Fate of 90Sr and U(VI) in Dounreay sediments following saline inundation and erosion.

There is concern that sea level rise associated with projected climate change will lead to the inundation, flooding and erosion of soils and sediments contaminated with radionuclides at coastal nuclear sites, such as Dounreay (UK), with seawater. Here batch and column experiments were designed to simulate these scenarios and sequential extractions were used to identify the key radionuclide solid phase associations. Strontium was exchangeable and was mobilised rapidly by ion exchange with seawater Mg(2+) in both batch and column experiments. In contrast, U was more strongly bound to the sediments and mobilisation was initially limited by the influence of the sediment on the pH of the water. Release was only observed when the pH increased above 6.9, suggesting that the formation of soluble U(VI)-carbonate species was important. Under dynamic flow conditions, long term release was significant (47%), but controlled by slow desorption kinetics from a range of binding sites.

Effect of organic complexing agents on the interactions of Cs(+), Sr(2+) and UO(2)(2+) with silica and natural sand.

Sorption processes play a key role in controlling radionuclide migration through subsurface environments and can be affected by the presence of anthropogenic organic complexing agents found at contaminated sites. The effect of these complexing agents on radionuclide-solid phase interactions is not well known. Therefore the aim of this study was to examine the processes by which EDTA, NTA and picolinate affect the sorption kinetics and equilibria of Cs(+), Sr(2+) and UO2(2+) onto natural sand. The caesium sorption rate and equilibrium were unaffected by the complexing agents. Strontium however showed greater interaction with EDTA and NTA in the presence of desorbed matrix cations than geochemical modelling predicted, with SrNTA(-) enhancing sorption and SrEDTA(2-) showing lower sorption than Sr(2+). Complexing agents reduced UO2(2+) sorption to silica and enhanced the sorption rate in the natural sand system. Elevated concentrations of picolinate reduced the sorption of Sr(2+) and increased the sorption rate of UO2(2+), demonstrating the potential importance of this complexing agent. These experiments provide a direct comparison of the sorption behaviour of Cs(+), Sr(2+) and UO2(2+)onto natural sand and an assessment of the relative effects of EDTA, NTA and picolinate on the selected elements.

Evaluation of electrospray ionisation mass spectrometry as a technique for the investigation of competitive interactions: a case study of the ternary Th-Mn-EDTA system.

RATIONALE: Electrospray ionisation mass spectrometry (ESI-MS) is a useful tool for exploring the speciation of solution-phase metal complexes; however, the quantification of ternary systems is challenging due to the differences in the electrospray response of different species. Here, the Th-Mn-EDTA system was investigated to evaluate the capability of ESI-MS for quantifying the species present. METHODS: Increasingly complex mixtures of Th(IV), Mn(II) and EDTA were analysed using manual flow injection of samples into an HPLC grade water mobile phase delivered to an ion trap mass spectrometer fitted with an ESI interface (ThermoQuest Finnigan Mat LCQ). Mass spectra were obtained in the positive and negative ion modes over a mass-to-charge (m/z) range from 50-2000. RESULTS: The instrumental response to EDTA was affected by the addition of Th(NO(3))(4) but not MnCl(2), while the response to both Th-EDTA and Mn-EDTA species was affected by addition of the other metal salt. Internal standards were also found to suppress signals to different extents. Therefore, each signal suppression was carefully quantified as the solution became more complex, and signal correction factors were used in conjunction with regular external calibration. Mixed metal signals were quantified adequately. CONCLUSIONS: This study showed the complexity of quantifying a ternary system involving different co-existing species. Nonetheless, the step-wise protocol developed provided quantitative data on the displacement of Mn from its EDTA complex by Th.

Mobilization of technetium from reduced sediments under seawater inundation and intrusion scenarios.

Predicted sea level rise would increase the vulnerability of low lying coastal legacy nuclear sites to inundation and intrusion with oxygenated seawater. This could have a significant impact on the mobility of redox-sensitive radionuclides such as Tc. Here, batch and column experiments were used to simulate and investigate the effect of these processes on the mobilization of Tc from sediments under a range of geochemically reduced conditions. Batch experiments showed that only a small proportion of Tc was rapidly (within 5 days) released from the sediments into seawater and groundwater. The subsequent Tc release was slowest and ultimately limited to the greatest extent (17%) in initially Fe-reducing sediments, when they were reoxidized in seawater. Thus, the cycling of iron and the impact of the water chemistry on iron mineralogy were important for hindering Tc release. Column experiments showed that iron minerals were less effective at retarding Tc release under flow-through conditions. Kinetically controlled and solubility limited Fe dissolution led to ongoing Tc release from the sediments; i.e. the retarding effect of iron phases was temporary, and significantly more Tc was mobilized (79-93%) compared with the batch experiments (17-45%). These results demonstrate the potential for Tc(IV) to be oxidized and mobilized from sediments at coastal nuclear sites resulting from predicted intrusion and inundation with oxic seawater.

The effect of EDTA on the groundwater transport of thorium through sand.

The effect of the anthropogenic complexing agent EDTA on thorium transport in groundwater has been studied using sand-packed columns and flow rates in the range of 20-100 m y⁻¹. The concentrations injected into the columns were in the range of 0.4-4 mM for Th and 4-40 mM for EDTA, and with EDTA:Th ratios in the range 1:1 to 10:1. The results show that EDTA can significantly increase Th transport, but two very different behaviours are observed at Th concentrations of 0.4 and 4 mM. At the lower concentration, Th breakthrough is retarded with respect to a conservative tracer, with a peak width that is consistent with a single K(d) value, followed by a longer tail, and the behaviour is very sensitive to the flow rate. However at 4 mM Th, the breakthrough peak appears near to that of the tracer, and the width of the peak is consistent with a distribution of K(d) values and/or a larger dispersivity than the tracer. Speciation and transport modelling have been used to interpret the data, and a model was developed that could explain the 0.4 mM behaviour. This suggests that ternary surface complexes are important in these systems, with at least two different species involved, although the complexity of Th speciation in these systems leads to significant uncertainty in the values of the equilibrium and kinetic parameters. For the 4 mM systems, the rapid transport observed could not be explained by a simple chemical model; instead it is likely that EDTA plays an important role in stabilising and transporting thorium colloids and clusters.

The effect of EDTA, NTA and picolinic acid on Th(IV) mobility in a ternary system with natural sand.

Organic complexing agents, such as ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and picolinic acid, have been widely used at nuclear sites and are therefore found as common co-contaminants in radioactive contaminated land. This study has explored the mechanisms by which these three complexing agents affect the sorption of Th(IV) to pure silica and a natural sand. EDTA, NTA and, to a lesser extent, picolinic acid decreased the sorption of Th to silica, demonstrating the formation and solubility of Th complexes. However, Th sorption to sand was kinetically controlled and complexation enhanced the rate of Th sorption. EDTA and NTA did not sorb significantly to the sand, and metal desorption indicated that the mechanism involved exchange with sand-associated metals. At equilibrium, however, Th sorption was not affected by the presence of the ligands, and modelling suggested that the interaction between Th and the surface binding sites controlled Th sorption thermodynamically.

A review of recent trends in electrospray ionisation-mass spectrometry for the analysis of metal-organic ligand complexes.

Electrospray ionisation-mass spectrometry (ESI-MS) is used in a wide variety of fields to examine the formation, stoichiometry and speciation of complexes involving metals and organic ligands. This article reviews the literature in this area over the past 5 years, examining trends in ESI-MS use and novel applications that enhance the scope of the technique. ESI-MS can provide direct information on changes in speciation with metal:ligand ratio and pH, identify metal oxidation state directly and allow insight into competitive interactions in ternary systems. However, both the instrumental set-up and artefacts in the electrospraying process can affect the species distribution observed, and changes in solution chemistry can affect the relative ion intensity of species. Therefore, ESI-MS data is at its most powerful when corroborated by data from other experimental techniques, such as pH potentiometry. The challenges in interpreting direct ESI-MS data quantitatively are discussed in detail, with reference to differences in the ion intensities of species, signal suppression and quantifying species distributions. The use of HPLC-ESI-MS is also reviewed, highlighting challenges and applications. Overall, the need for more standard reporting of quality assurance data is discussed, to strengthen the applications of ESI-MS to metal-organic ligand complexes further.

A review of the environmental corrosion, fate and bioavailability of munitions grade depleted uranium.

Depleted uranium (DU) is a by-product of nuclear fuel enrichment and is used in antitank penetrators due to its high density, self-sharpening, and pyrophoric properties. Military activities have left a legacy of DU waste in terrestrial and marine environments, and there have been only limited attempts to clean up affected environments. Ten years ago, very little information was available on the dispersion of DU as penetrators hit their targets or the fate of DU penetrators left behind in environmental systems. However, the marked increase in research since then has improved our knowledge of the environmental impact of firing DU and the factors that control the corrosion of DU and its subsequent migration through the environment. In this paper, the literature is reviewed and consolidated to provide a detailed overview of the current understanding of the environmental behaviour of DU and to highlight areas that need further consideration.

Corrosion and transport of depleted uranium in sand-rich environments.

The firing of depleted uranium (DU) weapons during conflicts and military testing has resulted in the deposition of DU in a variety of sand-rich environments. In this study, DU-amended dune sand microcosm and column experiments were carried out to investigate the corrosion of DU and the transport of corrosion products. Under field-moist conditions, DU corroded to metaschoepite ((UO(2))(8)O(2)(OH)(12).(H(2)O)(10)) at a rate of 0.10+/-0.012 g cm(-2)y(-1). This loosely bound corrosion product detached easily from the coupon and became distributed heterogeneously within the sand. The corrosion of DU caused significant changes in the geochemical environment, with NO(3)(-) and Fe(III) reduction observed. Column experiments showed that transport of metaschoepite was mainly dependent on its dissolution and the subsequent interaction of the resulting dissolved uranyl (UO(2)(2+)) species with sand particles. The modelling results predict that the transport of U released from metaschoepite dissolution is retarded, due to a slowly desorbing surface species (first order desorption rate constant=5.0 (+/-1.0)x10(-8)s(-1)). The concentrations of U eluting from the metaschoepite column were orders of magnitude higher than the World Health Organisation's recommended maximum admissible concentration for U in drinking water of 15 microg L(-1). Therefore, a relatively high level of mobile U contamination would be expected in the immediate proximity of a corroding penetrator in a sand-rich environment.

Biogeochemical controls on the corrosion of depleted uranium alloy in subsurface soils.

Military activities have left a legacy of depleted uranium (DU) penetrator waste in the near-surface terrestrial environment. To understand the fate of this DU alloy, the mechanisms and controlling factors of corrosion need to be determined. In this study, field-moist and waterlogged microcosms were used to investigate the effect of redox conditions and soil water content on the corrosion and fate of DU in subsurface soil, and the impact of corroding DU on the soil microbial population. The mechanism of corrosion and the corrosion products formed were highly dependent on the water status of the soil. Under field-moist conditions, DU corroded at a rate of 0.49 +/- 0.06 g cm(-2) y(-1) and the main U input to surrounding soil was large metaschoepite [(UO2)8O2(OH)12 x (H2O)10] particles. However, underwaterlogged conditions the rate of corrosion was significantly slower at 0.01-0.02 g cm(-2) y(-1) and occurred with the release of dissolved species to the surrounding environment. Corrosion ceases under reducing conditions, thus redox conditions are important in determining the persistence of penetrators in the environment. Corroding DU alters the redox conditions in the surrounding environment and both mechanisms of corrosion impact the microbial community.

Corrosion and fate of depleted uranium penetrators under progressively anaerobic conditions in estuarine sediment.

The testing of armor-piercing depleted uranium (DU) "penetrators" has resulted in the deposition of DU in the sediments of the Solway Firth, UK. In this study, DU-amended, microcosm experiments simulating Solway Firth sediments under high (31.5) and medium (16.5) salinity conditions were used to investigate the effect of salinity and biogeochemical conditions on the corrosion and fate of DU, and the impact of the corroding DU on the microbial population. Under suboxic conditions, the average corrosion rates were the same forthe 31.5 and 16.5 salinity systems at 0.056 +/- 0.006 g cm(-2) y(-1), implying that complete corrosion of a 120 mm penetrator would take approximately 540 years. Under sulfate-reducing conditions, corrosion ceased due to passivation of the surface. Corroding DU resulted in more reducing conditions and decreased microbial diversity as indicated by DNA sequencing and phylogenetic analysis. The lack of colloidal and particulate DU corrosion products, along with measurable dissolved U and a homogeneous association of U with the sediment, suggest that U was transported from the penetrator surface into the surrounding environment through dissolution of U(VI), with subsequent interactions resulting in the formation of secondary uranium species in the sediment.

The speciation, stability, solubility and biodegradation of organic co-contaminant radionuclide complexes: a review.

The potential migration of radionuclides is of concern at contaminated land sites and, in the long term, waste repositories. Pathways of migration need to be characterised on a predictive level so that management decisions can be made with confidence. A pathway that is relatively poorly understood at present is radionuclide solubilisation due to complexation by organic complexing agents that are present in mixed radioactive wastes, and at radioactively contaminated land sites. Interactions of the complexing agents with radionuclides and the host environment, and the response to changes in the physicochemical conditions make their role far from simple to elucidate. In addition, chemical and biodegradation of the organic materials may be important. In this paper, key co-contaminant organics are reviewed with emphasis on their environmental fate and impact on radionuclide migration.

Characterisation of thorium-ethylenediaminetetraacetic acid and thorium-nitrilotriacetic acid species by electrospray ionisation-mass spectrometry.

Electrospray ionisation-mass spectrometry (ESI-MS) has been used to investigate the speciation of Th in the presence of two common organic complexing agents found in radioactive wastes, EDTA and NTA. These ligands may enhance radionuclide migration from nuclear wastes and contaminated land, and characterisation of the complexes formed will improve our understanding of their environmental mobility. When acetic acid and ammonia were used to adjust the pH, the dominant Th-EDTA species changed from the mixed ligand [ThEDTAac](-) complex to [ThEDTAOH](-) and [ThEDTA(OH)(2)ac](3-) as the pH increased, with all species co-existing, to some extent, over the pH range (2.5-10.8). A previously suggested Th-NTA species, [ThNTA(2)](2-), dominates from pH 6.0-8.5 but at high pH (10.0-10.8) NTA was not able to solubilise Th to a measurable extent. In the presence of both EDTA and NTA, Th formed a mixed ligand complex, [ThEDTANTA](3-) which has also been characterised in independent experiments. The identification of the importance of [ThNTA(2)](2-), [ThEDTANTA](3-) and [ThEDTA(OH)(2)](2-) (with an additional acetate ligand) highlights that these species are not included in current speciation databases and thus may impact on predictions of the environmental mobility of Th. ESI-MS has therefore been used to identify and confirm fundamentally important Th complexes. It has proved to be a useful tool for elucidating radionuclide speciation, adding to our knowledge of Th geochemistry and providing a means of critically examining existing stability constant data.

Effect of organic co-contaminants on technetium and rhenium speciation and solubility under reducing conditions.

The chemical and biogeochemical reduction of pertechnetate (TcO4-) and perrhenate (ReO4-) have been compared alongside complexation of the reduced species by three anthropogenic ligands relevant to nuclear waste (ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and isosaccharinic acid (ISA)). An HPLC size-exclusion column coupled to ICP-MS was used to separate the species and quantify Tc and Re. During method development, ReO4- showed recalcitrance to direct chemical reduction by Sn(ll) under conditions that readily reduced TcO4- and resulted in Tc(IV)-organic complexes. In microcosm experiments of a silty loam soil containing Tc04-, ReO4-, and ISA (3.0 mM), EDTA (0.17 mM), or NTA (2.4 mM), anoxia developed to iron-reducing conditions during the 42 day experimental period. The majority of the TcO4- was reduced to particle-reactive Tc(IV) and removed from solution during nitrate reduction, but there was no chromatographic evidence of Tc(IV)-organic complexes in the porewater. Overall, the excess organic complexants added did not cause a measurable difference in the solubility of Tc(IV) over the control experiments in this organic-rich (12% organic carbon) soil. ReO4- did not undergo reduction, as shown by the constant porewater concentration and the chromatographic data, and thus Re does notfunction as an analogue forTc under environmental nitrate- and iron-reducing conditions.

Thorium complexation by hydroxamate siderophores in perturbed multicomponent systems using flow injection electrospray ionization mass spectrometry.

Flow injection electrospray ionization mass spectrometry has been shown to produce simple, characteristic m/z signals for Th-hydroxamate siderophore (desferrioxamine and ferrichrome) complexes, with Th complexed as a simple 4+ ion in the environmentally relevant pH range investigated (pH 5-9). All species of interest for this study were identified optimally in the positive mode; thus, multiple species were analyzed concurrently in a single spectrum. Complexation of Th by the two siderophores was rapid in 1:1 molar aqueous solution, reaching equilibrium before the first measurement was possible at 2 min. However, a significant proportion of the equimolar siderophore remained uncomplexed. Both siderophores rapidly exchanged Th for Fe when equimolar Fe(III) was added to the Th complexes, and only a small proportion of each siderophore remained complexed with Th at equilibrium (7-30 min). The results show a difference in the affinities of the two siderophores for the metals; ferrichrome has a 5-fold higher affinity than desferrioxamine for Th and a 5-fold lower affinity than desferrioxamine for Fe. Also, siderophore-complexed Th interacted strongly with a cation-exchange resin suggesting that, even when complexed by trianionic siderophores, Th mobility will be impeded by interactions with negatively charged binding sites in subsurface environmental matrixes. These results have important implications regarding siderophore-enhanced actinide(IV) mobility in the terrestrial environment.

Sampling, sample treatment and quality assurance issues for the determination of phosphorus species in natural waters and soils.

Phosphorus is an important macronutrient and the accurate determination of phosphorus species in environmental matrices such as natural waters and soils is essential for understanding the biogeochemical cycling of the element, studying its role in ecosystem health and monitoring compliance with legislation. This paper provides a critical review of sample collection, storage and treatment procedures for the determination of phosphorus species in environmental matrices. Issues such as phosphorus speciation, the molybdenum blue method, digestion procedures for organic phosphorus species, choice of model compounds for analytical studies, quality assurance and the availability of environmental CRMs for phosphate are also discussed in detail.

The impact of a disused mine on uranium transport in the River Fal, South West England.

Unfiltered and filtered (0.45 and 0.2 microm) water samples and sediment samples (sieved to <180 microm and 180-1000 microm) were collected along an approximately 15 km transect of the River Fal, Cornwall, UK, to examine the impact of the disused South Terras uranium mine on the uranium concentrations of the river water and underlying sediments. The uranium concentration of the water samples fluctuated along the river, with the 0.45 microm filtered water showing the largest, seven-fold, difference between minimum (0.19 microg L(-1)) and maximum (1.34 microg L(-1)) concentrations. The historical uranium mine and spoil heaps were not a significant source of uranium to the river water, as water concentrations were low next to the site, but a highly elevated uranium concentration (1000 mg kg(-1)) was found in sediment below an outflow pipe from this mine. Operationally defined "colloidal" (0.2-0.45 microm) and "dissolved" (<0.2 microm) uranium were the predominant forms of the element in the river water (35 and 45% respectively). The uranium concentration in the dissolved phase showed a correlation coefficient of 0.83 (n= 9) with the total cation concentration, suggesting that the uranium concentration in this fraction is directly linked to weathering of rocks and minerals. The observation that weathering is the dominant mechanism delivering uranium to the river water explains the low uranium concentrations in the river water close to South Terras mine, despite the proximity of the spoil heaps, and the maximum uranium concentrations close to a china clay mining area.

Comparison of two ICP-MS set-ups for measuring 99Tc in large volume water samples.

Large volume fjord and seawater samples have been radiochemically prepared for ICP-MS analysis in order to test the robustness of the procedure and to carry out a comparison of two ICP-MS set-ups. A sector field instrument (MicroMass PT2) coupled with an ultrasonic nebuliser and a quadrupole ICP-MS (Perkin-Elmer Elan 6000) coupled with an electrothermal vaporisation (ETV) unit were used. The results showed that the radiochemical procedure was robust, removing Ru and Mo to acceptable levels, and that the two set-ups gave results that were in agreement. The correlation coefficient between the sets of 11 results was 1.0 +/- 0.05. The importance of establishing the matrix effect when using an ETV is discussed.