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NASA NTRSDate not supplied

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↗
DOE OSTI2025

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↗
NASA NTRSDate not supplied

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↗
DOE OSTI2021

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↗
NASA NTRS2006

Heavy Isotope Composition of Oxygen in Zircon from Soil Sample 14163: Lunar Perspective of an Early Ocean on the Earth

Thirty oxygen analyses of a large (sub-millimetre) zircon grain from the lunar soil sample 14163 have been determined using CAMECA 1270 ion microprobe. The sample 14163 was returned form the Fra Mauro region by Apollo 14 mission. Zircon grain of 0.6-0.8 mm in size extracted from the sample was imaged using CL detector fitted to the Philips Electron Microscope in order to reveal internal structure. Oxygen isotopes have been analysed during two sessions. The first set of data was collected using the original mount where the grain was set in the resin attached to the glass slide. This resulted in the two complications: (i) standard zircon has to be analysed from the separate mount and (ii) the lunar zircon grain was rased in the holder compared to the standard. In order to investigate, if the elevated oxygen compositions observed during this session could have resulted from this difference in geometric configuration during the standard and sample analyses, the lunar zircon was extracted from the original mount, remounted with the standard chip in the new resin disk and reanalysed during the second session. All analyses made during the first session show delta O-18 values heavier than 6.0%. The second set of data has a wider spread of delta O-18 values with some values as low as 5.6%. Nevertheless, a half of observed delta O-18 values in this set is also higher than 6.0%. Slightly lighter oxygen compositions observed during the second session indicate possible dependence of measured delta O-18 values on the geometry of analysed samples. Presence of zircons with similar heavy oxygen isotope compositions on the Moon, which neither had liquid water or felic crust similar to that on the Earth nor ever developed regime similar to plate tectonics, suggests that other mechanisms can be responsible for elevated delta O-18 values in zircons. This implies that there is no support for the presence of an ocean on the surface of the early Earth and as the ocean appears to be an essential ingredient for the plate tectonics, there is no basis for belief that this mechanism was operating in the early history of the planet.

Nemchin, A. A.↗
DOE OSTI2024

Zircon-to-reidite phase transition enhanced by minor radiation damage: Implications for hypervelocity impacts

Reidite, a high-pressure phase of zircon, is increasingly identified at terrestrial impact sites. Despite its growing recognition, the potential applications for estimating minimum impact pressure face impediments due to existing discrepancies in the condition of zircon-reidite transformation, controversial models governing the transformation mechanism, and unclear effects of pre-existing radiation damage on reidite formation. Here, we show enhanced reidite formation by synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy analyses of zircon grains that have experienced different alpha-decay doses from U and Th impurities and subsequent pressurization in diamond anvil cells. Below ~1 × 10 18 α-decay events/g, the α-decay-induced isolated point defects in the still crystalline zircon facilitate the minor atomic readjustments required for reidite formation. However, above this dose, the loss of long-range periodicity in severely damaged or even metamict zircon inhibits the transformation. The enhanced reidite formation by minor radiation damage coincides with the more common occurrence of reidite at impact sites for which the precursor zircon has a relatively lower alphadecay- event dose before the impact event. In addition, the detailed atomic-scale structures of twinned reidite provide unambiguous evidence for a characteristic internal stress-induced martensitic transition. Furthermore, these findings have important implications for interpreting the formation conditions of natural reidite due to the convergence of pressure from the static, shockwave, and natural reidite samples.

58 GEOSCIENCES↗
NASA NTRS2019

Mechanisms and Consequences of Intra-Crystalline Enrichment of Ancient Radiogenic Pb in Detrital Hadean Zircons from the Jack Hills, Western Australia

The recent discovery of Pb* (radiogenic lead) -enriched domains (PEDs) in zircon using high-resolution scanning ion imaging, atom probe tomography and transmission electron microscopy indicates that the U-Pb isotopic system in zircon can be affected not only by Pb* loss but also by intra-crystalline Pb* enrichment. However, the formation mechanism of PEDs and the consequences for in-situ U-Pb dating remain elusive. To further understand these issues, scanning ion imaging and U-Pb dating were carried out on 51 Hadean detrital zircon grains from the Jack Hills, Western Australia. Of these, 8 grains were found to contain micrometer-scale PEDs with elevated Pb-207 and Pb-206 in the ion images. Isotope profiles across these PEDs confirm that they represent unsupported Pb* resulting from intra-grain mobilization and local enrichment of Pb* during ancient overprinting events. The PEDs are rare in most grains, with only 1 – 3 Pb* hotspots present in any ~70 μm × 70 μm imaged area, and are located either in dark-CL, high-U growth zones, or associated with bright-CL, low-Th recrystallized domains, suggesting that they were likely formed by local-scale processes. The PEDs located in dark-CL, high-U growth zones likely resulted from Pb* trapped in local, interconnected pathways produced by radiation damage during thermal overprinting events. Those associated with bright-CL, low-Th domains are interpreted as Pb* concentrated in nanoscale pores formed during fluid-present recrystallization of non-metamict zircon. Our interpretations therefore imply that intra-crystalline enrichment of Pb* in zircon can occur at various scales and through diverse mechanisms. Age calculations based on the ion images demonstrate that incorporation of PEDs in conventional in-situ SIMS spots produces spuriously old ages that are either reversely discordant or concordant, depending on the time of Pb* mobilization and the analytical precision. The implication is that careful investigation of intra-grain distribution of U-Th-Pb isotopes is required in order to better understand the U-Pb isotopic system and to obtain reliable crystallization ages for ancient zircons affected by complex Pb* mobilization and redistribution.

Unsupported radiogenic lead↗
DOE OSTI2023

Chemical abrasion: the mechanics of zircon dissolution

Chemical abrasion is a technique that combines thermal annealing and partial dissolution in hydrofluoric acid (HF) to selectively remove radiation-damaged portions of zircon crystals prior to U–Pb isotopic analysis, and it is applied ubiquitously to zircon prior to U–Pb isotope dilution thermal ionization mass spectrometry (ID-TIMS). The mechanics of zircon dissolution in HF and the impact of different leaching conditions on the zircon structure, however, are poorly resolved. We present a microstructural investigation that integrates microscale X-ray computed tomography (µCT), scanning electron microscopy, and Raman spectroscopy to evaluate zircon dissolution in HF. We show that µCT is an effective tool for imaging metamictization and complex dissolution networks in three dimensions. Acid frequently reaches crystal interiors via fractures spatially associated with radiation damage zoning and inclusions to dissolve soluble high-U zones, some inclusions, and material around fractures, leaving behind a more crystalline zircon residue. Other acid paths to crystal cores include the dissolution of surface-reaching inclusions and the percolation of acid across zones with high defect densities. In highly crystalline samples dissolution is crystallographically controlled with dissolution proceeding almost exclusively along the c axis. Increasing the leaching temperature from 180 to 210 °C results in deeper etching textures, wider acid paths, more complex internal dissolution networks, and greater volume losses. How a grain dissolves strongly depends on its initial radiation damage content and defect distribution as well as the size and position of inclusions. As such, the effectiveness of any chemical abrasion protocol for ID-TIMS U–Pb geochronology is likely sample-dependent. We also briefly discuss the implications of our findings for deep-time (U-Th)/He thermochronology.

58 GEOSCIENCES↗
NASA NTRS1993

Fingerprinting the K/T impact site and determining the time of impact by U-Pb dating of single shocked zircons from distal ejecta

U-Pb isotopic dating of single 1 - 3 micrograms zircons from K/T distal ejecta from a site in the Raton Basin, Colorado provides a powerful new tool with which to determine both the time of the impact event and the age of the basement at the impact site. Data for the least shocked zircons are slightly displaced from the 544 +/- 5 Ma primary age for a component of the target site, while those for highly shocked and granular grains are strongly displaced towards the time of impact at 65.5 +/- 3.0 Ma. Such shocked and granular zircons have never been reported from any source, including explosive volcanic rocks. Zircon is refractory and has one of the highest thermal blocking temperatures; hence, it can record both shock features and primary and secondary ages without modification by post-crystallization processes. Unlike shocked quartz, which can come from almost anywhere on the Earth's crust, shocked zircons can be shown to come from a specific site because basement ages vary on the scale of meters to kilometers. With U-Pb zircon dating, it is now possible to correlate ejecta layers derived from the same target site, test the single versus multiple impact hypothesis, and identify the target source of impact ejecta. The ages obtained in this study indicate that the Manson impact site, Iowa, which has basement rocks that are mid-Proterozoic in age, cannot be the source of K/T distal ejecta. The K/T distal ejecta probably originated from a single impact site because most grains have the same primary age.

Krogh, T. E.↗
NASA NTRS2005

Hadean Crustal Processes Revealed from Oxygen Isotopes and U-Th-Pb Depth Profiling of Pre-4.0 Ga Detrital Zircons from Western Australia

Because physical and chemical processes of the past are determined from analysis of a preserved geologic record, little is known about terrestrial crustal processes of the first 500 Ma during the so-called Hadean Eon. What is known from direct measurements has been derived almost exclusively from the study of greater than 4.0 Ga detrital zircons from the Jack Hills, Western Australia. The geochemistry of these zircons has direct application to understanding the origin and evolution of the rocks during the Hadean because: (i) U-Th-Pb age determinations by ion microprobe suggests the presence of crust as early as 4.37 Ga, or shortly after lunar formation; (ii) high-resolution U-Th-Pb zircon depth profiles reported here reveal several episodes of zircon growth in the Hadean previously unrecognized; (iii) core regions of pre-4.0 Ga zircons with igneous compositions are enriched in O-18 and contain metaluminous and peraluminous mineral inclusions, both features indicative of S-type grainitod protoliths. Study of these ancient zircons provides a unique window into the first half billion years that permits assessment of the potential of the Hadean Earth to host an emergent biosphere.

Trail, D.↗
NASA NTRS2009

Electron Backscatter Diffraction (EBSD) Analysis and U-Pb Geochronology of the Oldest Lunar Zircon: Constraining Early Lunar Differentiation and Dating Impact-Related Deformation

The evolution of the early moon was dominated by two processes (i) crystallization of the Lunar Magma Ocean (LMO) and differentiation of potassium-rare earth element-phosphorous-rich residual magma reservoir referred to as KREEP, and (ii) an intense meteorite bombardment referred to as lunar cataclysm . The exact timing of these processes is disputed, and resolution relies on collection and interpretation of precise age data. This study examines the microstructure and geochronology of zircon from lunar impact breccias collected during the Apollo 17 mission. A large zircon clast within lunar breccia 72215,195 shows sector zoning in optical microscopy, cathodoluminescence (CL) imaging and Raman mapping, and indicates that it was a relict fragment of a much larger magmatic grain. Sensitive high resolution ion microprobe (SHRIMP) U-Pb analysis of the zircon shows that U and Th concentration correlate with sector zoning, with darkest CL domains corresponding with high-U and Th (approx.150 and approx.100 ppm respectively), and the brightest-CL sectors containing approx.30-50 ppm U and approx.10-20 ppm Th. This indicates that variations in optical CL and Raman properties correspond to differential accumulation of alpha-radiation damage in each sector. Electron backscatter diffraction (EBSD) mapping shows that the quality of electron backscatter patterns (band contrast) varies with sector zoning, with the poorest quality patterns obtained from high-U and Th, dark-CL zones. EBSD mapping also reveals a deformation microstructure that is cryptic in optical, CL and Raman imaging. Two orthogonal sets of straight discrete and gradational low-angle boundaries accommodate approx.12 misorientation across the grain. The deformation bands are parallel to the crystallographic {a}-planes of the zircon, have misorientation axes parallel to the c-axis, and are geometrically consistent with formation by dislocation creep associated with <100>{010} slip. The deformation bands are unlike curved morphology of crystal-plastic microstructures in tectonically deformed terrestrial zircon, and geometrically similar to dislocation microstructures reported in experimentally shocked zircon. We interpret these crystal-plastic deformation microstructures to have resulted from a significant impact, either directly from impact shock, or during ductile flow directly following the impact. The deformation bands appear to continue undeflected through the non-indexed, radiation-damaged areas of the grain, which suggests that the orientation variation predates any significant mechanical weakening from radiation damage in the grain, and therefore occurred early in its history.

Timms, Nick↗
NASA NTRSDate not supplied

Zircon (U-Th)/He Impact Crater Thermochronometry and the Effects of Shock Microstructures on Helium Diffusion Kinetics

Accurate and precise age determination of impact cratering events remains challenging and often contentious; less than half of all known craters are regarded as accurately and precisely dated. Zircon (U-Th)/He (ZHe) dating of impactites can be employed to date medium to large impact structures as ZHe ages can be fully reset in minutes at T >1000°C, a plausible scenario in the central melt pool. In contrast, complete resetting of ZHe at 200-300°C, encountered near the crater margins or due to post-impact hydrothermal overprinting, may take >103-6 years. To test the reliability of ZHe impact dating, we have quantified the effects of shock-induced microstructures on helium diffusion kinetics in well-characterized variably shocked zircon. We investigated samples from two impact structures, the Chicxulub multi-ring crater and Ries complex crater, to compare diffusion kinetics from structures with different size, age, and hydrothermal system longevity. Shock microstructures were characterized by backscattered-electron imaging prior to determining the He diffusion kinetics by prograde and retrograde fractional-release experiments via light-bulb furnace with incremental step-heating (10°C) from 300°C to 600°C. Next, we examine the internal interconnectivity and sizes of the diffusion domains by EBSD. While we found that zircon with few shock microstructures exhibited no marked deviation from helium diffusion kinetics of undamaged zircon, zircon grains with planar microstructures and granular textures are characterized by a dramatic decrease in helium retentivity due to the reduction in the effective domain size and the introduction of interconnected fast diffusion pathways. A subset of grains were ZHe dated and showed that less deformed grains yielded a weighted mean age within error of the accepted impact ages, while the grains with planar microstructures or granular textures gave systematically younger ages. These new diffusion data and ZHe ages demonstrate that highly shocked grains are unsuitable for ZHe impact crater dating. Therefore, detailed characterization of impact-induced microstructures is critical for determining accurate ZHe impact ages and offers the possibility of investigating post-impact hydrothermal circulation.

Zircon↗
NASA NTRS2023

4.46 Ga Zircons Anchor Chronology of Lunar Magma Ocean

The crystallisation ages of lunar samples provide critical constraints on the minimum formation age of the Moon and its early evolution. Zircon crystals from Apollo 17 lunar impact melt breccia 72255 preserve ancient domains with a concordant average uranium-lead radiometric date of 4460 ± 31 Ma (Zhang et al., 2021), the oldest lunar zircon yet reported. To assess the possible mobility of radiogenic lead in zircon, which may lead to redistribution and clustering of Pb atoms that may cause a U-Pb age bias (Valley et al., 2014), we investigated a zircon grain from Zhang et al. (2021) by atom probe tomography (APT). The atomic spatial resolution analysis of individual mineral grains demonstrates the absence of nanoscale clustering of lead, which supports a 4.46 Ga ancient formation age for lunar zircon in sample 72255. This age pushes back the age of the first preserved lunar crust by ∼40 Myr and provides a minimum formation age for the Moon within 110 Myr after the formation of the solar system.

atom probe tomography↗
DOE OSTI2022

Thermoelastic properties of zircon: Implications for geothermobarometry

Abstract A thermal-pressure equation of state has been determined for zircon (ZrSiO4) that characterizes its thermoelastic behavior at metamorphic conditions. New pressure-volume (P-V) data from a “Mud Tank” zircon have been collected from 1 bar to 8.47(1) GPa using X-ray diffraction, and elastic moduli were measured from room temperature up to 1172 K by resonance ultrasound spectroscopy. These data were fitted simultaneously with temperature-volume (T-V) data from the literature in EosFit7c using a new scaling technique. The parameters of a third-order Birch-Murnaghan EoS with a Mie-Grüneisen-Debye model for thermal pressure have compressional EoS parameters K0T = 224.5(1.2) GPa, K0T' = 4.90(31) with a fixed initial molar volume V0 = 39.26 cm3/mol and thermal parameters γ0 = 0.868(15), q = 2.37(80), and ΘD = 848(38) K. EoS parameters that describe the variation of unit-cell parameters with pressure and temperature were determined using an isothermal-type EoS. This new EoS confirms that zircons are stiffer than garnets and exhibit a much lower thermal expansion. This results in steep isomekes between zircon and garnets, which makes zircon trapped as inclusions in garnets at metamorphic conditions a good piezothermometer.

Geochemistry & Geophysics↗
DOE OSTI2020

Crystal Chemistry and Structural Variations for Zircon Samples from Various Localities

This study investigates the variations of structural parameters and chemistry of a partially metamict and seven detrital zircon samples from different localities using single-crystal X-ray diffraction, synchrotron high-resolution powder X-ray diffraction, and electron-probe micro-analysis techniques. The unit-cell parameters for the eight zircon samples vary linearly with increasing unit-cell volume, V. A zircon sample from the Canadian Arctic Islands has the smallest unit-cell parameters, bond distances, ideal stoichiometric composition, unaffected by α-radiation damage, and is chemically pure. A zircon sample from Jemaa, Nigeria has the largest unit-cell parameters because of the effect of α-radiation doses received over a long time (2384 Ma). All the samples show good correlations between Zr and Si apfu (atom per formula unit) versus unit-cell volume, V. The α-radiation doses in the samples are lower than ~3.5 × 1015 α-decay events/mg. Substitutions of other cations at the Zr and Si sites control the variations of the structural parameters. Relatively large unit-cell parameters and bond distances occur because the Zr site accommodates other cations that have larger ionic radii than the Zr atom. Geological age increases the radiation doses in zircon and it is related to V.

58 GEOSCIENCES↗
DOE OSTI2025

Probing the Critical Element Chemistry of Coal-Combustion Fly Ash: Examination of Zircon and Associated Minerals from a Beneficiated Kentucky Fly Ash

Along with the principal rare earth (REE) minerals such as monazite, xenotime, and bastnasite, Y-and REE-bearing zircon and associated minerals survive the combustion process and are found in coal-combustion fly ash. Beneficiated fly ash from a power plant burning an eastern-Kentucky-sourced coal blend was found to have zircon (ZrSiO4), baddeleyite (ZrO2), fergusonite (YNbO4), yttriaite (Y2O3), and xenotime (YPO4). Previous studies of the same fly had also identified monazite with a broad REE suite. Scanning electron microscopy–electron dispersive spectroscopy (EDS) and transmission electron microscopy (TEM)–EDS as well as other TEM-based techniques revealed a variety of zircon associations, including heavy-REE suites with Y, Nb, and Hf. Hafnium is a common accessory element in zircons and the Y and Nb may be present as fergusonite (YNbO4) intermixed with zircon.

Berti, Debora (ORCID:0000000311237794)↗
NASA NTRS1996

Trace Element Zoning and Incipient Metamictization in a Lunar Zircon: Application of Three Microprobe Techniques

We have determined major (Si, Zr, Hf), minor (Al, Y, Fe, P), and trace element (Ca, Sc, Ti, Ba, REE, Th, U) concentrations and Raman spectra of a zoned, 200 microns zircon grain in lunar sample 14161,7069, a quartz monzodiorite breccia collected at the Apollo 14 site. Analyses were obtained on a thin section in situ with an ion microprobe, an electron microprobe, and a laser Raman microprobe. The zircon grain is optically zoned in birefringence, a reflection of variable (incomplete) metamictization resulting from zo- nation in U and Th concentrations. Variations in the concentrations of U and Th correlate strongly with those of other high-field-strength trace elements and with changes in Raman spectral parameters. Concentrations of U and Th range from 21 to 55 ppm and 6 to 31 ppm, respectively, and correlate with lower Raman peak intensities, wider Raman peaks, and shifted Si-O peak positions. Concentrations of heavy rare earth elements range over a factor of three to four and correlate with intensities of fluorescence peaks. Correlated variations in trace element concentrations reflect the original magmatic differentiation of the parental melt approx. 4 b.y. ago. Degradation of the zircon structure, as reflected by the observed Raman spectral parameters, has occurred in this sample over a range of alpha-decay event dose from approx. 5.2 x 10(exp 14) to 1.4 x 10(exp 15) decay events per milligram of zircon, as calculated from the U and Th concentrations. This dose is well below the approx. 10(exp 16) events per milligram cumulative dose that causes complete metamictization and indicates that laser Raman microprobe spectroscopy is an analytical technique that is very sensitive to the radiation-induced damage in zircon.

Wopenka, Brigitte↗
NASA NTRS2005

A Further Investigation of the Exceptional Zircon Aggregate in Lunar Thin Section 73235,82

Introduction: Smith et al. described an exceptional zircon assemblage in thin section 82 from lunar breccia 73235 which, in transmitted light, resembles a cluster of pomegranate seeds, situated in a clast dominated by bytownite (Fig.1). They reported that high-contrast back-scattered electron (BSE) images of the zircon assemblage clearly show an overgrowth around most of the crystals. Most significantly these authors reported that the age of the rims of ca 4.18Ga is 120 million years younger than age of the interiors, dated at ca 4.31Ga. Smith et al. concluded that ca 4.31 billion years ago a relatively large (500+micron) zircon crystallized within a clast of Ca rich plagioclase. The zircon was fractured into numerous smaller crystals and was subsequently overgrown by a second generation of zircon at approximately 4.18Ga.

Pidgeon, R. T.↗