NATURAL RADIATION-INDUCED DAMAGE IN QUARTZ. III. A NEW OZONIDE RADICAL IN DRUSY QUARTZ FROM THE ATHABASCA BASIN, SASKATCHEWAN

Abstract

Quartz crystals collected in druses, including one annealed at 400°C, from a fracture in the hanging-wall sandstone at the McArthur River uranium deposit in the Paleoproterozoic Athabasca basin, northern Saskatchewan, have been investigated by single-crystal X-band electron paramagnetic resonance (EPR) spectroscopy at room temperature and 110 K. The single-crystal EPR spectra allow us to distinguish eight paramagnetic defects, including one new center and seven previously reported centers. These centers, most of which were discovered in artificially irradiated crystals and only a few had been suggested to occur in natural quartz by powder EPR, are herewith positively established for the first time as natural radiation-induced defects by single-crystal EPR. The new center is similar in principal g-factor values to the ozonide radical (O 3 − ) in various minerals and synthetic compounds, and is characterized by its g-maximum and g-minimum axes approximately parallel to two O–O edges of the SiO 4 quasi-tetrahedron in the quartz structure. This geometry is also compatible with an ozonide radical formed from a silicon vacancy. The observed linewidths of the new ozonide radical vary from 0.087 to 0.257 mT, which are attributed to unresolved site-splittings or unresolved hyperfine splittings. This new ozonide radical is distinct from a previously reported ozonide radical in citrine quartz, which is characterized by the presence of a small 27 Al hyperfine structure. The new ozonide radical is probably linked to a Si atom in the neighboring tetrahedron and hence represents a general case in quartz, whereas the previously reported ozonide radical linked to a neighboring Al atom is a special variant in Al-bearing quartz. The presence of natural radiation-induced defects in drusy quartz is attributable to the presence of uranium in mineralized assemblages nearby or late hydrothermal fluids.