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Kathryn E. Watts

Publications and source records attributed to Kathryn E. Watts.

7 recordsLinked to original sources

Insights into Mountain Pass carbonatite formation from in-situ sulfur isotopes and geochemistry of sulfate and sulfide minerals

The Mountain Pass carbonatite stock hosts a world-class rare earth element deposit and may be classified as a carbonate-sulfate igneous rock, as it contains on average > 50 volume percent carbonate minerals and 20 to 30 volume percent sulfate minerals. The sulfates range in composition from barite to celestine and locally occur with sparse sulfide minerals. We investigate the origin of sulfur enrichment and the occurrence of sulfur-bearing minerals in the Mountain Pass carbonatite with in-situ sulfur isotope and mineral chemistry. Barite cores with δ 34 S of 1 to 3‰ do not coexist with sulfides, whereas celestine rims with δ 34 S of > 3‰ are associated with sulfides with δ 34 S < -10‰. We propose a model in which sulfur-bearing sediments were subducted during episodes of plate convergence in the Mojave Province that preceded Mountain Pass magmatism. Metasomatism of the overlying mantle by melts derived from the subducted sediments generated an unusually carbon- and sulfur-rich source to yield carbonatite magmas. Sulfur from primary carbonatite magmas and ~ 1 to 7% sulfur from subducted sediment melts yielded a slightly enriched δ 34 S composition (relative to depleted mantle δ 34 S of -1‰) for early crystallizing barite. Celestine rims on magmatic barite cores formed at low, hydrothermal temperatures (< 350 °C) based on S isotope thermometry for equilibrium celestine-galena and celestine-pyrite pairs. The sparse sulfides in the carbonatite stock are not in equilibrium with the primary barite cores and therefore do not permit S isotope thermometry estimates of magmatic temperatures. The S/Se ratios of sulfide minerals (> 3,400) typically exceed primitive mantle values (S/Se of 3,340), also consistent with their derivation from hydrothermal fluids. Trace occurrences of sulfide and sulfate minerals in alkaline silicate stocks related to the carbonatite stock have similar δ 34 S compositions and yield similarly low formation temperatures, suggesting regionally extensive and chemically similar sulfur-bearing hydrothermal fluids that imparted lithologically diverse rocks with a consistent sulfur isotope fingerprint.

California, Nevada

Complex carbonate ore mineralogy in the Mountain Pass carbonatite rare earth element deposit, USA

Economic concentrations of rare earth element (REE) minerals are uncommon in the Earth’s crust, with most occurring in carbonatites. Unlike most igneous rocks composed of silicate minerals, carbonatites are dominated by carbonate minerals, some of which can incorporate significant light REEs (LREEs; La, Ce, Pr, Nd). Technological applications of REEs are numerous and they have been identified as some of the most critical mineral commodities to the global economy. The Mountain Pass carbonatite stock in the Mojave Desert of California is the most economically significant REE deposit in the USA and contains a few to tens of percent (by volume) of the carbonate REE ore mineral bastnäsite. Despite the economic significance of the Mountain Pass deposit, studies of its ore mineralogy are limited. Here we present new carbonate ore mineralogy data for a compositionally diverse suite of carbonatitic rocks from the Mountain Pass stock and related dikes. Whole-rock geochemical data are integrated with mineral-scale textural and chemical data obtained by scanning electron microscopy (SEM), electron probe microanalysis (EPMA), and microRaman spectroscopy. Our results document a complex spectrum of REE-bearing carbonate minerals and intermediate mixed-layer structures. Mineral species include bastnäsite [REE(CO 3 )F], hydroxylbastnäsite [REE(CO 3 )OH], parisite [Ca(REE) 2 (CO 3 ) 3 F 2 ], synchysite [Ca(REE)(CO 3 ) 2 F], röntgenite [Ca 2 (Ce,La) 3 (CO 3 ) 5 F 3 ], and sahamalite [(Mg,Fe 2+ )(REE) 2 (CO 3 ) 4 ]. Carbonate ore mineralogy is heterogeneous within and between samples, including at the intracrystal scale. Complexly zoned crystals exhibit as many as five to six different compositional domains and syntaxial intergrowths, commonly with the more Ca-rich varieties (parisite, synchysite) forming crystal rims that surround relict bastnäsite cores. We attribute the phenocryst variability to changes in the chemistry and temperature of primary carbonatite magmas and evolved/exsolved fluids. Cross-cutting vein textures of calcite, celestine and various REE carbonate minerals, interstitial bastnäsite crystallization, breccia blocks lined by fine-grained bastnäsite, and the presence of hydroxylbastnäsite and partially hydroxylated bastnäsite point to the role of secondary hydrothermal processes in REE mineralization. Fluorcarbonate mineral compositions demonstrate that La and Ce are more structurally abundant in bastnäsite, whereas the more Ca-rich species (parisite, synchysite) contain a greater proportion of REE heavier than Pr (Nd, Sm, Eu, Gd) and Y. Atomic ratios of Pr/(Nd + Pr) are likewise variable, with the highest average value for bastnäsite (0.25) compared to parisite (0.22) and sychysite (0.21). This finding has geometallurgical implications, given that current mining operations are focused on recovery of Nd and Pr for high field strength permanent magnets and the Nd/Pr ratios are a critical factor in ore processing and magnet manufacture.

California

In-situ geochronology using LA-ICP-MS/MS: Application of the Lu-Hf system in carbonate, apatite and fluorite

Geochronology is a fundamental tool for reconstructing earth history and constraining the timing of ore deposit formation. Traditionally, U-rich minerals like zircon, titanite, monazite and apatite have been analysed to determine the timing of mineralization and alteration events. However, not all deposits or alteration assemblages contain these minerals, and the U-Pb system can be disturbed due to open system behaviour. We present a methodology for obtaining in-situ Lu-Hf dates from various minerals to demonstrate the potential for dating ore deposits that lack U-rich minerals. Carbonate, apatite and fluorite minerals from different tectonic settings and geological environments were analysed. We acquired Lu-Hf and REE (rare earth element) data from carbonate minerals from a carbonatite orebody and dike samples from the Mountain Pass REE carbonatite deposit in California, USA. We also tested a ‘double-dating’ method, where U-Th-Pb dates and Lu-Hf dates were obtained from the same analysis of apatite from rocks in the Michigan’s Great Lakes Tectonic Zone. Preliminary results for Lu-Hf dating of fluorite from carbonatite rocks in the Lemitar Mountains of New Mexico are also included. The analytical methodology shows promising results in each of these cases where there is sufficient parent Lu and U and measurable daughter Hf and Pb respectively.

Conference Paper

Lithium from magma to mine in an early Yellowstone hotspot caldera

Renewable energy technologies rely on the extraction of metals not historically in high demand, such as lithium (Li), for which ore deposit models are incompletely understood. One of the world’s largest Li deposits is hosted in lake sediments of the 16.4 Ma McDermitt caldera, which formed during the early stages of Yellowstone hotspot volcanism in the western United States. Eruptive and posteruptive mobility of Li are major challenges in elucidating deposit formation. Melt inclusions preserved in quartz crystals provide a means to assess pre-eruptive magmatic Li contents. Concentrations of Li determined by ion microprobe for melt inclusions in a McDermitt rhyolite lava are 400−1350 ppm, compared to 20−70 ppm Li in matrix rhyolite glasses. Synthesis with melt inclusion data for eight additional calderas demonstrates a recurrence of Li-rich rhyolitic magmas (200−2000 ppm Li) in the western part of the Yellowstone hotspot track. However, unlike the multicyclic caldera complexes with overlapping fault networks that may have compromised Li retention, the McDermitt caldera remained a closed hydrologic system throughout its evolution. Modeling indicates 100 km 3 of resurgent magma could yield 25−150 Mt Li in a magmatic fluid and supports accumulation of Li-rich magmatic fluid in a closed intracaldera lake, followed by evaporative concentration and sequestration of Li within clay minerals to generate the McDermitt deposit.

Idaho, Nevada, Oregon, Wyoming

Geochemistry and radiogenic isotopes constrain the mantle source region of the Mountain Pass Intrusive Suite, California

The Mountain Pass carbonatite stock is the largest rare earth element (REE) deposit and only active REE mine in the United States. The carbonatite intrusion and spatially associated alkaline silicate intrusions constitute the Mountain Pass Intrusive Suite, which is located within the Mojave Province in California. Both the carbonatite and the alkaline silicate rocks are enriched in large ion lithophile elements and light REEs, and less enriched to depleted in high field strength elements, indicating the mantle source region was metasomatically enriched in incompatible trace elements. The cause of this metasomatic mantle enrichment and the genetic relationship between the carbonatite and the alkaline silicate stocks are poorly understood. In this study, major and trace element geochemical data and isotopic (Rb-Sr, Sm-Nd, and Lu-Hf) data are presented to constrain genesis of the Mountain Pass Intrusive Suite, from mantle source region to the intrusion of the stocks. Our geochemical data are consistent with derivation of the alkaline silicate and carbonatite melts through partial melting from a shared mantle source region rather than through liquid immiscibility or fractional crystallization and separation of a carbothermal fluid. Although the Rb-Sr isotopic system in the Mountain Pass Intrusive Suite is disturbed at the whole-rock scale, the isotopic systems for whole-rock Sm-Nd (εNd i = ‐2.2 ± 0.8) and zircon Lu-Hf (εHf i = 0.1 ± 1.1) are robust and support mantle derivation of the magmas. Geochemical modeling using experimentally derived partition coefficients was used to identify possible causes of enrichment in incompatible elements through metasomatism in the mantle source region. Modeling of metasomatism by melts derived by partial melting of deeply subducted carbonated sediments approximates observed Mountain Pass Intrusive Suite trace element chemistry. Scattered εHf i in inherited zircon (2.8 ± 2.6) is consistent with derivation from an arc-related environment with substantial crustal contamination. Paleotectonic studies in the Mojave Province indicate that regional subduction preceded emplacement of the Mountain Pass Intrusive Suite by ∼300 Ma. Melting of the Mountain Pass source region may have been caused by post-collisional thermal relaxation and extension.

California

Fingerprinting magmatic REE deposit sources with zircon petrochronology

Carbonatites and associated alkaline silicate rocks are of considerable economic interest due to their enrichments in rare earth elements. The petrogenesis and source(s) of these complexes, however, are poorly understood. Models propose either mantle plume-derived carbon-rich melts or a mantle source enriched by subduction-related metasomatism. We use zircon trace elements to fingerprint carbonatite-alkaline complex sources, focusing on the economically significant 1.4 Ga Mountain Pass intrusive suite (MPIS). Autocrystic zircon from MPIS alkaline silicate rocks are enriched in Th and U relative to Nb suggesting a subduction influenced, oxidized source region. Lower Sc/Yb, higher Ti concentrations, and the absence of Eu anomalies in autocrystic zircon suggest derivation from a less hydrous, hotter, and deeper mantle source relative to arc-related 1.8–1.6 Ga inherited zircon. These data are best explained by syn- to post-collisional Mesoproterozoic reactivation of a subduction-metasomatized mantle source. The source and tectonic setting of the MPIS contrasts with Mesoproterozoic Gifford Creek and Bayan Obo carbonatites which exhibit plume-like compositions and are associated with rifts, suggesting different sources and tectonic settings for these economically significant deposits. We demonstrate that zircon petrochronology is a robust method for distinguishing carbonatite sources and can inform more targeted exploration strategies for critical mineral resources.

Conference Paper

Stable isotope composition and geochemistry of calcite and dolomite in the Mountain Pass carbonatite: A lens into petrogenesis

Carbonatites host most of the global rare earth element (REE) deposits. The petrogenesis of these rocks, including magmatic and post-magmatic processes, are poorly understood but critical in forming and upgrading these deposits. The Mountain Pass carbonatite, which hosts the only active REE mine in North America, is lithologically variable but consistently contains >50% calcite and/or dolomite. Multiple generations of carbonates are evident, suggesting bulk analysis of carbonate minerals would generate a mixed isotopic and geochemical signature. In-situ stable carbon and oxygen isotopes, combined with geochemical analysis and petrography, distinguish carbonate generations, trace the source region of the carbonatite magma, and link carbonate genesis to REE mineralization throughout the intrusion. Primary carbon and oxygen isotope values outside the accepted mantle range may suggest a subduction-related carbon and oxygen source in the mantle. Deformation textures in primary calcite indicate syn- or post-crystallization ductile flow. Carbonates with secondary textures and heavy δ 13 C and δ 18 O values are associated with ore mineralization, suggesting fluid mobilization was important in concentrating REE and upgrading of the Mountain Pass deposit.

California