David Read

A Comparative Evaluation of Metal Humic and Fulvic Acid Predictive Models

Research into the safe disposal of nuclear waste prompted a comparative study of the predictive capabilities and limitations of metal humic and fulvic acid binding models. Three approaches were investigated: (i) A simple ligand mixture approach; (ii) a continuous distribution approach; and (iii) an electrostatic discrete site approach. Appropriate geochemical equilibrium codes, incorporating the models designated, PHREEQESP, MINTEQA2 and PHREEQEV, were applied to three unrelated test problems, (1) Ni interactions with fulvic acid. (2) Eu interactions with fulvic and humic acids and (3) actinide speciation in Mol groundwater. The model predictions were compared with experimental data. Only PHREEQEV provided results in all three test cases. Overall it was concluded that of the approaches tested PHREEQEV currently offers the most advantages for predictive modelling.

Sorption of radionuclides to a cementitious backfill material under near-field conditions

Abstract The sorption behaviour of I-, Cs+ , Ni2+, Eu3+, Th4+ and UO22+ on NRVB (Nirex reference vault backfill) a possible vault backfill, at pH 12.8 was studied. Sorption isotherms generated were compared to results obtained in the presence of cellulose degradation products (CDP). Whereas Cs was not affected by the presence of the organic compounds, a notable reduction in the sorption of Th and Eu to cement was observed. The results also indicated limited removal of Ni from solution (with or without an organic ligand) by sorption, the concentration in solution seemingly being determined solely by solubility processes. In the case of uranium, the presence of CDP increased the sorption to cement by almost one order of magnitude. Further studies into the uptake of CDP by cement are being undertaken to identify the mechanism(s) responsible.

Recent developments in assessment of long-term radionuclide behavior in the geosphere-biosphere subsystem

Decisions on permitting, controlling and monitoring releases of radioactivity into the environment rely on a great variety of factors. Important among these is the prospective assessment of radionuclide behavior in the environment, including migration and accumulation among and within specific environmental media, and the resulting environmental and human health impacts. Models and techniques to undertake such assessments have been developed over several decades based on knowledge of the ecosystems involved, as well as monitoring of previous radionuclide releases to the environment, laboratory experiments and other related research. This paper presents developments in the assessment of radiation doses and related research for some of the key radionuclides identified as of potential significance in the context of releases to the biosphere from disposal facilities for solid radioactive waste. Since releases to the biosphere from disposal facilities involve transfers from the geosphere to the biosphere, an important aspect is the combined effects of surface hydrology, near-surface hydrogeology and chemical gradients on speciation and radionuclide mobility in the zone in which the geosphere and biosphere overlap (herein described as the geosphere-biosphere subsystem). In turn, these aspects of the environment can be modified as a result of environmental change over the thousands of years that have to be considered in radioactive waste disposal safety assessments. Building on the experience from improved understanding of the behavior of the key radionuclides, this paper proceeds to describe development of a generic methodology for representing the processes and environmental changes that are characteristic of the interface between the geosphere and the biosphere. The information that is provided and the methodology that is described are based on international collaborative work implemented through the BIOPROTA forum, www.bioprota.org.

Retention of chlorine-36 by a cementitious backfill

Abstract Radial diffusion experiments have been carried out to assess the migration of 36Cl, as chloride, through a cementitious backfill material. Further experiments in the presence of cellulose degradation products were performed to assess the effect of organic ligands on the extent and rate of chloride diffusion. Results show that breakthrough of 36Cl is dependent on chloride concentration: as the carrier concentration increases, both breakthrough time and the quantity retained by the cement matrix decreases. Experiments in the presence of cellulose degradation products also show a decrease in time to initial breakthrough. However, uptake at various carrier concentrations in the presence of organic ligands converges at 45% of the initial concentration as equilibrium is reached. The results are consistent with organic ligands blocking sites on the cement that would otherwise be available for chloride binding, though further work is required to confirm that this is the case. Post-experimental digital autoradiographs of the cement cylinders, and elemental mapping showed evidence of increased 36Cl activity associated with black ash-like particles in the matrix, believed to correspond to partially hydrated glassy calcium-silicate-sulfate-rich clinker.

Development of a method for rapid analysis of Ra-226 in groundwater and discharge water samples by ICP-QQQ-MS

A novel and rapid method has been developed for pre-concentration and measurement of 226Ra in groundwater and discharge water samples using the latest generation triple quadrupole inductively coupled plasma mass spectrometry (ICP-QQQ-MS). Cation exchange and extraction chromatography are capable of pre-concentration factors of ~200 based on 1L samples. The sensitivity and interference removal capability of ICP-QQQ-MS was assessed from spiked groundwaters, with the introduction of He collision gas required to minimise instrument background in high-matrix samples. The technique developed is potentially capable of detecting 226Ra activities as low as 5mBqL-1 when combined with pre-concentration prior to measurement.

The behaviour of 226Ra in high-volume environmental water samples on TK100 resin

Accurate, low-level measurement of 226Ra in high volume water samples requires rapid pre-concentration and robust separation techniques prior to measurement in order to comply with discharge limits and drinking water regulations. This study characterises the behaviour of 226Ra and interfering elements on recently developed TK100 (Triskem International) extraction chromatography resin. Distribution coefficients over a range of acid concentrations are given, along with an optimised procedure that shows rapid pre-concentration and separation of 226Ra on TK100 resin is achievable for high volume (1 L) water samples without the need for sample pre-treatment.

Solubility constraints affecting the migration of selenium through the cementitious backfill of a geological disposal facility

This work presents the study of the solubility of selenium under cementitious conditions and its diffusion, as SeO3(2-), through monolithic cement samples. The solubility studies were carried out under alkaline conditions similar to those anticipated in the near-field of a cement-based repository for low- and intermediate-level radioactive waste. Experiments were conducted in NaOH solution, 95%-saturated Ca(OH)2, water equilibrated with a potential backfill material (Nirex reference vault backfill, NRVB) and in solutions containing cellulose degradation products, with and without reducing agents. The highest selenium concentrations were found in NaOH solution. In the calcium-containing solutions, analysis of the precipitates suggests that the solubility controlling phase is Ca2SeO3(OH)2·2H2O, which appears as euhedral rhombic crystals. The presence of cellulose degradation products caused an increase in selenium concentration, possibly due to competitive complexation, thereby, limiting the amount of calcium available for precipitation. Iron coupons had a minor effect on selenium solubility in contrast to Na2S2O4, suggesting that effective reduction of Se(IV) occurs only at Eh values below -300mV. Radial through-diffusion experiments on NRVB and in a fly ash cement showed no evidence of selenium breakthrough after one year. However, autoradiography of the exposed surfaces indicated that some migration had occurred and that selenium was more mobile in the higher porosity backfill than in the fly ash cement.

Understanding uranium behaviour at the Askola uranium mineralization

Abstract Understanding the behaviour of uranium is essential when assessing the safety of a spent nuclear fuel repository. The geochemical behaviour of uranium, including its reactive transport chemistry, is also a matter of concern when assessing the environmental impact of uranium mining. Subsurface uranium mobility is believed to be primarily controlled by dissolution and (co)-precipitation of uranium mineral solids and adsorption to mineral surfaces. This paper describes a modelling exercise based on characterisation of samples taken from drilled cores at the uranium mineralization at Askola, Southern Finland. In the modelling exercise, current conditions are assumed to be oxidizing and saturated with groundwater. PHREEQC was used for modelling in conjunction with the Lawrence Livermore National Laboratory database, chosen for its extensive coverage of uranium species and mineral phases. It is postulated that weathering processes near the surface have led to uranium dissolution from the primary ore, leaching out from the matrix and migrating along water-conducting fractures with subsequent re-diffusion into the rock matrix. Electron microscopy studies show that precipitated uranium occupies intra-granular fractures in feldspars and quartz. In addition, secondary uranium was found to be distributed within goethite nodules as well as around the margins of iron-containing minerals in the form of silicate and phosphate precipitates. Equilibrium modelling calculations predict that uranium would be precipitated as uranyl silicates, most likely soddyite and uranophane, in the prevailing chemical conditions beneath Lakeakallio hill.

The solubility of nickel and its migration through the cementitious backfill of a geological disposal facility for nuclear waste

This work describes the solubility of nickel under the alkaline conditions anticipated in the near field of a cementitious repository for intermediate level nuclear waste. The measured solubility of Ni in 95%-saturated Ca(OH)2 solution is similar to values obtained in water equilibrated with a bespoke cementitious backfill material, on the order of 5×10(-7)M. Solubility in 0.02M NaOH is one order of magnitude lower. For all solutions, the solubility limiting phase is Ni(OH)2; powder X-ray diffraction and scanning transmission electron microscopy indicate that differences in crystallinity are the likely cause of the lower solubility observed in NaOH. The presence of cellulose degradation products causes an increase in the solubility of Ni by approximately one order of magnitude. The organic compounds significantly increase the rate of Ni transport under advective conditions and show measurable diffusive transport through intact monoliths of the cementitious backfill material.

Dose assessment from chronic exposure to industrial NORM in iron ore processing

Radiological exposures due to naturally occurring radioactive material (NORM) can occur during a wide range of work-related activities in the mineral processing and chemical industries. However, evaluation of such exposures in industrial settings remains a difficult exercise owing inter alia to the large number of personnel, operations and plants affected; assumptions that often have to be made concerning the actual duration and frequency of exposures; the complex chemistry and radioactive disequilibria involved and typically, the paucity of historical data. In our study, the challenges associated with assessing chronic exposure to fugitive dust enriched in 210Pb and 210Po and the determination of the associated internal dose by inhalation and ingestion are described by reference to a case study undertaken at an iron ore sintering plant between June 2013 and July 2015. The applicability of default dose coefficients and biokinetic models provided by the International Commission for Radiological Protection was verified by combining air and dust monitoring with information on the characteristics of the aerosols and in-vitro solubility experiments. The disparity between particulate matter 100 microns or less in diameter (PM100), particulate matter 10 microns or less in diameter (PM10) and 210Pb/210Po activity concentrations observed over the different monitoring campaigns and sampling locations confirmed that use positional short-term monitoring surveys to extrapolate intake over a year was not appropriate and could lead to unrealistic intake and dose figures. Personal air sampling is more appropriate for estimating the dose in such situations, though it is not always practical and may collect insufficient quantities of material for radiochemical analysis; this is an important constraint when dealing with low specific activity materials.