soot with smaller particles and a larger surface area than the latter), because of their chemical inactivity and the adsorptive properties. The results obtained in experimental conditions showed that soot particles could bind 2.3 to 50.2% of formaldehyde, depending on the particle size, relative humidity, amount of particles and the duration of the contact. The recovery of formaldehyde from the particles was also tested. Further investigation is planned under realistic conditions.     

Spatial distribution of trace metals in the Krka River, Croatia: an example of the self-purification

The spatial distribution of dissolved and total trace metals (Zn, Cd, Pb and Cu) in the Krka River (partly located in the Krka National Park) has been studied using a "clean" sampling, handling and analysis technique. Differential pulse anodic stripping voltammetry (DPASV) with a hanging mercury drop electrode (HMDE) has been used for trace metal analysis. The Krka River has been divided into the upper and lower flow region with respect to the metals concentration and main physico-chemical parameters. A significant increase in trace metal concentration as the result of the untreated waste water discharge downstream of Knin Town has been registered in the upper flow region. Due to a specific characteristic of the Krka, the so-called self-purification process, a decrease in the elevated trace metals concentration from the water column takes place at numerous small lakes formed by tufa barriers (at the end of the upper flow region). The clean groundwater input at the beginning of the lower flow region additionally contributes to the observed decrease in trace metals concentration in the Krka, maintaining them at a very low level in the remaining region of fresh-water flow. The determined median total concentrations were zinc 120-7400 ng l(-1), cadmium 3-8 ng l(-1), lead 11-250 ng l(-1) and copper 110-440 ng l(-1). Karst rivers, such as the Krka River, with extremely low natural concentrations of trace metals are highly sensitive to the anthropogenic influence. Therefore, such aquatic systems require implementation of strict protection regimes in the entire catchments area.