Vertical distribution and bioavailability of 137Cs in organic and mineral soils

The vertical distribution and bioavailability of ¹³⁷Cs in Histosols and mineral soils with different physicochemical properties from the southeast of Bavaria (Germany) more than ten years after the Chernobyl accident were the focus of this study. The vertical distribution of ¹³⁷Cs was low in the investigated soils. About 85–98 % of the total ¹³⁷Cs was located in the upper 10 cm of the mineral soils. Slightly higher ¹³⁷Cs percentages were observed in deeper soil layers of the peat soils. Although the organic matter is assumed to enhance ¹³⁷Cs mobility in soils, ¹³⁷Cs was also located in the upper 10 cm of the peat soils (73–85 %). The highest ¹³⁷Cs‐activities were found in the humus layers of forest soils, where 45–93 % of the total ¹³⁷Cs soil inventories were observed. To determine the bioavailability of radiocesium, the soil‐to‐plant transfer of ¹³⁷Cs and additionally added ¹³⁴Cs was investigated under controlled conditions. The results revealed that the ^134+137Cs soil‐to‐plant transfer factors as well as the percentages of NH₄‐exchangeable ^134+137Cs were much higher for the peat soils and humus layers than for the mineral soils. Nevertheless, the migration of ¹³⁷Cs from the humus layers to the underlying soils was low. Considering the high bioavailability and low migration of radiocesium in the humus layers, it is suggested that radiocesium is involved in a shortcut element cycle in the system humus layer‐plant uptake‐litter. Furthermore, the organic matter has to be taken into account for radiocesium immobilization.     

Dynamics of caesium in aerated and flooded soils: experimental assessment of ongoing adsorption and fixation

The fate of the radioisotopes of caesium (¹³⁴Cs, ¹³⁵Cs and ¹³⁷Cs) in the environment depends largely on the extent and reversibility of its adsorption on soil, but there is still debate as to the underlying mechanisms and the best experimental approach to study the processes. The aim of this study was to elucidate the variation of the interaction of a trace amount of ¹³⁷Cs with soil and to find the best methodology to monitor these changes. The loss of ¹³⁷Cs from solution has been monitored over 4 months in soil microcosms at 20°C under both flooded and aerated conditions, and with or without organic amendments (leaf compost or lucerne straw). These treatments were chosen to vary concentrations of potassium and ammonium that compete with Cs for adsorption. We distinguished between spatial heterogeneity within soil aggregates leading to diffusion limitation of adsorption, adsorption kinetics at the soil‐solution interface and changes in soil affinity caused by the dynamics of competing cations. The extractability of ¹³⁷Cs by stable Cs was used to probe the degree of fixation. Adsorption was initially under‐estimated, caused by equilibration of ¹³⁷Cs within soil aggregates at a sub‐millimetre scale. Ammonium produced under reducing conditions in flooded samples and potassium released by lucerne straw inhibited ¹³⁷Cs adsorption by up to a factor of 2. Important differences between samples were masked when soil was suspended in a simple electrolyte solution, thus diluting the competing cations, potassium and ammonium. There was evidence of increased fixation both during incubation and by air‐drying leading to up to a two‐fold decrease in extraction. Monitoring of dynamics of Cs and competing cations in soil solution provided useful information that was lost when soil was suspended in solution or air‐dried.     

The role of mineralization of the organic matter of soddy-podzolic and peat bog soils in the accumulation of <Superscript>137</Superscript>Cs by plants

The role of mineralization of soil organic matter (SOM) in the mobilization of ¹³⁷Cs was estimated on the basis of data on the biokinetic fractionation of the organic matter of soddy-podzolic sandy-loam and peat bog soils and on the coefficients of the soil-to-plant transfer of radiocesium under field conditions. The peat bog soils were richer than the soddy-podzolic soils in the total organic carbon (by 7.9–23.8 times), the potentially mineralizable carbon (by 2.4–6.5 times), and the carbon of the microbial biomass (by 2.9–4.6 times). The agricultural use of the soddy-podzolic and peat bog soils led to a decrease in the SOM mineralization capacity by 1.1–1.8 and 1.4–2.0 times, respectively. Simultaneously, the portions of the easily, moderately, and difficultly mineralizable fraction of the SOM active pool changed. The coefficients of the ¹³⁷Cs transfer from the peat bog soils to plants were 3.3–17.6 times higher than those for the soddy-podzolic soils. The content of ¹³⁷Cs in plants grown on the peat bog soils was 2–65 times higher than that in the mobile (salt-extractable) soil pool by the beginning of the growing season. Strong positive linear correlations were found between the coefficients of the soil-to-plant transfer of ¹³⁷Cs and the total content of the SOM, the content of the microbial biomass, the content of the potentially mineralizable carbon, and the intensity of its mineralization. It was concluded that the decisive factors controlling the intensity of the ¹³⁷Cs transfer from mineral and organic soils into plants are the SOM content and its mineralization potential. The mineralization of the SOM is accompanied by the release of both ¹³⁷Cs and mineral nitrogen; the latter facilitates the transfer of radiocesium into plants.     

Adsorption of radiocaesium on various soils: consequences of the effects of soil: solution composition on the distribution coefficient

The adsorption of a radioisotope of caesium, ¹³⁷Cs, has been interpretation and ratio and solution measured on four soils with differing clay mineralogies. All measurements have been made using unwashed soils in suspensions shaken for 2 h at 20°C. The effects of concentration in potassium and caesium, the nature of the background electrolyte and the soil:solution ratio have been investigated. The results are expressed either as the distribution coefficient, K_D or as Freundlich isotherms. The distribution coefficient of each of the soils decreases markedly as the concentration of caesium increases. The adsorption properties of the soils are not determined by the dominant clay mineralogy alone. Adsorption is always lower in 0.01 m CaCl₂ solution than in water. The addition of potassium has relatively little effect on adsorption of trace amounts of caesium; however, K_D decreases with increasing concentrations of stable caesium. The major reason for the dependence of K_D on the soil: solution ratio is found to be the non-linear adsorption isotherm; the influence of the varying compositions of the solution and exchange complex is minor. The validity of the use of a single K_D value as an indicator of adsorption capacity and the meaning of the relative values of the Freundlich parameters are considered. The implications of these findings for the use of radiotracers and the usefulness of K_D as an indicator of bioavailability are discussed.     

Cesium- und Strontiumaustauscheigenschaften von Marschböden

Cesium and Strontium Exchange Properties of Marsh Soils The cesium and strontium exchange properties of some typical marsh soils of the estuary and lower river Weser region were described. Soil samples were taken according to the existing soil maps 1:25000 of Lower Saxony e.g. a “sea marsh soil”. a “brackish marsh soil”, and a “river marsh soil”. The exchange properties were determined by Cs/Ca and Sr/Ca exchange curves (Q/I relations) as generally used in soil potassium research. In addition to the Q/I relations the following investigations were carried out: - Cs and Sr desorption experiments (one time equilibration with Ca⁺⁺ solutions) - Cs and Sr reexchange experiments (eight times equilibration with water, Ca⁺⁺, Ba⁺⁺, and K⁺ solutions) - the naturally-occuring Cs and Sr contents of the soils including amounts caused by imissions or fallout, respectively - clay mineral composition and swelling of layer silicates due to saturation with Ca⁺⁺, Sr⁺⁺, Cs⁺, and K⁺ ions. Q/I relations as well as desorption and reexchange experiments indicated strong cesium and low strontium fixation by the soils investigated. This was considered the reason for the stronger transfer of Sr from soil to plants as compared with Cs. Furthermore, the reexchange experiment revealed nearly complete reversibility of the Sr sorption reactions by equilibration with the divalent cations Ca⁺⁺ and Ba⁺⁺ and some Sr fixation after treatment with K⁺ solutions. However, cesium was much better reexchanged by K⁺ than by Ca⁺⁺ and Ba⁺⁺ ions. This led to the conclusion that Cs fixed in interlayer positions of clay minerals could be remobilized by potassium and ammonium fertilization. The naturally-occuring Cs contents of the soils were found to be below the detection limit of the analytical methods used. The contents of naturally-occuring exchangeable Sr, however, was in agreement with the amounts of “labile Sr” as derived from the Sr/Ca exchange curves. Concerning the cesium exchange properties a clear distinction between “sea and river marsh soils” on the one hand and “brackish marsh soils” on the other hand was established due to differences in clay mineral composition and swelling state of 1:2 layer silicates. The different cesium exchange properties of the two soil groups could also be verified by more or less pronounced hysteresis effects of sorption (Q/I relation) and desorption curves.     

Forms and rates of release of 137Cs in two peat soils

Cation exchange resin saturated with H⁺ and Ca²⁺ was used to extract ¹³⁷Cs from peat soil at two sites in Britain affected by ^l37Cs deposition following the Chernobyl accident. The technique identified three classes of ¹³⁷Cs, similar to those observed for K⁺ in soils: ‘Fast’, ‘Intermediate’ and ‘Slow’. These classes are probably related to the selectivity for ¹³⁷Cs of the cation exchange sites on the organic matter and the clay minerals, and to the structure of the soil. With one exception, most ¹³⁷Cs was in the ‘Slow’ form and was only very slowly released to the resins, if at all. However, there was enough ^l37Cs in the ‘Fast’ and ‘Intermediate’ forms to contaminate pasture and thus grazing animals for some years. Based on the resin technique, it is estimated that contamination will persist for several decades in uplands contaminated at these activity concentrations.     

In situ radiometric mapping of soil erosion and field-moist bulk density on cultivated fields

Abstract. Recent developments in in situγ ray spectrometry offer a new approach to measuring the activity of radionuclides such as ¹³⁷Cs and ⁴⁰K in soils, and thus estimating erosion or deposition rates and field moist bulk density (ρ_m). Such estimates would be rapid and involve minimal site disturbance, especially important where archaeological remains are present. This paper presents the results of a pilot investigation of an eroded field in Scotland in which a portable hyper pure germanium (HPGe) detector was used to measure γ ray spectra in situ. The gamma (γ) photon flux observed at the soil surface is a function of the ¹³⁷Cs inventory, its depth distribution characteristics and ρ_m. A coefficient, Q_Cs, derived from the forward scattering of ¹³⁷Cs γ ray photons within the soil profile relative to the ¹³⁷Cs full energy peak (662 keV), was used to correct the in situ calibration for changes in the ¹³⁷Cs vertical distribution in the ploughed field, a function of tillage, soil accumulation and ρ_m. Based on only 8 measurements, the agreement between in situγ ray spectrometry and soil sample measurements of ¹³⁷Cs inventories improved from a non significant r²=0.05 to a significant r²=0.62 (P<0.05). Erosion and deposition rates calculated from the corrected in situ¹³⁷Cs measurements had a similarly good agreement with those calculated from soil cores. Mean soil bulk density was also calculated using a separate coefficient, Q_K, derived from the forward scattering γ photons from ⁴⁰K within the soil relative to the ⁴⁰K full energy peak (1460 keV). Again there was good agreement with soil core measurements (r²=0.64; P<0.05). The precision of the in situ¹³⁷Cs measurement was limited by the precision with which Q_Cs can be estimated, a function of the low ¹³⁷Cs deposition levels associated with the weapons testing fallout and relatively low detector efficiency (35%). In contrast, the precision of the in situ ρ_m determination was only limited by the spatial variability associated with soil sampling.     

The extent and significance of bioturbation on 137Cs distributions in upland soils

Differences between measured ¹³⁷Cs activity–depth profiles and idealised undisturbed profiles generated from an exponential model suggest that faunal turbation has redistributed ¹³⁷Cs in mineral and organic upland soils in southern Scotland. Bioturbation is also demonstrated by the vertical displacement of other inputs to the soils of known age (non-native tree pollen and spheroidal carbonaceous particles, SCPs). The causes and mechanisms of bioturbation were further investigated by soil micromorphology. Well-drained mineral soils with active populations of earthworms are the most bioturbated, showing near-complete homogenisation to depths of about 20 cm. Enchytraeids also seem to remobilise ¹³⁷Cs by the digestion of organic matter and may be the main cause of ¹³⁷Cs redistribution in organic-rich upland soils. Relative rates of mixing are evaluated by comparing ¹³⁷Cs depth profiles.     

Factors affecting the sorption and fixation of caesium in acid organic soil

Radioactive caesium deposited on upland Britain following the Chernobyl accident in 1986 remains available for uptake by plants, despite the potential of the contaminated soils to fix Cs. The minimum concentration of Cs⁺ required to cause Cs⁺ fixation is 0.60 to 0.75 mm , and this is unlikely to be reached in any contaminated upland soil. It is suggested that the fixation is caused by interlayer collapse of the illitic clay. The observed Cs⁺ fixation in lowland mineral soils and its absence from acidic upland soils is explained by the action of K⁺ ions, which can also induce interlayer collapse. Although Cs⁺ ions are unlikely to be fixed in acid organic soils, they can be strongly sorbed on any unoccupied Cs-specific sorption sites in the narrow parts of illitic wedge zones. A method for determining the number of such sites is described. For two of the soils studied the number of sites ranged between 8 × 10^?8 and 1 × 10^?5 mmol kg^?1; for two others there appeared to be no unoccupied Cs-specific sites. Although Cs⁺ ions sorbed on such sites do not exchange with other ions, they can be desorbed if the concentration of Cs⁺ in solution is decreased. Thus, radioactive Cs in such soils will remain available for plant uptake, unless interlayer collapse can be induced.     

Adsorption and desorption of organotin compounds in organic and mineral soils

Organotin compounds (OTC) are deposited from the atmosphere into terrestrial ecosystems and can accumulate in soils. We studied the adsorption and desorption of methyltin and butyltin compounds in organic and mineral soils in batch experiments. The adsorption and desorption isotherms for all species and soils were linear over the concentration range of 10–100 ng Sn ml^?1. The strength of OTC adsorption correlated well with the carbon content and cation exchange capacity of the soil and was in the order mono‐ > di‐ > tri‐substituted OTCs and butyltin > methyltin compounds. The OTC adsorption coefficients were much larger in organic soils (K_d > 10⁴) than in mineral soils. The adsorption and desorption showed a pronounced hysteresis. Trimethyltin adsorption was partly reversible in all soils (desorption 2–12% of the adsorbed amounts). Dimethyltin, tributyltin and dibutyltin exhibited reversible adsorption only in mineral soils (desorption 4–33% of the adsorbed amounts). Mono‐substituted OTCs adsorbed almost irreversibly in all soils (desorption < 1% of adsorbed amounts). Trimethyltin was more mobile and more bioavailable in soils than other OTCs. It might therefore be leached from soils and accumulate in aquatic ecosystems. The other OTCs are scarcely mobile and are strongly retained in soils.     

Comparison of analytical procedures for determination of soil sorption coefficients of some triazine herbicides

Abstract

The sorption behavior of three triazine herbicides: atrazine, metribuzin, and terbutryn was studied in two different soils. Three experimental procedures to determine the K_f values were assayed: the conventional batch equilibration method in which the sorbed concentration is calculated by difference from the change in solution concentration; an alternative mass balance equilibrium batch technique in which the solution and the sorbed phase concentration are measured directly; and the flow equilibration method in which a solution of known concentration was passed through a column of soil until the effluent reached the same concentration as the input solution. Four concentrations of each herbicide were selected and results were fitted to the linearized form of the Freundlich isotherm. Recovery of the herbicides was studied in soil and water samples using the same four concentrations employed in the sorption assays. Average recoveries ranged from 86 to 104% with standard deviations lower than 10%. The K_oc (mg^1–1/n kg^‐1 L^l/n) values obtained ranged from 43 to 87 for atrazine, 27 to 114 for metribuzin, and 355 to 505 for terbutryn. The exponents 1/n of the Freundlich adsorption isotherms were lower than unity, with only one exception, and varied from 0.72 to 0.86 for atrazine, 0.73 to 1.12 for metribuzin, and 0.76 to 0.99 for terbutryn. The solution method gave values of K_oc that were 1.25, 1.55, and 2.65 (average of both soils) times those of the mass balance method for terbutryn, atrazine and metribuzin, respectively. When adsorption was low, the mass balance calculation method is recommended if the batch equilibration method is used, since the solution method can produce a considerable overestimation of adsorption. The flow equilibration method produced similar values of adsorption than the mass balance batch equilibration method and it made the experimental procedure easier since pesticide solution concentration need not to be measured once the equilibration time has been determined to ensure that the equilibrium was reached.     

Kalium-Dynamik und Kalium-Fixierung nordwestiranischer Böden

Dynamics and fixation of potassium in soils of North-West-Iran The following results were obtained from experiments conducted on two calcareous soils (A-horizon) and on two soil samples from fertilizer experimental plots (K₀ = control plot, K₅ = 1000 kg K₂O/ha) to study the dynamics and fixation of potassium in these soils: The K-exchange curve of K₅ sample when compared with K₀ sample showed that, as a consequence of high fertilizer dose, most of the specific adsorption sites for cations (particularly on illites and weathering products of illites) were occupied by K which, thus, resulted into lower K-adsorption as well as fixation. The shape of K-exchange curves of other three samples (Alluvial soil, 16, Brown soil 26 and K₀ sample, Fig. 5 and 6) indicates a typical bend at definite activity ratios. This bend in the exchange curves exists apparently in soils containing high content of illitic clay mineral fraction. This behaviour has been interpreted as a consequence of contraction of layers of illitic minerals which were formerly expanded due to loss of potassium. The K-desorption experiment, which then followed, showed that a major part of sorbed amounts of potassium could not be desorbed and remained fixed in the soil. Similar type bend as in the exchange curve was also observed in the potassium fixation curves (Fig. 6 and 7). Illite is the dominant clay mineral in all these soils which in Brown soil and K₀-sample is expanded at edges; the expansion goes back to 10 A on treatment with K which then does not expand again on saturation with Mg.     

Enhanced sorption and fixation of radiocaesium in soils amended with K-bentonites, submitted to wetting–drying cycles

The use of bentonites as soil amendment has met with little success in reducing plant uptake of radiocaesium. However, bentonites exchanged with K⁺ have pronounced Cs⁺ binding capacity when subjected to wetting–drying cycles. Fifty‐four different bentonites were collected and characterized for cation exchange capacity and chemical composition. The radiocaesium interception potential (RIP) increased up to 160‐fold (mean 25) when the bentonites were converted to the K‐form and subjected to wetting–drying cycles. This increase in radiocaesium sorption was ascribed to a collapse of the clay sheets into an illite‐like structure, and was most pronounced in bentonites with a high layer charge. The RIP values of K‐bentonites subjected to 25 wetting–drying cycles ranged from 0.22 to 44.3 mol kg^?1. The RIP yields, i.e. the RIP in soil–bentonite mixtures expressed per unit bentonite added, were even higher and ranged up to 99 mol kg^?1. This upper limit is about 10‐fold higher than the RIP value of illite (～ 10 mol kg^?1), the principal ¹³⁷Cs sorbent in soils of temperate climates. Wetting–drying also promoted fixation of radiocaesium in soils amended with K‐bentonites. About 30% of added ¹³⁷Cs could be desorbed with 1 m ammonium acetate (NH₄Ac) from an unamended soil after 25 wetting–drying cycles, while only between 8 and 21% of ¹³⁷Cs could be desorbed from a soil amended with bentonite and a K‐salt. These findings support the proposition that addition of K‐bentonite may be effective in reducing availability of ¹³⁷Cs in soils.     

Einfluß des Jahresniederschlags und der Bodenart auf die 137Cs-Tiefenverteilung in Böden Südchiles

The influence of mean annual rainfall and soil texture on the ¹³⁷Cs vertical distribution in soils from southern Chile The influence of mean annual rainfall and soil texture on the vertical distribution of ¹³⁷Cs from global fallout was studied in undisturbed volcanic ash soils from southern Chile. The areal concentration and translocation depth increase with the mean annual precipitation. In spite of the high rainfall at the sampled area (970 - 2500 mm a^?1), the highest ¹³⁷Cs contamination was found in the upper 10 cm layer. The vertical migration is reduced by the high adsorption capacity of these volcanic ash soils, but on the other side increased in soils with high large-pore volumen. The translocation depth reaches only up to 26 cm in the clay soils, 35 cm in the silty soils and 70 cm in the sandy soil.     

Validating the use of Cs measurements to estimate rates of soil redistribution by wind

Wind erosion has degraded over one-half billion hectares of land worldwide. ¹³⁷Cesium (¹³⁷Cs) has been used as a tracer to study long-term rates of soil redistribution by water and, to a lesser extent, by wind. Early studies assumed that the decline in ¹³⁷Cs activity for a potentially eroded soil relative to that for an uneroded soil was linearly proportional to soil loss. More recently, models have emerged that consider the effects of soil cultivation and the particle surface area-dependent partitioning of ¹³⁷Cs on soils. We investigated the partitioning of ¹³⁷Cs in wind-eroded sediments and with soil surface samples sieved into contiguous ranges of particle sizes. We also compared the ¹³⁷Cs activities and stratification of several adjacent soils with known wind erosion and deposition histories. Finally, we tested ¹³⁷Cs-based soil loss models with measured data from sites with documented histories. ¹³⁷Cs activities and mean particle diameters of aeolian samples agreed well with the ¹³⁷Cs activities and respective mean diameters of the sieved surface soil samples. Good agreement between model estimations and measured data indicated that ¹³⁷Cs models developed to estimate soil redistribution by water were also applicable to soil redistribution by wind provided that the models contained an appropriate particle size correction parameter.     

Cesium-137 concentration of forage corn and Italian ryegrass in a double cropping system under different rates of cattle farmyard manure application after the Fukushima Daiichi Nuclear Power Station accident in 2011

Abstract

Radioactive ¹³⁷Cs concentrations of forage corn (Zea mays L.) and Italian ryegrass (Lolium multiflorum Lam.) in a double cropping system under continuous cattle farmyard manure (FYM) application were observed for more than 2 years after the Fukushima Daiichi Nuclear Power Station accident in 2011. The experiment field is located 110 km southwest of the Fukushima Daiichi Nuclear Power Station, and the soil contains ¹³⁷Cs of 920 Bq kg^?1 on average. For crop cultivation, nitrogen fertilizer was applied in addition to FYM. The ¹³⁷Cs concentrations in corn decreased significantly between 2011 and 2012, but only differed significantly between 2012 and 2013 for the plot with no FYM application. For Italian ryegrass, no significant differences were observed between the harvest in 2012 and 2013 despite the FYM application rate. To minimize corn ¹³⁷Cs concentrations, the FYM application rate should be more than and equal to 30 Mg ha^?1 when FYM is used as the major nutrient source. Exchangeable potassium oxide (K₂O) greater than around 0.3 g kg^?1 was mostly maintained with the FYM application rates. Corn ¹³⁷Cs concentration appeared to increase at exchangeable K₂O levels below 0.15 g kg^?1. These results suggest that continuous FYM application can maintain soil nutrients including K₂O and thereby control radioactive Cs transfer from the soil. FYM application rate of 30 Mg ha^?1 is within the levels recommended by the prefectural governments around Fukushima Prefecture for crop production before the accident. These levels are sufficient to decrease the radioactive Cs concentrations for corn. However, unlike corn, differences in soil chemical properties by FYM application did not affect ¹³⁷Cs concentrations in Italian ryegrass in this study, although low exchangeable K₂O seemed to increase concentrations of stable ¹³³Cs. Further experiments should be conducted to understand the observed differences between corn and Italian ryegrass.     

Soil properties affecting solid–liquid distribution of As(V) in soils

The prediction of the mobility of arsenic (As) is crucial for predicting risks in soils contaminated with As. The objective of this study is to predict the distribution of As between solid and solution in soils based on soil properties and the fraction of As in soil that is reversibly adsorbed. We studied adsorption of As(V) in suspensions at radiotrace concentrations for 30 uncontaminated soils (pH 4.4–6.6). The solid–liquid distribution coefficient of As (K_d) varied from 14 to 4430 l kg^?1. The logarithm of the concentration of oxalate‐extractable Fe explained 63% of the variation in log K_d; by introducing the logarithm of the concentration of oxalate‐extractable P in the regression model, 85% of the variation in log K_d is explained. Double labelling experiments with ⁷³As(V) and ³²P(V) showed that the As to P adsorption selectivity coefficient decreased from 3.1 to 0.2 with increasing degree of P saturation of the amorphous oxides. The addition of As(V) (0–6 mmol kg^?1) reduced the K_d of ⁷³As up to 17‐fold, whereas corresponding additions of P(V) had smaller effects. These studies suggest that As(V) is adsorbed to amorphous oxides in soils and that sites of adsorption vary in their selectivity in respect of As and P. The concentration of isotopically exchangeable As in 27 contaminated soils (total As 13–1080 mg kg^?1) was between 1.2 and 19% (mean 8.2%) of its total concentration, illustrating that a major fraction of As is fixed. We propose a two‐site model of competitive As(V)–P(V) sorption in which amorphous Fe and Al oxides represent the site capacity and the isotopically exchangeable As represents the adsorbed phase. This model is fitted to ⁷³As adsorption data of uncontaminated soils and explains 69% of the variation of log K_d in these soils. The log K_d in contaminated soils predicted using this two‐site model correlated well with the observed log K_d (r = 0.75). We conclude that solubility of As is related to the available binding sites on amorphous oxides and to the fraction of As that is fixed.     

Exchangeable Cs/K ratio in soil is an index to estimate accumulation of radioactive and stable Cs in rice plant

Pot and field experiments were conducted to clarify the effect of soil exchangeable potassium (K) and cesium-137 (¹³⁷Cs) on ¹³⁷Cs accumulation and to establish soil index in rice (Oryza sativa L.). Four paddy soils in Fukushima Prefecture, Japan, showing different transfer factors for radioactive Cs derived from the accident of Fukushima Daiichi Nuclear Power Station in the field were compared in terms of ¹³⁷Cs accumulation in rice in a pot experiment. ¹³⁷Cs accumulation in shoots and brown rice widely varied among soils with the transfer factor ranging from 0.018 to 0.068 for shoots and 0.004 to 0.065 for brown rice. ¹³⁷Cs concentration in brown rice and shoots tended to decrease with higher levels of soil exchangeable K, and they were more closely related to the exchangeable Cs/K ratio. Similar relationships between the Cs/K ratio and Cs accumulation in plants were obtained for the stable isotope cesium-133 (¹³³Cs). The distributions of ¹³⁷Cs and ¹³³Cs in grains were also similar and variable among soils. The transfer factors obtained in pot experiments mostly agreed with field observations. The results imply that the exchangeable ¹³⁷Cs/K can be a potential soil index to estimate ¹³⁷Cs accumulation in rice.     

Soil solution concentration of Cd and Zn canbe predicted with a CaCl2 soil extract

Risk assessment of heavy metals in soil requires an estimate of the concentrations in the soil solution. In spite of the numerous studies on the distribution of Cd and Zn in soil, few measurements of the distribution coefficient in situ, K_d, have been reported. We determined the K_d of soils contaminated with Cd and Zn by measuring metal concentrations in the soil and in the soil solution and attempted to predict them from other soil variables by regression. Soil pH explained most of the variation in logK_d (R² = 0.55 for Cd and 0.70 for Zn). Introducing organic carbon content or cation exchange capacity (CEC) as second explanatory variable improved the prediction (R² = 0.67 for Cd and 0.72 for Zn), but these regression models, however, left more than a factor of 10 of uncertainty in the predicted K_d. This large degree of uncertainty may partly be due to the variable degree of metal fixation in contaminated soils. The labile metal content was measured by isotopic dilution (E value). The E value ranged from 18 to 92% of the total metal content for Cd and from 5 to 68% for Zn. The prediction of K_d improved when metals in solution were assumed to be in equilibrium with the labile metal pool instead of the total metal pool. It seems necessary therefore to discriminate between ‘labile’ and ‘fixed’ pools to predict K_d for Cd and Zn in field contaminated soils accurately. Dilute salt extracts (e.g. 0.01 m CaCl₂) can mimic soil solution and are unlikely to extract metals from the fixed pool. Concentrations of Cd and Zn in the soil solution were predicted from the concentrations of Cd and Zn in a 0.01 m CaCl₂ extract. These predictions were better correlated with the observations for field contaminated soils than the predictions based on the regression equations relating logK_d to soil properties (pH, CEC and organic C).     

Migration and Chemical Availability of 137Cs and 90Sr in SwedishLong-Term Experimental Pastures

Migration and chemical availability of ¹³⁷Cs and⁹⁰Sr in the long-term was studied on a36-yr-old deposition experiment on pastureconsisting of a sandy soil and a clay soil,contaminated in 1961 with radionuclides in aqueoussolution. Comparisons were made with a study of thesame soils in 1967. Soil samples to 55 cm depth wereanalysed for ¹³⁷Cs and ⁹⁰Sr to establish thevertical distribution. Chemical availability wasstudied using sequential extractions with H₂O,NH₄Ac, NH₂OH·HCl, H₂O₂ andHNO₃. Both ¹³⁷Cs and ⁹⁰Sr were found atall depths in both soil types. Cs-137 waspredominantly retained within the upper 10 cm (70%)in both soils. For ⁹⁰Sr, the soils differedsignificantly, retention within the upper 10 cm was27% in sandy soil and 47% in clay soil. Migrationsince 1967 was faster in the sandy soil for bothnuclides. More than 95% of ¹³⁷Cs was bound inthe acid-digestible and residual fractions in bothsoils. The residual fraction was larger in clay soil.⁹⁰Sr was highly available in both soils. Noresidual fraction was found, and the easilyexchangeable fraction was 63–75%.