Preliminary background ozone concentrations in the mountain and coastal areas of Bulgaria

Urban and non-urban rural ozone (O3) concentrations are high in Bulgaria and often exceed the European AOT40 ecosystem as well as the AOT60 human health standards. This paper presents preliminary estimates to establish background, non-urban O3 concentrations for the southern region of Bulgaria. Ozone concentrations from three distinctly different sites are presented: a mountain site influenced by mountain-valley wind flow; a coastal site influenced by sea-breeze wind flow; and a 1700-m mountain peak site without 'local' wind flow characteristics. The latter offers the best estimate of 46-50 ppb for a background O3 level. The highest non-urban hourly value, 118 ppb, was measured at the mountain-valley site.     

Theoretical study of the dechlorination reaction pathways of octachlorodibenzo-p-dioxin

The dechlorination reaction pathways of 1,2,3,4,6,7,8,9-octachlorodibenzo-p-dioxin (OCDD) by the hydrogen atom are investigated by the density-functional theory B3PW91 method. The dechlorination reactions have large exothermicity and small activation energies. The activation energies (approximately 5 kcal/mol) of the sigma-complex formation due to the hydrogen addition are lower than those (approximately 9 kcal/mol) of the direct chlorine abstraction. It is suggested that the sigma-complex plays an important role in the reactions, although it has scarcely been shown in previous studies of the dechlorination of dioxins. The sigma-complex formation is favored at low temperatures and the chlorine abstraction is favored at high temperatures. Furthermore, it is found that the lateral positions have a marginal preference over the longitudinal positions. The dechlorination of OCDD by the hydrogen atom is thus not likely to result in a dominant formation of the laterally substituted toxic congeners.     

Decarboxylation and alkaline colour fading reactions in presence of humic substances

Humic substances (HSs) can substantially influence velocity of reactions in the environment as shown on example of decarboxylation and alkaline colour (e.g., malachite green and crystal violet) fading reactions. In colour fading and decarboxylation reactions of 6-nitrobenzisoxazole-3-carboxylic acid HS act as inhibitors, but additions of surfactants change the pattern of reaction. The inhibitory activity of HSs much depends on their origin. The velocity of studied reactions depends also on pH, temperature and concentration of HS used. Possible micellar catalysis mechanism has been suggested.     

Microbially mediated redox processes in natural analogues for radioactive waste

Natural analogues allow scientists to investigate biogeochemical processes relevant to radioactive waste disposal that occur on time scales longer than those that may be studied by time-limited laboratory experiments. The Palmottu U-Th deposit in Finland and the Bangombé natural nuclear reactor in Gabon involve the study of natural uranium, and are both considered natural analogues for subsurface radioactive waste disposal. The microbial population naturally present in groundwater may affect the redox conditions, and hence, the radionuclide solubility and migration. Therefore, groundwater samples from the two sites were investigated for microbial populations. The total numbers of cells ranged from 10(4) to 10(6) cells ml(-1). Iron-reducing bacteria (IRB) were the largest culturable microbial population in the Palmottu groundwater and were present at up to 1.3 x 10(5) cells ml(-1). Sulfate-reducing bacteria (SRB) and acetogens could also be cultured from the Palmottu groundwater. The numbers of IRB and SRB were largest in groundwater with the lowest uranium concentrations. Removal of dissolved U(VI) from solution was concomitant with the growth of IRB enrichment cultures and the reduction of iron. The redox buffer in the Palmottu groundwater consists of iron and uranium species, both of which are affected by IRB. IRB and aerobic heterotrophs were cultured from the Bangombé groundwater, where redox potentials are buffered by iron and organic carbon species. Microbial populations similar to those found at Palmottu and Bangombé are found throughout the Fennoscandian Shield, a potential host rock for subsurface radioactive waste disposal. These results confirm that microorganisms can be expected to play a role in stabilizing radioactive waste disposed of in the subsurface by lowering redox potential and immobilizing radionuclides.     

Relationships between bacterial tolerance levels and forms of copper and zinc in soils

The effects of various fractions of copper (Cu) and zinc (Zn) on soil bacteria were evaluated by the heavy metal tolerance level of the bacterial community (IC50) in soil samples collected near a mine. The IC50 values had no relationship with the total concentrations of Zn and Cu in the soils, but were weakly correlated with the 0.05 M CaCl2-extractable form of each metal in the soils (Cu: R2 = 0.670, p < 0.01; Zn: R2 = 0.453, p < 0.05). It was found that the IC50 correlated strongly with the total concentration of each metal in the extracts from water-saturated soil samples, described below as "soil solution" (Cu: R2 = 0.789, p < 0.01; Zn: R2 = 0.617, p < 0.01). The speciation of these metals in the soil solutions was estimated using an equilibrium thermodynamic computer model, SOILCHEM. Simulated free Cu ion ranged from 18 to 98% of total Cu, and organic complexes of Cu ranged from < 1 to 56%. In all samples, Zn existing as the free ion was estimated to be more than 80% of total Zn in the soil solutions. The IC50 values were also correlated with the estimated free metal ion activities, but with slightly lower correlation coefficients than found for total concentration in the soil solutions (Cu: R2 = 0.735, p < 0.01; Zn: R2 = 0.610, p < 0.01). The results suggest that not only high metal ion activities, but also total dissolved metal concentrations in soil solutions may affect the bacterial community.     

Point- and nonpoint-source pesticide contamination in the Zwester Ohm catchment, Germany

Reducing pesticide loads in surface waters implies identifying the pathways responsible for the pollution. The current study documents the pesticide contamination of the river Zwester Ohm, a 4917-ha catchment in Germany with 41% of the land used for crop production. Discharges and concentrations of 19 pesticides were measured continuously at three locations for 15 mo. The load detected at the outlet of the catchment amounted to 9048 g a.i. The losses represent 0.22% of the pesticides applied by the farmers. The contamination showed a seasonal pattern following the pesticide application times. The wastewater treatment plant system (WWTPS) in the catchment (two wastewater treatment plants [WWTP], 14 combined sewer overflows (CSO), four CSO tanks) emits during dry weather periods purified sewage and during storm events sewage mixed with stormwater runoff into the river. The contribution by the WWTPS to the pesticide load was defined as point-source pollution (PSP). The load was dominated by PSP with at least 77% of the total pollution. No significant interdependencies between intrinsic properties of the pesticides, hydrometeorological factors, and the loads occurring in the stream could be found. Therefore, it is not possible to predict PSP for other catchments based on the results from this study. Whereas 65% of the total load entered the river via the WWTP, a portion of 12% was attributed to the CSO. The study points out that the influence of CSO on PSP should be taken into account in future catchment studies in areas with comparable agricultural structure.     

Radioactive contamination in the Arctic--sources, dose assessment and potential risks

Arctic residents, whose diets comprise a large proportion of traditional terrestrial and freshwater foodstuffs, have received the highest radiation exposures to artificial radionuclides in the Arctic. Doses to members of both the average population and selected indigenous population groups in the Arctic depend on the rates of consumption of locally-derived terrestrial and freshwater foodstuffs, including reindeer/caribou meat, freshwater fish, goat cheese, berries, mushrooms and lamb. The vulnerability of arctic populations, especially indigenous peoples, to radiocaesium deposition is much greater than for temperate populations due to the importance of terrestrial, semi-natural exposure pathways where there is high radiocaesium transfer and a long ecological half-life for this radionuclide. In contrast, arctic residents with diets largely comprising marine foodstuffs have received comparatively low radiation exposures because of the lower levels of contamination of marine organisms. Using arctic-specific information, the predicted collective dose is five times higher than that estimated by UNSCEAR for temperate areas. The greatest threats to human health and the environment posed by human and industrial activities in the Arctic are associated with the potential for accidents in the civilian and military nuclear sectors. Of most concern are the consequences of potential accidents in nuclear power plant reactors, during the handling and storage of nuclear weapons, in the decommissioning of nuclear submarines and in the disposal of spent nuclear fuel from vessels. It is important to foster a close association between risk assessment and practical programmes for the purposes of improving monitoring, formulating response strategies and implementing action plans.     

Comparative studies of health hazard from radon (Rn-222) in two selected lithologic formations in the Suwałki region (in Poland)

The aim of this work was to make a comparison of indoor radon concentrations in dwellings and in soil air in the area of two geological formations in the Suwa?ki region (Poland). The mean arithmetic airborne concentration was found to be the highest (301 Bq m (-3)) in the basements of buildings in the gravel and sand areas, whereas in the boulder clay areas it reached 587 Bq m (-3). Out of 54 measurements of radon concentrations performed at the ground floor, in eight cases concentrations were found to exceed 200 Bq m (-3) - permissible radon level in new-built houses in Poland and in three cases these values were even higher than 400 Bq m (-3). The highest radon levels were noted in houses with earthen basement floors and with direct entrance from the basement to rooms or kitchens. The mean arithmetic radon concentration in the soil air in the sandy and gravel formations was 39.7 kBq m (-3) and in clay formation it was 26.5 kBq m (-3). Higher radon levels were also found in the water obtained from household wells reaching 8367 Bq m (-3) as compared with tap water (2690 Bqm (-3)). The mean indoor concentration for the whole area under study was found to be 169.4 Bq m (-3), which is higher than the mean value for Poland (49.1 Bq m (-3)) by a factor of 3.5.     

Thermal neutron fluence from ultra low-level gamma-ray spectrometry of spoons activated during the JCO criticality accident at Tokai-mura in 1999

During the JCO-accident in Tokai-mura in 1999, the surrounding village was irradiated by an uncontrolled neutron flux. At some locations in that village, the thermal neutron flux was determined retrospectively by measurement of the very low activity of 51Cr and 60Co in stainless-steel spoons using gamma-ray spectrometry in underground laboratories. Activities determined in the HADES underground facility are presented here, together with calibrations performed using a well-defined thermal neutron flux to directly estimate the fluence of thermal neutrons independent of most assumptions. The results show measurable 51Cr in three samples and 60Co in four samples taken from locations at distances of up to 430m from the accident location despite the elapse of 4 half-lives of 51Cr before measurement. Effects of air transport of the samples were considered and shown to be negligible.     

Measurements of radon around closed uranium mines

There are several waste rock yards at closed uranium mines around Ningyo-toge, in the Western Honshu Island of Japan, and measurements of radon were carried out by both the passive method and the sampling method around these yards. As comparatively high radon concentrations were observed in two districts through routine measurements, more detailed measurements were made by the passive method in these districts. The impact of radon emanation from the waste rock yards was small for both residential districts and around these yards when considering the natural background level of radon. In addition, by simultaneous continuous measurements of radon and its progeny at two locations, it was estimated that the effective dose caused by the representative uranium waste rock yards was less than the public effective dose limit of 1 mSv year(-1) at the fenced boundary of the waste rock site.