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Tritium speciation in nuclear decommissioning materials

Kim, Dae Ji (2009) Tritium speciation in nuclear decommissioning materials University of Southampton, Faculty of Engineering Science and Mathematics, School of Ocean and Earth Science, Doctoral Thesis , 196pp.

Record type: Thesis (Doctoral)


Tritium is a by-product of civil nuclear reactors, military nuclear applications, fusion programmes and radiopharmaceutical production. It commonly occurs, though not exclusively, as tritiated water (HTO) or organically-bound tritium (OBT) in the environment but may exist as other forms in nuclear-related construction and fabrication materials. During the lifetime of nuclear sites (especially those involving heavy water) tritium becomes variably incorporated into the fabric of the buildings. When nuclear decommissioning works and environmental assessments are undertaken it is necessary to accurately evaluate tritium activities in a wide range of materials prior to any waste sentencing. Of the various materials comprising UK radioactive wastes, concrete and metal account for approximately 20% of the total weight of low level waste (LLW) and 12% and 35% of the total weight of intermediate level waste (ILW). Proper sampling and storage of samples are significant factors in achieving accurate tritium activities. The degree of loss of 3H and cross-contamination can be significantly reduced by storing samples in an air/water tight container in a freezer (-18°C). The potential for tritium contamination is dependent on the 3H form. Most 3H loss originates from tritiated water which is easily exchanged with atmospheric hydrogen in the form of water vapour at room temperature. However, the loss of more strongly bound 3H, produced in-situ in materials by neutron activation, is not significant even at room temperature. Such tritium is tightly retained in materials and does not readily exchange with water or diffuse. In nuclear reactor environments tritium may be produced via several neutron-induced reactions, 2H(n,g)3H, 6Li(n,a)3H, 10B(n,2a)3H and ternary fission (fission yield <0.01%). It may also exist as tritiated water (HTO) that is able to migrate readily and can adsorb onto various construction materials such as structural concrete. In such locations it exists as a weakly-bound form that can be lost at ambient temperatures. Bioshield concretes present a special case and systematic analysis of a sequence of sub-samples taken from a bioshield core (from UKAEA Winfrith) has identified a strongly-bound form of 3H in addition to the weakly bound form. The strongly bound 3H in concrete is held more strongly in mineral lattices and requires a temperature of >850°C to achieve quantitative recovery. This more strongly retained tritium originates from neutron capture of trace lithium (6Li and potentially 10B) distributed throughout minerals in the concrete. The highest proportion of strongly bound 3H was observed in the core sections closest to the core. Weakly bound tritium is associated with water loss from hydrated mineral components. Tritium is retained in metals by absorption by free water, hydrated surface oxidation layer, H ingress into bulk metal and also as lattice-bound tritium produced via in-situ neutron activation. Away from the possible influence of neutrons, the main 3H contamination to metals arises from absorption and diffusion via atmospheric exposure to the HTO. Here contamination is mainly confined to the metal surface layer. The tritium penetration rate into metal surfaces is controlled by the metal type and its surface condition. Where metals are exposed to a significant neutron flux and contain 6Li, 7Li and 10B then in situ 3H production will occur which may propagate beyond the surface layer. In such cases tritium may exist in two forms namely a weakly bound HTO form and a non-HTO strongly bound form. The HTO form is readily lost at moderate temperatures (~120°C) whereas the non-HTO requires up to 850°C for complete extraction.

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Published date: April 2009
Organisations: University of Southampton, Ocean and Earth Science


Local EPrints ID: 72145
PURE UUID: b393d5ea-8852-4701-9072-c9e5e8d3de61

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Date deposited: 22 Jan 2010
Last modified: 18 Jul 2017 23:56

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Author: Dae Ji Kim

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