Biomineralization of Uranium-Phosphates Fueled by Microbial Degradation of Isosaccharinic Acid (ISA).

Geological disposal is the globally preferred long-term solution for higher activity radioactive wastes (HAW) including intermediate level waste (ILW). In a cementitious disposal system, cellulosic waste items present in ILW may undergo alkaline hydrolysis, producing significant quantities of isosaccharinic acid (ISA), a chelating agent for radionuclides. Although microbial degradation of ISA has been demonstrated, its impact upon the fate of radionuclides in a geological disposal facility (GDF) is a topic of ongoing research. This study investigates the fate of U(VI) in pH-neutral, anoxic, microbial enrichment cultures, approaching conditions similar to the far field of a GDF, containing ISA as the sole carbon source, and elevated phosphate concentrations, incubated both (i) under fermentation and (ii) Fe(III)-reducing conditions. In the ISA-fermentation experiment, U(VI) was precipitated as insoluble U(VI)-phosphates, whereas under Fe(III)-reducing conditions, the majority of the uranium was precipitated as reduced U(IV)-phosphates, presumably formed via enzymatic reduction mediated by metal-reducing bacteria, including Geobacter species. Overall, this suggests the establishment of a microbially mediated "bio-barrier" extending into the far field geosphere surrounding a GDF is possible and this biobarrier has the potential to evolve in response to GDF evolution and can have a controlling impact on the fate of radionuclides.

Behaviour and mobility of U and Ra in sediments near an abandoned uranium mine, Cornwall, UK.

Sediment samples were collected from the vicinity of the abandoned South Terras uranium mine in south-west UK and analysed for uranium and (226)Ra to explore their geochemical dispersion. The radioactivity concentrations in the sediment samples were measured using alpha spectrometry for uranium, and gamma spectrometry for radium. Sequential chemical extraction was applied to selected sediments in order to investigate the speciation of the radionuclides and their association with stable elements. The activity ratio of the uranium isotopes was used to explore the mobility of uranium, and scanning electron microscopy (SEM) and electron microprobe analysis (EMPA) were used to characterise the sediments. The radiochemical results identified two locations with enhanced radioactivity, so two samples from these locations were further investigated. The geochemical distribution of the radionuclides in these two samples varies within the five operationally-defined fractions. In one sample, the majority of the uranium was released from the 'carbonate' fraction, followed by the organic fractions. Similarly, in the second sample, the uranium was mainly resealed from the carbonate fraction, although a considerable percentage associated with the resistant fraction. The fractionation trend of radium noticed to show some similarities to that of barium, as expected from the similarity in their chemistries. Geochemical distributions of the stable elements, such as Mn, Ti and As, were different in the enhanced radioactivity samples. The activity ratio of (234)U/(238)U shows different trends in the two sediments, signifying the impact of organic matter and/or the exchange between water and sediment. SEM and EMPA analysis identified uranium-bearing phases in association with potassium, calcium, iron, manganese and arsenic.

Dispersion of U-series natural radionuclides in stream sediments from Edale, UK.

The spatial distribution of (238)U-series radionuclides, specifically 238U, 234U, 230Th and 226Ra, has been determined in stream sediments from Edale, Derbyshire, United Kingdom, to explore the behaviour of U-series radionuclides during weathering. For uranium and thorium, two different extraction methods were used, total dissolution with HNO3/HF in a microwave and leaching with aqua regia. This was followed by radiochemical separation using extraction chromatography, then alpha spectrometry measurement. The total radium contents in the sediments were measured using gamma spectrometry, while the leached fraction was measured in the same way as for uranium and thorium. The total sediment content of uranium and thorium ranges from ∼10 up to ∼200 Bq kg(-1), while the radium specific activity lies between ∼15 and 180 Bq kg(-1). In the aqua regia extractions, the uranium and thorium contents are in the range of ∼5 to ∼100 Bq kg(-1), while the radium specific activities are similar to those measured by total dissolution. All the radionuclides show no correlation with organic matter content. The activity ratios 234U/238U, 230Th/238U and 226Ra/238U were used to determine the degree of radioactive disequilibrium. The data show disequilibrium in most of the sediments, with activity ratios of 234U/238U, 230Th/238U and 226Ra/238U>1, inconsistent with evolution through straightforward weathering processes. Multivariate cluster analysis based on five variables, the specific activities of 238U, 234U, 230Th, 226Ra and loss on ignition, was employed to group the data and identify five distinct clusters. There seems to be a link between high radionuclide concentrations and proximity to landslips.