Reactive barriers for Cs retention

¹³⁷Cs was dispersed globally by cold war activities and, more recently, by the Chernobyl accident. Engineered extraction of ¹³⁷Cs from soils and groundwaters is exceedingly difficult. Because the half-life of ¹³⁷Cs is only 30.2 years, remediation might be more effective (and less costly) if ¹³⁷Cs bioavailability could be demonstrably limited for even a few decades by use of a reactive barrier. Essentially permanent isolation must be demonstrated in those few settings where high nuclear level wastes contaminated the environment with ¹³⁵Cs (half-life 2.3×10⁶ years) in addition to ¹³⁷Cs. Clays are potentially a low-cost barrier to Cs movement, though their long-term effectiveness remains untested. To identify optimal clays for Cs retention, Cs desorption was measured for five common clays: Wyoming Montmorillonite (SWy-1), Georgia Kaolinites (KGa-1 and KGa-2), Fithian Illite (F-Ill), and K-Metabentonite (K-Mbt). Exchange sites were pre-saturated with 0.16 M CsCl for 14 days and readily exchangeable Cs was removed by a series of LiNO₃ and LiCl washes. Washed clays were then placed into dialysis bags and the Cs release to the deionized water outside the bags measured. Release rates from 75 to 139 days for SWy-1, K-Mbt and F-Ill were similar; 0.017% to 0.021% sorbed Cs released per day. Both kaolinites released Cs more rapidly (0.12% to 0.05% of the sorbed Cs per day). In a second set of experiments, clays were Cs-doped for 110 days and subjected to an extreme and prolonged rinsing process. All the clays exhibited some capacity for irreversible Cs uptake. However, the residual loading was greatest on K-Mbt (0.33 wt.% Cs). Thus, this clay would be the optimal material for constructing artifical reactive barriers.     

The use of clays to sequestrate organic pollutants. Leaching experiments

Leaching experiments are performed from clay-pollutant systems in order to evaluate the capability of clays to sequestrate organic pollutants from wastewaters. Reference kaolinite KGa-1b, montmorrillonite SWy-2 and reference soil BCR^®-700 are the sorbent materials. 2,4,6-trichloroaniline (2,4,6-TCA) and 4-chlorophenol (4-CP) are the typical pollutants, sorbed at amounts of 10.0 mg g⁻¹ and 5.8 mg g⁻¹ on SWy-2 and 7.3 mg g⁻¹ and 2.2 mg g⁻¹ on KGa-1b, respectively.The leaching agents are ultrapure water and model solutions of acid rain and surface waters that simulate meteoric leaching. 1.0 mM HNO₃, 1.0 mM H₂SO₄ solutions and a methanol/water 50/50 (v/v) mixture simulate leaching agents of industrial source.The results are compared and the preferential capability of the clays to sequestrate the more lipophilic 2,4,6-TCA is evidenced.The bond interactions are discussed and explained through preferential adsorption reactions. For montmorrillonite also a simultaneous intercalation in the phyllosilicate interlayer is proposed.     

Sorption studies of chloroanilines on kaolinite and montmorillonite

Batch experiments have been performed in order to evaluate the ability of the two reference clays kaolinite (KGa-1) and Na-montmorillonite (SWy-1) to retain three representative chloroanilines: 3-chloroaniline, 3,4-dichloroaniline and 2,4,6-trichloroaniline. Systems containing the clay mineral and the pollutant solution (at concentration levels ranging between 1.0 and 10.0mg/L) were considered and RP-HPLC methods were employed to follow the sorption processes as a function of time. The results indicate that montmorillonite shows a general higher sorption capacity with respect to kaolinite and that for both the reference clays, in the concentration range investigated, the amount of pollutant sorbed increases with concentration. The sorption coefficient K(d) ranges between 0.0030 L/g for the system 3-chloroaniline-kaolinite and 0.0488L/g for the system 2,4,6-trichloroaniline-montmorrillonite. The most lipophilic trichloroaniline shows the greater sorption. X-ray analyses suggest for kaolinite a preferential sorption onto the mineral surface, while for montmorillonite a progressive swelling of the structure is observed, likely due to sorption processes that also take place in the interlayer.     

Ecological half-life of caesium in roe deer (Capreolus capreolus)

Biological half-lives for various radionuclides have been determined for many animals kept in the laboratory or under controlled conditions. Only occasionally has been it possible to determine the ecological half-lives of radionuclides in wild animals, where the contamination has occurred in their natural habitats. Following the fallout from the Chernobyl accident and its subsequent ingestion by wildlife, no one knew how long it would take the wild animals to eliminate the radionuclides, and in particular radiocaesium, from their bodies. In this study of roe deer (Capreolus capreolus), bucks (males)were shot at weekly/fortnightly intervals from mid-May till the end of July, as part of the annual cull on an area, which included some young forestry (Stone Chest-National Grid Reference NY48090), planted in 1971/72. The ration of 137Cs:134Cs, typical of the Chernobyl fallout, was seldom observed in these animals due to the highly variable concentrations of 137Cs originating from bomb fallout. Therefore, 134Cs was used instead because its presence was almost entirely due to the Chernobyl fallout. After using log10 transformation of the 134Cs concentrations, a significant (p < 0.01) regression was obtained which accounted for 85% of the variation. From the regression, the ecological half-life for 134Cs was found to be 28.3 days.     

Experimental evidence of biomass burning as a source of atmospheric 137Cs,puy de Dôme (1465 m a.s.l.), France

The presence of cesium-137 (¹³⁷Cs) in the environment is mainly due to past nuclear tests and accidental reactor releases. Due to the half-life of ¹³⁷Cs (30.2 y), amounts of this radionuclide releases are in fact still detectable in soils, and at trace levels in the vegetation and the atmosphere. Since the middle of the 1990’s, the presence of ¹³⁷Cs in the atmosphere has long been attributed to the resuspension of terrestrial dust. Recently, modelling studies have demonstrated that an additional and possibly dominant source of this anthropogenic radionuclide is biomass burning. Here, we report the variations of atmospheric ¹³⁷Cs activity levels over a 2-year period at the puy de Dôme (1465 m a.s.l.), France in combination with measurements of the aerosol chemical composition, in particular with indicators for biomass burning (levoglucosan and potassium) and soil dust (calcium). Temporal co-variations of these chemical compounds in addition to back-trajectories are used to identify common source emissions. Significant correlation is found between these compounds. Hence, we experimentally confirm the modelling study highlighting the fact that the atmospheric ¹³⁷Cs is partly released by biomass burning. In addition, we observed that the correlations between the ¹³⁷Cs concentrations and levoglucosan and biomass burning K⁺ differ according to the season. This is in agreement with the temporal evolution of levoglucosan concentration, which has maxima in winter and minima in summer.     

Sorption of pesticides on kaolinite and montmorillonite as a function of hydrophilicity

Pesticides and other organic species are adsorbed by soil via different mechanisms, with bond strengths that depend on the properties of both the soil and the pesticide. Since the clay fraction in soil is a preferential sorbent for organic matter, reference kaolinite and montmorillonite are useful models for studying the mechanism and the strength of sorption. This paper presents the results of batch experiments to investigate the interactions of kaolinite KGa-1 and montmorillonite SWy-1 with the following pesticides and organic species resulting from the natural degradation of pesticides in the environment: atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine), simazine (1-chloro-3,5-bisethylamino-2,4,6-triazine), diuron [1,1-dimethyl-3-(3,4-dichlorophenyl)urea], aniline, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol. Each of these chemicals has different hydrophilicity. Systems containing 2.0 g of clay were put in contact with 100.0 mL of solutions of the pesticides at known concentration ranging from 1.0 to 5.0 mg/L, and the amount of solute adsorbed was evaluated through RP-HPLC analysis of the pesticide still present in the aqueous suspension. To test for electrostatic interactions between the clay surface and the pesticides, potentiometric titration was used to determine the permanent surface charge of clays. Experiments were performed at different pH values. The results indicate that, for the chemicals studied, neutral molecules are preferentially retained relative to ionized ones, and that montmorillonite is a more effective sorbent than kaolinite.     

Sorption of Pesticides on Kaolinite and Montmorillonite as a Function of Hydrophilicity

Pesticides and other organic species are adsorbed by soil via different mechanisms, with bond strengths that depend on the properties of both the soil and the pesticide. Since the clay fraction in soil is a preferential sorbent for organic matter, reference kaolinite and montmorillonite are useful models for studying the mechanism and the strength of sorption. This paper presents the results of batch experiments to investigate the interactions of kaolinite KGa-1 and montmorillonite SWy-1 with the following pesticides and organic species resulting from the natural degradation of pesticides in the environment: atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine), simazine (1-chloro-3,5-bisethylamino-2,4,6-triazine), diuron [1,1-dimethyl-3-(3,4-dichlorophenyl)urea], aniline, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol. Each of these chemicals has different hydrophilicity. Systems containing 2.0 g of clay were put in contact with 100.0 mL of solutions of the pesticides at known concentration ranging from 1.0 to 5.0 mg/L, and the amount of solute adsorbed was evaluated through RP-HPLC analysis of the pesticide still present in the aqueous suspension. To test for electrostatic interactions between the clay surface and the pesticides, potentiometric titration was used to determine the permanent surface charge of clays. Experiments were performed at different pH values. The results indicate that, for the chemicals studied, neutral molecules are preferentially retained relative to ionized ones, and that montmorillonite is a more effective sorbent than kaolinite.     

The occurrence and bioavailability of radioactive 137Cs in small forest lakes in Southern Finland

Following the Chernobyl accident in late April 1986, central Finland was subjected to considerable radioactive fallout. The radioactive isotope of caesium, (137)Cs, was potentially the most harmful isotope in the fallout because of its long half-life (30 years). (137)Cs activities remained unexpectedly low within the biota (algae, zooplankton, aquatic moss, fish) of some humic forest lakes in southern Finland compared to the clear water lakes within the same district. This observation suggested that humic substances, by binding (137)Cs chemically, may reduce its bioavailability in lake water. Our laboratory experiments (throughflow systems; gel chromatography) demonstrated that binding of (137)Cs by humic substances was negligible in untreated lake waters; only when most of the alkali metals had been removed with an ion exchange resin was any binding of (137)Cs by low molecular humic fractions apparent. Instead, the concentrations of cations (especially potassium) were of overwhelming importance for the bioavailability of (137)Cs within the lacustrine ecosystems. The concentrations of (137)Cs within food chains are expected to stay at a high level for many years especially in lakes with long water renewal times.     

Accumulation history of radionuclides in the lichen Stereocaulon vesuvianum from Mt. Vesuvius (south Italy)

The fruticose lichen Stereocaulon vesuvianum, growing on the slopes of Mt. Vesuvius (south Italy), was used as a biomonitor of 134Cs, 137Cs, 103Ru and 106Ru derived from the April 26 1986 Chernobyl nuclear reactor accident. Samples were taken at five different quotes (370, 490, 580, 780 and 960 m a.s.l.) and four successive dates (October 1986, December 1986, October 1987 and May 1999). At the first sampling, the concentrations (as Bq kg(-1) dry weight) ranged between 460 and 1020 for 134Cs, 1330 and 2500 for 137Cs, 90 and 200 for 103Ru and 360 and 710 for 106Ru, values generally lower in respect to those measured in soil and higher plants. Of the total 137Cs measured only 14% was due to 1950s and 1960s nuclear weapons tests fallout. Highest average activities of all nuclides were observed at the quote of 960 m and significant correlation (0.7相似文献   

Conceptual and Numerical Modeling of Radionuclide Transport and Retention in Near-Surface Systems

Scenarios of barrier failure and radionuclide release to the near-surface environment are important to consider within performance and safety assessments of repositories for nuclear waste. A geological repository for spent nuclear fuel is planned at Forsmark, Sweden. Conceptual and numerical reactive transport models were developed in order to assess the retention capacity of the Quaternary till and clay deposits for selected radionuclides, in the event of an activity release from the repository. The elements considered were carbon (C), chlorine (Cl), cesium (Cs), iodine (I), molybdenum (Mo), niobium (Nb), nickel (Ni), radium (Ra), selenium (Se), strontium (Sr), technetium (Tc), thorium (Th), and uranium (U). According to the numerical predictions, the repository-derived nuclides that would be most significantly retained are Th, Ni, and Cs, mainly through sorption onto clays, followed by U, C, Sr, and Ra, trapped by sorption and/or incorporation into mineral phases.     

Long term investigation of 137Cs in chicken meat and eggs from northwest Croatia

Abstract

This paper presents the results of long-term investigations of ¹³⁷Cs activity concentrations in chicken meat and eggs from northwest Croatia for the period 1987–2018. The research has been done as a part of monitoring program of radioactive contamination in Croatia. The highest activity concentrations in both of these foodstuffs were measured in 1987 and have been decreasing exponentially ever since. The Fukushima-Daiichi accident in 2011 did not cause any increase of ¹³⁷Cs activity concentrations. The ecological half-life for ¹³⁷Cs was estimated to be 8.0 and 8.4?years for chicken meat and eggs respectively. The correlation between ¹³⁷Cs in fallout and chicken meat as well as between ¹³⁷Cs in fallout and eggs is very good, the respective correlation coefficients being 0.79 and 0.72, indicating that fallout was the main source of ¹³⁷Cs contamination in both foodstuffs. The estimated effective doses received by adult members of the Croatian population due to the intake of radiocaesium by chicken meat and egg consumption for the overall observed period are very small, 2.0 and 0.6 µSv respectively. Therefore, chicken meat and chicken egg consumption was not a critical pathway for the transfer of radiocaesium to humans.     

Cesium migration in Hanford sediment: a multisite cation exchange model based on laboratory transport experiments

Cs+ transport experiments carried out in columns packed with uncontaminated Hanford formation sediment from the SX tank farm provide strong support for the use of a multisite, multicomponent cation exchange model to describe Cs+ migration in the Hanford vadose zone. The experimental results indicate a strong dependence of the effective Cs+ Kd on the concentrations of other cations, including Na+ that is present at high to extremely high concentrations in fluids leaking from the Hanford SX tanks. A strong dependence of the Cs+ Kd on the aqueous Cs+ concentration is also apparent, with retardation of Cs+ increasing from a value of 41 at a Cs+ concentration of 10(-4) M in the feed solution to as much as 282 at a Cs+ concentration of 5x10(-7) M, all in a background of 1 M NaNO3. The total cation exchange capacity (CEC) of the Hanford sediment was determined using 22Na isotopic equilibrium exchange in a flow-through column experiment. The value for the CEC of 120 microeq/g determined with this method is compatible with a value of 121.9 microeq/g determined by multi-cation elution. While two distinct exchange sites were proposed by Zachara et al. [Geochim. Cosmochim. Acta 66 (2002) 193] based on binary batch exchange experiments, a third site is proposed in this study to improve the fit of the Cs+-Na+ and Cs+-Ca+ exchange data and to capture self-sharpened Cs+ breakthrough curves at low concentrations of Cs+. Two of the proposed exchange sites represent frayed edge sites (FES) on weathered micas and constitute 0.02% and 0.22% of the total CEC. Both of the FES show a very strong selectivity for Cs+ over Na+ (K(Na-Cs)=10(7.22) and 10(4.93), respectively). The third site, accounting for over 99% of the total CEC, is associated with planar sites on expansible clays and shows a smaller Na+-Cs+ selectivity coefficient of 10(1.99). Parameters derived from a fit of binary batch experiments alone tend to under predict Cs+ retardation in the column experiments. The transport experiments indicate 72-90% of the Cs+ sorbed in experiments targeting exchange on FES was desorbed over a 10- and 24-day period, respectively. At high Cs+ concentrations, where sorption is controlled primarily by exchange on planar sites, 95% of the Cs+ desorption was desorbed. Most of the difficulty in desorbing Cs+ from FES is a result of the extremely high selectivity of these sites for Cs+, although truly irreversible sorption as high as 23% was suggested in one experiment. The conclusion that Cs+ exchange is largely reversible in a thermodynamic sense is supported by the ability to match Cs+ desorption curves almost quantitatively with an equilibrium reactive transport simulation. The model for Cs+ retardation developed here qualitatively explains the behavior of Cs+ in the Hanford vadose zone underneath a variety of leaking tanks with differing salt concentrations. The high selectivity of FES for Cs+ implies that future desorption and migration is very unlikely to occur under natural recharge conditions.     

Laboratory analyses of 137Cs uptake by sunflower, reed and poplar

The 137Cs uptake by three plant species (Phragmites australis L., Heliantus annus L., Populus simonii L.) was analyzed in a hydroponic medium (14 MBql(-1); 0.5 mM CsCl) during cultivation. The radioactivity disappearance from the medium was measured after 2, 4, 8, 16 and 32 days of cultivation. Radioactivity distribution within the plant was determined by autoradiography. We did not find differences between uptake of radioactive and stable caesium isotopes. Relations between the uptake of 137Cs and concentration of potassium and ammonium ions in medium were also tested. The highest uptake of radiocaesium by sunflower was obtained for medium with 1 mM K2SO4 (14.2%) and in case of ammonium ions for concentration ratio 6 mM NH4Cl : 3 mM NH4NO3 (13.2%). The obtained results make it possible to compare the capability and rate of 137Cs phytoremediation of different plant species.     

Bioaccumulation of cesium-137 by biota in different aquatic environments

Macroalgae, isopods and fish species were exposed to 137Cs in brackish and sea water conditions for 18 days to determine radionuclide concentration factors. The concentration factors of 137Cs in brown shrimp and polychaete species were also investigated under brackish water conditions. At equilibrium, the concentration factors in macroalgae, isopod, fish, brown shrimp and polychate samples were found to be 2.5, 33, 2, 16 and 11 at 16 degrees C in brackish water conditions, respectively. The accumulation rate in macroalgae species was influenced by temperatures between 6 degrees C and 16 degrees C. The bioaccumulation of 137Cs in isopods at low salinity regime was increased significantly. At the same time, the bioaccumulation rate in macroalgae species also showed slight increase at low salinity. On the other hand, the bioaccumulation rate of 137Cs in the fish species in sea water was higher than in brackish water.     

Fate of radiocesium in sewage treatment process released by the nuclear accident at Fukushima

The nuclear accident at the Fukushima Daiichi Nuclear Power Plant (FDNPP) which occurred after the Great East Japan Earthquake on March 11, 2011 resulted in releases of radionuclides such as ¹³⁴Cs (half-life:T_1/2 = 2.06 yr), ¹³⁷Cs (T_1/2 = 30.04 yr) and ¹³¹I (T_1/2 = 8.05 d) to the environment. For this paper, we observed the monthly variations of radiocesium (¹³⁴Cs and ¹³⁷Cs) and stable Cs concentrations in influent, effluent, sewage sludge, and sludge ash collected from a sewage treatment plant 280 km north of the FDNPP from July to December, 2011. Using the stable Cs results, we concluded the mass balance of Cs in the sewage treatment plant showed that about 10% of the Cs entering the sewage treatment plant would be transferred to the sewage sludge, and then Cs in the sewage sludge was totally recovered in the sludge ash. The behavior of Cs was similar to that of Rb, but it was not similar to that of K in the sewage treatment process.     

The influence of season and leaf age on concentrations of radiocaesium (137Cs), stable caesium (133Cs) and potassium in Agrostis capillaris

The transfer of radioactive caesium from soils to plants has been well researched. In contrast there is limited knowledge on natural stable 133Cs and its potential role as a predictor for radiocaesium behaviour. In a pot experiment with Agrostis capillaris close correlations were found between plant 137Cs and plant 133Cs concentrations (R2 90-96%). Season and leaf age had significant effects with concentrations increasing 10-30-fold between June and December. Simultaneously the plant concentrations of K, the nutrient analogue of Cs, decreased to around one third. In the soil the exchangeable fractions of K and 137Cs declined. No clear relationships were found between 137+133Cs in the plant and exchangeable K in the soil. However, at the end of the experiment the K content of the above-ground biomass was higher than the exchangeable pool in the soil, suggesting that depletion of soil K could be a key factor in the observed increase of plant 137+133Cs over time.     

Constraints on the use of 137Cs as a time-marker to support CRS and SIT chronologies

CRS and SIT are two (210)Pb-based models widely used in the radiometric dating of recent sediments. (210)Pb chronologies should be validated using at least one independent tracer, such as (137)Cs. This paper demonstrates that simple methods based on the identification of (137)Cs fallout peaks cannot provide a definitive support for CRS and SIT chronologies. Two main arguments will support this assertion: Firstly, the (137)Cs time-marks cannot support a CRS or SIT chronology if the derived sedimentation rates cannot explain the whole (137)Cs activity profile without postulating mixing. Secondly, the support by the (137)Cs time-marks for a given CRS or SIT chronology cannot be considered as definitive if other dating models can equally explain the whole set of data, thereby producing a different chronology. Several case studies selected from the literature are used to support the present discussion.     

Distribution coefficients (Kd) and desorption rates of Cs and Am in Black Sea sediments

The distribution coefficients (K_d) and desorption rates of ¹³⁷Cs and ²⁴¹Am radionuclides in bottom sediments at different locations in the Black Sea were studied under laboratory conditions. The K_d values were found to be 500 for ¹³⁷Cs and 3800 for ²⁴¹Am at the steady state and described exponential curves. Rapid uptake of the radionuclides occurred during the initial period and little accumulation happened after four days. The desorption rates for ¹³⁷Cs in different bottom sediments were best described by a three-component exponential model. The desorption half-times of ¹³⁷Cs ranged from 26 to 50 d at the slow components. However, the desorption rate of ²⁴¹Am described one component for all sediment samples and desorption half-time was found to be 75 d. In general, the results showed that the ²⁴¹Am radionuclide is more effectively transferred to bottom sediment and has longer turnover time than ¹³⁷Cs under Black Sea conditions.     

Radiocaesium activity concentrations in potatoes in Croatia after the Chernobyl accident and dose assessment

Systematic investigations of (137)Cs and (134)Cs activity concentrations in potatoes (Solanum tuberosum) for the post-Chernobyl period (1986-2005) in the Republic of Croatia are summarized. The correlation between (137)Cs activity concentrations in fallout and potatoes, has been found to be very good, the correlation coefficient being r = 0.88 with P(t) < 0.001 for 18 degrees of freedom. As the radiocaesium levels in potatoes decreased exponentially, the mean residence time of (137)Cs in potatoes was estimated by fitting the measured activity concentrations to the exponential curve. The mean residence time was found to be 6.8 +/- 1.1 years, the standard deviation being estimated by the Monte Carlo simulations. The initial observed (134)Cs:(137)Cs activity ratio in potatoes has been found to be quite variable, but slightly lesser than the theoretically predicted value of 0.5, calculated by applying the known inventory of these radionuclides in the Chernobyl reactor to the equation for the differential radioactive decay. This can be explained by presence of the pre-Chernobyl (137)Cs in soil that originated from nuclear fallout. The annual effective doses received by (134)Cs and (137)Cs intake due to consumption of potatoes estimated for an adult member of the Croatian population were found to be very small, as the per caput Dose for the entire 1986-2005 period was calculated to be about 2.9 microSv, (134)Cs accounting approximately for 1/3 of the entire dose. Therefore, after the Chernobyl accident consumption of potatoes was not the critical pathway for human intake of radiocaesium from the environment in Croatia.     

Dynamic equilibrium of radiocesium with stable cesium within the soil-mushroom system in Turkish pine forest

Mushrooms and soils collected from pine forests in Izmir, Turkey were measured for radiocesium and stable Cs in 2002. The ranges of (137)Cs and stable Cs concentrations in mushrooms were 9.84+/-1.67 to 401+/-3.85Bqkg(-1) dry weight and 0.040+/-0.004 to 11.3+/-1.09mgkg(-1) dry weight, respectively. The concentrations of (137)Cs and stable Cs in soils were 0.29+/-0.18 to 161+/-1.12Bqkg(-1) dry weight and 0.14+/-0.004 to 1.44+/-0.045mgkg(-1) dry weight, respectively. Even though different species were included, the concentration ratios of (137)Cs to stable Cs were fairly constant for samples collected at the same forest site, and were in the same order of magnitude as the (137)Cs to stable Cs ratios for the organic soil layers. The soil-to-mushroom transfer factors of (137)Cs and stable Cs were in the range of 0.19-3.15 and 0.17-12.3, respectively. The transfer factors of (137)Cs were significantly correlated to those of stable Cs.