Surface features and alteration products of natural zirconolite leached in silica-saturated solutions

Zirconolite, CaZrTi2O7, has been proposed as an immobilization phase for the disposition of excess weapons Pu and other actinides (e.g., 235U). Due to actinide incorporation, zirconolite is expected to sustain α-decay event damage and become aperiodic (=metamict) over time. The leaching behavior of metamict zirconolite is, therefore, of interest. Because groundwater in a variety of geologic settings contains up to saturation concentrations of silicic acid, H4SiO4, silica-saturated solutions were used. Natural, metamict (> 1026 α-decay events per mn3) zirconolite grains, nominally (Ca, Th)ZrTi2O7 (U.S. National Museum sample #B20392, Walawada, Sri Lanka) were leached in two separate silica-saturated solutions at 150 °C for 60 days. Surface features and alteration products were examined using scanning electron microscopy (SEM) and quantitative energy dispersive X-ray spectroscopy (EDS). Secondary electron (SEI) images of the surfaces of the leached grains from both experiments revealed pores, probably due to the accumulation of He-bubbles from α-decay events, of approximately 4% as estimated by contrast enhanced gray-scale analysis of digital images. SEI of the zirconolite surface before leaching showed a smooth surface. The pores not only increase the surface area of the metamict zirconolite, but also act as nucleation sites for alteration phase growth. One experiment was conducted in a silica-saturated solution containing approximately 100 ppm P as measured by atomic absorption spectroscopy (AAS). The main alteration phase was euhedral, monoclinic cheralite, (Th, Ca, Ce)(P, Si)O4 (monazite group). The second experiment was conducted in the absence of P. The main alteration phase was subhedral cubic thorianite, ThO2.

The structure of aperiodic, metamict (Ca, Th)ZrTi2O7 (zirconolite): An EXAFS study of the Zr, Th, and U sites

The structural environments of Zr, Th, and U in aperiodic (metamict) (Ca, Th)ZrTi2O7 were examined using Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Samples are aperiodic due to a radiation-induced transformation caused by alpha-decay event damage. In the aperiodic samples, Zr is mainly 7-coordinated [d(Zr−O) ≍ 2.14–2.17 ≍ 0.02 Å]; whereas, Th is mainly 8-coordinated [d(Th–O) ≍ 2.40−2.41 ≍ 0.03 Å]. Nearly identical bond lengths and coordination numbers for these elements were determined for an annealed, crystalline sample. The radiation-induced transition from the periodic to the aperiodic state is characterized by a significant broadening of the distribution of (Zr, Th)–O distances. In one metamict sample with ≍1.9 wt.% U3O8, U is essentially tetravalent. The absence of higher oxidation states (U6+) is consistent with the lack of evidence for alteration (samples are over 500 million years old). The reduced medium-range order around Zr, Th, and U is related to the increase of alpha-decay event damage and precludes decomposition of zirconolite into simple oxides of Zr, Th, or U. Comparison with other metamict (Zr, Th, U)-bearing phases (e.g., ZrSiO4 and ThSiO4) suggests that Zr4+, Th4+, and U4+ prefer 7-, 8-, and 6-coordinated sites, respectively, in aperiodic phases at ambient temperatures and pressures. Examination of the structure of crystalline (Ca, Th)ZrTi2O7 demonstrates that M–O–M angles (M = Ca, Ti, Zr, and Th) are relatively small (≍100–120° for edge-sharing polyhedra). A limited relaxation of the constraints of periodicity around M cations caused by radiation damage (e.g., tilting of polyhedra) dramatically affects the distribution of these angles. This type of structural relaxation may be the mechanism by which long-range periodicity is lost and medium-range order is reduced with increasing radiation damage, while the major cations retain their nearest-neighbor environments. This relaxation may also help explain the lattice expansion observed in zirkelites when they undergo radiation damage.

ON THE ABSENCE OF PHOTONS AMONG THE DECAY PRODUCTS OF THE 2.2 MICROSECOND MESON

An experiment is described which tests the hypothesis that the cosmic ray meson with a mean life of 2.2 μsec. decays into an electron and a photon. Geiger counter trays are used to select mesons incident on a graphite block, and to detect decay products emerging from the graphite. The electronic circuits record delayed coincidences that correspond to a decay event occurring between 0.6 and 5.3 μsec. after a meson is stopped. The absence of delayed coincidences of a type that could be attributed to the simultaneous emission of an electron and a photon, each of ~ 50 Mev., shows that the above hypothesis of the meson decay process is incorrect. The experiment also demonstrates the absence of a hypothetical unstable neutral meson among the decay products.