Nonstoichiometry and Li-ion transport in lithium zirconate: The role of oxygen vacancies
Abstract not provided
Zhan, Xiaowen↗
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Evaluating the paleomagnetic potential of single zircon crystals using the Bishop Tuff
We report zircon crystals offer a unique combination of suitability for high-precision radiometric dating and high resistance to alteration. Paleomagnetic experiments on ancient zircons may potentially constrain the history of the earliest geodynamo, which would hold broad implications for the early Earth's interior and atmosphere. However, the ability of zircons to record accurately the geomagnetic field has not been demonstrated. Here we conduct thermal and alternating field (AF) paleointensity experiments on 767.1 thousand year old (ka) zircons from the Bishop Tuff, California. The rapid emplacement of these zircons in a well-characterized magnetic field provides a high-fidelity test of the zircons' intrinsic paleomagnetic recording accuracy. Successful dual heating experiments on eleven zircons measured using a superconducting quantum interference device (SQUID) microscope yield a mean paleointensity of (1σ; after excluding possible maghemite-bearing zircons), which is consistent with high-precision results from Bishop Tuff whole rock (). High-resolution quantum diamond magnetic (QDM) mapping, electron microscopy, and X-ray tomography indicate that the bulk of the remanent magnetization in Bishop Tuff zircons is carried by Fe oxides associated with apatite inclusions, which may be susceptible to destruction via metamorphism and aqueous alteration in older zircons. As such, while zircons can reliably record the geomagnetic field, robust zircon-derived paleomagnetic results require careful characterization of the ferromagnetic carrier and demonstration of their occurrence in primary inclusions. We further conclude that a combination of quantum diamond magnetometry and high-resolution imaging can provide detailed, direct characterization of the ferromagnetic mineralogy of geological samples.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Detrital Shocked Zircon Provides First Radiometric Age Constraint of <1472 Ma for the Santa Fe Impact Structure, New Mexico, USA
Impact structures are prone to erosion, burial and tectonic deformation. The Santa Fe impact structure in New Mexico contains shatter cones and shocked quartz, but is highly tectonized and eroded; estimates of the impact age (1200-300 Ma) and size (6-13 km) are poorly constrained. Here we report the first occurrence of shock-twinned zircon identified both in modern sediments and bedrock at the Santa Fe impact structure. Zircon {112} twin lamellae are considered diagnostic evidence of shock deformation and have been identified at several impact structures including Vredefort, Sudbury, Ries, Rock Elm, and in lunar impact breccia. A total of 6619 grains from fifteen sediment samples and two rock samples were surveyed; seven shocked grains were identified (7/6619 = 0.1%). One shocked zircon was identified in a biotite schist shatter cone. Five of seven shocked zircon grains were EBSD mapped; three were analyzed with multiple SIMS spots. EBSD mapping revealed {112} deformation twin lamellae in each of the five zircon grains. U-Pb geochronology for three of the shocked zircon grains yield crystallization ages from 1715+/-22 to 1472+/-35 Ma. LA-ICPMS U-Th-Pb analysis of detrital zircon grains from five samples yielded Paleoproterozoic (1800-1600 Ma) and Mesoproterozoic (1500-1300 Ma) ages. We reveal the first confirmed shocked zircon at the Santa Fe structure. Zircon is the third shocked mineral identified at this site, in addition to xenotime and quartz]; the {112} twin lamellae indicate that exposed bedrock may have experienced shock pressures up to ~20 GPa. The 1472+/-35 Ma age determined from a shock-twinned zircon is the first reliable maximum impact age constraint based on analysis of shocked material and extends the window for the Santa Fe impact event into the Mesoproterozoic.
Montalvo, Pedro E.↗
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.↗
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↗
Quantifying the effect of late bombardment on terrestrial zircons
The first 500 million years of Earth history is thought to be a period of intense planetary bombardment, but the timing and flux of this meteorite bombardment is poorly understood. In particular, on the basis of an inferred lunar impact history, some workers have hypothesized a ~3.9 Ga terminal cataclysm (TC) in which there was marked increase in the impact flux affecting the Moon, the Earth and possibly other terrestrial planets. Minerals that survived this enigmatic period offer a way to test early planetary bombardment models as they may contain telltale micro- to nanoscale shock features. Here, we present results from a numerical modeling calculation that assesses the probability that a zircon residing in the crust would escape shock melting or shock deformation during a TC bombardment event. Even with conservative pressure estimates for zircon shock deformation and intermediate bombardment intensities, we find that only ~6% of ≥4.0 Ga crust would be expected to survive a 3.9 Ga cataclysm without experiencing either complete melting or zircon shock metamorphism. In this study, we couple this modeling with a search for shock effects in the oldest zircons from the Acasta Gneiss Complex, which would have been present in the Earth's crust during a putative 3.9 Ga TC. Spatially correlated electron and NanoSIMS ion microscopy of 4.02 Ga igneous zircons from Acasta reveals no evidence of ancient shock. These data, together with similar results from other Hadean zircon suites, confirm that a post-Hadean TC is unlikely to have occurred. We suggest that the dearth of pre-3.9 Ga terrestrial crust and zircons is instead best explained by endogenic processes related to the mechanisms of early crust formation. Our modeling allows us to evaluate bombardment scenarios from the terrestrial zircon record by applying probabilistic interpretations to zircon shock deformation data. This approach will be valuable for other planetary bodies, allowing broader conclusions to be drawn from geographically limited datasets.
58 GEOSCIENCES↗
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↗
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↗
Zircon age-temperature-compositional spectra in plutonic rocks
We present that geochronology can resolve dispersed zircon dates in plutonic rocks when magma cooling time scales exceed the temporal precision of individual U-Pb analyses; such age heterogeneity may indicate protracted crystallization between the temperatures of zircon saturation (T sat ) and rock solidification (T solid ). Diffusive growth models predict asymmetric distributions of zircon dates and crystallization temperatures in a cooling magma, with volumetrically abundant old, hot crystallization at T sat decreasing continuously to volumetrically minor young, cold crystallization at T solid . We present integrated geochronological and geochemical data from Bergell Intrusion tonalites (Central Alps, Europe) that document zircon compositional change over hundreds of thousands of years at the hand-sample scale, indicating melt compositional evolution during solidification. Ti-in-zircon thermometry, crystallization simulation using MELTS software, and U-Pb dates produce zircon mass-temperature-time distributions that are in excellent agreement with zircon growth models. In conclusion, these findings provide the first quantitative validation of longstanding expectations from zircon saturation theory by direct geochronological investigation, underscoring zircon’s capacity to quantify supersolidus cooling rates in magmas and resolve dynamic differentiation histories in the plutonic rock record.
58 GEOSCIENCES↗
Stepwise chemical abrasion–isotope dilution–thermal ionization mass spectrometry with trace element analysis of microfractured Hadean zircon
Abstract. The Hadean Jack Hills zircons represent the oldest known terrestrial material, providing a unique and truly direct record of Hadean Earth history. This zircon population has been extensively studied via high-spatial-resolution high-throughput in situ isotopic and elemental analysis techniques, such as secondary ionization mass spectrometry (SIMS), but not by comparatively destructive, high-temporal-precision (<0.05 % two-sigma) thermal ionization mass spectrometry (TIMS). In order to better understand the lead loss and alteration history of terrestrial Hadean zircons, we conduct stepwise chemical abrasion–isotope dilution–thermal ionization mass spectrometry with trace element analysis (CA-ID-TIMS-TEA) on manually microfractured Hadean Jack Hills zircon fragments previously dated by SIMS. We conducted three successive HF leaching steps on each individual zircon fragment, followed by column chromatography to isolate U–Pb and trace element fractions. Following isotopic and elemental analysis, the result is an independent age and trace element composition for each leachate of each zircon fragment. We observe ~50 Myr of age heterogeneity in concordant residues from a single zircon grain, along with a protracted history of post-Hadean Pb loss with at least two modes circa ~0 and 2–4 Ga. Meanwhile, stepwise leachate trace element chemistry reveals enrichments of light rare earth elements, uranium, thorium, and radiogenic lead in early leached domains relative to the zircon residue. In addition to confirming the efficacy of the LREE-I alteration index and providing new insight into the mechanism of chemical abrasion, the interpretation and reconciliation of these results suggest that Pb loss is largely driven by low-temperature aqueous recrystallization and that regional thermal events may act to halt – not initiate – Pb loss from metamict domains in the Hadean Jack Hills zircons.
Brenhin Keller, C. (ORCID:0000000174009428)↗
Role of zircon in tracing crustal growth and recycling
Single crystal ion probe ages of zircons is discussed, which allow much better time resolution compared to other geochronological methods, although the technique is not without problems. Rocks from two areas that contain composite zircon populations, including true magmatic zircons as well as a variety of xenocrystic types are described. It is often difficult to distinguish these; xenocrystic zircons, for example, cannot always be identified on the basis of morphology alone. Additional evidence is needed before making age interpretations. Evidence is also presented of zircon growth long after the original time of crystallization, in some cases apparently at temperatures less than 300 C. The spectacular discovery of 4.1 to 4.2 Ga detrital zircons in metaquartzites from the Mount Narryer area of Western Australia is described. Similar zircons with ages as old as 4276 Ma have been found in the nearby Jack Hills area. The source areas or parent lithologies of these zircons have not yet been determined, but the author expects that they may be unrecognized or buried antecedents of the K rich Narryer gneisses. U or Th concentrations of zircon cannot be used to discriminate between felsic and mafic source rocks.
Compston, W.↗
U-Pb isotopic results for single shocked and polycrystalline zircons record 550-65.5-Ma ages for a K-T target site and 2700-1850-Ma ages for the Sudbury impact event
The refractory mineral zircon develops distinct morphological features during shock metamorphism and retains these features under conditions that would anneal them in other minerals. In addition, weakly shocked zircon grains give primary ages for the impact site, while highly reconstituted (polycrystalline) single grains give ages that approach the age of the impact event. Data for a series of originally coeval grains will define a mixing line that gives both of these ages providing that no subsequent geological disturbances have overprinted the isotopic systematics. In this study, we have shown that the three zircon grain types described by Bohor, from both K-T distal ejecta (Fireball layer, Raton Basin, Colorado) and the Onaping Formation, represent a progressive increase in impact-related morphological change that coincides with a progressive increase in isotopic resetting in zircons from the ejecta and basement rocks. Unshocked grains are least affected by isotopic resetting while polycrystalline grains are most affected. U-Pb isotopic results for 12 of 14 single zircon grains from the Fireball layer plot on or close to a line recording a primary age of 550 +/- 10 Ma and a secondary age of 65.5 +/- 3 Ma. Data for the least and most shocked grains plot closest to the primary and secondary ages respectively. The two other grains each give ages between 300 and 350 Ma. This implies that the target ejecta was dominated by 550-Ma rocks and that the recrystallization features of the zircon were superimposed during the impact event at 65.5 Ma. A predominant age of 550 Ma for zircons from the Fireball layer provides an excellent opportunity to identify the impact site and to test the hypothesis that multiple impacts occurred at this time. A volcanic origin for the Fireball layer is ruled out by shock-related morphological changes in zircon and the fact that the least shocked grains are old. Basement Levack gneisses north of the Sudbury structure have a primary age of 2711 Ma. Data for three single zircons from this rock, which record a progressive increase in shock features, are displaced 24, 36, and 45 percent along a Pb-loss line toward the 1850 +/- 1 Ma minimum age for the impact as defined by the age of the norite. Southeast of the structure three shocked grains from the Murray granite record a primary age of 2468 Ma and are displaced 24, 41, and 56 percent toward the 1853 +/- 4 Ma even as defined by coexisting titanite.
Krogh, T. E.↗
A stochastic sampling approach to zircon eruption age interpretation
The accessory mineral zircon is widely used to constrain the timing of igneous processes such as magma crystallisation or eruption. However, zircon U-Pb ages record zircon crystallisation, which is not an instantaneous process. Zircon saturation calculations link zircon crystallisation, temperature, and melt fraction, allowing for the estimation of zircon crystallisation distributions as a function of time or temperature. Such distributions provide valuable prior information, enabling Bayesian estimates of magma eruption time and allowing for comparison of the relative accuracy of common weighted-mean and youngest-zircon age interpretations with synthetic datasets. We find that both traditional interpretations carry a risk of underestimating the uncertainty in eruption age; a low mean square of weighted deviates (MSWD) does not guarantee the accuracy of weighted-mean interpretations. In the absence of independent confirmation that crystallisation timescale is short relative to analytical uncertainties, a Bayesian approach frequently provides the most accurate results and is least likely to underestimate uncertainty. Finally, since U-Pb zircon studies now routinely resolve geological age dispersion due to increasing analytical precision, such considerations are increasingly critical to future progress in resolving rates and dates of Earth processes.
58 GEOSCIENCES↗
The internal structure and geodynamics of Mars inferred from a 4.2-Gyr zircon record
Combining U–Pb ages with Lu–Hf data in zircon provides insights into the magmatic history of rocky planets. The Northwest Africa (NWA) 7034/7533 meteorites are samples of the southern highlands of Mars containing zircon with ages as old as 4476.3 ± 0.9 Ma, interpreted to reflect reworking of the primordial Martian crust by impacts. We extracted a statistically significant zircon population (n= 57) from NWA 7533 that defines a temporal record spanning 4.2 Gyr. Ancient zircons record ages from 4485.5 ± 2.2 Ma to 4331.0 ± 1.4 Ma, defining a bimodal distribution with groupings at 4474 ± 10 Ma and 4442 ± 17 Ma. We interpret these to represent intense bombardment episodes at the planet’s surface, possibly triggered by the early migration of gas giant planets. The unradiogenic initial Hf-isotope composition of these zircons establishes that Mars’s igneous activity prior to ~4.3 Ga was limited to impact-related reworking of a chemically enriched, primordial crust. A group of younger detrital zircons record ages from 1548.0 ± 8.8 Ma to 299.5 ± 0.6 Ma. The only plausible sources for these grains are the temporally associated Elysium and Tharsis volcanic provinces that are the expressions of deep-seated mantle plumes. The chondritic-like Hf-isotope compositions of these zircons require the existence of a primitive and convecting mantle reservoir, indicating that Mars has been in a stagnant-lid tectonic regime for most of its history. Our results imply that zircon is ubiquitous on the Martian surface, providing a faithful record of the planet’s magmatic history.
58 GEOSCIENCES↗
Zircon (U-TH)/He Impact Crater Thermochronometry and the Effects of Shock Microstructures on Helium Diffusion Kinetics
Accurate age determinations of hyper-velocity impact and cratering events remains difficult and often controversial, while less than half of all known impact craters are regarded as accurately and precisely dated. Besides 40Ar/39Ar and U-Pb methods, zircon (U-Th)/He dating of impactites is a burgeoning technique to date large- to medium-sized impact structures. Zircon (U-Th)/He ages can be fully reset in minutes at 1000°C, T commonly reached in and directly adjacent to impact melt domains, whereas complete resetting of zircon (U-Th)/He at <300°C, which might be encountered near the crater margins or persist in post-impact hydrothermal systems, may take >103-4 years. However, there is a critical need to test the reliability of (U-Th)/He impact dating in shock deformed zircon, and to quantify helium diffusion kinetics in well-characterized grains with a broad spectrum of shock-induced defect substructures. For this purpose, we investigated samples from two impact structures, the 66 Ma Chicxulub multi-ring basin and the 15 Ma Ries complex crater, to compare zircon diffusion kinetics from impact structures with varying parameters, including size, age, and hydrothermal system longevity. Shock microstructures were characterized by backscattered-electron (BSE) imaging prior to determination of diffusion step-heating fractional release experiments using light-bulb furnace with prograde and retrograde incrementally 10°C steps from 300°C to 600°C. We find that zircon with low-level shock microstructures exhibit no significant deviation from helium diffusion kinetics of undamaged zircon. In contrast, zircon grains with planar deformation features and granular textures classified by SEM are characterized by a dramatic decrease in helium retentivity, similar to radiation damage, due to the reduction in the effective domain size and the introduction of fast diffusion pathways. This likely renders shocked grains more susceptible to impact-induced hydrothermal resetting. Hence, characterization of impact microstructure is critical for determining accurate impact ages, but also offers the opportunity to determine the magnitude and duration of post-impact hydrothermal circulation.
Catherine Ross↗
Temperature dependence of uranium and thorium partitioning in igneous zircons
Zircon is a key mineral in geochronology because of its chemical and physical durability and tendency to incorporate radioactive trace elements such as U and Th. Quantifying the partitioning of the actinide elements is critical to constrain initial non-secular equilibrium amounts of 230 Th in zircon. An excess or deficit of 206 Pb will be produced from such an initial excess/deficit of 230 Th from the secular equilibrium condition, which influences the calculated 206 Pb/ 238 U age (Schärer, 1984, Mattinson, 1973). However, there is no standard way to calculate Th/U partitioning ratios when applying age corrections to young igneous zircon, making uncertainties hard to estimate. To better understand U and Th partitioning of zircon/melt that is the cornerstone of the secular disequilibrium correction, zircon was synthesized in one-atmosphere experiments using basaltic andesite, andesite, and rhyolite starting materials, doped with Zr, U, and Th. Different experimental temperatures and oxygen fugacity conditions (ΔQFM−4 to ΔQFM+4) were explored to examine their effects on U and Th partitioning. In addition, we specifically quantify the effects of sector zoning, fractional crystallization, and melt composition on U and Th partitioning. By combining experimental and natural zircon data, we find that temperature has the primary control on the partitioning of U and Th in the zircon and calibrate an inverse relationship between these partition coefficients and crystallization temperatures. The calibrated equation can be applied to the 230 Th correction for an improvement in the accuracy of Th-corrected 206 Pb/ 238 U dates when the zircon crystallization temperature is known.
206Pb/238U dating↗
Zircon (U-Th)/He Impact Crater Thermochronometry and the Effects of Shock Microstructures on Helium Diffusion Kinetics
Absolute age determination of impact cratering events remains difficult and often controversial; a challenge that has resulted in < 50% of known impact craters regarded as accurately and precisely dated. Besides conventional 40Ar/39Ar and U-Pb methods, zircon (U-Th)/He (ZHe) dating of impactites has been applied to large- to medium-sized impact structures. ZHe dates can be fully reset in minutes at 1000°C, which is commonly reached in central sections of the melt sheet, whereas resetting of ZHe at <300°C, which might be encountered near the crater margins or persist in post-impact hydrothermal systems, may take >103-6 years. There is a critical need to quantify the effects of shock-induced microstructures and impact metamorphism on helium diffusion kinetics in well-characterized, variably shocked zircon to further establish the reliability of (U-Th)/He for dating impacts. For this purpose, we investigated suevite and impact melt samples from two impact structures, the Chicxulub multi-ring basin and the Ries complex crater, which enables us to compare zircon helium diffusion kinetics from impact structures with differing sizes, ages, and hydrothermal system longevities. Shock microstructures were characterized by backscattered-electron (BSE) imaging prior to diffusion step-heating fractional release experiments using light-bulb furnace with prograde and retrograde incremental 10°C steps from 250°C to 600°C. Afterward, we characterize the diffusion domain sizes and their interconnectivity within the shocked zircon grains using electron backscatter diffraction (EBSD). We find that zircon with few shock microstructures exhibit no significant deviation from helium diffusion kinetics of undamaged zircon. In contrast, zircon grains with planar deformation features (PDFs) and granular textures classified by BSE and EBSD are characterized by a dramatic decrease in helium retentivity, similar to radiation damaged grains, due to a reduction in the effective domain size and the introduction of interconnected fast diffusion pathways created by shock microstructures. A subset of grains were dated by ZHe after the external morphology of the grains was determined by BSE imaging. The euhedral grains yielded a weighted mean age within the uncertainty of the accepted impact ages, whereas the grains with PDFs or granular textures exhibited younger ages. Thus, these diffusion experiments and ZHe dates suggest that the dramatic decrease in domain size likely renders shocked grains more susceptible to impact-induced hydrothermal resetting and subsequent overprinting. Hence, characterization of shock microstructures is critical for determining accurate impact ages using ZHe methods especially when applied to previously unconstrained craters. The thermochronometer also offers the opportunity to determine the magnitude and duration of post-impact hydrothermal circulation.
zircon↗
Oxygen isotope ratios in zircon and garnet: A record of assimilation and fractional crystallization in the Dinkey Dome peraluminous granite, Sierra Nevada, California
Abstract The 119 Ma Dinkey Dome pluton in the central Sierra Nevada Batholith is a peraluminous granite and contains magmatic garnet and zircon that are complexly zoned with respect to oxygen isotope ratios. Intracrystalline SIMS analysis tests the relative importance of magmatic differentiation processes vs. partial melting of metasedimentary rocks. Whereas δ18O values of bulk zircon concentrates are uniform across the entire pluton (7.7‰ VSMOW), zircon crystals are zoned in δ18O by up to 1.8‰, and when compared to late garnet, show evidence of changing magma chemistry during multiple interactions of the magma with wall rock during crustal transit. The evolution from an early high-δ18O magma [δ18O(WR) = 9.8‰] toward lower values is shown by high-δ18O zircon cores (7.8‰) and lower δ 18O rims (6.8‰). Garnets from the northwest side of the pluton show a final increase in δ18O with rims reaching 8.1‰. In situ REE measurements show zircon is magmatic and grew before garnets. Additionally, δ18O in garnets from the western side of the pluton are consistently higher (avg = 7.3‰) relative to the west (avg = 5.9‰). These δ18O variations in zircon and garnet record different stages of assimilation and fractional crystallization whereby an initially high-δ18O magma partially melted low-δ18O wallrock and was subsequently contaminated near the current level of emplacement by higher δ18O melts. Collectively, the comparison of δ18O zoning in garnet and zircon shows how a peraluminous pluton can be constructed from multiple batches of variably contaminated melts, especially in early stages of arc magmatism where magmas encounter significant heterogeneity of wall-rock assemblages. Collectively, peraluminous magmas in the Sierran arc are limited to small <100 km2 plutons that are intimately associated with metasedimentary wall rocks and often surrounded by later and larger metaluminous tonalite and granodiorite plutons. The general associations suggest that early-stage arc magmas sample crustal heterogeneities in small melt batches, but that with progressive invigoration of the arc, such compositions are more effectively blended with mantle melts in source regions. Thus, peraluminous magmas provide important details of the nascent Sierran arc and pre-batholithic crustal structure.
Geochemistry & Geophysics↗