Adsorption models of Cs radionuclide and Sr (II) on some Egyptian soils

Distribution of cesium (¹³⁴Cs and ¹³⁷Cs) and strontium (Sr-II) between soil/water phases depends on many factors such as concentration of these ions between phases, the cation exchange capacity (CEC) of the soil as well as its clay content, chemical composition (especially Na, K, Ca, and Mg ions), grain size distribution, calcite, iron oxide content, and organic coatings. Distribution coefficients (Kd) of cesium (labeled with ¹³⁷Cs) and strontium were measured on the grain size distributions ≥32 μm of four soil samples. These soils were obtained from four different locations within Inshas site in Egypt and three groundwater samples were obtained from the same site locations. X-ray diffraction showed that the soil samples consisted mainly of quartz mixed with the minor amounts of kaolonite and clay minerals. Sorption experiments were carried out at strontium aqueous concentrations range 10⁻⁷ to 10⁻⁴ mol l⁻¹. The CEC and Kds for cesium and strontium were measured at the same metal concentrations range. Distribution coefficients of cesium were found to be influenced by the composition of the soil, while the distribution coefficients of strontium were found to depend on calcium concentrations in the soil/groundwater system. The aim of this study was to determine the safety assessment of disposal ¹³⁷Cs radionuclide and Sr(II) in the aquifer regions inside the Inshas site. Sequential extraction tests showed that, strontium was associated with the carbonate fractions and majority of cesium was sorbed on the iron oxides and the residue.     

The influence of the sorptive properties of organic soils on the migration rate of 137Cs

Using a compartment model, the migration rates of 137Cs were calculated for two types of organic soils: a low peat-muck soil and a black earth. The migration rates of 137Cs in the tested soils turned out to be significantly higher than in mineral types examined earlier and ranged from 0.6 to 12.3 cm/year. The partition coefficients (Kd) were also determined for samples with varying organic matter content (OM) that were taken from different layers of the studied soils. The experimental results indicate that there is a clear relationship between Kd values and OM. The investigation was widened by microcalorimetric measurements which confirmed that the adsorption of 137Cs on the organic soils is low.     

A relationship between the natural radioactivity and mineralogical composition of the Ponnaiyar river sediments, India

The natural radiation level has been determined for the sediment samples of Ponnaiyar River, India with an aim of evaluating the radiation hazard. The average activity concentrations are within the world and Indian average values although some extreme values have been determined. The magnetic susceptibility measurement has been carried out to know the magnetization nature of the sediments. More downstream (mouth) of the river has quite higher magnetic susceptibility values. The mineralogical characterizations of the sediments have been carried out using Fourier Transform Infrared (FTIR) spectroscopic and XRD technique. The minerals such as quartz, microcline feldspar, orthoclase feldspar, kaolinite, calcite, gibbsite, montmorillonite, smectite, palygorskite and organic carbon are identified from FTIR analysis. Few minerals like zircon, monazite and hornblende are identified only in XRD analysis. The relative distribution of major minerals is determined by calculating extinction coefficient. The calculated values show that the amount of quartz is greater than microcline feldspar and very much greater than kaolinite in all the sites. The content of quartz and microcline feldspar is decreases, and kaolinite gradually increases towards the river mouth. Multivariate Statistical analyses were carried out between the parameters obtained from radioactivity analysis and other analyses to know the existing relations. Obtained results are discussed and suggested that the natural radioactivity level of the present sediments is mainly controlled by clay content and lesser extent to magnetic susceptibility.     

太湖东北部沉积物理化特征及磷赋存形态研究

对太湖东部和北部8个沉积物样品进行了理化性质及磷赋存形态分析,在此基础上探讨了沉积物各理化性质与磷赋存形态间的相关关系。研究结果表明：太湖沉积物的总磷含量为307.43～1454.39 mg/kg,阳离子交换量为15.18～22.68 meq/100g土,有机质含量为1.66%～3.45%;颗粒组成以粉砂级和粘粒级为主,占总量的54.39%～76.83%;主要矿物组成为石英和长石,粘土矿物以伊利石/蒙脱石混层为主,其次是伊利石、绿泥石和高岭石;沉积物中氧化物以SiO2、Al2O3和TFe2O3为主,且它们的含量随沉积物中总磷含量的不同变化较大。磷的形态以无机磷为主,污染较重沉积物中铁/铝磷的含量明显升高,有机磷的比例降低,钙磷变化不大。沉积物的各理化性质与磷赋存形态间关系密切,随着沉积物中总磷含量的增加, 阳离子交换量和有机质的含量都逐渐升高,细颗粒含量（<2 μm）逐渐增多,铁/铝形态的磷在总磷中所占比例也逐渐增大。     

Modelling the role of humic acid in radiocaesium distribution in a British upland peat soil

The significance of exchange sites on organic matter in the retention of radiocaesium in highly organic soils remains unclear. To quantify this retention, we measured the binding of 134Cs to a humic acid isolated from a British upland peat soil, under a range of chemical conditions. We interpreted our results using Humic Ion Binding Model V, a model of humic substance chemistry which simulates ion exchange by non-specific accumulation of cations adjacent to the humic molecules. Model V could simulate the humic acid-solution partitioning of Cs under all the solution conditions used. The model was used to estimate the contribution of organic matter to Cs sorption by the whole soil composite. An estimate of Cs sorption by illite frayed edge sites was also made. These simulations show that organic matter may play only a minor role in binding Cs. even in highly organic soils.     

Cesium and strontium sorption by selected tropical and subtropical soils around nuclear facilities

The dynamics of Cs and Sr sorption by soils, especially in the subtropics and tropics, as influenced by soil components are not fully understood. The rates and capacities of Cs and Sr sorption by selected subtropical and tropical soils in Taiwan were investigated to facilitate our understanding of the transformation and dynamics of Cs and Sr in soils developed under highly weathering intensity. The Langmuir isotherms and kinetic rates of Cs and Sr sorption on the Ap1 and Bt1 horizons of the Long-Tan (Lt) and the A and Bt1 horizons of the Kuan-Shan (Kt), Mao-Lin (Tml) and Chi-Lo (Cl) soils were selected for this study. Air-dried soil (<2 mm) samples were reacted with of 7.5 × 10⁻⁵ to 1.88 × 10⁻³ M of CsCl (pH 4.0) or 1.14 × 10⁻⁴ to 2.85 × 10⁻³ M of SrCl₂ (pH 4.0) solutions at 25 °C. The sorption maximum capacity (q_m) of Cs by the Ap1 and Bt1 horizons of the Lt soil (62.24 and 70.70 mmol Cs kg⁻¹ soil) were significantly (p < 0.05) higher than those by the A and Bt1 horizons of the Kt and Cl soils (26.46 and 27.49 mmol Cs kg⁻¹ soil in Kt soil and 34.83 and 29.96 mmol Cs kg⁻¹ soil in Cl soil, respectively), however, the sorption maximum capacity values of the Lt and Tml soils did not show significant differences. The amounts of pyrophosphate extractable Fe (Fe_p) were correlated significantly with the Cs and Sr sorption capacities (for Cs sorption, r² = 0.97, p < 1.0 × 10⁻⁴; for Sr sorption, r² = 0.82, p < 2.0 × 10⁻³). The partition coefficient of radiocesium sorbed on soil showed the following order: Cl soil ? Kt soil > Tml soil > Lt soil. It was due to clay minerals. The second-order kinetic model was applied to the Cs and Sr sorption data. The rate constant of Cs or Sr sorption on the four soils was substantiality increased with increasing temperature. This is attributable to the availability of more energy for bond breaking and bond formation brought about by the higher temperatures. The rate constant of Cs sorption at 308 K was 1.39-2.09 times higher than that at 278 K in the four soils. The activation energy of Cs and Sr sorbed by the four soils ranged from 7.2 to 16.7 kJ mol⁻¹ and from 15.2 to 22.4 kJ mol⁻¹, respectively. Therefore, the limiting step of the Cs⁺ or Sr²⁺ sorption on the soils was diffusion-controlled processes. The reactive components, which are significantly correlated with the Langmuir sorption maxima of Cs and Sr by these soils, substantially influenced their kinetic rates of Cs and Sr sorption. The data indicate that among components of the subtropical and tropical soils studied, short-range ordered sesquioxides especially Al- and Fe-oxides complexed with organics play important roles in influencing their capacity and dynamics of Cs and Sr sorption.     

Soil microorganisms determine the sorption of radionuclides within organic soil systems

The potential of soil microorganisms to enhance the retention of (137)Cs and (85)Sr in organic systems was assessed in a series of experiments. A biologically active, 'mineral-free', organic material, produced under laboratory conditions from leaves, was used as the uptake matrix in all experiments to minimise potential interference from competing clay minerals. Biological uptake and release were differentiated from abiotic processes by comparing the sorption of radionuclides in sterilised organic material with sterile material inoculated with soil extracts or single fungal strains. Our results show conclusively that living components of soil systems are of primary importance in the uptake of radionuclides in organic material. The presence of soil microorganisms significantly enhanced the retention of Cs in organic systems and approximately 70% of the Cs spike was strongly (irreversibly) bound (remained non-extractable) in the presence of microorganisms compared to only approximately 10% in abiotic systems. Sorption of (85)Sr was not significantly influenced by the presence of soil microorganisms. A non-linear temperature response was observed for the retention in biotic systems with increased uptake at between 10 and 30 degrees C and lower retention at temperatures above or below the optimum range. The optimum temperatures for biological uptake were between 15 and 20 degrees C for Cs, and 25 and 30 degrees C for Sr. Our results indicate that single strains of soil and saprotrophic fungi make an important contribution to the sorption of Cs and Sr in organic systems, but can only account for part of the strong, irreversible binding observed in biotic systems. Single strains of soil fungi increased the amount of non-extractable (137)Cs (by approximately 30%) and (85)Sr (by approximately 20%) in the organic systems as compared to abiotic systems, but the major fraction of (137)Cs and (85)Sr sorbed in systems inoculated with saprotrophic fungi remained extractable.     

Availability and immobilization of 137Cs in subtropical high mountain forest and grassland soils

To understand the behavior of (137)Cs in undisturbed soils after nuclear fallout deposition between the 1940s and 1980s, we investigated the speciation of (137)Cs in soils in forest and its adjacent grassland from a volcano and subalpine area in Taiwan. We performed sequential extraction of (137)Cs (i.e., fractions readily exchangeable, bound to microbial biomass, bound to Fe-Mn oxides, bound to organic matter, persistently bound and residual). For both the forest and grassland soils, (137)Cs was mainly present in the persistently bound (31-41%) and residual (22-62%) fractions. The proportions of (137)Cs labile fractions--bound to exchangeable sites, microbial biomass, Mn-Fe oxides, and organic matter--were lower than those of the recalcitrant fractions. The labile fractions in the forest soils were also higher than those in the grassland soils, especially in the volcanic soil. The results suggest that the labile form of (137)Cs was mostly transferred to the persistently bound and resistant fractions after long-term deposition of fallout. The readily exchangeable (137)Cs fraction was higher in soils with higher organic matter content or minor amounts of 2:1 silicate clay minerals.     

Soil-water distribution coefficients and plant transfer factors for (134)Cs, (85)Sr and (65)Zn under field conditions in tropical Australia

Measurements of soil-to-plant transfer of (134)Cs, (85)Sr and (65)Zn from two tropical red earth soils ('Blain' and 'Tippera') to sorghum and mung crops have been undertaken in the north of Australia. The aim of the study was to identify factors that control bioaccumulation of these radionuclides in tropical regions, for which few previous data are available. Batch sorption experiments were conducted to determine the distribution coefficient (K(d)) of the selected radionuclides at pH values similar to natural pH values, which ranged from about 5.5 to 6.7. In addition, K(d) values were obtained at one pH unit above and below the soil-water equilibrium pH values to determine the effect of pH. The adsorption of Cs showed no pH dependence, but the K(d) values for the Tippera soils (2300-4100 ml/g) exceeded those for the Blain soils (800-1200 ml/g) at equilibrium pH. This was related to the greater clay content of the Tippera soil. Both Sr and Zn were more strongly adsorbed at higher pH values, but the K(d) values showed less dependence on the soil type. Strontium K(d)s were 30-60 ml/g whilst Zn ranged from 160 to 1630 ml/g for the two soils at equilibrium pH. With the possible exception of Sr, there was no evidence for downward movement of radionuclides through the soils during the course of the growing season. There was some evidence of surface movement of labelled soil particles. Soil-to-plant transfer factors varied slightly between the soils. The average results for sorghum were 0.1-0.3 g/g for Cs, 0.4-0.8 g/g for Sr and 18-26 g/g for Zn (dry weight) with the initial values relating to Blain and the following values to Tippera. Similar values were observed for the mung bean samples. The transfer factors for Cs and Sr were not substantially different from the typical values observed in temperate studies. However, Zn transfer factors for plants grown on both these tropical soils were greater than for soils in temperate climates (by more than an order of magnitude). This may be related to trace nutrient deficiency and/or the growth of fungal populations in these soils. The results indicate that transfer factors depend on climatic region together with soil type and chemistry and underline the value of specific bioaccumulation data for radionuclides in tropical soils.     

Investigation of 85Sr adsorption on selected soils of different horizons

Studies on the mechanism of (90)Sr migration in soil require many processes to be considered. One of the most important is sorption on the surface of mineral components of the soil. In this study adsorption of (85)Sr on a variety of soil types from different horizons has been investigated. Adsorption isotherms show various affinities of (85)Sr, depending on soil type and to a lesser extent the horizon. An important effect of pH was found with a maximum in the range 5-7. The influence of calcium ions on the extent of adsorption of (85)Sr isotope on soil samples from surface horizons of four sites is presented. Depending on the soil type differing degrees of competitive adsorption of Sr and Ca were observed. Desorption of (85)Sr by distilled water as well as Ca(NO(3))(2) solution was also examined. Both methods resulted in the removal of a considerable proportion of the adsorbed isotope from the soil. Additionally the kinetics of the desorption process were studied.     

Distribution of organic carbon, selected stable elements and artificial radionuclides among dissolved, colloidal and particulate phases in the Rhône River (France): preliminary results

The behaviour of radionuclides discharged from nuclear facilities in the Rh?ne River depends on their distribution among the dissolved, colloidal and particulate phases. A large water sample was fractionated using sequential ultrafiltration. Size distributions of organic carbon, Fe, Al, Si, Ca, Mg, Cu, Zn, 137Cs, 60Co and 106Ru were obtained. Our results show that organic colloids account for 11% of the total organic carbon content. Approximately 20% of the dissolved (< 450 nm) Fe and Al are in colloidal classes. 137Cs is not significantly transferred by the colloidal phase while 25% of 60Co or 106Ru is associated with organic and inorganic colloids.     

Transfer factors of radioactive Cs,Sr, Mn,Co and Zn from Japanese soils to root and leaf of radish

Transfer factors (TFs) of some selected radionuclides from ten different Japanese soils to radish have been studied by radiotracer experiments. The geometric mean values of TFs (on a wet weight basis) of radioactive Cs, Sr, Co, Mn and Zn for edible parts of radish (tuber) were 0.0090. 0.029, 0.00094, 0.0034 and 0.067, respectively. TFs for leaf were higher than those for tuber. The geometric mean values of leaf/tuber ratios were 4.1 for Cs, 4.9 for Sr, 1.6 for Co, 11 for Mn and 1.9 for Zn. Most of the Cs TFs obtained for andosol, which is the most common arable soil in Japan, were higher than those for the other soils. This might be due to the high concentrations of organic matter and alophen in andosol. The obtained TFs were compared to reference values of IAEA Technical Report 364.     

Possible role of organic matter in radiocaesium adsorption in soils

The aim of this review is to examine the hypothesis that organic matter decreases the adsorption of radiocaesium on clay minerals. The factors that determine radiocaesium mobility and bioavailability in soil are briefly outlined to show why a relationship between soil organic matter content and enhanced Cs bioavailability is paradoxical. In all the investigations reviewed the ionic compositions of both the solid and the solution phases have been strictly controlled. We show that the addition of organic matter to reference clay minerals causes decreases of up to an order of magnitude in the distribution coefficient of radiocaesium. Similarly, the chemical removal of organic matter from the clay-sized fraction of soil usually leads to an increase in Cs adsorption. We suggest that the nature of the organic matter and its interaction with mineral surfaces are as important as the amount present.     

Behavior and analysis of Cesium adsorption on montmorillonite mineral

The adsorption of Cs by montmorillonite and the effects of experimental conditions on adsorption were investigated by using ¹³⁴Cs as a radioactive tracer. Additionally, the Cs-adsorbed and the modified montmorillonite were analyzed by X-ray Diffractometer System (XRD) and Scanning Electron Microscopy (SEM). The results showed that the adsorption of Cs by montmorillonite was efficient in the initial concentration (C₀) of 30 μg/L Cs nitrate solution with 20 g/L montmorillonite at room temperature. In this condition, more than 98% Cs⁺ ions could be adsorbed at pH 8. The adsorption equilibrium was achieved within 5 min and the relationship between the concentration of Cs⁺ in aqueous solutions and adsorption capacities of Cs⁺ can be described by the Langmuir adsorption isotherm. The adsorption rate would decrease when temperature increase from 0 °C to 50 °C or in presence of coexistent K⁺, Na⁺ and Ca²⁺, while modification by (NH₄)₂SO₄, [Ag(NH₃)₂]⁺, [Cu(NH₃)₄]²⁺ or 450 °C could improve the adsorption abilities of montmorillonite for Cs⁺. However, more than 89% of adsorbed Cs⁺ on montmorillonite could be desorbed by 2 mol/L HNO₃ solutions. The XRD and SEM analysis further showed that the structure of the Cs-adsorbed or modified montmorillonite were different from that of the original one.     

Soil organic horizons as a major source for radiocesium biorecycling in forest ecosystems

Here we review some of the main processes and key parameters affecting the mobility of radiocesium in soils of semi-natural areas. We further illustrate them in a collection of soil surface horizons which largely differ in their organic matter contents. In soils, specific retention of radiocesium occurs in a very small number of sorbing sites, which are the frayed edge sites (FES) born out of weathered micaceous minerals. The FES abundance directly governs the mobility of trace Cs in the rhizosphere and thus its transfer from soil to plant. Here, we show that the accumulation of organic matter in topsoils can exert a dilution of FES-bearing minerals in the thick humus of some forest soils. Consequently, such accumulation significantly contributes to increasing 137Cs soil-to-plant transfer. Potassium depletion and extensive exploration of the organic horizons by plant roots can further enhance the contamination hazard. As humus thickness depends on both ecological conditions and forest management. our observations support the following ideas: (1) forest ecosystems can be classified according to their sensitivity to radiocesium bio-recycling, (2) specific forest management could be searched to decrease such bio-recycling.     

Plant uptake and downward migration of 85Sr and 137Cs after their deposition on to flooded rice fields: lysimeter experiments with and without the addition of KCl and lime

In order to study the plant uptake and downward migration of radiostrontium and radiocesium deposited on to a flooded rice field, 85Sr and 137Cs were applied to the standing water over an acidic sandy soil in planted lysimeters. The plant uptake was quantified with the areal transfer factor (TFa, m2 kg(-1)-dry plant). Following the spiking 14 days after transplanting, the TFa values for the hulled seeds were 3.9 x 10(-4) for 85Sr and 1.4 x 10(-4) for 137Cs, whereas those for the straws were 1.3 x 10(-2) and 3.2 x 10(-4), respectively. The 137Cs TFa from the spiking at the anthesis/milky-ripe stage was several times higher than that from the earlier spiking, whereas the difference was much less in the 85Sr TFa. Such an increase in the 137Cs TFa was attributed mainly to an enhanced plant-base uptake. The addition of KCl and lime after the spiking significantly reduced the TFa values of both radionuclides. The reducing effect was greater for the later spiking. An appreciable fraction of the applied activity leached out of the lysimeter for 85Sr, whereas a negligible fraction leached for 137Cs. The leaching was remarkably increased by the KCl and lime addition for both. A conspicuous localization of 137Cs with respect to the soil surface was observed. In a batch experiment, the 137Cs concentration in the standing water decreased more rapidly than that of 85Sr, both of which were fitted to the power functions of the elapsed time. To add KCl and lime slowed such decreases to lessen the distribution coefficients (Kd) of both 85Sr and 137Cs.     

239+240Pu, 90Sr and 137Cs inventories in surface soils of Vietnam

Fallout 239+240Pu, 238Pu, 90Sr and 137Cs inventories in surface soils were measured for 20 locations in northern Vietnam yielding the mean values (+/- standard error) of 26.5+/-3.8 Bq m(-2) for 239+240Pu, 1048+/-143 Bq m(-2) for 137Cs and 212+/-28 Bq m(-2) for 90Sr. The concentrations of 137Cs and plutonium isotopes strongly correlate with each other resulting in a stable 239+240Pu/137Cs inventory ratio of 0.025+/-0.002. Among soil parameters, organic matter and fulvic acids strongly correlate with caesium and plutonium isotopes, especially in the 0-10 cm layer. 137Cs and 239+240Pu are distributed rather similarly over the 0-10 cm and 10-20 cm layers. At locations with high contents of sand (82-93%) along the South China Sea coast, the downward percolation by rainwater results in a higher accumulation of 239+240Pu and 137Cs in the 10-20 cm layer. The mean 137Cs/ 90Sr inventory ratio is 9.3+/-2.2, and the correlation is weak between these isotopes.     

乌江流域石灰土中铀等元素形态与铀活性

以中国西南乌江流域石灰土为例，运用逐级提取(Sequential Extraction，SEE)技术，并结合化学成分和相关参数数据，研究了石灰土中铀(U)等元素的形态，并在此基础上探讨了石灰土中U的活动性及释放潜力，旨在增进对U等元素生物地球化学循环的了解，同时也为流域U污染防治提供科学依据。研究结果表明：①石灰土中Mn主要存在于锰(氢)氧化物中，Ca主要存在于碳酸盐和硅酸盐矿物中，P主要存在于硅酸盐矿物和有机质中，U主要赋存于硅酸盐等残留部分中，其次赋存于有机质结合部分和碳酸盐矿物中；②石灰土剖面中活动态U所占的比例为10%~30%，平均17%，说明石灰土中的部分U在酸性和氧化-还原界面等条件下具有一定的迁移活性，即在上述条件下，石灰土中的部分U可释放进入周围水体或植物中；③石灰土中U的潜在释放量为036~150 g/t，平均U潜在释放量为076 g/t，因此，在酸雨和侵蚀等作用下，石灰土U释放可显著提高乌江河水U通量。     

Adsorption and desorption of iodine by various Chinese soils: I. Iodate

In order to assess the adsorption of iodate by different soils from China, a series of batch experiments were conducted. It was found that soils rich in iron oxide had high affinity for iodate. Iodate adsorption isotherms could be well fitted with both Langmuir and Freundlich equations. Iodate adsorption by 20 different soils from China revealed that iodate adsorption was significantly correlated with soil organic matter negatively and positively with free iron oxide contents. At initial concentration of 4 mg I L(-1), iodate adsorption ranged between 9 and 34 mg kg(-1) soil. No correlation between iodate adsorption and cation exchange capacity and soil pH was found. For a single soil, there was a significant linear relationship between the amounts of iodate adsorbed and desorbed, but for a group of different soils, the relationship between the amounts of iodate adsorption and desorption followed a nonlinear relationship, the deviation mainly occurred at high adsorption side. The relationship between K(d) and free aluminum oxide and free iron oxide contents showed an exponential relationship for various soils with exception of the soil from Hetian in Xinjiang.     

An overview of the effect of organic matter on soil-radiocaesium interaction: implications in root uptake

This paper aims to give an overview of the effect of organic matter on soil-radiocaesium interaction and its implications on soil-to-plant transfer. Studies carried out after the Chernobyl accident have shown that high 137CS soil-to-plant transfer persists in organic soils over years. In most of these soils, the specific sites in clays control radiocaesium adsorption, organic compounds having an indirect effect. Only in organic soils with more than 95% of organic matter content and negligible clay content does adsorption occur mostly on non-specific sites. After a contamination event, two main factors account for the high transfer: the low solid-liquid distribution coefficient, which is due to the low clay content and high NH4+ concentration in the soil solution, and the low K+ availability, which enhances root uptake. The estimation of the reversibly adsorbed fraction, by means of desorption protocols, agrees with the former conclusions, since it cannot be correlated with the organic matter content and shows the lack of specificity of the adsorption in the organic phase. Moreover, the time-dependent pattern of the exchangeable fraction is related to soil-plant transfer dynamics.