Availability of 99Tc in undisturbed soil cores

Models for safety assessment of radioactive waste repositories need accurate values of the soil-to-plant transfer of radionuclides. In oxidizing environments, (99)Tc is expected to occur as pertechnetate ((99)TcO(4)(-)). Due to its high mobility, leaching of this element in the field might be important, potentially affecting the reliability of estimated transfer parameters of (99)Tc as measured in closed experimental systems such as hydroponics or pot experiments. The aim of this experiment was to measure the leaching of (99)Tc in undisturbed irrigated soil cores under cultivation as well as plant uptake and to study the possible competition between the two transfer pathways. Undisturbed soil cores (50 x 50 cm) were sampled from a Rendzic Leptosol (R), a colluvial Fluvic Cambisol (F) and a Dystric Cambisol (D) using PVC tubes (three cores sampled per soil type). Each core was equipped with a leachate collector at the bottom, allowing the monitoring of (99)Tc leaching through the cores. Cores were placed in a greenhouse and maize (Zea mays L., cv. DEA, Pioneer) was sown. After 135 d, maize was harvested and radioactivity determined in both plant and water samples. Results showed that during the growing period, leaching of (99)Tc was limited, due to the high evapotranspiration rate of maize. After harvest, leaching of (99)Tc went on because of the absence of evapotranspiration. Effective uptake (EU) of (99)Tc in leaves and grains was calculated. EU reached 70% of the input in the leaves and was not significantly different among soils. These results confirmed those obtained from pot experiments, even though leaching was allowed to occur in close-to-reality hydraulical conditions. As a consequence, it was concluded that pot experiments are an adequate surrogate for more complex "close-to-reality" experimental systems for measuring transfer factors.     

Accumulation of 99Tc in duckweed Lemna minor L. as a function of growth rate and 99Tc concentration.

This study focuses on the question of whether short-term studies can be used to forecast the accumulation of the long-lived fission product 99Tc in duckweed, Lemna minor L., grown in the field; in other words, are the accumulation parameters independent of changing growth rates typical of natural populations of duckweed. Two processes determine the 99Tc accumulation: (i) uptake and release of 99TcO4-, characterised by a concentration factor, Kd, and (ii) first-order reduction and complexation of TcVII, characterised by kred. At various 99Tc concentrations, the growth, total Tc and TcO4- accumulation were monitored over 10 days; parameters were fitted and compared with earlier results. Both Kd and kred turn out to be independent of time, concentration and growth rate up to a concentration of 10(-6)mol l(-1) 99TcO4-. Concentrations above this level result in toxic effects. The Tc accumulation in field populations of duckweed at Tc concentrations which generally occur in the environment can be forecasted by using the results from short-term experiments.     

Effect of low continuous 99Tc intake on its absorption and metabolism in young rats

A continuous daily oral dose of (99)TcO(4)(-) (5 Bq g(-1) day(-1)) was given to young rats for 56 days. In one group the intake was continued for 98 days, while in the other the intake was stopped to facilitate the determination of biological half lives in different organs and tissues. The absorbed fraction of (99)Tc increased from 0.7 to 0.9 during the experimental period (m=0.85 sigma=0.02). The whole body retained fraction (m=0.15 sigma=0.05) indicated a storage in the tissues. The liver and kidneys showed increasing concentrations of (99)Tc until a plateau was reached after 6 and 9 weeks, then a rapid decline after the intake was stopped (half life of 6 and 5 days respectively). In hair and thyroid tissue, the accumulation of (99)Tc increased linearly then declined very slowly after the intake was stopped and did not reach a plateau during the experiment. No significant amounts of (99)Tc were detected in the muscular tissues or in the walls of the digestive tract. After the contamination period, urinary and fecal excretions fell off very quickly (1 week), but significant, though low, quantities of urinary and fecal excretions were still observed 6 weeks after stopping intake.     

Soil availability,plant uptake and soil to plant transfer of 99Tc--a review

The fission yield of 99Tc from 239Pu and 235U is similar to that of 137Cs or 90Sr and it is therefore an important component of nuclear weapons fall-out, nuclear waste and releases from nuclear facilities. There is particular current interest in 99Tc transfer from soil to plants for: (a) environmental impact assessments for terrestrial nuclear waste repositories, and (b) assessments of the potential for phytoextraction of radionuclides from contaminated effluent and soil. Vascular plants have a high 99Tc uptake capacity, a strong tendency to transport it to shoot material and accumulate it in vegetative rather than reproductive structures. The mechanisms that control 99Tc entry to plants have not been identified and there has been little discussion of the potential for phytoextraction of 99Tc contaminated effluents or soil. Here we review soil availability, plant uptake mechanisms and soil to plant transfer of 99Tc in the light of recent advances in soil science, plant molecular biology and phytoextraction technologies. We conclude that 99Tc might not be highly available in the long term from up to 50% of soils worldwide, and that no single mechanism that might be easily targeted by recombinant DNA technologies controls 99Tc uptake by plants. Overall, we suggest that Tc might be less available in terrestrial ecosystems than is often assumed but that nevertheless the potential of phytoextraction as a decontamination strategy is probably greater for 99Tc than for any other nuclide of radioecological interest.     

Technetium species induced in maize as measured by phosphorimager

Leaves of plants have the ability to accumulate the long-lived fission product (99)Tc. In the present work, an attempt was made to separate and characterize technetium species formed in maize grown on soil contaminated with Tc(VII)O(4)(-) solution. Data obtained from selective extraction, a Phosphorimager and liquid scintillation were employed.     

Environmental conditions for the formation of insoluble Tc in water ponds located above paddy fields

Optimum conditions for the formation of insoluble Tc (Tc in >0.2 microm size fraction) were studied using a microcosm including water ponds above a paddy field to understand Tc behavior in such fields. In the microcosm, soluble TcO(4)(-) was converted to insoluble forms, but no changes in the form of Tc were observed in filtered microcosm samples which were microorganisms-free. The formation of insoluble Tc was inhibited by the addition of the antibiotic chloramphenicol. In addition, the reduction of soluble Tc(VII)O(4)(-) to low-valence oxide was not observed in the filtered microcosm samples, although reducing conditions were present. These results indicated that bacteria were involved in the formation of insoluble Tc. Since oxidizing conditions influence bacterial metabolism, the formation of insoluble Tc by bacteria was studied under aerobic and anaerobic conditions. The results showed that anaerobic conditions were favorable for the formation of insoluble Tc. In addition, the addition of formate as an electron donor to a microcosm sample facilitated the formation of insoluble Tc. The results suggested that insoluble Tc in the water ponds above paddy fields was caused by bacteria, which were shown to couple the oxidation of formate to the reduction of Tc(VII) during anaerobic respiration.     

Determination of bioavailable rhenium fraction in agricultural soils

Rhenium (Re) mobility in agricultural soils was studied in order to obtain information relevant to (99)Tc mobility in soil-to-plant systems. Since water soluble Tc and Re are highly bioavailable, extraction of Re with water was carried out in addition to a total Re determination in the soils. The geometric means of total Re for paddy field, upland field and other soils were 0.34, 0.23, and 0.28 ng g(-1), respectively, while those of water soluble Re (<0.45 microm membrane filterable) were 0.053, 0.015 and 0.008 ng g(-1), respectively. There were no differences for total Re among soil uses; however, the water soluble Re/total Re ratio was significantly higher in paddy field soils (16%) than in other soil uses (6% for upland fields and 3% for other uses). Rhenium mobility and plant availability were higher in paddy fields than in other agricultural fields, and similar phenomena would be expected for (99)Tc.     

The influence of temperature and hydration on the sorption properties of bentonite

The effects of exposure to synthetic groundwater at elevated temperature gradients on the sorption properties of bentonite were investigated using the Mock-Up-Cz experiment. This experiment simulated the vertical placement of a container of radioactive waste according to the Swedish KBS-3 system for a period of more than 3 years. The mineralogical composition, as well as its chemical and physico-chemical properties, including the uptake of (99)TcO(4)(-) and (134)Cs(+), was used to evaluate the chemical changes caused by the long-term exposure of bentonite buffer to thermal and hydration gradients. It was found that the bentonite material was predominantly stable. No more than 2% of the montmorillonite was transformed due to thermal and moisture gradients. It was concluded that the new-formed mineral phases have no significant influence on the ion exchange and sorption properties of bulk bentonite samples.     

Sea-to-land transfer of technetium-99 through the use of contaminated seaweed as an agricultural soil conditioner

The use of seaweed as an agricultural soil conditioner gives rise to a potential pathway for the transfer of Technetium-99 ((99)Tc) from marine to terrestrial ecosystems and thence to man. However, to date there is little information on the extent of the release of (99)Tc from seaweed into soil and the mechanisms involved. This pot experiment has shown that (99)Tc is released fairly rapidly from Fucus vesiculosus into a sandy coastal soil. Despite low temperature conditions, 60% of the (99)Tc added with the seaweed had accumulated in the soil 15 weeks after addition. Concurrent CO(2) monitoring (used as a measure of microbial decomposition or catabolism) suggested that the initial (99)Tc release (up to 40% in the first 8 weeks) was due to leaching from the seaweed and that microbial decomposition was responsible for the release of the remaining (99)Tc in the latter phase (12-15 weeks).     

Soil migration and plant uptake of technetium from a fluctuating water table

Soil columns (50x15 cm) were used to determine the potential for 95mTc (as a surrogate for 99Tc which is an important component of some radioactive waste) to migrate from a contaminated, fluctuating water table, through sandy loam soil and into perennial ryegrass. Upward migration was significantly retarded with, generally, only the bottom few centimetres of soil becoming contaminated over the 6 months of the experiment. This is thought to have been due to the presence of anoxic conditions within the water table leading to the reduction of pertechnetate to Tc(IV) species which are relatively insoluble. However, some evidence of very slow upward migration over time was found. Only a small and inconsistent transfer of activity into the perennial ryegrass was observed. Whilst these observations would suggest that 99Tc is less important than radionuclides such as 129I and 36Cl in terms of the risk associated with radioactive waste disposal, the potential for a slow upward migration, and/or a pulse-release following the re-oxidation of reduced soil in which 99Tc has accumulated should not be overlooked.     

徐州市某水泥厂附近土壤中黑碳和有机质的磁学响应

以徐州某水泥厂附近土壤样品为例,分析了土壤中黑碳(BC)和有机质(OM)的含量,并研究了不同利用类型土壤中黑碳和有机质的磁学响应。结果表明,研究区域黑碳含量和有机质含量的平均值分别为12.35 g/kg和112.33 g/kg。林地样品的黑碳和有机质含量均与频率磁化率正相关,耕地样品的黑碳含量和有机质含量均与频率磁化率负相关,说明不同类型土壤中黑碳和有机质的来源不同,且人为活动对土壤理化性质影响较大。不同利用方式土壤的黑碳含量与磁化率(χ)、非磁滞剩磁磁化率(χARM)、软剩磁(SOFT)、饱和等温剩磁(SIRM)显著正相关;有机质含量和χ,SOFT,SIRM正相关,初步判断这些参数可以作为黑碳或有机质的代用指标。     

Long-term study of 99Tc in the marine environment on the Swedish west coast

The activity concentration of (99)Tc in brown seaweed (Fucus vesiculosus and Fucus serratus) and seawater were analysed in samples collected in 1991, 1995 and 2001 at several stations along the Swedish west coast. In addition to these locations, a well-defined site (S?rdal, 56.76 degrees N, 12.63 degrees E) was included with (99)Tc activity concentration data in seaweed from 1967 to 2000. Over the years, the major source of (99)Tc in the coastal waters of western Sweden has been the radioactive liquid discharge from the nuclear fuel reprocessing plant in Sellafield (UK) transported via ocean currents in the North Sea. The (99)Tc activity concentration in seaweed at the S?rdal site increased from approximately 30 Bq kg(-1) up to 230 Bq kg(-1) (dry weight) between 1997 and 2000 due to the Sellafield EARP (Enhanced Actinide Removal Plant) discharges in 1995-1996, yielding an approximate transport time of 4-5 years between the Irish Sea and the Kattegat. Due to the very sharp gradient in (99)Tc concentration between the Baltic Sea and the North Sea, (99)Tc is presently one of the best transit tracers for the recent ventilation events in the Baltic Sea.     

Radiocaesium soil-to-wood transfer in commercial willow short rotation coppice on contaminated farm land

The feasibility of willow short rotation coppice (SRC) for energy production as a revaluation tool for severely radiocaesium-contaminated land was studied. The effects of crop age, clone and soil type on the radiocaesium levels in the wood were assessed following sampling in 14 existing willow SRC fields, planted on radiocaesium-contaminated land in Sweden following Chernobyl deposition. There was only one plot where willow stands of different maturity (R6S2 and R5S4: R, root age and S, shoot age) and clone (Rapp and L78183 both of age category R5S4) were sampled and no significant differences were found. The soils differed among others in clay fraction (3-34%), radiocaesium interception potential (515-6884 meq kg(-1)), soil solution K (0.09-0.95 mM), exchangeable K (0.58-5.77 meq kg(-1)) and cation exchange capacity (31-250 meq kg(-1)). The soil-to-wood transfer factor (TF) of radiocaesium differed significantly between soil types. The TF recorded was generally small (0.00086-0.016 kg kg(-1)), except for willows established on sandy soil (0.19-0.46 kg kg(-1)). Apart from the weak yet significant exponential correlation between the Cs-TF and the solid/liquid distribution coefficient (R2 = 0.54) or the radiocaesium interception potential, RIP (R2 = 0.66), no single significant correlations between soil characteristics and TF were found. The wood-soil solution 137Cs concentration factor (CF) was significantly related to the potassium concentration in the soil solution. A different relation was, however, found between the sandy Tr?dje soils (CF = 1078.8 x m(K)(-1.83), R2 = 0.99) and the other soils (CF = 35.75 x m(K)(-0.61), R2 =0.61). Differences in the ageing rate of radiocaesium in the soil (hypothesised fraction of bioavailable caesium subjected to fast ageing for Tr?dje soils only 1% compared to other soils), exchangeable soil K (0.8-1.8 meq kg(-1) for Tr?dje soils and 1.5-5.8 meq kg(-1) for the other soils) and the ammonium concentration in the soil solution (0.09-0.31 mM NH4+ for the Tr?dje soils compared to 0.003-0.11 mM NH4+ for the other soils) are put forward as potential factors explaining the higher CF and TF observed for the Tr?dje soils. Though from the dataset available it was not possible to unequivocally predict the Cs-soil-to-wood-transfer, the generally low TFs observed point to the particular suitability for establishment of SRC on radiocaesium-contaminated land.     

Seasonal variations in activity concentrations of 99Tc and 137Cs in the edible meat fraction of crabs and lobsters from the central Irish Sea

Discharges of most radionuclides into the Irish Sea from the BNFL site at Sellafield have decreased over the past 20 years or so. For a few radionuclides, however, discharges have peaked more recently. Notably, operation of the Enhanced Actinide Removal Plant (EARP) since 1994 has led to an increase in discharges of (99)Tc, as a result of the treatment of previously stored waste, with consequent increases in (99)Tc activity concentrations in a number of marine species, particularly in crustaceans such as lobsters. Previous research has considered the significance of factors such as sex and body weight on radionuclide concentrations. The current project set out to investigate whether seasonal variations in radionuclide concentrations in crabs and lobsters occur, with particular emphasis on the dynamics of (99)Tc and (137)Cs. Organisms were obtained from a site off the Isle of Man, where radionuclide concentrations were measurable but the site was sufficiently distant from Sellafield that the radionuclides were well mixed in the water column and not likely to be influenced by the pulsed nature of discharges of (99)Tc. Crab and lobster samples were collected monthly, between February 2000 and February 2001. Fifteen or 16 individuals (evenly split as male and female) of each species were collected on each occasion. Seawater samples were also collected over the 12-month period. Activity concentrations of (99)Tc in the edible meat fraction (both brown and white meat) ranged from 0.23 to 2.46 Bq kg(-1) (fresh weight (fw)) in crabs and 124 to 216 Bq kg(-1) (fw) in lobsters, with no observed seasonal variations. Activity concentrations of (137)Cs in both crab and lobster were lower, ranging from <0.16 to 0.85 Bq kg(-1) for crab meat (fw) and <0.3 to 3.3 Bq kg(-1) for lobster meat (fw). A statistically significant increase in activity concentrations of (137)Cs in the meat was observed in the summer months for both crab and lobster. The cause has not been investigated but may be related to the laying down of energy reserves during the active feeding period over the summer. At all times, uptake of (99)Tc is higher in the brown meat fraction of both crabs and lobsters, whilst (137)Cs is more uniformly distributed. These results are used to discuss the implications for sampling and monitoring programmes.     

Seasonal changes of redox potential and microbial activity in two agricultural soils of tropical Australia: some implications for soil-to-plant transfer of radionuclides

Very little is known of the factors controlling soil-to-plant transfer of radionuclides in tropical environments. As part of an IAEA/FAO coordinated research project (CRP) designed to elucidate some of those factors, near-surface samples of two agricultural red-earth soils (Blain and Tippera) were collected from a study site in the Northern Territory. The climate is tropical monsoonal with crops being grown over the wet season from December to March/April. It is important to understand soil variables that may be related to this dramatic seasonality. In this investigation, soil redox state and microbial populations were assessed before and after the growing season with a view to generating hypotheses for future evaluation. The X-ray absorption near edge structure (XANES) technique was used to determine overall changes in the solid-state redox speciation of Fe and Mn in soils across the growing period. Fe speciation did not change but approximately 10% of the total Mn was oxidised from Mn(II) to Mn(III) and Mn(IV) in both soils between October 1999 and April 2000. An apparent disconnect between Fe and Mn was not unexpected given the >10 times higher concentration of Fe in the soils compared with Mn. These results have implications for the bioavailability of redox sensitive radionuclides such as Tc and Pu. Similarly, microbial population estimates were derived before and after the growing period. Total bacterial populations did not vary from 10(6) to 10(7) colonies per gram. Fungal populations increased over the growing season from 3-6 x 10(5) to 1-4 x 10(6) colonies per gram of soil. Fungi have the potential to decrease soil pH and hence increase the bioavailability of radionuclides such as Cs. In addition, fungi act to facilitate plant nutrition. This could lead to enhanced accumulation of nutrient analogues (e.g. Sr and Ra for Ca; Tc for Mn), but this effect may be masked by improved biomass production.     

Temporal trends for 99Tc in Norwegian coastal environments and spatial distribution in the Barents Sea

The objective of this study was to reassess 99Tc transit times and transfer factors, from Sellafield to northern Norway, and to determine the extent of 99Tc migration to the Barents Sea. Filtered seawater samples were collected on a monthly basis from Hilles?y, northern Norway, and in February 1999 from the Barents Sea. Results showed an increase in levels of 99Tc at Hilles?y where activity concentrations have increased from a baseline of 0.2-0.4Bq m(-3) to a maximum of 1.6 Bq m(-3). A transit time of 42 months and a transfer factor of 6Bq m(-3) per PBq a(-1) have been derived, using cross-correlation analysis. The current study predicts that future levels are unlikely to increase dramatically over the levels observed in 1998. Levels of 99Tc in the Barents Sea ranged from 0.2 Bq m(-3) to 1.1 Bq m(-3) showing the influence of new 99Tc inputs by early 1999.     

Soil-to-plant halogens transfer studies 1. Root uptake of radioiodine by plants

Long-term controlled experiments under natural conditions in the field have been carried out in the Chernobyl Exclusion zone in order to determine the parameters governing radioiodine transfer to plants from four types of soils (podzoluvisol, greyzem and typical and meadow chernozem) homogeneously contaminated in the 20-cm upper layer with an addition of (125)I. An absence of (125)I depletion in arable soil layers due to volatilization was noted up to one year after contamination. During one year, depletion due to the vertical migration of radioiodine from the arable layer of each of the soils did not exceed 4% of the total (125)I content. Radioiodine concentration ratios (CR) were obtained in radish roots, lettuce leaves, bean pods, and wheat grain and straw. The highest CR values were observed in podzoluvisol: 0.01-0.03 for radish roots and lettuce leaves, 0.003-0.004 for bean pods and 0.001 for wheat grains. In the other three soils, these values were one order of magnitude lower. The parameters relating to changes in radioiodine bioavailability were determined, based on the contamination dynamics of plants in field conditions.     

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.     

四湖地区渍害稻田土壤有机质及其氧化稳定性

采用定点调查和大田采样的方法，较系统地研究了不同渍害程度的稻田土壤有机质和活性有机质与土壤主要农化指标之间的关系。结果表明：(1)活性有机质与土壤全氮、碱解氮和速效磷等肥力指标间的相关系数均达极显著水平，且比土壤有机质与其对应肥力指标间的相关系数均要大，比有机质更能反映出土壤有效养分的供应。(2)从通径分析结果看出：碱解氮对活性有机质的直接效应要小于速效磷对活性有机质的直接效应，前者为27.3％，后者为46．1％。渍害土壤中与活性有机质关系最密切的土壤肥力指标是速效磷和碱解氮。(3)初步认为用有机质氧化稳定性(Kos值)比用有机质含量或活性有机质含量能够更好地作为渍害土壤判断渍害程度的标准。     

Retention and phytoavailability of radioniobium in soils

Radioniobium is present in long-lived nuclear waste as a result of the activation of zirconium pellets associated with the nuclear fuel. The behaviour of niobium (Nb) in the environment and especially its fate in the soil-plant system has not been thoroughly investigated so far. In safety assessment of French long-lived nuclear waste disposal, data concerning the mobility and the bioavailability of Nb in soils are needed as well as general trends of its fate in the specific environment around the site of French underground research laboratory. Therefore, we investigated the mobility of 95Nb in three different soils typical of the area of north-eastern France and its uptake by two plants, rye grass (Lolium perenne L.) and winter wheat (Triticum aestivum L.). Soil:solution distribution of 95Nb was observed in 1:10 batch experiments with deionized water for a 3-day period. Results showed that K(d) values were high (in the order of 10(3) L kg(-1)) and were still significantly increasing after 3 days. A mathematical model, fitted to describe the decrease of the radioactivity after 3 days, is proposed to calculate sorption ratios--SR--(rather than K(d) values as equilibrium was not reached) over longer periods. Soil-to-plant concentration ratios (CR) were measured in shoots and roots of the two plants after cultivation on two soils spiked with (95)Nb (406kBqkg(-1)). Soil-to-root dry weight CR were high (0.30-1.52) and could probably be due to efficient uptake into the roots. However, no transfer of Nb to plant shoots was detected in any of the soils. Nb is thus a rather immobile element in soils and its transfer to plants seems limited to underground parts. It would therefore tend to accumulate in surface horizons of soils in case of long-term continuous surface release.