Characterization of cores from an in-situ recovery mined uranium deposit in Wyoming: Implications for post-mining restoration

Abstract

In-situ recovery (ISR) of uranium (U) from sandstone-type roll-front deposits is a technology that involves the injection of solutions that consist of ground water fortified with oxygen and carbonate to promote the oxidative dissolution of U, which is pumped to recovery facilities located at the surface that capture the dissolved U and recycle the treated water. The ISR process alters the geochemical conditions in the subsurface creating conditions that are more favorable to the migration of uranium and other metals associated with the uranium deposit. There is a lack of clear understanding of the impact of ISR mining on the aquifer and host rocks of the post-mined site and the fate of residual U and other metals within the mined ore zone. We performed detailed petrographic, mineralogical, and geochemical analyses of several samples taken from about 7 m of core of the formerly the ISR-mined Smith Ranch-Highland uranium deposit in Wyoming. We show that previously mined cores contain significant residual uranium (U) present as coatings on pyrite and carbonaceous fragments. Coffinite was identified in three samples. Core samples with higher organic (N 1 wt.%) and clay (N6-17 wt.%) contents yielded higher 234 U/ 238 U activity ratios (1.0-1.48) than those with lower organic and clay fractions. The ISR mining was inefficient in mobilizing U from the carbonaceous materials, which retained considerable U concentrations (374-11,534 ppm). This is in contrast with the deeper part of the ore zone, which was highly depleted in U and had very low 234 U/ 238 U activity ratios. This probably is due to greater contact with the lixiviant (leaching solution) during ISR mining. EXAFS analyses performed on grains with the highest U and Fe concentrations reveal that Fe is present in a reduced form as pyrite and U occurs mostly as U(IV) complexed by organic matter or as U(IV) phases of carbonate complexes. Moreover, U-O distances of~2.05 Å were noted, indicating the potential formation of other poorly defined U(IV/VI) species. We also noted a small contribution from U_O at 1.79 Å, which indicates that U is partially oxidized. There is no apparent U-S or U-Fe interaction in any of the U spectra analyzed. However, SEM analysis of thin sections prepared from the same core material reveals surficial U associated with pyrite which is probably a minor fraction of the total U present as thin coatings on the surface of pyrite. Our data show the presence of different structurally variable uranium forms associated with the mined cores. U associated with carbonaceous materials is probably from the original U mobilization that accumulated in the organic matter-rich areas under reducing conditions during shallow burial diagenesis. U associated with pyrite represents a small fraction of the total U and was likely deposited as a result of chemical reduction by pyrite. Our data suggest that areas rich in carbonaceous materials had limited exposure to the lixiviant solution, continue to be reducing, and still hold significant U resources. Because of t...

Uranium(IV) adsorption by natural organic matter in anoxic sediments

“…Finally, adsorbed U(IV) is likely to be more kinetically labile than UO 2+x (14,27), and this has important ramifications for U mobility in the environment: U(IV) could be more mobile under anoxic conditions than anticipated, and more sensitive to redox fluctuations, with implications for the longevity of U contamination in the subsurface (10) as well as its extractability from ores (12).…”

“…Our research further implies that models that seek to predict U behavior in the subsurface, e.g., for the purpose of remediation of contaminated groundwater (41) or in situ mining of U roll-front ore deposits (12), should include U(IV) complexation reactions, especially with organic matter. Research is needed to quantify the affinity of U(IV) for whole sediments and individual environmentally important solid phases, as has been done for U(VI).…”

“…For many years researchers assumed that sparingly soluble minerals, such as UO 2+x , controlled the aqueous concentration of U(IV) and mediated the oxidation of U(IV) to U(VI) under anoxic conditions (5,6). In fact, many researchers have shown that UO 2+x either is not observed in sediments, or is a minor phase (7)(8)(9)(10)(11)(12)(13). The chemical reactivity of U(IV) is controlled by its speciation; for instance, researchers have noted that some biogenically produced forms of U(IV), termed "noncrystalline U(IV)," oxidize more rapidly than does UO 2+x (14).…”

“…The chemical reactivity of U(IV) is controlled by its speciation; for instance, researchers have noted that some biogenically produced forms of U(IV), termed "noncrystalline U(IV)," oxidize more rapidly than does UO 2+x (14). Thus, knowledge of U(IV) speciation is essential to understand U processes and behavior in low-temperature geochemical environments, including ore deposits (12), marine basins (15,16), and contaminated aquifers (8). However, an alternative description has not been fully developed to complement U(IV) mineral formation in sediments under environmentally relevant conditions, and this gap represents a major weakness in our geochemical knowledge of this critical element.…”

Potential aquifer vulnerability in regions down-gradient from uranium in situ recovery (ISR) sites

“…Parameters related to geochemical rates are generally lacking, particularly kinetic data on mineral-water reactions involving metals and metalloids. Petrographic, mineralogical, and geochemical studies of core samples from ISR sites are needed to feed into the model architecture (see WoldeGabriel et al, 2014;Gallegos et al, 2015).…”