Effects of flow on uranium speciation in soils impacted by acidic waste fluids.

Radioactive acidic liquid waste is a common byproduct of uranium (U) and plutonium (Pu) enrichment and recycling processes whose accidental and planned release has led to a significant input of U into soils and sediments across the world, including at the U.S. DOE's Hanford site (WA, USA). Because of the particularly hazardous nature of U, it is important to predict its speciation when introduced into soils and sediments by acidic waste fluids. Of fundamental importance are the coupled effects of acid-driven mineral transformation and reactive transport on U speciation. To evaluate the effect of waste-fluid residence time and co-associated dissolved phosphate concentrations on U speciation in impacted soils and sediments, uncontaminated surface materials (from the Hanford Site) were reacted with U-containing synthetic acidic waste fluids (pH 2) amended with dissolved phosphate concentrations in both batch (no flow) and flow-through column systems for 7-365 days. By comparing dissolved U behavior and solid phase speciation as a function of flow regimen, we found that the availability of proton-promoted dissolution products (such as Si) to sequester U into uranyl silicates was dependent on waste fluid-sediment contact time as uranyl silicates were not detected in short contact time flow-through systems but were detected in no-flow, long contact time, reactors. Moreover, the dominance of uranyl phosphate as neoprecipitate U scavenger (principally in the form of meta-ankoleite) in phosphate amended systems confirmed the importance of phosphate amendments for an efficient sequestration of U in the soils and sediments. Overall, our experiments suggest that the formation of uranyl silicates in soils impacted by acidic waste fluids is likely to be limited unless reaction products are allowed to accumulate in soil pores, highlighting the importance of investigating soil U speciation in flow-through, transport-driven systems as opposed to no-flow, batch systems. This study provides insights into uranium speciation and its potential changes under acidic conditions for better prediction of risks and subsequent development of efficient remediation strategies.

Discharges of Nuclear Medicine Radioisotopes: The Impact of an Abatement System.

ABSTRACT: Clinical uses of radiopharmaceuticals imply the administration of radioactive substances that are mainly excreted through urine. The Nuclear Medicine Department at the Instituto Nacional de Cancerología (INC-COL) in Bogota, Colombia, administers radiopharmaceuticals for diagnostics and treatment to many patients, resulting in tens of cubic meters of radioactive waste water (WW) every day. As Colombian regulatory limits for liquid radioactive discharges to the sewer system are lower than in other countries, longer WW decay times are required, even when an in-house waste water treatment plant (WWTP) is used. To fulfill the requirements for controlled disposal of radioactive discharges, a complementary abatement system was implemented to retain WW for periods as long as 360 d, and was connected to the hospital´s WWTP. These holding times can cause major changes in the WW physicochemical parameters, reaching levels higher than acceptable. In this study, we evaluate the decontamination and decay efficiency of the retention system using water quality parameters and the amount of radioactivity in the effluents stored in the tanks and the WWTP. According to the results, to maintain the physicochemical parameters below acceptable levels, biological and chemical treatment of decayed WW is necessary before discharging it into urban waste water. Using the principles of dilution, retention, and decay, an integral radioactive WW management system was implemented favoring the quality of discharges and activity levels to the sewer system, with efficiencies close to 100% for WW from discharges in diagnostic procedures ranging from 98% (131I) to 100% (177Lu) for WW from discharges in therapeutic procedures. Activity concentration assessment in medically-derived radionuclides using an in-house waste water treatment plant (WWTP) and a complementary abatement system; an in-house WWTP could be used as an abatement system for short-lived radionuclides; and a tank-based abatement system attached to the in-house WWTP showed higher efficiencies for long-lived radionuclides and adequate physicochemical parameters for the discharge to the city sewage system.

Using molybdenum carbiding to induce digestion of carbon in H2O2: A sustainable approach to eliminate radioactivity for hazardous graphite waste inherited from nuclear enterprise.

To properly manage nuclear wastes is critical to sustainable utilization of nuclear power and environment health. Here, we show an innovative carbiding strategy for sustainable management of radioactive graphite through digestion of carbon in H2O2. The combined action of intermolecular oxidation of graphite by MoO3 and molybdenum carbiding demonstrates success in gasifying graphite and sequestrating uranium for a simulated uranium-contaminated graphite waste. The carbiding process plays a triple role: (1) converting graphite into atomic carbon digestible in H2O2, (2) generating oxalic ligands in the presence of H2O2 to favor U-precipitation, and (3) delivering oxalic ligands to coordinate to MoVI-oxo anionic species to improve sample batching capacity. We demonstrate > 99% of uranium to be sequestrated for the simulated waste with graphite matrix completely gasifying while no detectable U-migration occurred during operation. This method has further been extended to removal of surface carbon layers for graphite monolith and thus can be used to decontaminate monolithic graphite waste with emission of a minimal amount of secondary waste. We believe this work not only provides a sustainable approach to tackle the managing issue of heavily metal contaminated graphite waste, but also indicates a promising methodology toward surface decontamination for irradiated graphite in general.

Assessment of Radiological Hazard of Radioactive Waste Using Effective or Organ Doses: How This May Affect Final Waste Disposal.

ABSTRACT: The radiological hazard of spent nuclear fuel and radioactive waste slows down further development of nuclear energy systems. The authors evaluate timescales required to reduce the radiological hazard of accumulated waste to the reference level of natural uranium that had been consumed by the nuclear energy system. The estimate of this time scale depends on the radiological hazard metric used in the calculations. In this study, two metrics are compared: (1) the committed effective dose based on ICRP Publication 72 and (2) the lifetime radiation risk calculated with use of organ doses and recent radiation risk models recommended by ICRP. The effective dose of the waste reaches the reference level 300 y after the accumulation of waste, while lifetime attributable risk of waste converges to natural uranium in 100 y. Thus, the lifetime attributable risk (LAR) metric is more appropriate to estimate the time requirements for radioactive waste storage and disposal. The effective dose metric significantly overestimates this timescale as it is not intended for quantifying radiation-related risks.

Radionuclide geochemistry evolution in the Long-term In-situ Test (LIT) at Grimsel Test Site (Switzerland).

The Long-term In-situ Test (LIT) of the Colloid Formation and Migration project (CFM) at the Grimsel Test Site, investigates the generation of bentonite colloids and, hence, radionuclide mobilization within a well-defined and controlled shear zone in a crystalline rock. In this context, the determination of radionuclide aqueous speciation is essential to understand whether radionuclides are easily transported or immobilized by precipitation or uptake processes in the bentonite barrier included in a repository concept for nuclear waste, and mimic in the LIT experiment. The objective of this work is to determine the aqueous speciation of seven radionuclides (i.e. 75Se(VI), 99Tc(VII),233U(VI), 237Np(V), 241Am(III), Th(IV) and 242Pu(IV)) by thermodynamic calculations in different water compositions representing the geochemical evolution through the LIT. A comparison of the results obtained from two different modelling groups allows the identification of the geochemical key parameters affecting radionuclide mobility in this context and the corresponding numerical and conceptual uncertainties. Particularly, silicate complexes of trivalent actinides and uranium(VI) carbonato complexes (i.e. CanUO2(CO3)3(4-2n) n = 1 or 2) seem to be crucial in these environments, even at reducing conditions. Conceptual uncertainties like inclusion/exclusion of tetravalent actinide-bearing colloids formation and polyselenides have clearly been identified.

Preparation and related properties of geopolymer solidified uranium tailings bodies with various fibers and fiber content.

Uranium tailing ponds are a potential major source of radioactive pollution. Solidification treatment can control the diffusion and migration of radioactive elements in uranium tailings to safeguard the surrounding ecological environment. A literature review and field investigation were conducted in this study prior to fabricating 11 solidified uranium tailing samples with different proportions of PVA fiber, basalt fiber, metakaolin, and fly ash, and the weight percentage of uranium tailings in the solidified body is 61.11%. The pore structure, volume resistivity, compressive strength, radon exhalation rate variations, and U(VI) leaching performance of the samples were analyzed. The pore size of the solidified samples is mainly between 1 and 50 nm, the pore volume is between 2.461 and 5.852 × 10-2 cm3/g, the volume resistivity is between 1020.00 and 1937.33 Ω·m, and the compressive strength is between 20.61 and 36.91 MPa. The radon exhalation rate is between 0.0397 and 0.0853 Bq·m-2·s-1. The cumulative leaching fraction of U(VI) is between 2.095 and 2.869 × 10-2 cm, and the uranium immobilization rate is between 83.46 and 85.97%. Based on a comprehensive analysis of the physical and mechanical properties, radon exhalation rates, and U(VI) leaching performance of the solidified samples, the basalt fiber is found to outperform PVA fiber overall. The solidification effect is optimal when 0.6% basalt fiber is added.

Assessment of POFA -Cementitious material as backfill barrier in DSRS borehole disposal: 226Ra confinement.

Disused Sealed Radioactive Sources (DSRS) borehole disposal is an innovative concept recommended by international atomic energy agency (IAEA) to improve the safety and security of the management end point for these sources. A green application of Palm Oil Fuel Ash (POFA) as a supplementary material for cementitious backfill barrier in DSRS borehole disposal facility is proposed. Samples with up to 50% POFA replacement complied with the mechanical and hydraulic performance requirements for backfill barriers in retrievable radioactive waste disposal facilities. The structures of one year old OPC and optimum OPC-POFA cement backfills were evaluated using FESEM, XRD, EDXRF, BET, and TGA and their 226 Ra confinement performances were assessed. 30% POFA replacement improved the geochemical conditions by reducing competitive Ca2+ release into the disposal environment. It enhanced 226Ra confinement performance independently on the amount of water intrusion or releases below 2% of 1 Ci source. The improved performance is attributed to the higher fraction of active sites of OPC-POFA backfill compared to that of OPC backfill. 226Ra sorption onto C-S-H is irreversible, spontaneous, endothermic, and independent on the degree of the surface filling. The provided experimental data and theoretical analysis proved the feasibility of this green use of POFA in reducing the radiological hazard of 226Ra.

Organic complexation of U(VI) in reducing soils at a natural analogue site: Implications for uranium transport.

Understanding the long-term fate, stability, and bioavailability of uranium (U) in the environment is important for the management of nuclear legacy sites and radioactive wastes. Analysis of U behavior at natural analogue sites permits evaluation of U biogeochemistry under conditions more representative of long-term equilibrium. Here, we have used bulk geochemical and microbial community analysis of soils, coupled with X-ray absorption spectroscopy and µ-focus X-ray fluorescence mapping, to gain a mechanistic understanding of the fate of U transported into an organic-rich soil from a pitchblende vein at the UK Needle's Eye Natural Analogue site. U is highly enriched in the Needle's Eye soils (∼1600 mg kg-1). We show that this enrichment is largely controlled by U(VI) complexation with soil organic matter and not U(VI) bioreduction. Instead, organic-associated U(VI) seems to remain stable under microbially-mediated Fe(III)-reducing conditions. U(IV) (as non-crystalline U(IV)) was only observed at greater depths at the site (>25 cm); the soil here was comparatively mineral-rich, organic-poor, and sulfate-reducing/methanogenic. Furthermore, nanocrystalline UO2, an alternative product of U(VI) reduction in soils, was not observed at the site, and U did not appear to be associated with Fe-bearing minerals. Organic-rich soils appear to have the potential to impede U groundwater transport, irrespective of ambient redox conditions.

Radiometrical and physico-chemical characterisation of contaminated glass waste from a glass dump in Sweden.

Around former glass factories in south eastern Sweden, there are dozens of dumps whose radioactivity and physico-chemical properties were not investigated previously. Thus, radiometric and physico-chemical characteristics of waste at Madesjö glass dump were studied to evaluate pre-recycling storage requirements and potential radiological and environmental risks. The material was sieved, hand-sorted, leached and scanned with X-Ray Fluorescence (XRF). External dose rates and activity concentrations of Naturally Occurring Radioactive Materials from 238U, 232Th series and 40K were also measured coupled with a radiological risk assessment. Results showed that the waste was 95% glass and dominated by fine fractions (<11.3 mm) at 43.6%. The fine fraction had pH 7.8, 2.6% moisture content, 123 mg kg-1 Total Dissolved Solids, 37.2 mg kg-1 Dissolved Organic Carbon and 10.5 mg kg-1 fluorides. Compared with Swedish EPA guidelines, the elements As, Cd, Pb and Zn were in hazardous concentrations while Pb leached more than the limits for inert and non-hazardous wastes. With 40K activity concentration up to 3000 Bq kg-1, enhanced external dose rates of 40K were established (0.20 µSv h-1) although no radiological risk was found since both External Hazard Index (Hex) and Gamma Index (Iγ) were <1. The glass dump needs remediation and storage of the waste materials under a safe hazardous waste class 'Bank Account' storage cell as a secondary resource for potential future recycling.

Use of Routine Environmental Monitoring Data to Establish a Dose-based Compliance System for a Low-level Radioactive Waste Disposal Site.

A dose-based compliance methodology was developed for Waste Control Specialists, LLC, low-level radioactive waste facility in Andrews, Texas, that allows routine environmental measurement data to be evaluated not only at the end of a year to determine regulatory compliance, but also throughout the year as new data become available, providing a continuous assessment of the facility. The first step in the methodology is a screening step to determine the potential presence of site emissions in the environment, and screening levels are established for each environmental media sampled. The screening accounts for spatial variations observed in background for soil and temporal fluctuations observed in background for air. For groundwater, the natural activity concentrations in groundwater wells at the facility are highly variable, and therefore the methodology uses ratios for screening levels. The methodology compares the ratio of gross alpha to U + U to identify potentially abnormal alpha activity and the ratio of U to U to identify the potential presence of depleted uranium. Compliance evaluation is conducted for any samples that fail the screening step. Compliance evaluation uses the radionuclide-specific measurements to first determine (1) if the dose exceeds the background dose and if so, (2) the dose consequences, so that the appropriate investigation or action occurs. The compliance evaluation is applied to all environmental samples throughout the year and on an annual basis to determine regulatory compliance. The methodology is implemented in a cloud-based software application that is also made accessible to the regulator. The benefits of the methodology over the existing system are presented.

Natural radioactivity and radiation hazard assessment of industrial wastes from the coastal phosphate treatment plants of Gabes (Tunisia, Southern Mediterranean Sea).

This work is a first contribution to the knowledge of natural radionuclides (226Ra, 238U, 40K, and 232Th) activities in phosphate rock (NORM), phosphogypsum, and phosphogypsum foam (TENORM) from the coastal fertilizer plants of Gabes (Southeastern Tunisia) and the assessment of their radiation hazards on human health and the surrounding environment. In the three studied materials, activities were found to be in the range of 35.4 (40K)-375.1 (226Ra), 10.0 (40K)-220.2 (226Ra), and 79.2 (232Th)-1168.6 Bq kg-1 (226Ra), respectively. Considering the studied radionuclides and materials, the corresponding decreasing activity orders were found to be 226Ra > 238U > 40K > 232Th and PGF > PR > PG, respectively. All human health hazard indices exceeded the worldwide recommended safety limits, which show that the workers in Gabes phosphate fertilizer plants as well as the neighboring human community may potentially be exposed to significant radiation, which may cause several diseases and malformations. It is therefore recommended to avoid and/or reduce the potential fertilizer industry radioactive impact in the area.

Shifts in bentonite bacterial community and mineralogy in response to uranium and glycerol-2-phosphate exposure.

The multi-barrier deep geological repository system is currently considered as one of the safest option for the disposal of high-level radioactive wastes. Indigenous microorganisms of bentonites may affect the structure and stability of these clays through Fe-containing minerals biotransformation and radionuclides mobilization. The present work aimed to investigate the behavior of bentonite and its bacterial community in the case of a uranium leakage from the waste containers. Hence, bentonite microcosms were amended with uranyl nitrate (U) and glycerol-2-phosphate (G2P) and incubated aerobically for 6 months. Next generation 16S rRNA gene sequencing revealed that the bacterial populations of all treated microcosms were dominated by Actinobacteria and Proteobacteria, accounting for >50% of the community. Additionally, G2P and nitrate had a remarkable effect on the bacterial diversity of bentonites by the enrichment of bacteria involved in the nitrogen and carbon biogeochemical cycles (e.g. Azotobacter). A significant presence of sulfate-reducing bacteria such as Desulfonauticus and Desulfomicrobium were detected in the U-treated microcosms. The actinobacteria Amycolatopsis was enriched in G2P­uranium amended bentonites. High-Angle Annular Dark-Field Scanning Transmission Electron Microscopy analyses showed the capacity of Amycolatopsis and a bentonite consortium formed by Bradyrhizobium-Rhizobium and Pseudomonas to precipitate U as U phosphate mineral phases, probably due to the phosphatase activity. The different amendments did not affect the mineralogy of the bentonite pointing to a high structural stability. These results would help to predict the impact of microbial processes on the biogeochemical cycles of elements (N and U) within the bentonite barrier under repository relevant conditions and to determine the changes in the microbial community induced by a uranium release.

ASSESSMENT OF RADIOLOGICAL HAZARDS OF USING PETROLEUM RAW MATERIALS AND THEIR WASTE.

Activity concentrations of 238U, 232Th and 40K in raw and waste petroleum materials (Egypt and Kuwait) were measured using gamma ray spectrometer. The average values of 226Ra, 232Th and 40K were 21.1 ± 3.2, 7.6 ± 1.3 and 88.4 ± 8.2 Bq kg-1 for Egyptian samples while for Kuwaiti samples, they were 25.2 ± 3.4, 6.1 ± 2.2 and 67.8 ± 6.4 Bq kg-1, respectively. All samples had activity less than the exemption level recommended by the International Atomic Energy Agency. Moreover, radiological indices of radium equivalent, external, internal, alpha and gamma indices and radiation dose as well were calculated and their values were lower than the recommended regulatory limits. Thus, radiation exposure to petroleum materials did not present a significant radiological hazard.

Evidence of microalgal isotopic fractionation through enrichment of depleted uranium.

Resulting from the nuclear fuel cycle, large amounts of depleted uranium (DU) tails are piling up, waiting for possible use or final disposal. To date, the recovery of the residual 235U isotope contained in DU has been conducted only marginally by physical processes. Relative isotope abundances are often mediated by biological processes, and the biologically driven U isotopic fractionation has been previously identified in reducing bacteria. Our results indicate that the cells of two microalgal strains (freshwater Chlamydomonas sp. (ChlGS) and marine Tetraselmis mediterranea (TmmRU)) took up DU from the exposure solutions, inducing U isotopic fractionation with a preference for the fissile 235U isotope over 238U. The n(235U)/n(238U) isotopic fractionation magnitudes (δ235) were 23.6 ± 12.5‰ and 370.4 ± 103.9‰, respectively. These results open up new perspectives on the re-enrichment of DU tailings, offering a potential biological alternative to obtain reprocessed natural-equivalent uranium. Additionally, the findings present implications for identifying biological signatures in the geologic records.

Bio-inspired nano-traps for uranium extraction from seawater and recovery from nuclear waste.

Nature can efficiently recognize specific ions by exerting second-sphere interactions onto well-folded protein scaffolds. However, a considerable challenge remains to artificially manipulate such affinity, while being cost-effective in managing immense amounts of water samples. Here, we propose an effective approach to regulate uranyl capture performance by creating bio-inspired nano-traps, illustrated by constructing chelating moieties into porous frameworks, where the binding motif's coordinative interaction towards uranyl is enhanced by introducing an assistant group, reminiscent of biological systems. Representatively, the porous framework bearing 2-aminobenzamidoxime is exceptional in sequestering high uranium concentrations with sufficient capacities (530 mg g-1) and trace quantities, including uranium in real seawater (4.36 mg g-1, triple the benchmark). Using a combination of spectroscopic, crystallographic, and theory calculation studies, it is revealed that the amino substituent assists in lowering the charge on uranyl in the complex and serves as a hydrogen bond acceptor, boosting the overall uranyl affinity of amidoxime.

Experience of on-site disposal of production uranium-graphite nuclear reactor.

The paper reported the experience gained in the course of decommissioning EI-2 Production Uranium-Graphite Nuclear Reactor. EI-2 was a production Uranium-Graphite Nuclear Reactor located on the Production and Demonstration Center for Uranium-Graphite Reactors JSC (PDC UGR JSC) site of Seversk City, Tomsk Region, Russia. EI-2 commenced its operation in 1958, and was shut down on December 28, 1990, having operated for the period of 33 years all together. The extra pure grade graphite for the moderator, water for the coolant, and uranium metal for the fuel were used in the reactor. During the operation nitrogen gas was passed through the graphite stack of the reactor. In the process of decommissioning the PDC UGR JSC site the cavities in the reactor space were filled with clay-based materials. A specific composite barrier material based on clays and minerals of Siberian Region was developed for the purpose. Numerical modeling demonstrated the developed clay composite would make efficient geological barriers preventing release of radionuclides into the environment.

SEISMIC PREDICTION USING UNATTACHED RADON DECAY PRODUCTS.

Long-term measurements of the 222Rn concentration, 222Rn decay product activity, particle size distribution, and unattached, and attached 222Rn decay products, were made at two locations using the 22 y radon decay product 210Pb as their tracer. The particle size sampler collects both short lived 222Rn decay products that ultimately decay to 210Pb on the filters, and also airborne 210Pb. The measurements were made outdoors, at a suburban home and at Fernald, OH, a former uranium processing facility, on top of one of the two 226Ra storage silos containing 150 TBq 226Ra. The size distributions showed the unattached fractions, i.e. particle diameter 2-4 nm, to be 1.5% at the home and 14% at the silos. The unattached fraction of 218Po can be shown to be an immediate measure of the 222Rn concentration. The data indicates detection of the pressure driven 222Rn flow at the silo and with the enhanced measurement capability of a filtered air source versus the usual 222Rn gas measurement. It is proposed that real time measurements of unattached 218Po may be used to identify rapidly changing 222Rn concentrations associated with pressure driven soil air flow associated with seismic activity.

Uranium isotopes in tree bark as a spatial tracer of environmental contamination near former uranium processing facilities in southwest Ohio.

Inappropriate handling of radioactive waste at nuclear facilities can introduce non-natural uranium (U) into the environment via the air or groundwater, leading to anthropogenic increases in U concentrations. Uranium isotopic analyses of natural materials (e.g. soil, plants or water) provide a means to distinguish between natural and anthropogenic U in areas near sources of radionuclides to the environment. This study examines the utility of two different tree bark transects for resolving the areal extent of U atmospheric contamination using several locations in southwest Ohio that historically processed U. This study is the first to utilize tree bark sampling transects to assess environmental contamination emanating from a nuclear facility. The former Fernald Feed Materials Production Center (FFMPC; Ross, Ohio) produced U metal from natural U ores and recycled nuclear materials from 1951 to 1989. Alba Craft Laboratory (Oxford, Ohio) machined several hundred tons of natural U metal from the FFMPC between 1952 and 1957. The Herring-Hall-Marvin Safe Company (HHM; Hamilton, Ohio) intermittently fabricated slugs rolled from natural U metal stock for use in nuclear reactors from 1943 to 1951. We have measured U concentrations and isotope signatures in tree bark sampled along an ∼35 km SSE-NNW transect from the former FFMPC to the vicinity of the former Alba Craft laboratories (transect #1) and an ∼20 km SW- NE (prevailing local wind direction) transect from the FFMPC to the vicinity of the former HHM (transect #2), with a focus on old trees with thick, persistent bark that could potentially record a time-integrated signature of environmental releases of U related to anthropogenic activity. Our results demonstrate the presence of anthropogenic U contamination in tree bark from the entire study area in both transects, with U concentrations within 1 km of the FFMPC up to ∼400 times local background levels of 0.066 ppm. Tree bark samples from the Alba Craft and HHM transects exhibit increasing U concentrations within ∼5 and ∼10 km, respectively of the FFMPC. The 236U/238U isotopic ratios in tree bark from both transects increase progressively towards the FFMPC with values as high as 2.00 × 10-4 at the FFMPC. Tree bark sampled within 1 km of the FFMPC exhibits clear evidence for both enriched and depleted uranium with 235U/238U values from 0.00461 to 0.00736, with 234U/238U activity ratio ranging from 0.53 to 0.96, and 236U/238U from 6.05 × 10-5 to 1.05 × 10-4. Tree bark from transect #1 between 1 and 30 km from the FFMPC exhibits depleted and natural 235U/238U values ranging from 0.00552 to 0.00726 [234U/238U activity ratio: 0.69-1.04; 236U/238U: 2.49 × 10-6 - 2.00 × 10-4]. Tree bark from transect #2 sampled between 1 and ∼20 km away from the FFMPC exhibits evidence of enriched and depleted U in the environment with 235U/238U ranging from 0.00635 to 0.00738 [234U/238U activity ratio: 0.83-0.98; 236U/238U: 1.43 × 10-5 - 2.00 × 10-4]. Results from scanning electron microscopy with energy dispersive spectrometry provides evidence for U-rich particles as the source of contamination found in tree bark growing within 1-3 km of the former FFMPC. Such observations are consistent with the previously observed 14 µm U-rich particle identified in tree bark sampled within 1 km of the FFMPC (Conte et al., 2015). Overall, this study shows the usefulness of a tree bark sample transect to assess the areal extent of atmospheric contaminant U stemming from nuclear facilities.

Uranium Release from Acidic Weathered Hanford Sediments: Single-Pass Flow-Through and Column Experiments.

The reaction of acidic radioactive waste with sediments can induce mineral transformation reactions that, in turn, control contaminant fate. Here, sediment weathering by synthetic uranium-containing acid solutions was investigated using bench-scale experiments to simulate waste disposal conditions at Hanford's cribs (Hanford, WA). During acid weathering, the presence of phosphate exerted a strong influence over uranium mineralogy and a rapidly precipitated, crystalline uranium phosphate phase (meta-ankoleite [K(UO2)(PO4)·3H2O]) was identified using spectroscopic and diffraction-based techniques. In phosphate-free system, uranium oxyhydroxide minerals such as K-compreignacite [K2(UO2)6O4(OH)6·7H2O] were formed. Single-pass flow-through (SPFT) and column leaching experiments using synthetic Hanford pore water showed that uranium precipitated as meta-ankoleite during acid weathering was strongly retained in the sediments, with an average release rate of 2.67 × 10-12 mol g-1 s-1. In the absence of phosphate, uranium release was controlled by dissolution of uranium oxyhydroxide (compreignacite-type) mineral with a release rate of 1.05-2.42 × 10-10 mol g-1 s-1. The uranium mineralogy and release rates determined for both systems in this study support the development of accurate U-release models for the prediction of contaminant transport. These results suggest that phosphate minerals may be a good candidate for uranium remediation approaches at contaminated sites.

Retardation of uranium and thorium by a cementitious backfill developed for radioactive waste disposal.

The solubility of uranium and thorium has been measured under the conditions anticipated in a cementitious, geological disposal facility for low and intermediate level radioactive waste. Similar solubilities were obtained for thorium in all media, comprising NaOH, Ca(OH)2 and water equilibrated with a cement designed as repository backfill (NRVB, Nirex Reference Vault Backfill). In contrast, the solubility of U(VI) was one order of magnitude higher in NaOH than in the remaining solutions. The presence of cellulose degradation products (CDP) results in a comparable solubility increase for both elements. Extended X-ray Absorption Fine Structure (EXAFS) data suggest that the solubility-limiting phase for uranium corresponds to a becquerelite-type solid whereas thermodynamic modelling predicts a poorly crystalline, hydrated calcium uranate phase. The solubility-limiting phase for thorium was ThO2 of intermediate crystallinity. No breakthrough of either uranium or thorium was observed in diffusion experiments involving NRVB after three years. Nevertheless, backscattering electron microscopy and microfocus X-ray fluorescence confirmed that uranium had penetrated about 40 µm into the cement, implying active diffusion governed by slow dissolution-precipitation kinetics. Precise identification of the uranium solid proved difficult, displaying characteristics of both calcium uranate and becquerelite.