Spatial patterns and ratios of ¹³7Cs, 9°Sr, and Pu isotopes in the top layer of undisturbed meadow soils as indicators for contamination origin.

Spatial distribution of activity concentrations of (137)Cs, (90)Sr, and (239,240)Pu in the top layer of undisturbed meadow soils was compared between two regional transects across Lithuania: one in the SW region, more affected by the Chernobyl radioactive fallout, and the other in the NE region. Radiochemical, γ-, α-, ß-, and mass spectrometric methods were used to determine the radionuclide activity. Our results validate that higher activity concentrations in the top soil layer were present in the SW region, despite the fact that sampling was performed after 22 years of the Chernobyl Nuclear Power Plant (NPP) accident. Using the activity concentration ratio (137)Cs/(239,240)Puglobal, the contribution of the Chernobyl NPP accident to the total radiocesium activity concentrations in these meadow soils was evaluated and found to be in the range of 6.5-59.1%. Meanwhile, the activity concentration ratio (238)Pu/(239,240)Pu showed that Chernobyl-derived Pu occurred at almost half of the sampling sites. The locations with maximal values of 47% of Chernobyl-derived Pu material were close to northeastern Poland, where deposition of most of non-volatile radioisotopes from the Chernobyl plume was determined.

Evaluation of Physico-Chemical Characteristics of Cement Superplasticizer Based on Polymelamine Sulphonate.

Cementitious materials are used to construct an engineered barrier in repositories for radioactive waste. The cement matrix may contain a variety of organic compounds, some of which are polymeric admixtures used as plasticizers. Superplasticizers (SPs) are highly effective organic cement additives for reducing water amount, increasing workability, homogeneity, plasticity and the non-segregation of mortars and grouts, improving mechanical properties and resistance to destructive environments. SPs in cement could have an impact on the long-term safety of the disposals of radioactive waste. These organic agents can leach from the cementitious matrix into groundwater and may affect the migration behaviour of radionuclides. The detailed chemical composition and other characteristics of the cement (CEM I 42.5 R, Sweden) used for the leaching experiments were evaluated. It contained mainly CaO (52.51 ± 1.37, %), and the surface area of the cement particles was 13.2 ± 1.3 m2/g. An insignificant increase in pH (from 12.6 ± 0.1 to 12.8 ± 0.1) was observed for the leachates over 10 days. A commercially available cement superplasticizer based on polymelamine sulphonate (PMS) Peramin SMF10 (Peramin AB, Sweden) was chosen for the research. The product's chemical composition was analysed using wavelength-dispersive X-ray fluorescence (WD-XRF) spectroscopy, while other physico-chemical properties of the PMS superplasticizer were assessed by Raman spectroscopy and thermo-gravimetric analysis. In aqueous solutions and powders of PMS, the same most intensive features were observed at 774 cm-1 (ring out-of-plane deformation), 977 cm-1 (C-N-C bending, SO stretching) and 1055 cm-1 (C-N=C bending) in the Raman spectra. At up to 270 °C, the polymer was thermally stable. Raman and UV/Vis spectroscopies were used to assess the rate of the alkaline degradation of PMS superplasticizer in different aqueous solutions. No changes were observed in the hydrolytic solutions with any of the above analytical methods over a period of 3 years. The results obtained revealed a good thermal and chemical stability (in highly alkaline media, pH = 9.9-12.9) of the PMS polymer.

Analysis of the vertical distribution of 137Cs and 239,240Pu in waterlogged and non-boggy soils by the sequential extraction method.

Mobile capabilities of 137Cs, 239,240Pu and some stable element physicochemical forms were studied in soil layers at a depth of 6-8 cm (maximum concentrations of radionuclides) of non-boggy and waterlogged soil cores sampled on the shores of Lake Bedugnis (Lithuania). Soil samples were acidic with small amount of clay (muscovite). The radionuclide activity concentrations were about 2.5 times higher in non-boggy soil. It was explained by different conditions of deposition of radioactive fallout at these sampling sites and density of the soil samples. The value of the exchangeable fraction of radionuclides is shown to be an indicator of their migration capabilities in the soil. Under anaerobic conditions in waterlogged soil (stagnant pore water conditions) and due to the presence of clay admixture, ∼90% of 137Cs was concentrated in the residual fraction and its mobility was low. 239,240Pu was concentrated mainly in organic matter with rather large exchangeable fractions (∼9.6-∼13.9%). Under oxidizing conditions in non-boggy soil (dynamic pore water conditions in the case of rain), 239,240Pu was mostly concentrated in the oxide fraction. Its exchangeable fractions were less than those in waterlogged soil and, respectively, its mobility was lower. In non-boggy soils, exchangeable fractions of 137Cs were large and varied in the range of 10.1-12.2%, which indicated its high mobility. In the case, 137Cs adsorption by clay materials was reduced and its residual fraction did not exceed 71.3%. The obtained data show that in the area of Lake Bedugnis, the migration capabilities of 137Cs and 239,240Pu change in antiphase.

Impact of soil organic matter on Pu migration in five Lithuanian surface soils.

Pu distribution coefficient Kd variation was experimentally determined and examined in natural soil samples considering the type of soil, particle size, pH, the concentration of macroelements and organic matter content. This research was carried out with sand, silty sand, peat, clayey sand and clayey loam samples by applying 236Pu tracer in flow-through column tests. Due to relatively short contact time of 0.5-40 h the tests are considered as have not reached equilibrium state and represent the fast-moving contaminants retardation processes closer to field conditions. Every soil sample was fractionated into two particle size fractions: ≤0.25 mm and 0.25 ÷ 0.5 mm. Analysis revealed that Kd of Pu is higher for the smaller soil particle fraction (≤0.25 mm). The experimental study with 1.6, 4, 6 and 9 pH tracer solution revealed a tendency of elevated Kd when 4 pH and 6 pH solutions were applied, but obtained Kd values were not correlated with initial soil pH due to high buffering capacity of soils. This study shows a very significant influence (r = 0.98) of organic matter content on the Pu distribution coefficient. The Kd of Pu for the fine fraction of peat soil with high organic matter content (67%) reached maximum values of 6597 L/kg and 6200 L/kg when tracer solution was applied of pH = 4 and pH = 6, respectively. In comparison, the minimum Kd value of 3.9 L/kg was obtained for the coarse silty sand fraction with the lowest organic matter content of 1.3% at tracer pH = 1.6. A statistically reliable high correlations of r = 0.95 and 0.94 were also observed between Kd and specific soil elements Mg and Pb content in soils, respectively. The content of Fe in soils was significantly correlated (r = 0.67) with the Kd values of plutonium as well. However, the organic matter content in soils appeared to be the governing factor determining good correlations and causing the highest Kd of Pu values.

Distribution of radiocarbon in sediments of the cooling pond of RBMK type Ignalina Nuclear Power Plant in Lithuania.

The vertical distribution of radiocarbon (14C) was examined in the bottom sediment core, taken from Lake Druksiai, which has served as a cooling pond since 1983 for the 26 years of the Ignalina Nuclear Power Plant (INPP) operation using two RBMK-1500 reactors (Russian acronym for"Channelized Large Power Reactor"). 14C specific activity was measured in alkali-soluble and -insoluble fractions of the sediment layers. Complementary measurements of the 210Pb and 137Cs activity of the samples provided the possibility to evaluate the date of every layer formation, covering the 1947-2013 period. In addition, 14C distribution was examined in the scales of pelagic fish caught between 1980 and 2012. Our measurements reveal that, during the period 1947-1999, the radiocarbon specific activity in both fractions exhibits a parallel course with a difference of 5 ± 1 pMC (percent of modern carbon) being higher in alkali-soluble fraction, although 14C specific activity in both fractions increased by 11.4-13.6 pMC during the first 15 years of plant operation. However, during the 2000-2009 period, other than previously seen, a dissolved inorganic carbon (DIC) → aquatic primary producers → sediments 14C incorporation pattern occurred, as the radiocarbon specific activity difference between alkali-soluble and -insoluble fractions reached 94, 25, and 20 pMC in 2000, 2006, and 2008, respectively. Measurements in different sediment fractions allowed us to identify the unexpected organic nature of 14C contained in liquid effluences from the INPP in 2000-2009. The discrepancy between 14C specific activity in fish scales samples and DIC after 2000 also confirmed the possibility of organic 14C contamination. Possible reasons for this phenomenon might be industrial processes introduced at the INPP, such as the start of operation of the cementation facility for spent ion exchange resins, decontamination procedures, and various maintenance activities of reactor aging systems and equipment.

Uncertainty of determination of 158Tb in the RBMK nuclear reactor waste.

The activity of 158Tb was measured in waste samples from the Ignalina NPP Unit I RBMK-1500 reactor using gamma-ray spectrometry. The origin of 158Tb and the other observed gamma-ray emitters has been studied by using SCALE 6.1 modeling and comparing radionuclide ratios in the RBMK-1500 radioactive waste. The results of the calculation of the massic activity of gamma-ray emitters were used for interpretation of the total gamma-ray spectrum and the determination of 158Tb massic activity uncertainty in the waste of RBMK-1500.

Study of plutonium migration and/or accumulation in soil under field and laboratory conditions.

This study investigated the dependence of Pu3+ and Pu4+ vertical distribution on the soil characteristics in soddy and forest soil. Soil samples were analysed for organic matter and pH. Special columns with contaminated (239Pu) soil surface were kept for 326 days under field conditions. The analysis of the contaminated soil layers (5 cm each, totalling 20 cm) showed that 81% of 239Pu4+, 44% of 239Pu3+ and 82% of 239Pu4+, 61% of 239Pu3+ were accumulated in the 0-5 cm layer of soddy and forest soil. Sequential extraction of the soddy soil 30 days after surface contamination with 239Pu, 137Cs and 90Sr showed the following differences in radionuclide distribution: the largest amount of 239Pu (60%) and 137Cs (70%) were extracted from the residual fraction while 90Sr in this fraction reached only about 10%. This suggests that organic substances and some inorganic compounds, which usually are the main components of the residual fraction, affect the retention and migration of plutonium in the soil.

Behaviour of (99)Tc in aqueous solutions in the presence of iron oxides and microorganisms.

A set of experiments was performed to determine the factors that influence TcO4(-) interaction with Fe-bearing minerals and to explore the effect of microbial activity on the behaviour of Tc(VII) in solution, in the presence of iron oxides under oxidizing medium. Gradual sorption of TcO4(-) (aq) onto wustite/magnetite was observed under alkaline conditions (pH 8-9). No pronounced effect of TcO4(-) (aq) interaction with hematite was observed in the investigating alkaline systems. At low pH values (2.7-4.5), TcO4(-) retention on hematite increases, suggesting that the process is dependent on pH. Sorption of (99)Tc (VII) onto hematite at pH 7.6-8.0 was achieved because of the presence of specific microorganisms.

Effect of microorganisms on the plutonium oxidation states.

Particular microbes from substrates at the low-level radioactive waste repository in the Ignalina NPP territory were exposed to (239)Pu (IV) at low pH under aerobic conditions. Pu(III) and Pu(IV) were separated and quantitatively evaluated using the modified anion exchange method and alpha spectrometry. Tested bacteria Bacillus mycoides and Serratia marcescens were more effective in Pu reduction than Rhodococcus fascians. Fungi Paecillomyces lilacinus and Absidia spinosa var. spinosa as well as bacterium Rhodococcus fascians did not alter the plutonium oxidation state.