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The Zircon-Reidite Shock Transformation: A Tem Study of Reidite Produced at A Newly Established 21.2 GPa Shock Pressure Threshold

The high-pressure polymorph of zircon (Zr2SiO4) is reidite, a phase with the scheelite structure that was first discovered to form at ca. 12 GPa in static high-pressure experiments [1]. Reidite was subsequently found to occur in naturally shocked zircons from several terrestrial impact localities [2,3], as well as in shock recovery-reverberation experiments performed above 20 GPa [4]. The nature and distribution of reidite occurrences in terrestrial impact localities has pointed to its potential use as a shock pressure indicator, as well as to the importance of understanding its age-reset effects in zircon geochronology [3]. In this study we have used coordinated SEM/Electron Backscatter Diffraction (EBSD) and Field-Emission Scanning Transmission Electron Microscopy (FE-STEM) to study the micro- and nanostructure of reidite and its shocked zircon host produced at 21.2 GPa under experimental shock recovery/reverberation conditions [5]. Our results document the TEM microstructure of reidite formed at a 21.2 GPa experimental shock pressure that is significantly lower than that observed in previous studies [4]. At these conditions the sample developed a diverse set of microstructures that have not been previously documented on the TEM scale.

shock metamorphism↗

Microstructural Changes and Pb Mobility During the Zircon to Reidite Transformation: Implications for Planetary Impact Chronology

Impact events modify and leave behind a complex history of rock metamorphism on terrestrial planets. Evidence for an impact event may be recorded in physical changes to minerals, such as mineral deformation and formation of high P-T polymorphs, but also in the form of chemical fingerprints, such as enhanced elemental diffusion and isotopic mixing. Here we explore laboratory shock-induced physical and chemical changes to zircon and feldspar, the former of which is of interest because its trace elements abundances and isotope ratios are used extensively in geochemistry and geochronology. To this end, a granular mixture of Bishop Tuff sanidine and Kuehl Lake zircon, both with well characterized Pb isotope compositions, was prepared and then shocked via a flat plate accelerator. The peak pressure of the experiment, as calculated by the impedance matching method, was ~24 GPa although a broader range of P-T conditions is anticipated due to starting sample porosity. Unshocked and shocked materials were characterized via scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), and Raman spectroscopy. These methods show that the starting zircon material had abundant metamict regions, and the conversion of the feldspar to glass in the post-shock material. Analyses of the shocked product also yielded multiple occurrences of the high-pressure ZrSiO 4 polymorph reidite, with some domains up to 300 μm across. The possibility of U-Pb system disturbance was evaluated via laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and secondary ion mass spectrometry (SIMS). The isotopic data reveal that disturbance of the U-Pb geochronometer in the reidite was minimal (<2% for the main U-Pb geochronometers). To better constrain the P-T conditions during the shock experiment, we complement impedance matching pressure calculations with iSALE2D impact simulations. The simulated results yield a range of P-T conditions experienced during the experiment and show that much of the sample may have reached >30 GPa, which is consistent with formation of reidite. In the recovered shocked material, we identified lamellae of reidite, some of which interlock with zircon lamellae. Reidite {112} twins were identified, which we interpret to have formed to reduce stress between the crystal structure of the host zircon and reidite. These two findings support the interpretation that shear transformation enabled the transition of zircon to reidite. The size and presence of reidite found here indicate that this phase is probably common in impact-shocked crustal rocks that experienced ~25 to ~35 GPa, especially when the target material has porosity. Additionally, shock loading of the zircon and transformation to reidite at these pressures in porous materials is unlikely to significantly disturb the U-Pb system in zircon and that the reidite inherits the primary U and Pb elemental and isotopic ratios from the zircon.

Bishop Tuff↗

Zircon, Baddeleyite, and Reidite Found in Ries Crater Suevite

Introduction: Impact events can generate superheated impact melts and even vapor [1]. In the past decade, evidence of the high temperatures and high pressures of the impact process has been found in the impact melt from terrestrial craters (e.g., Mistastin Lake [2], Meteor Crater [3]) and even on the Moon [4–5]. Often, these studies involve zircon or zirconium-bearing phases. Zircon is a particularly useful mineral, due to its robustness and durability against weathering. It is used principally for chronology, but it has a multitude of geologic applications, including geothermometry and fingerprinting magma sources. Here we focus on its capability of recording impact conditions. Grains of zircon (ZrSiO4) are converted at high temperature and/or pressure during an impact event to reidite (a high-pressure polymorph of ZrSiO4) or to tetragonal-ZrO2 + SiO2 [6]. Reidite and tertragonal-ZrO2 leave identifying relicts in the rocks, markers of the high pressures and/or temperatures these rocks underwent. Ries Crater is a 26-km-diameter peak ring crater in southern Germany that formed approximately 15 Ma [7–9]. Ries is the type locality of the polymict impact breccia known as suevite. Here, we report a microanalytical study of suevite from the Ries impact structure. These analyses are used to inform our understanding of the pressure and temperature conditions involved in creating a polymict impact breccia such as suevite in a peak ring crater. Sample Description: The sample, denoted 16RS08, originates from Otting Quarry, at 48.8777° N, 10.7921° E, approximately 17 km from the center of the Ries Crater in Germany (approximately 4 km outside the crater rim). The material recorded in sample 16RS08 is therefore considered an outer suevite. The outer suevite is a discontinuous layer of polymict impact breccia that occurs outside the central ring of Ries, up to 22 km from the center of the crater [9]. Lithic clasts in the outer suevite consist primarily of crystalline basement rocks (gneiss, granite, amphibolite), with less than 5% of lithic clasts being overlying sedimentary rocks (limestone, sandstone, shale) [9]. The thin section studied contains variably shocked lithic and mineral clasts, impact glass, and interstitial minerals that make up the matrix of the breccia (Fig. 1) [9]. Methods: We used a Cameca SX100 electron probe microanalyzer (EPMA) located in the Kuiper Materials Imaging and Characterization Facility (KMICF) at the University of Arizona to obtain 15 elemental X-ray maps of 16RS08. We next used the JEOL 7900F SEM at the Astromaterials Research & Exploration Science (ARES) at NASA Johnson Space Center (JSC) to obtain electron backscatter diffraction (EBSD) maps and energy dispersive X-ray spectroscopy (EDS) maps of select portions of the section. The EBSD data were collected under beam conditions of 20 kV, and ~9 μA, with step sizes varying from 0.05 to 2 μm. Following EBSD data collection, we processed the data using AZtecCrystal and MTEX, a free MATLAB toolbox. Results: We used the elemental X-ray maps to identify the areas of interest in the section, particularly phosphates and Zr-bearing grains. These areas of interest were then targeted for follow up EBSD and EDS analyses. We have identified, through combined EBSD and EDS analysis, the presence of zircon, reidite, and monoclinic-ZrO2 (baddeleyite) in 16RS08. In 16RS08, we have found singular grains of zircon, zircon with a vermicular baddeleyite halo (Fig. 2a), and granular zircon with reidite (Fig. 2b). The different Zr-rich phases and their corresponding textures signifies that this sample underwent a broad spectrum of pressure and temperature conditions during the impact event. For example, zircons surrounded by a vermicular baddeleyite and SiO2 intergrowth (i.e., Fig. 2a) have been shown to preserve evidence of the extremely high temperatures of impact melt, upwards of 2370 °C [2, 6]. Similarly, reidite and granular zircon (i.e., Fig. 2b) have been shown to preserve evidence of high pressure, as the transition to reidite occurs >30 GPa [3, 6]. Future Work: Next, we will process the EBSD and EDS data for these Zr-rich grains, specifically looking for indicators of cubic- or tetragonal-ZrO2 in the baddeleyite remnants and of shock-precursors to the reidite. To further inform our work, we will also obtain BSE images of these grains using a Hitachi S-4800 SEM in KMICF at the University of Arizona, as well as geochemical spot analyses via EPMA. The data collected will be used to constrain the formation conditions of the Ries Crater outer suevite. Acknowledgments: We thank Ken Domanik and Jerry Chang for their support with data collection. This work was supported by a University of Arizona RII Core Facilities Pilot Program grant and start-up funds to JJB. TME thanks A. Cavosie and N. Timms for assistance during field sampling. We acknowledge support from NASA’s Planetary Science Research program for analysis performed at JSC. References: [1] Melosh H. J. (1989) Oxf. U. Press. [2] Timms et al. (2017) EPSL 477, 52–58. [3] Cavosie et al. (2016) Geology 44:9, 703–706. [4] White et al. (2020) Nature Astr. 4, 974–978. [5] Crow C. A. et al. (2017) GCA 202, 264–284. [6] Timms et al. (2017) Earth-Sci. Rev. 165, 185–202. [7] Schmieder M. et al. (2018) GCA 220, 146–157. [8] Schwarz W. H. et al. (2020) M&PS 55:2, 312–325. [9] Stöffler et al. (2013) M&PS 43:4, 515–589.

Zircon↗

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↗

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.↗

Shock Deformation in Zircon, a Comparison of Results from Shock-Reverberation and Single-Shock Experiments

The utility of the mineral zircon, ZrSiO4, as a shock-metamorphic geobarometer and geochronometer, has been steadily growing within the planetary science community. Zircon is an accessory phase found in many terrestrial rock types, lunar samples, lunar meteorites, martian meteorites and various other achondrites. Because zircon is refractory and has a high closure temperature for Pb diffusion, it has been used to determine the ages of some of the oldest material on Earth and elsewhere in the Solar System. Furthermore, major (O) and trace-element (REE, Ti, Hf) abundances and isotope compositions of zircon help characterize the petrogenetic environments and sources from which they crystallized. The response of zircon to impact-induced shock deformation is predominantly crystallographic, including dislocation creep and the formation of planar and sub-planar, low-angle grain boundaries; the formation of mechanical {112} twins; transformation to the high pressure polymorph reidite; the development of polycrystalline microtextures; and dissociation to the oxide constituents SiO2 and ZrO2. Shock microstructures can also variably affect the U- Pb isotope systematics of zircon and, in some instances, be used to constrain the impact age. While numerous studies have characterized shock deformation in zircon recovered from a variety of terrestrial impact craters and ejecta deposits and Apollo samples, experimental studies of shock deformation in zircon are limited to a handful of examples in the literature. In addition, the formation conditions (e.g., P, T) of various shock microstructures, such as planar-deformation bands, twins, and reidite lamellae, remain poorly con-strained. Furthermore, previous shocked-zircon experimental charges have not been analyzed using modern analytical equipment. This study will therefore under-take an new set of zircon shock experiments, which will then be microstructurally characterized using state-of-the-art instrumentation within the Astromaterials Research and Exploration Science Division (ARES), NASA Johnson Space Center.

Erickon, T. M.↗

Spatial U-Pb Age Distribution in Shock-Recrystallized Zircon – A Case Study from the Rochechouart Impact Structure, France

Age determination of impact structures via the zircon U–Pb system remains challenging and often ambiguous due to highly variable effects of shock metamorphism on U-Pb geochronology. It is, therefore, crucial to link the observed zircon microtextures, including their temperature and pressure conditions associated with their formation, directly to the U–Pb ages preserved. Here, we analyzed three recrystallized zircon grains and one plastically deformed zircon crystal from the medium-sized Rochechouart impact structure in the northwestern Massif Central of France. For the Rochechouart impact structure the impact age (206.92 ± 0.32 Ma [40Ar/39Ar]) as well as the 2 tectono-themal history is well established making this study site ideal to test concepts about U-Pb systematics in shocked zircon and to differentiate between shock-driven age resetting and preimpact crystallization and metamorphic overprinting. Zircon microstructures were studied using scanning electron imaging, cathodoluminescence imaging, and electron backscatter diffraction (EBSD) mapping. Further, we conducted U–Pb Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) depth-profiling analysis, allowing us to interpret the resultant age data in discrete steps with increasing ablation time/depth. The U–Pb depth profiling data demonstrate that plastically strained grains are incompletely reset and preserve rim and interior age domains reflecting typical pre-impact (pre-Variscan and Variscan) regional tectonic ages. Our results also reveal that the granular crystals encountered contain microstructural evidence for “former reidite in granular neoblastic” (FRIGN) zircon, reflecting both high-pressure (⩾30GPa) and high temperature (⩾1200℃) conditions. This signifies that FRIGN zircon is now known from an additional, medium sized, impact structure further supporting the hypothesis that this impact induced microstructure is commonly preserved. In addition, FRIGN zircon has a high potential to preserve completely impact-reset crystal domains (~204 to 207 Ma) that can be identified by our combined analytical approach of U–Pb depth profiling and EBSD mapping, and thus are suitable for determining reliable impact ages

U-Pb depth profiling↗

Discovery of coesite and shocked quartz associated with the upper Eocene cpx spherule layer

At least two major impact ejecta layers have been discovered in upper Eocene strata. The upper layer is the North American microtektite layer. lt consists tektite fragments, microtektites, and shocked mineral grains (e.g., quartz and feldspar with multiple sets of PDFs, coesite and reidite (a high-pressure polymorph of zircon)). The slightly older layer contains clinopyroxene-bearing (cpx) spherules and microtektites associated with an Ir anomaly. The North American tektite layer may be derived from the Chesapeake Bay impact structure, and the cpx spherule layer may from the Popigai impact crater. A cpx spherule layer associated with a positive Ir anomaly was recently found at ODP Site 709, western Indian Ocean. A large sample (Hole 709C, core 31, section 4, 145-150 cm), originally used for a study of interstitial water by shipboard scientists, was acquired for the purpose of recovering a large number of spherules for various petrographic and geochemical studies. A split of the sample (50.35 g) was disaggregated and wet-sieved. More than 17,000 cpx spherules and several hundred microtektites (larger than 125 microns) were recovered from the sample. Rare white opaque grains were observed in the 125-250 micron size fraction after removal of the carbonate component using dilute HCI. Seven of the white opaque grains were X-rayed using a Gandolfi camera and six were found to be coesite (probably mixed with lechatelierite). Eighty translucent colorless grains from the 63-125 micron size fraction were studied with a petrographic microscope. Four of the grains exhibit one to two sets of planar deformation features (PDFs). The only other possible known occurrence of shocked minerals associated with the cpx spherule layer is at Massignano, Italy, where pancake-shaped clay spherules (thought to be diagenetically altered cpx spherules are associated with a positive Ir anomaly and Ni- rich spinel crystals. Shocked quartz grains with multiple sets of PDFs also occur at this site. Until now, unmelted impact ejecta have not been found associated with the cpx spherules at any of the other 20 sites around the world and this is the first time that coesite has been found associated with the cpx spherule layer. The discovery of coesite and shocked quartz associated with the cpx spherules at Site 709 in Indian Ocean is further evidence for the impact origin of the cpx spherule layer. We hope that future discovery of other unmelted minerals from this sample may provide materials to establish constraints on the provenance of this late Eocene ejecta.

Liu, S.↗

Where are the Shocked Grains in the Hadean Zircon Record? Insights on the Preservation of Shocked Zircon and Their U-Pb Systematics

While the earliest history of many planetary bodies within the inner Solar System is dominated by intense bombardment, this record is missing from Earth due to active tectonics and erosion. Where-as rocks from the earliest history of Earth are absent, mineral relics, such as ancient detrital zircon concentrated in sediments within the Jack Hills, Narryer, Illara and Maynard Hills greenstone belts of the Yilgarn Craton in Western Australia preserve a record of this time.Shock in zircon: During shock deformation, resulting from hyper-velocity impact, zircon can be modified in crystallographically-controlled ways. This includes the development of planar and subplanar low-angle grain boundaries, the formation of mechanical twins, transformation to the high pressure polymorph reidite, development of polycrystalline microtexture, and dissociation to its dioxide constituents SiO2 and ZrO2.

Erickson, T. M.↗

A Diversity of Temperature and Pressure Conditions Recorded by Zircon within Suevite from Ries Crater, Germany

The temperature and pressure conditions experienced by rocks during an impact event can be constrained using petrologic and microstructural analysis and is crucial to providing ground truth to the impact cratering process. Suevite is a polymict, impact melt-bearing breccia, specific to Ries crater in Germany. There are competing models for suevite formation and emplacement, such as clastic flows pushed out of the crater rim or ejecta plume fallback. Knowledge of the temperature and pressure pathways recorded by grains within the suevite can help distinguish between these and other models. The accessory phase zircon (ZrSiO4) and its high-pressure polymorph reidite are particularly useful in such circumstances as they are highly refractory minerals that can record the high-temperature and/or high-pressure conditions of an impact event. Here we present evidence for a wide array of temperature and pressure conditions recorded in zircon grains within a single thin section of suevite. Zircons in this study range from unshocked to highly shocked (>53 GPa), and record temperatures more than 1673 °C. These findings confirm previous studies concluding that suevites contain material exposed to very diverse pressure and temperature conditions during initial shock compression and excavation but do not, as a whole, experience extreme temperatures (>1673 °C) or pressures (>30 GPa).

mineralogy↗