Separation of anthropogenic radionuclides from aqueous environment using raw and modified biosorbents.

In this study, two types of biosorbents were used to remove 137Cs and plutonium isotopes from aqueous solutions - moss (Ptilium crista - castrensis) and oak sawdust (Quercus robur), both in the form of natural and modified state. Sorbent modification significantly increases the sorbent surface area (for moss sorbents - from 4.0 to 47.2 m2/g, and for sawdust sorbents - from 1.1 to 26.3 m2/g), pore volume (from 10-3 to 10-2), concentration and amount of basic cations and anions, as well as active functional groups on the sorbent surface. The main functional groups on the surface of natural sorbents modified with iron hydroxide interacting with analytes are carboxyl and hydroxyl groups. For carbonized sawdust and its subsequent activation with concentrated HCl, in addition to carboxyl and hydroxyl groups, acetyl groups also become active. Carbonated sawdust treated with HCl showed the highest average removal efficiency and sorption capacity for radiocesium and plutonium isotopes in laboratory column experiments - for 137Cs ∼78.6% and ∼196.6 Bq/g and for 239+240Pu ∼83% and ∼41.5 Bq/g, respectively. The moss and moss modified with iron hydroxide also showed good properties of adsorbing plutonium isotopes in field (in-situ) experiments. The best results on the sorption of 137Cs in field experiments were shown by carbonated sawdust activated with HCl, and for isotopes of plutonium - the raw moss and moss modified with iron hydroxide. The results of the study showed that sorbents can be used not only for purification of water from plutonium isotopes but allow the operational sampling and more accurate measurement of radiocesium and plutonium isotopes in the fresh water reservoirs by the dynamic flow method.

137Cs and plutonium isotopes accumulation/retention in bottom sediments and soil in Lithuania: A case study of the activity concentration of anthropogenic radionuclides and their provenance before the start of operation of the Belarusian Nuclear Power Plant (NPP).

Knowledge of the background activity concentrations of anthropogenic radionuclides before the start of operations of the new nuclear facilities in Belarus is of great value worldwide. Inland water bodies in Lithuania (specifically the Neris River, the Nemunas River and the Curonian Lagoon) are near the site of the Belarusian NPP under construction and, for this reason, sediments and flooded soils from these sensitive areas were analysed for radiocesium and plutonium isotopes (macrophytes were analysed only for 137Cs) in 2011-2012. The 137Cs and 239+240Pu activity concentrations in bottom sediments from the Nemunas River, sampled in 1995-1996 and re-calculated to the year 2016, were compared with those of 2011-2012. The obtained activity of 137Cs in bottom sediments of the Nemunas River and Curonian Lagoon varied from 1 Bq/kg to 47.0 Bq/kg. The activity of 137Cs in the tested soils ranged from 5.3 B g/kg to 32.9 Bq/kg. The 239+240Pu activity in bottom sediments of the studied sampling sites varied between 0.016 and 0.34 Bq/kg and in flooded soils from 0.064 to 0.55 Bq/kg. The 238Pu activity values were very low or lower than the detection limit. The activity of 137Cs in macrophytes varied from values lower than the detection limit to 6 Bq/kg. A strong positive linear correlation for bottom sediments was calculated between: 239+240Pu and total organic carbon (TOC), r = 0.86, p-value 0.01; 239+240Pu and silt, r = 0.80, p-value 0.029; 137Cs and silt, r = 0.78, p-value 0.04; and 137Cs and TOC, r = 0.85, p-value 0.015. The similar peculiarities of 137Cs and 239+240Pu accumulation in bottom sediments and flooded soil allow us to assume that 137Cs can be used as a tracer for 239+240Pu in the initial stage of searching for radionuclide accumulation zones. A remaining impact of the Chernobyl fallout in average comprised: in the Lower Nemunas River and Curonian Lagoon sediments - 51%, in the Middle Nemunas River -90% and in the floodplains of the Nemunas River - 59%, while the provenance of plutonium in studied bottom sediments and flooded soil was the global fallout.

Study of the formation of the primary 137Cs vertical profile in the organic matter-rich sediments.

A laboratory study of the formation of the primary vertical profile of the 137Cs activity concentration in the anaerobic organic matter-rich sediments was carried out. The incubation was performed using sediment baths method (initial thickness of the water layer over the sediments ∼40 cm, initial radiocesium activity concentration in water ∼14.53 Bq·L-1). An exponential profile (R2∼0.999) with the half-height width of ∼0.65 cm was formed after ∼32 days of the incubation. A further course of the experiment (sediments were sampled after 64, 130 and 293 days of the incubation) revealed deviations in the form of the radiocesium activity concentration profile related to the appearance of the additional Gauss factor with the increasing half-height width of ∼1.2, ∼1.3 and ∼3 cm, respectively. In spite of the evident growth of the half-height width, the radiocesium migration rate decreased from 0.02 cm·day-1 for the first 32 days of incubation down to 0.009 cm·day-1 at the end of the incubation experiment. Such a time-dependent decrease in the radiocesium migration is possibly related to the beginning of the second radiocesium migration phase depending on the retardation factor. Besides diffusion, the formation of vertical profiles of radiocesium activity concentrations in sediments was additionally induced by effects of buoyancy of the upper sediment layer due to the seepage of the above lying water into sediments.

On the mechanism of the enrichment in radiocesium of near-bottom water in Lake Juodis, Lithuania.

Evidence of the thermodynamic origin of a mechanism for radiocesium enrichment of near-bottom water based on the analysis of vertical profiles of standard water variables (pH, temperature, oxygen concentrations and conductivity) in Lake Juodis is presented. This mechanism is shown to be related to disturbances in the thermohalinic stability (buoyancy effects) of sediment interstitial liquids inducing their interfacial transfer. The mechanism reveals itself even in aerobic waters during cooling processes in autumn under weather conditions inducing the formation of a steep temperature gradient in the surface sediments. These gradients may be formed due to intense sediment cooling as well as in cases of cooling interruptions owing to the arrival of warm air masses inducing temperature stratification of the water column. In the latter case, a sharp decrease in the heat flux from sediments through the stagnant water column promotes relative overheating of the sediment surface layer and the consequent initiation of buoyancy forces inducing interfacial transfer of sediment interstitial liquids enriched in dissolved material. Intrusions of interstitial liquids and their vertical thermodynamic transfer through the water column are followed by the formation of a specific vertical structure consisting of a set of evenly mixed water layers which are especially distinctly observable under ice cover in winter. The mechanism is responsible for lake water contamination by radiocesium and other pollutants dissolved in interstitial liquids. The investigation results explain the phenomenon of "super warm" lakes where temperatures of near-bottom waters under ice in winter are higher than 4 degrees C.

On seasonal variations of radiocesium speciation in the surface sediments of Lake Juodis, Lithuania.

Data on radiocesium speciation measured seasonally in black silt surface sediments in the shallow terrace and in the deepest southern part of Lake Juodis (Lithuania) in 2004-2005 are presented. It is shown that seasonal variations of radiocesium exchangeable fractions in the sediments in the shallow terrace are mainly related to its redistribution due to the vital cycle of green algae covering bottom surfaces - processes of their growth and decomposition. A seasonal course of those fractions in surface sediments of the deepest bottom areas of the lake follows a distinct pattern and is annually recycling. It is maximum in winter and declines due to stagnant bottom water zone disruption in summer. It is shown that surface sediments in the deepest bottom areas of the lake are not a radiocesium source during the formation of the anaerobic zone in bottom water in winter, and act in that case as its acceptor. The radiocesium remobilization to the bottom water is seasonal and site-specific. It is suggested to be due to three main processes: its diffusion from deeper and more active sediments, its redistribution during decomposition of organics freshly accumulated in surface sediments and a radiocesium flux induced by the mechanism of the seasonal anaerobic zone formation in near-bottom water.

On the radiocesium carbonate barrier in organics-rich sediments of Lake Juodis, Lithuania.

Radiocesium vertical profiles in organics-rich sediments of running shallow eutrophic Lake Juodis (Lithuania) were studied in relation to seasonal variations of vertical profiles (in water column and sediments) of standard variables (pH, redox potential, temperature, oxygen concentrations, conductivity). It is shown that the sedimentation rate, radiocesium mobility and its vertical profiles in sediments are controlled by the vital cycle (processes of the growth, accumulation and decomposition) of green algae covering the main bottom areas of the lake. It is also shown that calcite deposits are formed in the shallow bottom areas that are oxygenated throughout the year because of the photosynthetic activity of the green algae covering the sediment. Formation of the calcite coatings on freshly accumulated organics is remarkable for causing elevated densities of sediment solids in the upper part of the respective vertical profiles. These calcite deposits behave as a barrier for radiocesium backward flux to the bottom water making the respective bottom areas a radionuclide sink. Together with the jelly-structured sediments lying below these deposits, the calcite preserves the shape of the primary radiocesium vertical profiles formed due to free-ion diffusion after the deposition event. It was determined that bottom areas anaerobic in winter are the main radiocesium source in the water column and cause characteristic radiocesium redistribution in surface sediments.