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Project update presentation for Powder River Basin CORE-CM project
Project update presentation for the Powder River Basin CORE-CM project
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Phase modifiers are low molecular weight molecules added to solvent extraction separations to improve the physical performance of the separation system, for example by increasing the concentration of metal ions that can be separated or improving the compatibility of the two solvents.
An amidoxime and carboxylate containing polymer adsorbent derived from acrylic fiber has shown extremely high efficiencies for extracting critical materials and precious metals from seawater. Among 50 extractable elements, the lanthanides, cobalt, and palladium were ranked near the top with KD values in the order of 107, about an order of magnitude higher than that of uranium. The KD value of the lanthanides increased linearly with the atomic number indicating charge density is a factor controlling trivalent lanthanide extractability in seawater. The data given in this report provides crucial information regarding the strategies of ocean mining of critical materials and precious metals.
Citric acid has been identified as an environmentally sustainable organic acid capable of leaching up to ~30% of easily accessible REEs from underclay material. An analysis of the leaching profiles was performed to discern the reaction rates, extraction efficiencies, and potential leaching mechanisms of REEs and cations of interest from ion-adsorbed underclays. The initial leaching stage follows a slow intraparticle diffusion mechanism followed by a second stage controlled by a mixed diffusion regime. The leaching profiles of Ca and P were similar to those of REEs, suggesting that REEs are most likely derived from mineral surfaces such as hydroxyapatite or crandallite rather than predominately from underclays. Fitting to a modified diffusion control model found diffusion-controlled leaching to be the primary mechanism whereas non-diffusive mechanisms made up about 22% of the extracted REEs. Gangue cations associated with underclays had less non-diffusive leaching than REE species, indicating that their leaching kinetics may be dominated by diffusion from within the material or potentially from product layer formation. Fitting to Boyd plots further indicated that REEs were leached following intraparticle diffusion control. These results have important implications for the development of more efficient and sustainable methods for extracting REEs or critical minerals from alternative feedstocks.
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Experimental determinations of the mineral/liquid partition coefficients of REE (La, Sm, Eu, Gd, Tb, Yb and Lu), Sc and Sr are reported for the minerals perovskite, spinel and melilite in synthetic systems. Perovskite concentrates light REE with respect to the residual liquid but shows no preference for heavy REE. Spinel greatly discriminates against the incorporation of REE, especially light REE, into its crystal structure. The partition of REE into melilite from a silicate liquid is quite dependent upon both the bulk melt and melilite solid-solution (gehlenite and akermanite components) compositions. As such, melilite can be enriched in REE or will reject REE with corresponding strong negative or strong positive Eu anomalies, respectively.
Partition coefficients were determined for Gd, Lu, Hf and Zr among ilmenite, armalcolite, and synthetic high-Ti mare basaltic melts at temperatures from 1122 deg to 1150 deg, and at oxygen fugacities of IW x 10 exp 0.5, by in situ analysis with an electron microprobe, using samples doped to present concentration levels. Coefficients for Zr were also measured for samples containing 600-1600 ppm Zr using this microprobe. In addition, coefficients were determined for Hf and Zr between chromian ulvospinel and melt, for Hf between pigeonite and melt, and for Lu between olivine and melt by microprobe analysis of samples doped to present levels. Values measured using the microprobe were in agreement with the values measured by analyzing mineral separates from the same run products by isotope dilution. Coefficient values for ilmenite are less than 0.01 for the LREE, are around 0.1 for the HREE, and are several times greater than this for Zr and Hf.
REE data on metasedimentary rocks from two different types of high-grade Archean terrains are presented and analyzed. The value of REEs as indicators of crustal evolution is explained; the three geologic settings (in North America, Southern Africa, and Australia) from which the samples were obtained are described; and the data are presented in extensive tables and graphs and discussed in terms of metamorphic effects, the role of accessory phases, provenance, and tectonic implications (recycling, the previous extent of high-grade terrains, and a model of Archean crustal growth). The diversity of REE patterns in shallow-shelf metasediments is attributed to local provenance, while the Eu-depleted post-Archean patterns are associated with K-rich plutons from small, stable early Archean terrains.
The relationship between the Nd isotopic composition in the Atlantic waters and the origin and circulation of the water masses was investigated. Samples were collected in the western North Atlantic between 7 and 54 deg N. The isotopic composition (Nd-143/Nd-144 ratios) showed extensive vertical structure at all locations. In regions where a thermocline was well-developed, large isotopic shifts were observed across the base of the thermocline, while regions without a thermocline were characterized by much more gradual shifts in isotopic composition with depth. The data reveal an excellent correlation between the Nd isotopic distribution in the western North Atlantic water column and the distribution of water masses identified from temperature and salinity measurements.
This paper reports on the results of ion-probe measurements of REE concentrations in individual grains of the Shergotty meteorite. The phases analyzed included whitlockite, apatite, baddeleyite, augite, pigeonite, maskelynite, and K-rich glass; the whitlockite and apatite phases were also analyzed for U. Results indicate that whitlockite contains the bulk of the REE in Shergotty, with no evidence for distinct light-REE patterns in texturally different whitlockites. The results on the evolution of the REE abundances in the Shergotty late-stage interstitial melt, inferred from the analysis of whitlockite, are consistent with closed system crystallization. No metasomatic alteration is required to explain the REE data. It is concluded that there is no compelling reason to attribute chronological significance to the Sm-Nd array, as was done by Jagoutz and Waenke (1986).
Analyses of mineral REE and selected minor and trace elements were carried out on individual grains of pyroxenes, whitlockite, maskelynite, and olivine of the Antarctic shergottite ALHA77005, and the results are used to interpret its parent magma and crystallization history. The results of mineral compositions and textural observations suggest that ALHA77005 is a cumulate with about half cumulus material (olivine + chromite) and half postcumulus phases. Most of the REEs in ALHA77005 reside in whitlockite whose modal concentration is about 1 percent. Mineral REE data support previous suggestions that plagioclase and whitlockite crystallized late, and that low-Ca pyroxene initiated crystallization before high-Ca pyroxene. The REE patterns for the intercumulus liquid, calculated from distribution coefficients for ALHA77005 pyroxene, plagioclase, and whitlockite, are in very good agreement and are similar to that of Shergotty.
Data are presented on ion microprobe measurements of REE and selected trace element abundances in individual grains of merrillite, fassaite, olivine, kirschsteinite, and plagioclase of Lewis Cliff 86010 (LEW 86010) meteorite and in merrillite and fassaite grains of Angra dos Reis (ADOR). Results show a close relationship between the two meteorites and support a magmatic origin for LEW 86010. However, the measurements indicate that, despite numerous common characteristics, the two meteorites must have been produced in separate magmatic events involving similar but distinct processes and parent melts.
Results are presented of trace-element analyses of three lunar zircons. The major-element and REE compositions were determined using electron microprobes, and a correction was made for zircon for Zr-Si-O molecular interferences in the La to Pr mass region. The three zircons were found to exhibit similar REE abundances and patterns. Results of the analyses confirm earlier studies (Hess et al., 1975; Watson, 1976; Neal and Taylor, 1989) on the partitioning behavior of trace elements in immiscible liquid-liquid pairs. The results also support the postulated importance of silicate liquid immiscibility in the differentiation of the upper mantle and crust of the moon.
In the lunar magma ocean model, ferroan anorthosites (FANs) are expected to be derived from a relatively undifferentiated source with chondritic REE abundances and yield the oldest radiometric ages of any lunar rocks. Samarium-neodymium-isotopic analyses of 60025 and 67016 yielded ages of 4.44 +/- 0.02 Ga and 4.53 +/- 0.12 Ga and initial Epsilon(sub Nd)(sup 143) values in excess of -0.5. These ages are within error of ages determined on some Mg-suite rocks by researchers. Thus, the existing data are not completely consistent with the standard magma ocean model. We have completed isotopic analysis on the pristine FAN 62236 in order to place further constraints on lunar crust-forming processes.
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