Characterization of U ore from a roll-front U deposit: Implications of dominant U-Ti mineral for ore genesis and post solution-mining U immobilization

Abstract:

Reductive immobilization of dissolved U(VI) is an important process that gives rise to roll-front U deposits as well as offers a remediation strategy after in situ recovery (ISR) mining of roll-fronts by oxidative dissolution of the U ore. About 25% of the global and over 90% of all U resources in the United States consist of roll-front deposits. Accordingly, ~50% of global U mining and almost all current U mining in the United States is ISR mining. Therefore, it is important to identify the U immobilization pathways for an improved understanding of the U ore genesis and postmining U(VI) remediation. Here, we characterize (XRD, XRF, SEM/EDS, QEMSCAN) the U ore from a roll-front U deposit and sediments downgradient of the ore from an ISR site at Rosita, TX, USA.

The dominant U mineral in Rosita U ore is brannerite (nominally U⁴⁺Ti₂O₆, up to 0.032 wt%), followed by coffinite and U-oxides. The U mineralized sand is composed of quartz (41-53%), calcite (15-30%), plagioclase (11-19%), microcline (2-9%), clinoptilolite (0.5-7%) with minor amounts of pyrite/marcasite (2-7%) and clays/micas (1-4%), and very little organic C (<0.1%). Ore zone samples contain minor amounts (<2%) of hematite, V-oxides/V-Ti-Fe-oxides and sulfidized Fe-Ti oxides with variable Fe, Ti and S ratios locally hosting low levels of U. The dominant sulfide mineral is marcasite. We observe a complex relationship between U-Ti minerals and sulfide/silicate phases where U minerals occur as inclusions, irregularly developed veins or intergrowths. Except for the U concentrations, the downgradient sediments are compositionally similar to the ore and contain abundant smectite/illite (7-45%).

The predominance of brannerite implies direct reduction of U(VI) on surfaces of reduced Fe-Ti oxides as a major ore-forming mechanism. Our results reveal an as yet unidentified mechanism of ore genesis that differs from the current model that presupposes the sulfidized Fe-Ti oxides as the main reductant of U(VI). Furthermore, previous research demonstrated formation of U-Ti phases structurally similar to brannerite during reduction of U(VI) by titanomagnetites. Abundant Fe-Ti oxides in the downgradient sediments suggest that the interaction between postmining residual U(VI) and Fe-Ti oxides may play a major role in natural remediation of U at Rosita and similar ISR sites.