Quantifying summed fullerene nC60 and related transformation products in water using LC LTQ Orbitrap MS and application to environmental samples

The application of engineered nanomaterials increases strongly. Development of analytical techniques and their application to environmental samples is essential for human and environmental risk assessment of the nanoparticles. The objective of this study was to develop a sensitive analytical method to quantify nC(60) in water, using accurate mass screening liquid chromatography-hybrid linear ion trap Orbitrap mass spectrometry. nC(60) can be transformed by oxidation, reduction and photochemical reaction. Therefore, the formation of some transformation products of nC(60) was studied as well. Finally, the developed analytical method was applied to surface water samples from several locations in the Netherlands. The developed method enabled to detect and quantify aqueous concentrations of the summed nC(60) and its transformation products as low as 5 ng/L. It was observed that nC(60) transformation products exceed quantities of the parent C(60). Despite the high sensitivity of the developed method, no nC(60) or transformation products were detected in an array of Dutch surface waters. This might be due to low emissions, losses in the aqueous phase by sedimentation, sorption or further transformation processes.     

Evaluating and reducing a model of radiocaesium soil-plant uptake

An existing model of radiocaesium transfer to grasses was extended to include wheat and barley and parameterised using data from a wide range of soils and contact times. The model structure was revised and evaluated using a subset of the available data which was not used for model parameterisation. The resulting model was then used as a basis for systematic model reduction to test the utility of the model components. This analysis suggested that the use of 4 model variables (relating to radiocaesium adsorption on organic matter and the pH sensitivity of soil solution potassium concentration) and 1 model input (pH) are not required. The results of this analysis were used to develop a reduced model which was further evaluated in terms of comparisons to observations. The reduced model had an improved empirical performance and fewer adjustable parameters and soil characteristic inputs.     

Estimating sediment and caesium-137 fluxes in the Ribble Estuary through time-series airborne remote sensing

High spatial and temporal resolution airborne imagery were acquired for the Ribble Estuary, North West England in 1997 and 2003, to assess the application of time-series airborne remote sensing to quantify total suspended sediment and radionuclide fluxes during a flood and ebb tide sequence. Concomitant measurements of suspended particulate matter (SPM) and water column turbidity were obtained during the time-series image acquisition for the flood and ebb tide sequence on the 17th July 2003 to verify the assumption of a vertically well mixed estuary and thus justifying the vertical extrapolation of spatially integrated estimate of surface SPM. The ¹³⁷Cs activity concentrations were calculated from a relatively stable relationship between SPM and ¹³⁷Cs for the Ribble Estuary. Total estuary wide budgets of sediment and ¹³⁷Cs were obtained by combining the image-derived estimates of surface SPM and ¹³⁷Cs with estimates of water volume from a two-dimensional hydrodynamic model (VERSE) developed for the Ribble Estuary. These indicate that around 10,000 tonnes of sediment and 2.72 GBq of ¹³⁷Cs were deposited over the tidal sequence monitored in July 2003. This compared favourably with bed height elevation change estimated from field work. An uncertainty analysis on the total sediment and ¹³⁷Cs flux yielded a total budget of the order of 40% on the final estimate. The results represent a novel approach to providing a spatially integrated estimate of the total net sediment and radionuclide flux in an intertidal environment over a flood and ebb tide sequence.     

Sorption of selenate on soils and pure phases: kinetic parameters and stabilisation

This study was conducted to identify the principle selenate carrier phases for two selected soils, by comparing their reactivity with selenate to that of pure phases of the solids. Silica, calcium carbonate, aluminium hydroxide, goethite, bentonite and humic acid were selected as the main soil carrier phases. Comparisons were made first on the parameter values obtained with the best fit of a kinetic sorption model which can discriminate instantaneous sorption from kinetically limited sorption. Then comparisons were made of the ability for each solid to stabilise selenate by measuring the ratio of the partition coefficient for sorption (Kd_sorption) over that of the desorption (Kd_desorption). Kinetics and stabilisation were used to help elucidate the nature of interactions with the test solid phases for a large range of selenate concentrations. The experiments were conducted over 165 h in batch reactors, the solid being isolated from the solution by dialysis tubing, at two pH (5.4 and 8) and three selenate concentrations (1 × 10⁻³, 1 × 10⁻⁶ and 1 × 10⁻⁸ mol L⁻¹). The results obtained showed that only aluminium hydroxide can sorb selenate throughout the studied pH range (pH 5.4 to 8.0). The sorption capacity on this mineral was high (Kd_sorption > 100 to 1 × 10⁴ L kg⁻¹) and the selenate was mainly stabilized by the formation of inner sphere complexes. The sorption on goethite occurred at pH 5.4 (Kd_sorption 52 L kg⁻¹), mainly as outer sphere complexes, and was null at pH 8. On silica, a weak sorption was observed only at pH 5.4 and at 165 h (Kd_sorption 4 L kg⁻¹). On bentonite, calcium carbonate and humic acid no significant sorption was observed. Concerning the two soils studied, different behaviours were observed for selenate. For soil Ro (pH 5.4), Kd_sorption was low (8 L kg⁻¹) compared to soil Bu (pH 8) (70 L kg⁻¹). The sorption behaviour of selenate on soil Ro was mainly due to outer sphere complexes, as for goethite, whereas for soil Bu the sorption was mainly attributed to inner sphere complexes followed by reduction mechanisms, probably initiated by microorganisms, in which no steady state was reached at the end of the 165 h experiments. The sorption of selenate decreased when concentrations reached 1 × 10⁻³ mol L⁻¹, due to solid saturation, except for aluminium hydroxide. Reduction of selenate seemed also to occur on goethite and soil Ro, for the same concentration, but without preventing a decrease in sorption. Thus, this work shows that the comparison of selenate behaviour between soil and pure phases helps to elucidate the main carrier phases and sorption mechanisms in soil.     

Radiological maps for Trabzon, Turkey

The activity concentrations and absorbed gamma dose rates due to primordial radionuclides and ¹³⁷Cs have been ascertained in 222 soil samples in 18 counties of the Trabzon province of Turkey using a HPGe detector. The mean activity concentrations of ²³⁸U, ²³²Th, ⁴⁰K and ¹³⁷Cs in soil samples were 41, 35, 437 and 21 Bq kg⁻¹, respectively. Based on the measured concentrations of these radionuclides, the mean absorbed gamma dose in air was calculated as 59 nGy h⁻¹ and hence, the mean annual effective dose due to terrestrial gamma radiation was calculated as 72 μSv y⁻¹. In addition, outdoor in situ gamma dose rate (D) measurements were performed in the same 222 locations using a portable NaI detector and the annual effective dose was calculated to be 66 μSv y⁻¹ from these results. The results presented in this study are compared with other parts of Turkey. Radiological maps of the Trabzon province were composed using the results obtained from the study.     

Effect of americium-241 on luminous bacteria. Role of peroxides

The effect of americium-241 (²⁴¹Am), an alpha-emitting radionuclide of high specific activity, on luminous bacteria Photobacterium phosphoreum was studied. Traces of ²⁴¹Am in nutrient media (0.16-6.67 kBq/L) suppressed the growth of bacteria, but enhanced luminescence intensity and quantum yield at room temperature. Lower temperature (4 °C) increased the time of bacterial luminescence and revealed a stage of bioluminescence inhibition after 150 h of bioluminescence registration start. The role of conditions of exposure the bacterial cells to the ²⁴¹Am is discussed. The effect of ²⁴¹Am on luminous bacteria was attributed to peroxide compounds generated in water solutions as secondary products of radioactive decay. Increase of peroxide concentration in ²⁴¹Am solutions was demonstrated; and the similarity of ²⁴¹Am and hydrogen peroxide effects on bacterial luminescence was revealed. The study provides a scientific basis for elaboration of bioluminescence-based assay to monitor radiotoxicity of alpha-emitting radionuclides in aquatic solutions.     

Noninvasive molecular genetic analysis in studying the ecology of the snow leopard: Problems and prospects

Molecular genetic methods were used to perform the species and individual identification of 117 samples of hair and feces of carnivores collected in natural habitats. The species were identified for 85.5% of the samples. The analysis of the nucleotide sequences of the cytochrome b mitochondrial gene was used to identify the samples of hair and feces of snow leopards (Uncia uncia, 40%), red foxes (Vulpes vulpes, 48%), wolves (Canis lupus, 6%), and lynx (Lynx lynx, 5%). The analysis of eight microsatellite loci allowed the genotypes of 13 snow leopards to be described. The sex of 11 animals was identified.     

The state of predatory mammal populations in the impact zone of the Kalinin Nuclear Power Plant as inferred from their phene pool

The states of the populations of five dominant species of predatory mammals living in the area affected by the Kalinin Nuclear Power Plant (NPP) and in remote districts of Tver’ oblast have been compared. A total of 1120 skulls, including 708 skulls from the vicinity of the NPP, have been examined. The data on parameters characterizing similarities between the samples, the degree and structure of intrapopulation diversity, and ontogenetic stability suggest with a high probability that the Kalinin NPP has no effect on wild populations of predatory mammals.