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.     

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.     

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).     

Variability in the edible fraction content of 60Co, 99Tc, 110mAg, 137Cs and 241Am between individual crabs and lobsters from Sellafield (north eastern Irish Sea)

We investigated the variability of anthropogenic radionuclide content of the edible fractions of individual edible crabs (Cancer pagurus L.) and European lobsters (Homarus gammarus L.) caught commercially in the Sellafield offshore area. Sixteen female and 18 male crabs and 20 female and 17 male lobsters were selected from commercial catches made between 25 May and 5 June 1997. Each gender group was selected to be within the known weight range for commercially caught crustacea from the area. Four artificial radionuclides (60Co, 110mAg, 137Cs or 241Am) were detected by gamma-spectrometry. The edible fraction content of these radionuclides between males and females for either species were not statistically significantly different. 99Tc was analysed by chemical separation and beta-counting. 99Tc concentrations in female crabs tended to be higher (172 +/- 205 (16) Bq kg-1(wet); mean +/- standard deviation (n samples)) than those in males (85 +/- 58 (18) Bq kg-1 (wet)), although this was not a statistically significant difference. For both male and female crabs, 99Tc concentrations tended to decrease with increasing whole live weights. For 99Tc in lobsters the picture is less clear. Female lobsters contained more activity (14800 +/- 7400 (20) Bq kg-1 (wet)) than males (7100 +/- 3900 (17) Bq kg-1 (wet)). The results were used to discuss the implications for sampling and monitoring.     

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.     

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.     

Influence of climatic conditions and soil type on 99TcO4- uptake by rye grass

Climatic changes over the long term will modify significantly the biosphere, with glaciation events probably taking place in the next 100 000 years. This is important to safety assessments of nuclear waste disposal facilities that contain high-level and long-lived waste.The soils will evolve toward new situations, and their properties will be consequently modified (e.g. an increase of soil organic matter may be expected in a cooler climate). These changes in soil properties would affect the mobility and the soil-to-plant transfer of radionuclides such as (99)Tc. This study aimed at simulating the cooling of climatic conditions for soils representative of a Jurassic limestone plateau, and the effect on transfer parameters of (99)TcO(4)(-) in the soil-plant systems was investigated. The cooler conditions were simulated by increasing elevation, a surrogate for climate change. Soils were sampled in similar geological background and topography at different elevations in the north east of France (Lorraine and Jura). Soil/solution distribution coefficients (K(d)) of (99)TcO(4)(-) were measured on soil samples in short-term batch experiments with 1:10 soil:solution ratio. Rye grass was grown on the soils spiked with (99)TcO(4)(-) at temperature regimes adapted to each soil. Also, two different temperature regimes (cold and temperate) were applied to one soil to test the effect of plant physiology and evapotranspiration on (99)TcO(4)(-) uptake. K(d) values did not show significant differences among soils in aerobic conditions, and were not significantly different from 0. During plant culture, reduction of (99)Tc was never totally achieved in soils, including in a peaty OM soil. Concentration ratios (CR) were calculated on a dry weight basis and ranged from 20 to 370. CR were always higher in high temperature regimes than in cold temperatures. They were also inversely correlated with soil organic matter (OM) content. A decrease of CR values from 5 to 10-fold was observed with increasing soil OM. Results suggested that the water holding capacity, in which (99)Tc is diluted, the nitrification potential of the soils and the evapotranspiration of plants (efficiency of uptake of soluble (99)TcO(4)(-)) were strongly involved in these differences.     

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.     

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.     

Technetium-99 in the Irish marine environment

Technetium-99 activity concentrations in seawater and biota from Irish coastal waters are presented. Time series measurements of 99Tc in seawater and Fucus vesiculosus from the western Irish Sea show that activity concentrations have increased in line with the increase in discharges of 99Tc from Sellafield. The peak in activity concentrations in both seawater and Fucus vesiculosus occurred in 1997 approximately two years after the peak in 99Tc discharges. The highest activity concentration recorded in Fucus vesiculosus showed a 29-fold increase over the mean concentration for the period 1988-1993. Technetium-99 activity concentrations were measured in fish, lobsters, prawns, mussels and oysters landed at major fishing ports on the east and northeast coasts of Ireland between 1996 and 1998. Concentration factors for 99Tc in the brown seaweed Fucus vesiculosus and certain species of fish, crustaceans and molluscs from the Irish Sea were estimated. In general, these concentration factors were higher than those in the literature which were derived from laboratory studies, but agreed well with values which were based on field studies. The mean committed effective doses to Irish typical and heavy seafood consumers due to 99Tc in the period 1996-1998 were 0.061 and 0.24 microSv, respectively.     

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.     

A model for the bioaccumulation of (99)Tc in lobsters (Homarus gammarus) from the West Cumbrian coast

A biokinetic model is presented that simulates the uptake and release of (99)Tc by the European lobster (Homarus gammarus). This organism is of significant radioecological interest since lobsters, in contrast to most other organisms, have a high affinity for (99)Tc. The model is designed to represent annually averaged (99)Tc concentrations in lobsters from the Cumbrian coast, where significant levels of (99)Tc have been released under authorisation by the nuclear fuel reprocessing plant at BNFL Sellafield.This paper describes the construction of the model, how it was calibrated using data from published literature, and preliminary results indicating that model output agrees well with the available monitoring data. Given that this model successfully combines laboratory and field data, this research could potentially make a significant contribution to the field, as, to date, it has been difficult to predict and explain concentrations of (99)Tc in lobsters.     

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.     

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.     

Determination of technetium-99 using electrothermal vaporization inductively coupled plasma-mass spectrometry (ETV-ICP-MS) and NH4OH as chemical modifier

In recent years, developments in ICP-MS have led to improved methods for determination of long-lived radionuclides. This paper reports the use of NH(4)OH as a matrix modifier and ETV sample introduction for the determination of technetium-99 ((99)Tc) in a variety of environmental and biological samples, using Re as carrier and (99m)Tc as yield monitor in the chemical separation method. Addition of an excess of NH(4)OH led to a stable (99)Tc signal, reduced memory effect, better reproducibility and reduced detection limits. Following radiochemical separation of (99)Tc from the sample matrix, detection limits in the order of a few microBq have been achieved. ETV has also proved applicable for rapid, direct analysis of a number of environmental samples having relatively high concentrations of (99)Tc (sediment extracts and river water close to nuclear installations). However, in this case, control of matrix effects (signal reduction and enhancement) using standard additions is necessary.     

Tritiated water metabolism in rats — A radiological protection study

The metabolism of tritiated water was studied in the rat during 580 days. The results on urinary and fecal excretion, total activity retention in 25 tissues or organs, cumulated activities from the 4th to the 582nd day are presented and discussed. They are in agreement with other similar studies if compared over the same length of experimentation. The activity retained by the spinal cord is twice that retained in the brain, and is considered as the organ whose long half-lived component is the most active.     

Vertical distributions of (99)Tc and the (99)Tc/(137)Cs activity ratio in the coastal water off Aomori, Japan

Using a sector-field ICP-MS the vertical distributions of the ⁹⁹Tc concentration and ⁹⁹Tc/¹³⁷Cs activity ratio were measured in the coastal waters off Aomori Prefecture, Japan, where a spent-nuclear-fuel reprocessing plant has begun test operation. The ⁹⁹Tc concentrations in surface water ranged from 1.8 to 2.4 mBq/m³, no greater than the estimated background level. Relatively high ⁹⁹Tc/¹³⁷Cs activity ratios (10-12 × 10⁻⁴) would be caused by the inflow of the high-⁹⁹Tc/¹³⁷Cs water mass from the Japan Sea. There is no observable contamination from the reprocessing plant in the investigated area. The ⁹⁹Tc concentration and the ⁹⁹Tc/¹³⁷Cs activity ratio in water column showed gradual decreases with depth. Our results implied that ⁹⁹Tc behaves in a more conservative manner than ¹³⁷Cs in marine environments.     

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.     

Changes in epidemiologic associations with different exposure metrics: A case study of phthalate exposure associations with body mass index and waist circumference

The use of human biomonitoring data to characterize exposure to environmental contaminants in epidemiology studies has expanded greatly in recent years. Substantial variability in effect measures may arise when using different exposure metrics for a given contaminant, and it is often not clear which metric is the best surrogate for the ‘causal’ or ‘true’ exposure. Here we evaluated variability and potential bias in epidemiologic associations resulting from the use of different phthalate exposure metrics in the 2009–2010 National Health and Nutrition Examination Survey (NHANES). We examined associations between urinary phthalate metabolites and the outcomes of body mass index (BMI) and waist circumference (WC). We examined each of the following NHANES-derived exposure metrics for metabolites of individual phthalates: molar excretion rate (nmol/min), molar amount (nmol), molar concentration (nmol/mL, with and without additional model adjustment for creatinine), creatinine corrected molar concentration (nmol/g creatinine), and reconstructed daily phthalate intake (nmol/kg/day). In order to investigate potential biasing effect of each metric, we first assumed that daily intake of the parent phthalate is the causal exposure. We then constructed a simulated population based on the 2009–2010 NHANES, and randomly assigned each individual a di-2-ethylhexyl phthalate (DEHP) intake dose based on a published distribution, but independent of any other factor. Accordingly, all associations between these randomly assigned intake doses and individuals' BMI and WC should be null. Next, demographic data in the NHANES were incorporated into a pharmacokinetic model to predict urinary molar excretions of five DEHP metabolites based on the randomly assigned DEHP intake. The predicted molar excretions were then used to calculate the same exposure metrics listed above. Three exposure metrics (randomly generated intake, excretion rate, urine concentration) showed no significant associations with BMI, which supports the null hypothesis stated above. In contrast, metrics adjusted for creatinine showed a significant negative correlation, and reconstructed daily intake showed a significant positive correlation, indicating the introduction of bias away from the true (i.e., null) association. Interestingly, trends in the simulation analysis were similar to those seen in the observed NHANES data. Our findings show that, at least in this example case, the choice of exposure metric can introduce significant bias of varying magnitude and direction into the calculation of epidemiologic associations.     

Uptake and depuration of 131I by the edible periwinkle Littorina littorea: uptake from seawater

Uptake and depuration experiments for the edible periwinkle Littorina littorea have been performed using 131I-labelled seawater. Throughout the experimental phase the winkles were fed on unlabelled Chondrus crispus. 131I concentrations in winkles during uptake followed linear first-order kinetics with an uptake half-time of 11 days, whereas for depuration a triphasic sequence with biological half-lives of 4, 23 and 56 days was determined. In general, iodine turnover in winkles via labelled seawater appears to be slower than observed for other molluscs (2-3 days). Most of the activity prior to and after depuration is found to be in the shell, with indications that shell and soft parts accumulate and depurate 131I at a similar rate. The operculum displays the highest specific activity of all fractions with a concentration factor of 750 l kg(-1). Concentration factors for whole winkle, shell, soft parts and digestive gland are in the order of 40-60 l kg(-1), higher than the IAEA recommended CF value for iodine in molluscs of 10 l kg(-1). The 131I CF in winkles is closer to that of the conservative radionuclides 99Tc and 137Cs than the CF of the particle reactive radionuclides (239,240)Pu and 241Am.