Search NASA⌕ Search

SEARCH · Search NASA

Results for “zirconates”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
NASA NTRSDate not supplied

4.32 Billion Year Old Impact Melts at Apollo 14: Dating the Procellarum Basin?

Introduction: Recent work has improved our understanding of lunar crustal structure and basin evolution on the Moon, but its early impact history and implications for solar system dynamics remain poorly established [1,2]. In particular, there is a derth of absolute ages, especially for the period >4.0 Ga, that could be related to basin-forming events. Here we present U-Pb isotopic data for Zr-rich minerals found in impact-melt fragments from Apollo 14 soil sample 14163 that, when combined with previously published data, dates an impact event at 4324±15 Ma. The compositions and ages of these impact-melt fragments provide unique information about the timing of early impact events and the composition of the lunar crust. Results: Fourteen rocklets ranging in size from 1 to 3 mm were extracted from soil 14163. Most are impactmelt rocks with 10-30% clasts of mostly pyroxene and plagioclase (100 to 500 μm) in a crystalline matrix. Textures of the matrix vary from subophitic, formed by intergrowths of 10-20 μm plagioclase and pyroxene crystals, to poikilitic, with plagioclase and pyroxene reaching 20-50 μm size. Some fragments that contain no visible clasts have similar textures are also interpreted as impact-melt rocks. All fragments contain notably large proportions of euhedral to subhedral ilmenite, zircon, apatite/merrillite and less abundant zirconolite and baddeleyite in the melt matrices. These grains often form intricate intergrowths with each other and rock-forming minerals, indicating their crystallization from the melt (Fig. 1). However, some slightly larger (~50 μm) zircon and phosphate grains can be interpreted as relict clasts based on their granular textures and relationships with the surrounding phases (Fig. 1). This implies that zircon and phosphate minerals were present in the target rocks. Some of these grains were profoundly remelted during the impact, which resulted in an oversaturation of the melt in Zr and P and crystallization of new grains of Zrrich minerals and phosphates during melt solidification. The presence of zircon and phosphates indicates that the melts were significantly enriched in KREEP components and ties their provenance to the Procellarum- KREEP Terrane (PKT) [3]. Combined U-Pb zircon data obtained for all fragments form two main clusters on a concordia diagram (Fig. 2), between about 4.3 and 3.9 Ga. Phosphate data mostly concentrate on the younger end of this age range but some analyses are almost as old as the older zircon grains (Fig. 2). Figure 1: Zircon (Zr) and phosphate (Apt; Mer) grains in impact melt fragments from Apollo 14 soil 14161. A-zircon grains crystallized from impact melt; B-phosphate grain inherited from the target; C- granular zircon grains Our interpretation of these data is that all U-rich minerals experienced variable resetting of the U-Pb system, with phosphate, where closure temperature is significantly lower than that in zircon, affected more profoundly by Pb loss than zircon. Our best estimate of the time of formation of zircon and phosphate is based on statistically valid analysis of grains interpreted texturally as grown from the impact melt (Fig. 2). Ten of these analyses define an age of 4324±15 Ma (MSWD=3.0, probability of fit P=0.002). Our best estimate for the time of resetting is obtained by combining data from phosphates that are statistically indistinguishable from 3.9 Ga within the analytical uncertainties. This group is represented by 18 analyses of 15 phosphate grains from different fragments (Fig. 2) and defines an age of 3922±6 Ma (MSWD=1.2, P=0.23). Conversely, a minimum age of the target lithologies, remelted in the impact that produced the rocklets studied here (Fig. 2), can be determined from the five oldest analyses of zircon clasts at 4338±13 Ma (MSWD=1.5, P=0.2), which is indistinguishable from the age of the impact melt within the uncertainties. The obtained ages, combined with textural evidence, imply that the impact melt was formed at 4324±15 Ma, and that it occurred in a zircon-rich target with a minimum age of 4338±13 Ma. Further reworking occurred during a second impact event at 3922±6 Ma. Discussion: The younger age of 3922±6 Ma can be interpreted as the time of the Imbrium impact. The older age of 4324±15 Ma would then be the time of formation of the impact melt, which was then caught in the Imbrium ejecta either at the Apollo 14 landing site or within the target rocks of the Imbrium impact. The presence of abundant accessory phases such as zircons and phosphates is consistent with a substantial KREEP component in the analyzed particles. The current distribution of KREEP on the lunar surface appears to be strongly influenced by Imbrum ejecta [4] so interpretation of the 4.32 Ga age depends in part on assumed structure of the pre-impact crust and distribution of KREEP within the crust. If KREEP was present only in the deep crust at 4.32 Ga, then a basin-scale impact possibly analogous to Imbrium or larger may be necessary to excavate a KREEPy impact melt at this time. However, if KREEPy materials were present closer to the surface perhaps due to redistribution related to Mg-suite magmatism, then smaller impacts might be able to rework KREEPy compositions at shallower depths. The coherence of the data on the particles analysed here suggests a large volume of melt that has been preserved since 4.32 Ga, consistent with a large impact event. Relict zircons and mineral clasts suggests that the igneous crust in the vicinity of this impact was well developed by at least 4.34 Ga, similar to the model age of KREEP and older than the isochron ages of many Mg-suite cumulates [5]. A problem that confronts all lunar sample studies using the current collection is that the pre-Imbrium geology of the PKT (the source of these 4.32 Ga impact melts) is not well constrained. The South Pole-Aitken basin contains regions that are moderately enriched in Th, but its ejecta is Th-poor [6]; therefore these A14 fragments are probably not SPA ejecta. Alternatively, these fragments may represent formation of a hypothesized Procellarum basin [7] although the lack of a clearly defined basin ejecta signature is a potential problem with that interpretation. In any case, they provide a younger limit on the age of lunar differentiation and formation of KREEP within the lunar crust. Figure 2: U-Pb data for zircon and phosphate grains from impact melt fragments. A-all data; B-data used for age calculations. References: [1] Orgel C., Michael G., Fassett C. I., van der Bogert C. H., Riedel C., Kneissl T., and Hiesinger H. (2018) J. Geophys. Res. Planets 123, 748- 762. [2] Evans A. J., Andrews-Hanna J. C., Head J. W., Soderblom J. M., Solomon S. C., and Zuber M. T. (2018) J. Geophys. Planets. 123, 1596-1617. [3] Jolliff, B.L., Gillis, J.J., Haskin, L.A., Korotev, R.L. and Wieczorek, M.A. (2000) J. Geophys. Res: Planets 105, 4197-4216. [4] Haskin L. A. (1998) J. Geophys. Res. Planets 103, 1679-1689. [5] Borg L.E., Gaffney A.M., and Shearer C.K. (2015) MAPS 50, 715-732. [6] Moriarty, D.P., Watkins, R.N., Valencia, S.N., Kendall, J.D., Evans, A.J., Dygert, N. and Petro, N.E. (2021) J. Geophys. Res. Planets 126. [7] Zhu, M.H., Wünnemann, K., Potter, R.W., Kleine, T. and Morbidelli, A. (2019) J. Geophys. Res: Planets 124, 2117-2140

M D Norman↗
DOE OSTI2019

Oxygen isotopic investigation of silicic magmatism in the Stillwater caldera complex, Nevada: Generation of large-volume, low-δ 18 O rhyolitic tuffs and assessment of their regional context in the Great Basin of the western United States

Successive caldera-forming eruptions from ca. 30 to 25 Ma generated a large nested caldera complex in western Nevada that was subsequently dissected by Basin and Range extension, providing extraordinary cross-sectional views through diverse volcanic and plutonic rocks. A high-resolution oxygen isotopic study was conducted on units that represent all major parts of the Job Canyon, Louderback Mountains, Poco Canyon, and Elevenmile Canyon caldera cycles (29.2–25.1 Ma), and several Cretaceous plutons that flank the Stillwater caldera complex. We provide new oxygen and strontium isotope data for 12 additional caldera centers in the Great Basin, which are synthesized with >150 published oxygen and strontium isotope analyses for regional Mesozoic basement rocks. Stillwater zircons span a large isotopic range (δ 18 O zircon of 3.6‰–8.2‰), and all caldera cycles possess low-δ 18 O zircons. In some cases, they are a small proportion of the total populations, and in others, they dominate, such as in the low-δ 18 O rhyolitic tuffs of Job Canyon and Poco Canyon (δ 18 O zircon = 4.0‰–4.3‰; δ 18 O magma = 5.5‰–6‰). These are the first low-δ 18 O rhyolites documented in middle Cenozoic calderas of the Great Basin, adding to the global occurrence of these important magma types that fingerprint recycling of shallow crust altered by low-δ 18 O meteoric waters. The appearance of low-δ 18 O rhyolites in the Stillwater caldera complex is overprinted on a Great Basin–wide trend of miogeoclinal sediment contribution to silicic magmas that elevates δ 18 O compositions, making identification of 18 O depletions difficult. Though not a nominally low-δ 18 O rhyolite, the tuff of Elevenmile Canyon possesses both low-δ 18 O and high-δ 18 O zircon cores that are overgrown by homogenized zircon rims that approximate the bulk zircon average, pointing to batch assembly of isotopically diverse upper crustal melts to generate one of the most voluminous (2500–5000 km 3 ) tuff eruptions in the Great Basin. Despite overlapping in space and time, each caldera-forming cycle of the Stillwater complex has a unique oxygen isotope record as retained in single zircons. Most plutons that were spatially and temporally coincident with calderas have isotopic compositions that diverge from the caldera-forming tuffs and cannot be their cogenetic remnants.

58 GEOSCIENCES↗
DOE OSTI2018

Using eclogite retrogression to track the rapid exhumation of the Pliocene Papua New Guinea UHP Terrane

The D’Entrecasteaux Islands of eastern Papua New Guinea (PNG) host the youngest known ultrahigh-pressure terrane on Earth and represent the only location where ultrahigh-pressure (UHP) rocks have been exhumed in an active rift. The PNG (U)HP rocks, consisting of Pliocene eclogites, garnet amphibolites and migmatitic gneisses, are exposed in five domal structures across the Islands. Zirconium-in-rutile thermometry records peak temperatures of ~780°C from the eastern Oiatabu and nearby central Mailolo Domes, and hotter temperatures of ~825–865°C within the western Goodenough Dome. Uranium–lead (U–Pb) and trace element zircon compositions from a suite of eclogite, host gneiss, felsic dikes and pegmatite from three domes document the rapid exhumation history of the PNG UHP terrane. High-spatial resolution laser-ablation split-stream inductively coupled plasma-mass spectrometry (LASS ICP-MS) analyses of select eclogite zircons exhibit no resolvable age zoning within single crystals. The same eclogite zircons, combined with separate zircons extracted from additional eclogite, host gneiss and felsic intrusions, were subsequently analysed by high-precision U–Pb chemical-abrasion isotope-dilution thermal ionization mass spectrometry and solution ICP-MS trace element analysis (TIMS-TEA). The results record discrete tectonic events across the three domes at sub-million year timescales: (1) (re)crystallization of host gneiss within the lower crust exposed in the eastern Oiatabu Dome from c.5·7–4·5 Ma; (2) initial retrogression and local decompression melting of eclogites from the Oiatabu and Mailolo Domes at c.4·6–4·3 Ma; (3) melt crystallization of weakly deformed felsic dikes of the Oiatabu Dome at c.3·0–2·9 Ma; and (4) retrogression and melt crystallization within eclogite–amphibolite-facies rocks in the western Goodenough Dome at c.2·9–2·6 Ma. In comparison to Zr-in-rutile peak temperature estimates, Ti-in-zircon temperatures >800°C may reflect increased temperatures during exhumation that resulted in partial melting of the eclogites. Inclusions of crystallized hydrous melt consisting of Na-rich plagioclase ± K-feldspar + quartz within eclogite zircons document this process. The elevated temperatures and the presence of the polyphase inclusions are the first documentation of partial melting of the (U)HP eclogites within PNG during initial retrogression from c.4·6–4·3 Ma. Finally, overall, U–Pb zircon geochronology and geochemistry track both the timing of retrogressive overprinting within the lower-to-middle crust and final upper crustal emplacement over a relatively short span of ~2 Myr during the rapid (≥2·3 cm/yr) exhumation of the youngest known (U)HP eclogites.

58 GEOSCIENCES↗
DOE OSTI2022

Geochronology of Cambrian Sedimentary and Volcanic Rocks in the Illinois Basin: Defining the Illinois Aulacogen

The Wabash #1 well, drilled for the Wabash CarbonSAFE Project and located in Vigo County, Indiana, USA, was drilled in early 2020 as a stratigraphic test well to characterize and evaluate the basal Cambrian Mt. Simon Sandstone for carbon dioxide storage (TD=8750 ft; 2667 m). The Wabash #1 well is located along the eastern flank of a newly interpreted Cambrian aulacogen that occurs in western Indiana and eastern Illinois. Here we present 938 new detrital zircon U-Pb ages (LA-ICPMS) from early Cambrian sandstones sampled near the base of the well. A basalt lava flow was penetrated at ~8530 ft (2600 m) and has an 40 Ar/ 39 Ar age of 525.03 +/- 1.10 Ma, which represents the first known Cambrian crust in the Illinois Basin. The two sandstone samples from beneath the basalt are dominated by zircons derived from the Midcontinent Granite-Rhyolite terrane. The sandstone samples from above the basalt reflect a mixture of these locally derived Mazatzal and Granite-Rhyolite terrane zircons, but also distal Archean, Grenville, and Yavapai zircons. Each sample has small numbers of Cambrian zircons, which is consistent with those in basal Cambrian sandstones in other deep wells to the west. These early Cambrian detrital zircons and early Cambrian age of the basalt, combined with sediment thickness patterns permit the interpretation of the Illinois aulacogen, which formed during the final stage of Rodinian rifting.

58 GEOSCIENCES↗
NASA NTRSDate not supplied

TEMPERATURE CONSTRAINT OF THE MISTASTIN LAKE IMPACT STRUCTURE IMPACT MELT ROCKS

Impact melt is a product of hypervelocity cratering events formed by the instantaneous melting of near-surface target rocks. The temperatures of impact melt upon formation are believed to be superheated, vastly exceeding the liquidus temperature of igneous rocks formed via endogenic processes. However, quantitative understanding of the formation and duration of superheated temperatures remains incomplete. To date, only one datum on the hottest post-shock temperature (>2370 °C) has been derived by Timms et al. (2017) [1]. These authors studied the microstructures and crystallographic orientations preserved within a rim of vermicular ZrO2 of a zircon grain entrained within impact glass at the Mistastin Lake impact structure, Canada. Diagnostic crystallographic orientation indicated the presence of cubic zirconia, requiring a minimum temperature for the impact melt of >2370°C from the dissociation of zircon to cubic zirconia and liquid SiO2. With only one temperature datum, it cannot be stated whether the temperature of the impact melt sheet was homogenous across the entire structure or if the thermal history of the melt varied with spatial distribution. In this study, we present a preliminary investigation of 70 zircon grains, 22 of which exhibit rims of vermicular ZrO2 dissociation textures, similar to those studied by Timms et al. (2017). To acquire a more accurate temperature profile representative of impact melt, zircon crystals were collected from different types of impact melt bearing units, including additional samples of the impact glass studied by Timms et al. (2017). Of the 22 zircon grains with dissociation textures, at least 4 grains in the impact glass show diagnostic evidence of pre-existing cubic zirconia, and 1 grain from a glass-bearing breccia exhibits granular zircon textures, possible evidence of a transition from high-P to high-T conditions. These results show the heterogeneous post-shock temperature distribution of superheated impact melt within the Mistastin impact structure. [1] Timms, N.E., Erickson, T.M., Zanetti, M.R., Pearce, M.A., Cayron, C., Cavosie, A.J., Reddy, S.M., Wittmann, A. and Carpenter, P.K., 2017. Cubic zirconia in> 2370° C impact melt records Earth's hottest crust. Earth and Planetary Science Letters, 477, pp.52-58.

rock↗
NASA NTRS2024

Microstructural Evolution of the Civet Cat Norite (72255)

The ‘Civet Cat Norite’ is a ~ 2.5 cm clast within the Apollo impact melt breccia sample 72255 collected during Apollo 17 EVA 2 at Boulder 1. The norite is primarily composed of plagioclase and orthopyroxene with fine-scale exsolution lamellae of augite. The plagioclase and orthopyroxene (OPX) coexist with minor quartz and augitic clinopyroxene (CPX), and accessory apatite, baddeleyite, chromite, ilmenite, loveringite, merrillite, rutile and zircon. The major minerals range from 1 to 4 mm in size and show a cataclastic texture indicated by banding of the light and dark phases]. The chemical composition of the orthopyroxene, augitic exsolution lamellae, and exsolved oxides suggest the norite crystallized in the lower crust of the Moon (10 – 70 km depth) and was subsequently excavated by impact(s). Shock pressure estimates for the norite range from 15 – 35 GPa based on maskeleynite formation within the plagioclase, kink banding in pyroxenes, and granular recrystallization in the accessory phosphates. Previous Rb-Sr and 40 Ar/ 39 Ar analyses recalculated with modern decay constants yield relatively young ages of 4.16 ± 0.05 Ga and 3.99 ± 0.03 Ga, respectively. However, recent U-Pb analyses of some zircon grains from within the Civet Cat yield an age of 4.45 ± 0.03 Ga. While this is the oldest age for any rock recovered from the Moon, the full age spread of zircon from the Civet Cat range from ca. 4.46 to 4.02 Ga, indicating variable Pb-loss and complicating interpretation of the primary age. Recent atom probe analyses indicate minimal Pb mobilization within the oldest zircon grain from Civet Cat, supporting the interpretation that these ancient zircon ages reflect the age of the norite, rather than an apparent antiquity caused by reverse discordance. To investigate the potential antiquity and deep crustal origin of the Civet Cat norite, we have undertaken high resolution microstructural analyses of the major, minor, and accessory minerals to characterize the primary igneous textures and secondary overprinting by impact and metamorphism. The employed analytical techniques include scanning electron microscope-based electron backscatter diffraction (EBSD) analyses, electron probe microanalyzer (EPMA) chemical analyses, and transmission electron microscopy (TEM) of pyroxene, plagioclase, quartz, zircon, and phosphates.

T M Erickson↗
DOE OSTI2024

A preliminary investigation into the feasibility of laser ablation U–Pb isotope ratio measurement via all‐faraday cup detection with 10 11 ‐ and 10 13 ‐Ω amplifiers on the Neoma multicollector‐inductively coupled plasma‐mass spectrometer

Rationale Signal detection for uranium–lead (U–Pb) dating of zircon is typically performed via ion counters. Here, we develop a preliminary understanding of the strengths and limitations of faraday‐cup‐based detection. Methods A suite of zircon reference materials and the NIST‐610 glass were sampled using laser ablation followed by U–Pb isotope ratio measurement on a Neoma multicollector‐inductively coupled plasma‐mass spectrometer. Results We were able to produce geologically accurate 207 Pb/ 206 Pb, 206 Pb/ 238 U, and 207 Pb/ 235 U ratios for the NIST‐610 glass and the zircon standards, with ages ranging from ~2.5 Ga to ~337 Ma (TanBrown A, Oracle, 91550, Mud Tank, Temora, and Plešovice). Two of the younger zircon standards examined (94‐35, ~55.6 Ma, and Fish Canyon, 28.6 Ma) yielded accurate 206 Pb/ 238 U but not 207 Pb/ 235 U or 207 Pb/ 206 Pb ratios, whereas the youngest zircon standard (Penglai, ~4.4 Ma) failed for all three ratios of interest. The accuracy and precision of the all‐faraday method are directly tied to signal intensity, with reliable data capable of being produced even when both isotopes in a ratio have signals below ~0.001 V (equivalent to ~62 500 cps on an ion counter). Conclusion The all‐faraday cup multicollection method provides sufficient sensitivity to obtain geologically meaningful U–Pb data, with possible advantages being that laser pit depth‐dependent changes in the observed interelemental fractionation behavior may be easier to correct using a static collector configuration compared to when the ion beam is swept across a single detector while also removing the need for an interdetector‐type calibration. Further work is needed to refine the all‐faraday cup method (e.g., application of background subtraction and common Pb corrections, outlier removal, and interelement as well as down‐hole fractionation corrections), but our initial results demonstrate that the faraday detector method has sufficient sensitivity to warrant further study.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2023

High-Pressure Structural and Thermodynamic Properties of Cerium Orthosilicates (CeSiO 4 )

Pressure-induced phase transitions from the zircon structure-type (I4 1 /amd) to the scheelite structure type (I4 1 /a) are known for many ternary oxides systems (ABO 4 ). In this work, we present the first high-pressure study on synthetic stetindite (CeSiO 4 ) by a combination of in situ high-pressure synchrotron powder X-ray diffraction up to 36 GPa, implemented with and without dual sided laser heating, and in situ high-pressure Raman spectroscopy up to 43 GPa. Two phase transitions were identified: zircon to a high-pressure low-symmetry (HPLS) phase at 15 GPa and then to a scheelite at 18 GPa. The latter from HPLS scheelite phase was found irreversible; i.e., scheelite is fully quenchable at ambient conditions, as in other zircon-type phases. The bulk moduli (K 0 ) of stetindite, HPLS, and high-pressure scheelite phases were determined, respectively, as 171(5), 105(4), and 221(40) GPa by fitting to a second-order Birch-Murnaghan equation of state. The pressure derivatives of vibrational modes and Gru''neisen parameters of the zircon-structured polymorph are similar to those of other orthosilicate minerals. In conclusion, due to the larger ionic radii of Ce 4+ , with respect to Zr 4+ , stetindite was found to possess a softer bulk modulus and undergo the phase transitions at a lower pressure than zircon (ZrSiO 4 ), such observations are consistent with what were found in coffinite (USiO 4 ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

Early Archean tonalite gneiss in the upper peninsula of Michigan

Geochronological results on tonalite gneiss of northern Michigan that is 3.56 Ga or slightly older is presented. Tonalitic augen gneiss and structurally overlying biotite gneiss and schist are exposed in a dome near Watersmeet. They are part of an extensive gneiss terrane of southern Minnesota, Wisconsin and Michigan that includes rocks of early to late Archean ages and lies south of the Wawa volcanic subprovince. Two samples of the augen gneiss and one of the biotite gneiss show zircon grains of similar shape, zoning, color, and development of crystal faces. These zircons give Pb/U isotopic ratios that plot on a chord of 3,560 + or - 40 m.y. upper intersect and of 1,250 + or m.y. lower intersect. The 3,560 m.y. number is believed to be a minimum age because analysis of one of the least discordant zircon fractions by ion microprobe that gave a nearly concordant age of 3,650 m.y. The 1,250 m.y. lower intersect is without geological significance: it is interpreted to be a result of multiple lead loss at 2.7, 1.8, and 0.5 Ga by U/Pb in zircon. Archean rocks 10 to 25 km northwest of the Watersmeet dome give a 2.75 Ga age on zircons. Quartz monzonite here is dated at 2.65 Ga.

Peterman, Z. E.↗
NASA NTRS2018

Novel Shock Microstructures in Accessory Minerals from the Haughton Dome, Devon Island, Nunavut, Canada

The 23 km-diameter, ca. 24 Ma Haughton Dome impact structure in the Canadian Arctic on Devon Island, Nunavut (89deg41′W, 75deg22′N) occurred within a two layered target composed of a shallowly-dipping ~1700 m thick succession of Paleozoic limestones and evaporates overlying ca.1.9 Ga high grade gneisses [1, 2]. Within the structure a well preserved impact melt bearing breccia unit contains a variety of shocked clasts from the pre-impact sediments and basement gneisses [3]. Due to their high level of preservation a variety of studies have been undertaken on the clast population of the melt bearing breccia, including characterization of shock within the accessory minerals of the basement lithologies [4, 5]. This study presents high resolution electron backscatter diffraction (EBSD) microstructural data for zircon and monazite from historic samples of the basement gneiss, in which bulk shock pressures have been previously constrained based on major phases [4, 6]. Shocked zircon and monazite grains have been investigated from shock stage 1b (sample 72110), 2 (7273) and 3 (7192, Dig-9) [4, 6]. At lower shock levels zircon displays planar microstructures consistent with mechanical shock {112} twin formation [7] and deviatoric transformation to the high pressure polymorph reidite [8]. Zircon grains from shock stage three show a more chaotic microstructure with multiple orientations of tightly spaced sets of reidite that are variably recrystallized to zircon neoblasts. Monazite from lower shock stages contains a number of mechanical twin orientations that are indicative of shock deformation [9]. At higher shock pressures a lath like structure of interlocking twin orientations has been identified. This microstructure is suggestive of a reversion transformation from a high pressure polymorph [10] and is the first evidence for the transformation of monazite during shock.

Erickson, Timmons M.↗
NASA NTRSDate not supplied

Deciphering Extreme Mineral Records; Microstructural Phase Heritage of Shocked Materials

High-pressure minerals such as coesite, stishovite, and reidite are often used as indicators of shock metamorphism. However, high-pressure and high-temperature phases are metastable at ambient conditions and, therefore, often revert to a more energetically favorable phase. During solid-state transformations, the crystallographic orientations of the stable polymorph are controlled by the transformation pathway from the parent. Microstructural orientation analysis using electron backscatter diffraction (EBSD) of the stable phase can reveal systematic intercrystalline orientation relationships (OR) diagnostic of solid-state transformations from these high-pressure or high-temperature polymorph phases (Cayron et al., 2006). Knowledge of polymorph stability fields for a given system can thus be used to infer minimum shock P and/or T conditions that rocks have experienced, which are otherwise unavailable using traditional thermobarometers such as element partition coefficients. Using orientation relationships to infer the former presence of mineral phases has been termed microstructural “phase heritage”, and has successfully been used to probe for evidence of extreme pressures and temperatures resulting from hypervelocity impacts. The reconstruction of polymorphs of ZrSiO4 (zircon, reidite) and ZrO2 (baddeleyite) have further elucidated the behavior of these phases under hypervelocity impact conditions (Timms et al., 2017a; White et al., 2018), and OR analysis of shocked monazite has identified a previously unrecognized tetragonal high-P polymorph (Erickson et al., 2019). Zircon will convert to the low tetragonal polymorph reidite at shock stresses above ~21 GPa. However, upon decompression at temperatures above 1200 °C reidite will revert to zircon (Kusaba et al., 1985). Recrystallized zircon neoblasts encased in impact melt often show systematic misorientation relationships of 90° about <110> indicative of reversion from the reidite (Fig. 1), and preserving cryptic evidence of the high-P history that is often erased by the post shock thermal spike (Cavosie et al., 2016). Microstructural OR analysis of a dissociated zircon corona composed of baddeleyite (monoclinic-ZrO2) has identified the former presence of cubic zirconia within impact melt glass from the Mistastin Lake impact structure, Labrador, CA. Based on stability fields in the ZrO2-SiO2 binary phase diagram, cubic zirconia records thermal conditions in excess of 2370 °C at ambient P, indicating that the Mistastin impact melt is the hottest rock identified on Earth’s surface (Timms et al., 2017b). Shock-deformed monazite (monoclinic La,Ce,ThPO4) containing lamellae comprised of interlocking laths has been identified from the Haughton Dome impact structure, Nunavut, Canada and Nördlinger-Ries Crater, southern Germany. The lath-structured lamellae are composed of four systematic orientation variants, which OR analyses indicate originate from a tetragonal parent whereby the [010]monoclinic aligns with either [100] or [010]tetragonal (Erickson et al., 2019). These results highlight utility of microstructural phase heritage analyses for the identification of unstable high-P or high-T polymorphs that uniquely record the extremely transient shock conditions produced by hypervelocity impacts.

Timmons Erickson↗
DOE OSTI2018

Potassic, High-Silica Hadean Crust.

Understanding Hadean(>4 Ga) Earth requires knowledge of its crust. The composition of the crust and volatiles migrating through it directly influence the makeup of the atmosphere, the composition of seawater, and nutrient availability. Despite its importance, there is little known and less agreed upon regarding the nature of the Hadean crust. By analyzing the Sr-87/Sr-86 ratio of apatite inclusions in Archean zircons from Nuvvuagittuq, Canada, we show that its protolith had formed a high (>1) Rb/Sr ratio reservoir by at least 4.2 Ga. This result implies that the early crust had a broad range of igneous rocks, extending from mafic to highly silicic compositions

early Earth↗
DOE OSTI2016

Blue and red up-conversion light emission in TM-doped A 2 B 2 O 7 oxides

The crystal structure and light emission property of Yb/Tm doped gadolinium titanate and gadolinium zirconate with chemical composition of A 2 B 2 O 7 were studied by x-ray diffraction (XRD) and optical spectroscopy measurements, respectively. XRD results suggest that the rare earth titanates have an ordered pyrochlore structure and a defect-fluorite structure for the zirconates. Photoluminescence activated with 1064 nm infrared laser light shows different light emission behaviors for the titanate and zirconate samples, which is related to the different site occupancy of Tm 3+ in the lattice of the samples. Only a weak near-infrared (NIR) (~800 nm) light emission was observed in the titanate samples while a strong blue and red up-conversion emission was detected in the Tm 3+ -doped zirconate samples. As a result, the strong blue and red emission is due to the 7-fold coordinated Tm 3+ in the structure.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Thermodynamics of CeSiO 4 : Implications for Actinide Orthosilicates

Zircon (ZrSiO 4 : I4 1 /amd) can accommodate actinides, such as thorium, uranium, and plutonium. The zircon structure has been determined for several of the end member compositions of other actinides, such as plutonium and neptunium. However, the thermodynamic properties of these actinide zircon structure-types are largely unknown due to the difficulties in synthesizing these materials and handling transuranium actinides. Thus, we have completed a thermodynamic study of cerium orthosilicate, stetindite (CeSiO 4 ), a surrogate of PuSiO 4 . For the first time, the standard enthalpy of formation of CeSiO 4 was obtained by high temperature oxide melt solution calorimetry to be -1971.9 ± 3.6 kJ/mol. Stetindite is energetically metastable with respect to CeO 2 and SiO 2 by 27.5 ± 3.1 kJ/mol. The metastability explains the rarity of the natural occurrence of stetindite and the difficulty of its synthesis. Applying the obtained enthalpy of formation of CeSiO 4 from this work, along with those previously reported for USiO 4 and ThSiO 4 , we developed an empirical energetic relation for actinide orthosilicates. Here, the predicted enthalpies of formation of AnSiO 4 are then made with a discussion of future strategies to efficiently immobilize Pu or minor actinides in the zircon structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1985

Chemical constraints on the evolution of Archean continental crust

One of the challenges of Archean geochronology is to find isotopic systems that preserve an indication of a rock's primary age in spite of the effects of later metamorphism. Zircon dating has been used widely with considerable success but not without difficulty, especially in polymetamorphic terrains. Zircons in such cases commonly are found to have lost radiogenic Pb, and despite fractionizing the zircons or abrading them to remove disturbed portions; it often is not possible to define a pattern of Pb loss from which the original age can confidently be inferred. The refinement of techniques to enable extremely small samples, or even single crystals, to be analyzed has contributed greatly to solving the problem but even those techniques cannot resolve the micron scale isotopic heterogeneities within single zircons in which much of their history is recorded. That can only be done by ion microprobe. Progress reports on studies of four Archean rocks, each of which illustrates the power and potential of ion microprobe analysis in solving problems of Archean geochronology are discussed.

Weaver, B. L.↗
DOE OSTI2016

Oxygen isotope evolution of the Lake Owyhee volcanic field, Oregon, and implications for the low-δ 18 O magmatism of the Snake River Plain–Yellowstone hotspot and other low-δ 18 O large igneous provinces

The Snake River Plain–Yellowstone (SRP-Y) hotspot track represents the largest known low-δ 18 O igneous province; however, debate persists regarding the timing and distribution of meteoric hydrothermal alteration and subsequent melting/assimilation relative to hotspot magmatism. To further constrain alteration relations for SRP-Y low-δ 18 O magmatism, we present in situ δ 18 O and U–Pb analyses of zircon, and laser fluorination δ 18 O analyses of phenocrysts, from the Lake Owyhee volcanic field (LOVF) of east-central Oregon. U–Pb data place LOVF magmatism between 16.3 and 15.4 Ma, and contain no evidence for xenocrystic zircon. LOVF δ 18 O(Zrc) values demonstrate (1) both low-δ 18 O and high-δ 18 O caldera-forming and pre-/post-caldera magmas, (2) relative increases in δ 18 O between low-δ 18 O caldera-forming and post-caldera units, and (3) low-δ 18 O magmatism associated with extension of the Oregon-Idaho Graben. The new data, along with new compilations of (1) in situ zircon δ 18 O data for the SRP-Y, and (2) regional δ 18 O(WR) and δ 18 O(magma) patterns, further constrain the thermal and structural associations for hydrothermal alteration in the SRP-Y. Models for low-δ 18 O magmatism must be compatible with (1) δ 18 O(magma) trends within individual SRP-Y eruptive centers, (2) along axis trends in δ 18 O(magma), and (3) the high concentration of low-δ 18 O magmas relative to the surrounding regions. When considered with the structural and thermal evolution of the SRP-Y, these constraints support low-δ 18 O magma genesis originating from syn-hotspot meteoric hydrothermal alteration, driven by hotspot-derived thermal fluxes superimposed on extensional tectonics. Lastly, this model is not restricted to continental hotspot settings and may apply to several other low-δ 18 O igneous provinces with similar thermal and structural associations.

58 GEOSCIENCES↗
DOE OSTI2015

Energetics of bismuth vanadate

Bismuth vanadate has gained considerable interest as a photoanode for water splitting reactions under visible light. It exists in four different polymorphs, out of which three of them have been synthesized. Thermodynamic properties of these three polymorphs are investigated using high temperature oxide melt solution calorimetry. The monoclinic scheelite phase which exhibits photocatalytic activity under visible light is found to be the most stable polymorph, followed by tetragonal scheelite which exhibits activity under UV light. The photocatalytically inactive tetragonal zircon form is found to be the least stable polymorph. The small difference in enthalpy of formation between the two scheelite structures (−8 kJ/mol) is in accord with the reversibility of the transformation between them and the larger difference between the most stable monoclinic phase and the least stable tetragonal zircon phase (−23 kJ/mol) is in accord with the irreversible (monoclinic→tetragonal zircon) phase transformation. - Graphical abstract: Schematic representation of polymorphic transitions in BiVO{sub 4} along with their formation enthalpies. - Highlights: • Bismuth vanadate crystallizes in three different polymorphs. • High temperature calorimetric measurements were made to determine their formation enthalpies. • Enthalpy of formation decreases in the order BV-ms→BV-ts→BV-tz. • Photocatalytically active monoclinic-BiVO{sub 4} was found to be the most stable polymorph.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗