Open AccessTHE FATE OF THE EPSILON PHASE IN UO2 OF THE OKLO NATURAL FISSON REACTORS
Author(s) -
Satoshi Utsunomiya,
Rodney C. Ewing
Publication year - 2005
Language(s) - English
Resource type - Reports
DOI - 10.2172/860243
Subject(s) - uraninite , spent nuclear fuel , phase (matter) , metal , transmission electron microscopy , analytical chemistry (journal) , chemistry , nuclear chemistry , radiochemistry , crystallography , uranium , mineralogy , materials science , metallurgy , nanotechnology , environmental chemistry , organic chemistry
In spent nuclear fuel (SNF), the micron- to nano-sized epsilon phase (Mo-Ru-Pd-Tc-Rh) is an important host of {sup 99}Tc which has a long half life (2.13 x 10{sup 5} years) and can be an important contributor to dose in safety assessments of nuclear waste repositories. In order to examine the occurrence and the fate of the epsilon phase during the corrosion of SNF over long time periods, samples of uraninite from the Oklo natural reactors ({approx}2.0 Ga) have been investigated using transmission electron microscopy (TEM). Because essentially all of the {sup 99}Tc has decayed to {sup 99}Ru, this study focuses on 4d-elements of the epsilon phase. Samples were obtained from the research collection at University of Michigan representing reactor zone (RZ) 10 (836, 819,687) and from RZ 13 (864,910). Several phases with 4d-metals have been identified within UO{sub 2} matrix at the scale of 50-700 nm; fioodite, PdBi{sub 2}, with trace amounts of As, Fe, and Te, and palladodymite or rhodarsenide, (Pd,Rh){sub 2}As. The most abundant 4d-metal phase is ruthenarsinite, (Ru,Ni)As, which has a representative composition: As, 59.9; Coy 2.5; Ni, 5.2; Ru, 18.6; Rh, 8.4; Pd, 3.1; Sb, 2.4 in atomic%. Ruthenarsenite nanoparticles are typically surrounded by Pb-rich domains, galena in most cases; whereas, some particles reveal a complexly zoned composition within the grain, such as a Pb-rich domain at the core and enrichment of Ni, Co, and As at the rim. Some ruthenarsenites and Rh-Bi-particles are embedded in surrounding alteration products, e.g., chlorite, adjacent to uraninite (no further than {approx}5 {micro}m). A few of those particles are still coated by a Pb-rich layer. Based on these results, the history that epsilon phases have experienced can be described as follows: (1) The original epsilon phase was changed to, in most cases, ruthenarsenite, by As-rich fluids with other trace metals. Dissolution and a simultaneous precipitation may be responsible for the phase change. (2) All Mo and most of the Tc were released from the epsilon phase. Galena precipitated surrounding the 4d-metal phases. (3) Once the uraninite matrix has dissolved, the epsilon nanoparticles were released and ''captured'' within alteration phases that are immediately adjacent to the uraninite