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.

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.

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).

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.

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 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.

Assessing the impact of ionizing radiation on aquatic invertebrates: a critical review.

There is growing scientific, regulatory and public concern over anthropogenic input of radionuclides to the aquatic environment, especially given the issues surrounding existing nuclear waste, future energy demand and past or potential nuclear accidents. A change in the approach to how we protect the environment from ionizing radiation has also underlined the importance of assessing its impact on nonhuman biota. This review presents a thorough and critical examination of the available information on the effects of ionizing radiation on aquatic invertebrates, which constitute approximately 90% of extant life on the planet and play vital roles in ecosystem functioning.

Temporal record of Pu isotopes in inter-tidal sediments from the northeastern Irish Sea.

A depth profile of (239)Pu and (240)Pu specific activities and isotope ratios was determined in an inter-tidal sediment core from the Esk Estuary in the northeastern Irish Sea. The study site has been impacted with plutonium through routine radionuclide discharges from the Sellafield nuclear reprocessing plant in Cumbria, NW England. A pronounced sub-surface maximum of ~10 k Bq kg(-1) was observed for (239+240)Pu, corresponding to the peak in Pu discharge from Sellafield in 1973, with a decreasing trend with depth down to ~0.

Spatial and temporal distribution of Pu in the Northwest Pacific Ocean using modern coral archives.

Historical (239)Pu activity concentrations and (240)Pu/(239)Pu atom ratios were determined in skeletons of dated modern corals collected from three locations (Chuuk Lagoon, Ishigaki Island and Iki Island) to identify spatial and temporal variations in Pu inputs to the Northwest Pacific Ocean. The main Pu source in the Northwest Pacific is fallout from atmospheric nuclear weapons testing which consists of global fallout and close-in fallout from the former US Pacific Proving Grounds (PPG) in the Marshall Islands. PPG close-in fallout dominated the Pu input in the 1950s, as was observed with higher (240)Pu/(239)Pu atom ratios (>0.

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.

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.

Ultra-trace determination of plutonium in marine samples using multi-collector inductively coupled plasma mass spectrometry.

Sources of plutonium isotopes to the marine environment are well defined, both spatially and temporally, which makes Pu a potential tracer for oceanic processes. This paper presents the selection, optimisation and validation of a sample preparation method for the ultra-trace determination of Pu isotopes ((240)Pu and (239)Pu) in marine samples by multi-collector (MC) ICP-MS. The method was optimised for the removal of the interference from (238)U and the chemical recovery of Pu.

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).

Plutonium isotopes as tracers for ocean processes: a review.

Since the first nuclear weapons tests in the 1940s, pulsed inputs of plutonium isotopes have served as excellent tracers for understanding sources, pathways, dynamics and the fate of pollutants and particles in the marine environment. Due to the well-defined spatial and temporal inputs of Pu, the long half-lives of (240)Pu and (239)Pu and its unique chemical properties, Pu is a potential tracer for various physical and biogeochemical ocean processes, including circulation, sedimentation and biological productivity, and hence a means of assessing the impacts of global climate change. Due to the source dependency of the Pu isotopic signature, plutonium isotopes are beginning to be exploited as tools for the evaluation and improvement of regional and global ocean models that will enhance understanding of past and future changes in the oceans.

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.

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.

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 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.

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.

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.

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.

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.

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.