Electron-paramagnetic-resonance spectroscopy study of radiation-damage-induced cathodoluminescence in quartz, Athabasca Basin
This thesis presents the results of a combined cathodoluminescence (CL) and electron paramagnetic resonance (EPR) spectroscopic study of quartz from the uranium-mineralized Athabasca Basin. CL imaging not only distinguishes detrital quartz grains from their secondary overgrowths but also is able to differentiate two generations of overgrowths in the Athabasca sandstones. Moreover, the Athabasca quartz samples are characterized by three types of bright CL: 1) haloes around U- and Th-bearing mineral inclusions, 2) patches associated with U-bearing minerals in matrices or pores and 3) continuous rims in samples with or without any visible U-bearing minerals. These three types of bright CL are all of constant widths of ~35-45 ƒÝm, indicative of bombardments of alpha particles emitted from the 238U, 235U and 232Th decay series. CL spectral analyses show that the radiation damaged areas, relative to their undamaged hosts, are characterized by intense but broad emission bands at ~350 nm and 620-650 nm. Detailed EPR measurements of the Athabasca quartz samples revealed six paramagnetic defects: one oxygen vacancy center (E1'), three silicon vacancy hole centers (O23¡V/H+(I), O23¡V/H+(II) and O23¡V/M+) and two O2¡V peroxy centers. Moreover, dissolution experiments using concentrated HF showed that that the silicon vacancy hole centers and the peroxy centers are concentrated in the radiation-damaged rims/fractures, whereas the oxygen vacancy center (E1') is evenly distributed in quartz grains. CL and EPR data of quartz samples after isochronal annealing experiments suggest that the silicon vacancy hole centers and the peroxy centers are most likely responsible for the characteristic ultraviolet CL and the red CL, respectively. CL haloes in detrital quartz grains are ubiquitous in the Athabasca sandstones. CL patches are also widespread but are best developed in altered sandstones close to the unconformity or faults/fractures. Continuous CL rims, however, are more restricted in occurrences and are best developed at the high-grade Cigar Lake and McArthur River deposits, where they are restricted to lithological boundaries and faults and are pervasively developed in mineralized samples and associated alteration haloes close to the unconformity. At the Key Lake deposit, continuous rims occur only in mineralized samples close to the unconformity. Continuous CL rims are absent in basement rocks below mineralization, including those at the Cigar Lake and McArthur River deposits. The occurrence of radiation damages in Athabasca quartz have also been confirmed by detailed EPR measurements, which are significantly more sensitive than CL imaging. Continuous CL rims on Athabasca quartz grains most likely record bombardments of alpha particles emitted from U-bearing mineralization fluids. Therefore, their associations with the unconformity, lithological boundaries and faults provide direct evidence for those structures being the pathways for mineralization fluids. The exclusive occurrence of continuous CL rims on detrital quartz grains and the abundance of U-bearing minerals in both generations of overgrowths suggest that U mineralization must have commenced during early diagenesis and continued during the formation of overgrowths. The absence of significant radiation damages in altered basement rocks supports the hypothesis that the basement was not a major source for uranium mineralization in the Athabasca basin. The common occurrence of CL haloes in euhedral quartz grains and CL patches associated with U-bearing minerals in faults, fractures and voids provide further (visual) evidence for late remobilization of uranium.
Athabasca Basin, quartz, cathodoluminescence, EPR
Master of Science (M.Sc.)