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Breccia boulders scattered around the 25 Ma Cone Crater near the Apollo 14 landing site provide a potential source of material ejected from the underlying Fra Mauro formation, which is int ...

The U-Th-Pb isotopic data from detrital zircon grains from five samples of Archean quartzite from the Mt. Alfred area of the Illaara greenstone belt in the Yilgarn Craton of Western Australia are presented in this study. The zircon grains are typically fractured and contain both irregular and oscillatory zoned internal structures as revealed by cathodoluminescence imaging. Concordant 207Pb/206Pb ages range between 3109 ± 17 and 3918 ± 16 Ma (2σ), with three main age peaks at ca. 3640, 3690 and 3760 Ma. Older 207Pb/206Pb ages up to 4067 ± 5 Ma are strongly affected by at least one recent disturbance event, however one single-grain discordia yields an upper intercept age of 4107 ± 12 (MSWD = 1.2). A further sixteen zircon grains with multiple analyses define discordia that suggest U-Pb disturbance events in the Neoarchean and the Mesozoic, the latter as a result of invasive low temperature weathering solutions. The notable lack of grains with ages less than ∼3.6 Ga in the Mt. Alfred detrital zircon population differentiates it from other quartzite samples from both the Illaara Formation and the Eoarchean zircon-bearing metasedimentary rocks of the Narryer Terrane. Also, the limited spread of zircon ages between 3640 and 3760 Ma suggests a relatively uniform and possibly local source region. However, no rocks of this age have been found in the Youanmi Terrane. This implies either the distal transport of similarly aged clastic sediments at 3.1 Ga from the Narryer Gneiss Complex (NGC) to the Mt. Alfred area, or the previous existence of NGC-like rocks near the Illaara greenstone belt that are either not currently recognised or have since been destroyed.

In this paper, we compare the U-Pb zircon age distribution pattern of sample 14311 from the Apollo 14 landing site with those from other breccias collected at the same landing site. Zircons in breccia 14311 show major age peaks at 4340 and 4240 Ma and small peaks at 4110, 4030, and 3960 Ma. The zircon age patterns of breccia 14311 and other Apollo 14 breccias are statistically different suggesting a separate provenance and transportation history for these breccias. This interpretation is supported by different U-Pb Ca-phosphate and exposure ages for breccia 14311 (Ca-phosphate age: 3938 ± 4 Ma, exposure age: ~550–660 Ma) from the other Apollo 14 breccias (Ca-phosphate age: 3927 ± 2 Ma, compatible with the Imbrium impact, exposure age: ~25–30 Ma). Based on these observations, we consider two hypotheses for the origin and transportation history of sample 14311. (1) Breccia 14311 was formed in the Procellarum KREEP terrane by a 3938 Ma-old impact and deposited near the future site of the Imbrium basin. The breccia was integrated into the Fra Mauro Formation during the deposition of the Imbrium impact ejecta at 3927 Ma. The zircons were annealed by mare basalt flooding at 3400 Ma at Apollo 14 landing site. Eventually, at approximately 660 Ma, a small and local impact event excavated this sample and it has been at the surface of the Moon since this time. (2) Breccia 14311 was formed by a 3938 Ma-old impact. The location of the sample is not known at that time but at 3400 Ma, it was located nearby or buried by hot basaltic flows. It was transported from where it was deposited to the Apollo 14 landing site by an impact at approximately 660 Ma, possibly related to the formation of the Copernicus crater and has remained at the surface of the Moon since this event. This latter hypothesis is the simplest scenario for the formation and transportation history of the 14311 breccia. GEO KAW Early Planetary Evolution

We report the result of a SIMS U–Th–Pb and O–OH study of 44 ancient zircons from the Jack Hills in Western Australia with ages ranging from 4.3 Ga to 3.3 Ga. We have investigated the behaviour of oxygen isotopes and water in the grains by determining δ18O and OH values at a number of locations on the polished surfaces of each grain. We have divided the zircons into five groups on the basis of their U–Th–Pb and OH-oxygen isotopic behaviour. The first group has concordant U–Th–Pb ages, minimal common Pb, δ18O values consistent with zircons derived from mantle source rocks and no detectable OH content. U–Th–Pb systems in zircons from Groups 2, 3 and 4 vary from concordant to extremely discordant where influenced by cracks. Discordia intercepts with concordia at approximately zero Ma age are interpreted as disturbance of the zircon U–Th–Pb systems by weathering solutions during the extensive, deep weathering that has affected the Archean Yilgarn Craton of Western Australia since at least the Permian. Weathering solutions entering cracks have resulted in an influx of Th and U. δ18O values of Group 2 grains fall approximately within the “mantle” range and OH is within background levels or slightly elevated. δ18O values of Group 3 grains are characterised by an initial trend of decreasing δ18O with increasing OH content. With further increase in OH this trend reverses and δ18O becomes heavier with increasing OH. Group 4 grains have a distinct trend of increasing δ18O with increasing OH. These trends are explained in terms of the reaction of percolating water with the metamict zircon structure and appear to be independent of analytical overlap with cracks. Group five zircons are characterised by U–Pb systems that appear to consist of more than one age but show only minor U–Pb discordance. Nevertheless trends in δ18O versus OH in this group of grains resemble trends seen in the other groups. The observed trends of δ18O with OH in the Jack Hills zircons are similar to those reported in a previous study of zircons from an Archean granite from south-western Australia.

Impact breccia 14311, was collected from the Apollo 14 landing site as a potential sample of the underlying Fra Mauro Formation. Published zircon U-Pb ages of >4000 Ma date the source material of the breccia and the apatite U-Pb age of ~3940 Ma is interpreted as dating thermal resetting of the apatite U-Pb systems. In this contribution we present new age information on the late stage thermal history of the breccia based on the annealing of radiation damage in the zircons. From Raman spectroscopic determination of the radiation damage within SIMS analytical spots on the zircons and the U and Th concentrations determined on these spots, we demonstrate that the radiation damage in the zircons has been annealed and we estimate the age of annealing at 3410 ± 80 Ma. This age is interpreted as a cooling age following heating of the breccia to above the annealing temperature of ~230 °C for stage 1 radiation damage in zircon, but below the temperature needed to reset the U-Pb system of apatite (~500 °C). It is proposed that this thermal event was associated with the prolonged period of Mare volcanism, from 3150 to 3750 Ma, that generated massive basalt flows in the vicinity of the sample location.

In this contribution we describe the influx of non-formula elements (Fe, Ca, Al, Y, U and Th) into fractures and selected zone lamellae in zircons from Jack Hills during recent weathering and discuss the effects of this on overlapping SIMS U-Th-Pb and oxygen isotope analyses. Previous research has recognised the importance of fractures in the generation of anomalous U-Th-Pb and oxygen isotope systems. In this report we show that besides fractures specific zones in euhedrally zoned zircon can act as pathways for the influx of weathering solutions and contain a similar range of trace element materials as do the fractures. Whereas zero-age discordant U-Pb systems of Jack Hills zircons have been explained by many authors in terms of Pb loss, present results confirm conclusions of our previous study that the main discordance mechanism of Jack Hills zircons is U-Th gain, due to overlap of SIMS analyses with mineralized fractures and zone lamellae with excess weathering-fluid-deposited U and Th. We explain the anomalously light and heavy oxygen isotopes and significant OH in SIMS analyses that overlap fractures and mineralized zones as due to the presence in the fractures of Ca, Fe, Al oxides and hydroxides with complexly fractionated oxygen isotopic systems. There is a suggestion in some of the elemental maps that there has been minor dispersion of trace elements away from fractures. But SIMS U-Th-Pb and oxygen isotope analyses on parts of the zircon away from fractures and mineralized zones show no evidence of interaction with weathering-fluid, indicating that penetration of weathering fluids into the body of the zircon at the location of the SIMS spots has not occurred. Results of this study have implications for other SIMS U-Th-Pb and oxygen isotope studies of zircons from rocks that have been subjected to weathering and also for early TIMS U-Pb measurements of bulk zircon samples that show zero Ma U-Pb discordance.

Five Hadean (> 4 Ga) aged zircon grains from the Jack Hills metasedimentary belt have been investigated by a secondary ion mass spectrometry scanning ion image technique. This technique has the ability to obtain accurate and precise full U-Pb systematics on a scale

The discovery of Hadean to Paleoarchean zircons in a metaconglomerate from Jack Hills, Western Australia, has catalyzed intensive study of these zircons and their mineral inclusions, as they represent unique geochemical archives that can be used to unravel the geological evolution of early Earth. Here, we report the occurrence and physical properties of previously undetected CO2 inclusions that were identified in 3.36–3.47 Ga and 3.80–4.13 Ga zircon grains by confocal micro-Raman spectroscopy. Minimum P–T conditions of zircon formation were determined from the highest density of the inclusions, determined from the density-dependence of the Fermi diad splitting in the Raman spectrum and Ti-in-zircon thermometry. For both age periods, the CO2 densities and Ti-in-zircon temperatures correspond to high-grade metamorphic conditions (≥5 to ≥7 kbar/~670 to 770 °C) that are typical of mid-crustal regional metamorphism throughout Earth’s history. In addition, fully enclosed, highly disordered graphitic carbon inclusions were identified in two zircon grains from the older population that also contained CO2 inclusions. Transmission electron microscopy on one of these inclusions revealed that carbon forms a thin amorphous film on the inclusion wall, whereas the rest of the volume was probably occupied by CO2 prior to analysis. This indicates a close relationship between CO2 and the reduced carbon inclusions and, in particular that the carbon precipitated from a CO2-rich fluid, which is inconsistent with the recently proposed biogenic origin of carbon inclusions found in Hadean zircons from Jack Hills.

We report the results of a differential scanning calorimeter (DSC) study of the annealing of a metamict Sri Lankan zircon. Raman measurements on most chips of the powdered zircon starting material, Sri Lankan zircon (WZ19), showed no evidence of a crystalline structure, whereas a few chips retained residual Raman bands typical of highly radiation damaged zircon. DSC runs on aliquots of the powdered sample were heated to 850 and 1000 °C at rates of 2 and 10 °C/min and to 1500 °C at a rate of 10 °C/min. Raman spectroscopy was used to investigate the crystallinity of grains at selected temperature stages. Exothermal peaks were observed at about 910 and 1260 °C during the DSC run to 1500 °C. The 910 °C peak was demonstrated by Raman spectroscopy to mark the crystallization of tetragonal zirconia and the exothermic peak at about 1260 °C was demonstrated to represent the reaction of zirconia and amorphous silica to form crystalline zircon. The degree of crystallinity of these grains was almost identical to that of highly crystalline zircons from recent gem gravels from New South Wales. A small number of experimental chips from DSC analyses under 1000 °C were found to have zircon Raman bands that indicated they had undergone partial annealing. The present experimental results suggest that reconstitution of amorphous zircon to the crystalline state by dry annealing will rarely occur in terrestrial geological settings, even under extreme metamorphic conditions.

Rare Hadean zircon grains represent the only direct sample of the Earth older than 4.0 Ga. As such, they have tremendous potential to illuminate our knowledge of this period of Earth's history for which there is no extant rock record. In this study we revisit the existing dataset, supplemented by new analyses, to identify those grains from which a robust age may be inferred. This rigorous filtering approach identifies four distinct zircon growth events in the Hadean between ca. 4.4 Ga and 4.0 Ga, and allows a reassessment of conclusions made from the determination of the O- and Hf-isotope systematics in these grains. Notably, we find no firm evidence for involvement of supracrustal reservoirs in zircon genesis prior to 4.15 Ga and, while our filtered Hf-isotope data support interpretations for a mafic protocrust, there are insufficient analyses to constrain its evolution accurately. Clearly, further work is required and needs to be conducted in a systematic manner that first seeks to establish both the age and homogeneity of any given grain before proceeding to other types of analysis.

Previous age estimates of the Imbrium impact range from 3770 to 3920 Ma, with the latter being the most commonly accepted age of this basin-forming event. The occurrence of Ca-phosphates i ...

The crystal structure of zircon is gradually broken down by the decay of small amounts of U and Th present in zirconium lattice sites. It has been observed that, with increasing radiation damage, zircon can lose radiogenic Pb and at the same time gain water from the environment. The disturbance of the U-Pb system is a major problem in zircon U-Pb geochronology. Water penetration appears to be an important factor in Pb loss but to explore this further a technique is needed for making fine-scale in situ measurements of water on the polished surface of radiation damaged zircons. Our research has shown that Attenuated Total Reflectance Fourier Transform Infra Red (ATR-FTIR) spectroscopy with a synchrotron source and thermal analysis can be successfully used to map the fine-scale distribution of OH/H 2 O in radiation damaged zircons. The radiation damaged zircons were found to have an OH/H 2 O content varying from 0.4% to 5% with maxima occurring in the heavily damaged (metamict) zones noted for their disturbed U-Pb systems. Whilst thermal analysis confirmed the presence of OH and possibly H 2 O the infrared spectra did not distinguish between them.

The suggestion that the accumulation of radiation damage in zircons could be used as a dating method was first proposed in the 1950s. In the original technique radiation damage was determined by X-ray diffraction however, this is not suitable for the small sample analysis needed in modern geochronology. It is now possible to measure radiation damage and U and Th contents on micron-sized areas on the polished surface of zircon grains using Raman spectroscopy and SIMS mass spectrometry. This opens the way for a reassessment of the potential of radiation damage ages and the purpose of this contribution is to re-examine the technique through its application to zircons from two granitoids from the Archean Yilgarn Craton and ancient detrital zircons from the Jack Hills in Western Australia. The three examples show internally consistent radiation damage ages that are also in accord with independent geochronological evidence. The 420 ± 110 Ma radiation damage age for the Darling Range granite is coincident with 500–400 Ma biotite Rb–Sr ages in the same region of the Yilgarn Craton. Likewise a tonalite from the Youanmi Terrane in the Craton with a 1650 ± 150 Ma zircon radiation damage age, lies within the domain of a 1600 Ma event recorded by biotite Rb–Sr ages. The Jack Hills zircons have a 1120 ± 130 Ma radiation damage age that is explained by a complex damage accumulation and annealing history culminating in a mild heating event indicated by biotite Ar–Ar ages of about 1140 Ma. The positive results for the three case histories suggest that radiation damage ages could play a useful role in dating low temperature thermal events.

[1] Zircon and phosphate grains from matrix and quartz-monzodiorite (QMD) clasts in two thin sections of Apollo 15 impact melt breccia 15405 were investigated using optical microscopy, scanning electron microscopy, Raman spectroscopy, and ion microprobe U-Pb analyses. U-Pb results for zircon grains with well-defined cathodoluminescence zoning define the primary (i.e., magmatic) crystallization age as 4330 ± 6 Ma (2σ). One zircon consists of a preserved inner part surrounded by a porous polycrystalline (“granular”) mixture of zircon and baddeleyite, indicating incomplete reaction of the zircon with melt. Previous work showed that this microstructure could form at pressures above 60 GPa and a temperature close to ~1700°C and is evidence of an impact-related melting event. The U-Pb system of this grain indicates a resetting event at 1940 ± 10 Ma, interpreted as the age of this impact (impact #1). Other zircon and phosphate grains also have disturbed U-Pb systems, showing an even younger reset event (impact #2) at 1407 ± 57 Ma. Evidence of impact is supported by microstructures of zircon and baddeleyite such as secondary rims. These impacts are tentatively identified as those having formed Autolycus and Aristillius craters.

Zircons from Archean granites from the Darling Range Batholith in the Yilgarn Craton of Western Australia have been shown to have complexly discordant U–Pb systems with a strong component of zero age disturbance. The only geological event that has affected the granites in recent times is the pervasive regional weathering. Our aim in this study was to investigate the effects of weathering on the U–Pb and oxygen systems of the zircons, and to this end, we report secondary ion mass spectrometry (SIMS) results of OH, oxygen and U–Pb isotope systems of six typical zircons from a sample of the granite. These results confirmed the presence of OH in highly radiation-damaged parts of the zircons, demonstrating fluid interaction within grains. The presence of OH was accompanied by significant changes in the 18O/16O ratios. The data suggest trends where δ18O values in individual grains both increase and decrease with increasing OH. SIMS measurements showed the U–Pb systems are variably and unsystematically discordant in radiation-damaged parts of the zircons, particularly those with elevated OH contents. The complex U–Pb systems are interpreted in terms of multiple disturbance events between 450 and 0 Ma involving low-temperature fluid-induced movement of radiogenic Pb, decoupled from parent U and Th, within the radiation-damaged zircons, together with some Pb loss.

In this paper, we describe primary and secondary microstructures and textural characteristics found in lunar zircon and discuss the relationships between these features and the zircon U–Pb isotopic systems and the significance of these features for understanding lunar processes. Lunar zircons can be classified according to: (i) textural relationships between zircon and surrounding minerals in the host breccias, (ii) the internal microstructures of the zircon grains as identified by optical microscopy, cathodoluminescence (CL) imaging and electron backscattered diffraction (EBSD) mapping and (iii) results of in situ ion microprobe analyses of the Th–U–Pb isotopic systems. Primary zircon can occur as part of a cogenetic mineral assemblage (lithic clast) or as an individual mineral clast and is unzoned, or has sector and/or oscillatory zoning. The age of primary zircon is obtained when multiple ion microprobe analyses across the polished surface of the grain give reproducible and essentially concordant data. A secondary set of microstructures, superimposed on primary zircon, include localised recrystallised domains, localised amorphous domains, crystal–plastic deformation, planar deformation features and fractures, and are associated with impact processes. The first two secondary microstructures often yield internally consistent and close to concordant U–Pb ages that we interpret as dating impact events. Others secondary microstructures such as planar deformation features, crystal–plastic deformation and micro-fractures can provide channels for Pb diffusion and result in partial resetting of the U–Pb isotopic systems.

The full U-Pb isotopic systematics in a complex lunar zircon ‘Pomegranate’ from lunar impact breccia 73235 have been investigated by the development of a novel Secondary Ion Mass Spectrometry (SIMS) scanning ion imaging (SII) technique. This technique offers at least a four-fold increase in analytical spatial resolution over traditional SIMS analyses in zircon. Results from this study confirm the hypothesis that the Pomegranate zircon crystallized at 4.302 ± 0.013 Ga and experienced an impact that formed, U-enriched zircon around primary zircon cores at 4.184 ± 0.007 Ga (2σ, all uncertainties). The increase in spatial resolution offered by this technique has facilitated targeting of primary zircon that was previously inaccessible to conventional spot analyses. This approach has yielded results indicating that individual grains with a diffusive distance of less than ~ 4 μm have been reset to the young impact age, while individual grains with a diffusive distance larger than ~ 6 μm have retained the old crystallization age. Assuming a broad range in cooling rate of 0.5–50 °C/year, which has been observed in a suite of similar lunar breccias, a maximum localized temperature generated by the impact that reset small primary zircon and created new, high-U zircon is estimated to be between 1100 and 1280 °C.

– The microstructures of lunar zircon grains from breccia samples 72215, 73215, 73235, and 76295 collected during the Apollo 17 mission have been characterized via optical microscopy, cathodoluminescence imaging, and electron backscatter diffraction mapping. These zircon grains preserve deformation microstructures that show a wide range in style and complexity. Planar deformation features (PDFs) are documented in lunar zircon for the first time, and occur along {001}, {110}, and {112}, typically with 0.1–25 μm spacing. The widest PDFs associated with {112} contain microtwin lamellae with 65°/ misorientation relationships. Deformation bands parallel to {100} planes and irregular low-angle ( misorientation axes. This geometry is consistent with a dislocation glide system with {010} during dislocation creep. Nonplanar fractures, recrystallized domains with sharp, irregular interfaces, and localized annealing textures along fractures are also observed. No occurrences of reidite were detected. Shock-deformation microstructures in zircon are explained in terms of elastic anisotropy of zircon. PDFs form along a limited number of specific {hkl} planes that are perpendicular to directions of high Young’s modulus, suggesting that PDFs are likely to be planes of longitudinal lattice damage. Twinned {112} PDFs also contain directions of high shear modulus. A conceptual model is proposed for the development of different deformation microstructures during an impact event. This “shock-deformation mechanism map” is used to explain the relative timing, conditions, and complexity relationships between impact-related deformation microstructures in zircon.

Sample 73235 is one of several aphanitic impact melt breccias collected by the Apollo 17 mission at stations 2 and 3 on the slopes of the South Massif. This study presents a detailed investigation of internal structures and U-Pb ages of large zircon grains from this breccia sample. New data combined with the results of previous studies of zircon grains from the same location indicate that most zircon clasts in breccias from stations 2 and 3 formed during multiple magmatic events between 4.37 and 4.31 Ga, although the oldest zircon crystallized at about 4.42 Ga and the youngest at 4.21 Ga. In addition, zircons from the aphanitic breccias record several impact events prior to the ∼3.9 Ga Late Heavy Bombardment. The results indicate that the zircons probably crystallized at different locations within the Procellarum KREEEP Terrane and were later excavated and modified by several impacts and delivered to the same locality within separate ejecta blankets. This locality became a source of material that formed the aphanitic impact melt breccias of the South Massif during a ∼3.9 Ga impact. However, the zircons, showing old impact features, are not modified by this ∼3.9 Ga impact event suggesting that (i) this common source area was located at the periphery of excavation cavity, and (ii) the > 3.9 Ga ages recorded by the zircon grains could date large (basin-forming) events as significant as major later (∼3.9 Ga) collisions such as Imbrium and Serenitatis.

Evidence for the early history of the Archean Yilgarn Craton has been largely obliterated by the craton-wide emplacement of granitic rocks at ca. 2650 Ma. However, detrital zircons from rare, ca. 3.1 Ga quartz-rich metasediments preserved in the Yilgarn Craton provide an opportunity to investigate the age structure and composition of the pre-existing basement and therefore provide a valuable record of the early history of crustal components that combined to form the Yilgarn Craton. In this report we present the results of an ion microprobe (SHRIMP) U-Pb geochronological study of detrital zircons from six samples of quartzites from the Toodyay-Lake Grace Domain (TLGD) in the South West Terrane of the Yilgarn Craton. Consistent features in the detrital zircon age spectra in all samples demonstrate a basic uniformity in the composition of the source rocks. The results suggest a provenance dominated by ca. 3350 to 3200 Ma granitic rocks with an age peak at ca. 3265 Ma. No granites of this age have so far been identified in the south-western part of the Yilgarn Craton, although ca. 3280 Ma granites occur in the Narryer Terrane in the northwestern corner of the craton. A second consistent zircon age component suggests an earlier episode of granite emplacement at ca. 3500 to 3400 Ma. A minor component of material contributed zircons as old as 3850 Ma to the pre-2650 Ma basement of the proto-Yilgarn Craton. Our zircon age results suggest that the provenance of the TLGD was different from that of the ca. 3.1 Ga quartzites and metaconglomerates from Mt Narryer and the Jack Hills in the Narryer Terrane and from the Maynard Hills greenstone belt in the Southern Cross Domain. Although the zircon age spectra are not consistent with an origin from presently exposed gneisses from the Narryer Terrane, the presence of granite and pegmatite in the Narryer Terrane close in age to the main zircon age peak in the TLGD sediments suggests a possible connection. Some detrital zircons in the TLGD have been altered hydrothermally or overgrown by zircon rims during the ca. 2650 Ma sillimanite-grade metamorphism that affected the southern part of the TLGD.

Detrital zircon crystals from the Jack Hills metasedimentary belt, Western Australia, are the only surviving vestiges of Hadean crust and represent an extraordinary archive into the nature of the early Earth. We report the results of an in situ isotopic study of 68 Jack Hills zircons in which the Hf and Pb isotope ratios were measured concurrently, allowing a better integration of isotope tracer information (176Hf/177Hf) with crystallization age (207Pb/206Pb). These data are augmented by Hf isotope data from zircons of the surrounding Narryer gneisses (3.65–3.30 Ga) and from Neoarchaean granites that intrude the Jack Hills belt. The detrital zircons define a subchondritic eHf–time array that attests to a far simpler evolution for the Hadean Earth than claimed by recent studies. This evolution is consistent with the protracted intra-crustal reworking of an enriched, dominantly mafic protolith that was extracted from primordial mantle at 4.4–4.5 Ga, perhaps during the solidification of a terrestrial magma ocean. There is no evidence for the existence of strongly depleted Hadean mantle, or for juvenile input into the parental magmas to the Jack Hills zircons. This simple Hf isotope evolution is difficult to reconcile with modern plate tectonic processes. Strongly unradiogenic Hf isotope compositions of zircons from several Archaean gneiss terranes, including the Narryer and Acasta gneisses, suggest that Hadean source reservoirs were tapped by granitic magmas throughout the Archaean. This supports the notion of a long-lived and globally extensive Hadean protocrust that may have comprised the nuclei of some Archaean cratons.

Rare heavy mineral bands within quartzite cobbles were identified in two conglomerate units within the Jack Hills belt, Western Australia. Seven zircon-bearing cobbles were analysed from one location (site 152) and three from another (site 154), both approximately 1 km west of the site where zircons in excess of 4 Ga are abundant (W74 ‘discovery’ site). Individual pebbles from the 152 site reveal three distinctive features, containing either zircons > 3.0 Ga in age, 4 Ga was discovered from the entire suite of pebbles, in contrast to the well-studied W74 site. A single detrital zircon with an age of 1220 ± 42 Ma from location 152 is the youngest grain so far reported from sedimentary rocks at Jack Hills. It shows magmatic oscillatory zoning and thus implies at least two sedimentary cycles within the Proterozoic; requiring erosion of an igneous precursor, incorporation into a clastic sediment, induration and subsequent erosion and transport to be hosted in the conglomerate. The nearest source for rocks of this age is the Bangemall Supergroup in the Collier Basin, ∼ 100 km northeast in the Capricorn Orogen. This would imply tectonic interleaving of originally more extensive Bangemall rocks, possibly related to activity along the Cargarah Shear Zone that traverses the Jack Hills belt. The lack of > 4.1 Ga zircons in the pebbles is highly significant, suggesting the immediate source of ancient zircons was no longer present at the Earth's surface. This equates with a general lack of ancient crystals noted in rocks that contain Proterozoic zircons from previous studies and implies that such grains diminish in number as earlier sedimentary rocks were successively recycled.

An investigation of rare earth elements (REE) in 15 zircon grains from lunar breccia sample 14321, combined with published analyses, has allowed lunar zircon grains to be separated into four distinctive types. Type-1 zircon is characterized by the relative depletion of light REE (LREE) resulting in a steep chondrite-normalized pattern. Type-2 zircon shows relative enrichment in the LREE compared to type-1 grains. Type-3 zircon also shows relatively high concentrations of LREE as well as a relative depletion in the heavy REE (HREE), which results in a relatively flat chondrite-normalized pattern. Type-4 zircon grains are characterized by the steepest chondrite-normalized REE pattern, with the lowest LREE and the highest HREE as well as by a distinctive positive Ce anomaly. Multiple analyses of REE in a complex impact modified zircon from breccia sample 73235 suggest a possibility that the very light REE from La to Nd were mobilized during impact. However, the main differences between the identified zircon types appear to be primary and reflect the original crystallization environment of zircon grains. These differences are not linked to major changes associated with the different suites of plutonic rocks, such as Mg- and alkali-suites, and quartz monzodiorites (QMD), but instead reflect small-scale variations in residual pockets of melt where zircon grains crystallized. For example, the presence of plagioclase in the immediate vicinity of zircon was responsible for the type-1 zircon REE pattern, whereas type-2 zircon was formed in the presence of pyroxene. The only exception is type-4 zircon, which was probably associated with some felsite and “granite” samples representing very late differentiates of lunar mafic magmas.

We report secondary ion mass spectrometry (SIMS) U-Pb analyses of zircon and apatite from four breccia samples from the Apollo 14 landing site. The zircon and apatite grains occur as cogenetic minerals in lithic clasts in two of the breccias and as unrelated mineral clasts in the matrices of the other two. SIMS U-Pb analyses show that the ages of zircon grains range from 4023 ± 24 Ma to 4342 ± 5 Ma, whereas all apatite grains define an isochron corresponding to an age of 3926 ± 3 Ma. The disparity in the ages of cogenetic apatite and zircon demonstrates that the apatite U-Pb systems have been completely reset at 3926 ± 3 Ma, whereas the U-Pb system of zircon has not been noticeably disturbed at this time. The apatite U-Pb age is slightly older than the ages determined by other methods on Apollo 14 materials highlighting need to reconcile decay constants used for the U-Pb, Ar-Ar and Rb-Sr systems. We interpret the apatite age as a time of formation of the Fra Mauro Formation. If the interpretation of this Formation as an Imbrium ejecta is correct, apatite also determines the timing of Imbrium impact. The contrast in the Pb loss behavior of apatite and zircon places constraints on the temperature history of the Apollo 14 breccias and we estimate, from the experimentally determined Pb diffusion constants and an approximation of the original depth of the excavated samples in the Fra Mauro Formation, that the breccias experienced an initial temperature of about 1300-1100 °C, but cooled within the first five to ten years.

Lunar breccia 73217 is composed of plagioclase and pyroxene clasts originating from a single gabbronorite intrusion, mixed with a silica-rich glass interpreted to represent an impact melt. A study of accessory minerals in a thin section from this breccia (73217,52) identified three different types of zircon and anhedral grains of apatite which represent distinct generations of accessory phases and provide a unique opportunity to investigate the thermal history of the sample. Equant, anhedral zircon grains that probably formed in the gabbronorite, referred to as type-1, have consistent U–Pb ages of 4332 ± 7 Ma. A similar age of 4335 ± 5 Ma was obtained from acicular zircon (type-2) grains interpreted to have formed from impact melt. A polycrystalline zircon aggregate (type-3) occurs as a rim around a baddeleyite grain and has a much younger age of 3929 ± 10 Ma, similar to the 3936 ± 17 Ma age of apatite grains found in the thin section. A combined apatite-type-3 zircon age of 3934 ± 12 Ma is proposed as the age of the Serenitatis impact event and associated thermal pulse. X-ray mapping and electron probe analyses showed that Ti is inhomogeneous in the zircon grains on the sub-micrometer scale. However, model temperatures estimated from SHRIMP analyses of Ti-concentration in the 10 μm diameter spots on the polished surfaces of type-1 and type-2 zircons range between about 1300 and 900 °C respectively, whereas Ti-concentrations determined for the type-3 zircon are higher at about 1400–1500 °C. A combination of U–Pb ages, Ti-concentration data and detailed imaging and petrographic studies of the zircon grains shows that the gabbronorite parent of the zircon clasts formed shortly before the 4335 ± 5 Ma impact, which mixed the clasts and the felsic melt and projected the sample closer to the surface where fast cooling resulted in the crystallization of acicular zircon (type-2). The 3934 ± 12 Ma Serenitatis event resulted in partial remelting of the glass and formation of polycrystalline zircon (type-3). This event also reset the U–Pb system of apatite, formed merrillite coronas around some apatite grains, and probably re-equilibrated some pyroxenes in the clasts. Although there have been arguments for pre-3.9 Ga impacts based on other types of samples, the age of the acicular zircon at 4335 ± 5 Ma provides the first evidence of impact melt significantly predating the lunar cataclysm. Our data, combined with other chronological results, demonstrate the occurrence of pre-3.9 Ga impacts on the Moon and suggest that the lunar impact history consisted of a series of intense bombardment episodes interspersed with relatively calm periods of low impact flux.

The presently favoured concept for the early evolution of the Moon involves consolidation of debris from a giant impact of a Mars sized body with Earth forming a primitive Moon with a thick global layer of melt referred to as the Lunar Magma Ocean1 . It is widely accepted that many significant features observed on the Moon today are the result of crystallisation of this magma ocean. However, controversy exists over the precise timing and duration of the crystallisation process. Resolution of this problem depends on the establishment of precise and robust key crystallisation time points. We report a 4417 6 Myr old zircon in lunar breccia sample 72215,195, which provides a precisely determined younger limit for the solidification of the Lunar Magma Ocean. A model based on these data, together with the age of the Moon forming giant impact, defines an exponential time frame for crystallisation and suggests formation of anorthositic crust after about 80-85% of the magma ocean was solidified. In combination with other zircon ages the 4417 +/- 6 Myr age also suggests that the very small (less than a few per cent) residual portion of the magma ocean continued to solidify during the following 300-500 m.y.

We report the results of a SIMS U–Pb study of 112 zircons from breccia samples from the Apollo 14 and 17 landing sites. Zircon occurs in the breccia matrices as rounded, irregular shaped, broken and rarely euhedral grains and as constituent minerals in a variety of lithic clasts ranging in composition from ultra-mafic and mafic rocks to highly evolved granophyres. Crystallisation of zircon in magmatic rocks is governed by the zirconium saturation in the melt. As a consequence, the presence of zircon in mafic rocks on the Moon implies enrichment of their parent melts in the KREEP component. Our SIMS results show that the ages of zircons from mafic to ultramafic clasts range from ca. 4.35 Ga to ca. 4.00 Ga demonstrating multiple generations of KREEPy mafic and ultramafic magmas over this time period. Individual zircon clasts in breccia matrices have a similar age range to zircons in igneous clasts and all represent zircons that have been incorporated into the breccia from older parents. The age distributions of zircons from breccias from both the Apollo 14 and Apollo 17 landing sites are essentially identical in the range 4.35–4.20 Ga. However, whereas Apollo 14 zircons additionally show ages from 4.20 to 3.90 Ga, no zircons from Apollo 17 samples have primary ages less than ca. 4.20 Ga. Also, in contrast to previous suggestions that the magmatism in the lunar crust is continuous our results show that the zircon age distribution is uneven, with distinct peaks of magmatic activity at ca. 4.35 Ga, ca. 4.20 Ga in Apollo 14 and 17 and a possible third peak in zircons from Apollo 14 at ca. 4.00 Ga. To explain the differences in the zircon age distributions between the Apollo 14 and 17 landing sites we propose that episodes of KREEP magmatism were generated from a primary reservoir, and that this reservoir contracted over time towards the centre of Procellarum KREEP terrane. We attribute the peaks in KREEP magmatism to impact induced emplacement of KREEP magma from a primary mantle source or to a progressive thermal build-up in the mantle source until the temperature exceeds the threshold for generation of KREEP magma, which is transported into the crust by an unspecified possibly plume-like process.

Detrital zircons more than 4 billion years old from the Jack Hills metasedimentary belt, Yilgarn craton, Western Australia, are the oldest identified fragments of the Earth's crust and are unique in preserving information on the earliest evolution of the Earth. Inclusions of quartz, K-feldspar and monazite in the zircons, in combination with an enrichment of light rare-earth elements and an estimated low zircon crystallization temperature, have previously been used as evidence for early recycling of continental crust, leading to the production of granitic melts in the Hadean era. Here we present the discovery of microdiamond inclusions in Jack Hills zircons with an age range from 3,058 +/- 7 to 4,252 +/- 7 million years. These include the oldest known diamonds found in terrestrial rocks, and introduce a new dimension to the debate on the origin of these zircons and the evolution of the early Earth. The spread of ages indicates that either conditions required for diamond formation were repeated several times during early Earth history or that there was significant recycling of ancient diamond. Mineralogical features of the Jack Hills diamonds-such as their occurrence in zircon, their association with graphite and their Raman spectroscopic characteristics-resemble those of diamonds formed during ultrahigh-pressure metamorphism and, unless conditions on the early Earth were unique, imply a relatively thick continental lithosphere and crust-mantle interaction at least 4,250 million years ago.

The Jack Hills greenstone belt is situated along the southern margin of the Narryer Terrane in the northwest of the Yilgarn Craton, in fault contact with Archean granitic gneiss and granitic rocks. The belt has endured a long deformation history and the effects of recrystallisation, alteration, and the occurrence of a substantial proportion of lithologically similar metasedimentary rocks makes it difficult to correlate units and assign a stratigraphy. We have therefore divided the lithological units into four associations. These are: (1) an association of banded iron formation, chert, quartzite, mafic and ultramafic rocks; (2) an association of pelitic and semi-pelitic schist, quartzite, and mafic schist; (3) an association of mature clastic rocks including pebble metaconglomerate; (4) an association of Proterozoic metasedimentary rocks. Some of the second association was probably part of the same succession as association 1. The first two associations are of Archean age, were probably deposited at c. 3000 Ma, and have been intruded by Neoarchean granitic rocks. The mature clastic rocks of association 3 host ≥4.0 Ga detrital zircons that have been the focus of most previous work on the belt because they provide insight into early Earth processes. The mature clastic association may also have been deposited at c. 3000 Ma, but there is no direct evidence of intrusion by the Neoarchean granites, and it has a different, simpler, structural history than the first two associations. The maximum depositional age and deformation history of the Proterozoic metasedimentary rocks of association 4 suggest it may have been deposited during the late stages of the Capricorn Orogeny. This could have occurred in small transpressional pull-aparts within the Cargarah Shear Zone, which is a major, dextral, transpressional east-trending shear zone that was active during the Capricorn Orogeny between c. 1830 and c. 1780 Ma. Reactivation of the shear zone and overprinting by semi-brittle faulting has produced a complex network of fault slivers, and further sedimentation may have occurred after the Capricorn Orogeny.

Results are reported of an investigation of the age and origin of the exceptional zircon aggregate in an anorthositic clast from lunar breccia 73235. Cathodoluminescence and birefringence images show that the aggregate consists of numerous angular fragments of sector zoned primary zircon in a matrix of secondary zircon with an overall texture that resembles a pseudotachylite. SIMS U–Pb analyses of the primary fragments and the matrix yielded two clearly defined ages, an age of 4.315 ± 0.015 Ga and initial Th/U ratio of 0.21–0.35 for the primary zircon and an age of 4.187 ± 0.011 Ga and Th/U of 0.04–0.17, for the secondary zircon matrix. A Raman spectroscopic study the secondary matrix zircon was undertaken to investigate its structure. Results showed that the matrix has a zircon structure but there is also evidence for the presence of an amorphous component. Implications of the structural and U–Pb age data are discussed in terms of the origin and evolution of the aggregate and the history of lunar events. It is proposed that an original single, millimetre-sized, sector zoned zircon, formed at 4.31 Ga, was subjected to a severe shock event at 4.18 Ga. This event resulted in the fracturing of the zircon, the displacement and rotation of fragments, the compression of the aggregate to a lensoid shape, and the shock reduction of zircon to sub-micron-sized and amorphous granules in crush zones in the mosaic of fractures. Volatilisation loss of Pb and the addition of U to the secondary zircon is attributed to processes activated by the extreme thermal pulse which accompanied the 4.18 Ga shock event. Shock effects are seen in some of the primary fragments but Raman spectra of the primary and secondary zircon show no evidence for pressure-induced transformation of zircon to a scheelite structure. The zircon U–Pb system has not been affected by the ca. 3.95 Ga thermal pulse that accompanied formation of the host breccia although this event has largely reset the K–Ar systems.

The Cycladic blueschist unit (CBU) in the central Aegean Sea comprises a pre‐Alpidic crystalline basement that is overlain by thrust sheets of a metamorphosed volcanosedimentary sequence. Melanges are widespread and enclose a wide variety of meta‐igneous rock fragments in a serpentinitic and/or metasedimentary matrix. Previous geochronology has documented the general temporal framework for the Alpidic metamorphic history but did not produce well‐constrained protolith ages for the main volcanosedimentary succession and for melange blocks. This issue is addressed here in an ion probe U‐Pb zircon study focusing on the islands of Andros, Sifnos, and Ios. The new results indicate a consistent regional pattern of Triassic ages (ca. 237–245 Ma) for the magmatic precursors of metatuffaceous and metavolcanic rocks, which occur as intercalations within metasediments. This narrow range of igneous crystallization ages records an important period of volcanic activity in the larger study area. On Andros, such ...

SHRIMP U–Pb analyses are reported for a detrital zircon population from a sample of sillimanite-bearing quartzite from the Narryer sedimentary succession in the Narryer Terrane of the northwestern Yilgarn Craton. The detrital zircons define two distinctive age groups, an older group from 4000 Ga to 4280 Ma and a younger group from 3750 to 3250 Ma. The abundance of older group zircons of about 12% far exceeds the abundance of about 2% reported in the first discovery of ancient zircons in a quartzite from the Narryer metasediments, and is equivalent to the abundance of >3900 Ma zircons in metaconglomerate sample W74 from the Jack Hills, confirmed by new measurements reported in this paper. Most analyses of the Narryer and the Jack Hills detrital zircon populations are discordant. The Jack Hills zircon analyses are dominated by strong recent Pb loss whereas the Narryer zircon analyses have had a more complex history and have experienced at least one Pb loss event, possibly associated with the high-grade metamorphism at ca. 2700 Ma, and a further disturbance of the U–Pb systems during relatively recent times. Although the number of analyses is limited and many of the zircon analyses are discordant, the age distributions of the older (>3900 Ma) zircons from the Narryer and Jack Hills samples are different, suggesting a complex provenance for the ancient zircons. The distribution of ages in the younger population of Mt Narryer zircons is similar to that reported for zircons from the surrounding Meeberrie gneiss, supporting previous suggestions that zircons from the gneisses or their precursors were a major contributor to the detrital zircon suite. The younger zircon population from Jack Hills sample (W74), lacks the strong age peak from 3600 to 3750 Ma present in the Narryer zircon population, and conversely the strong zircon age group at ca. 3350–3500 Ma in the Jack Hills population is only weakly represented in the Narryer zircon population. The age distributions for the Narryer and the Jack Hills zircon populations are taken as benchmarks for comparing zircon populations from quartzite occurrences elsewhere in the Yilgarn Craton.

New data are presented on internal structures, U–Pb systematics and oxygen isotope compositions of eight detrital zircons with ages greater than 4.2 Ga, from the Jack Hills metasedimentary belt, Australia. Cathodoluminescence imaging, ion-microprobe U–Pb and oxygen isotope results show evidence for an extensive period of complex zircon growth, secondary reaction and U–Pb isotopic disturbance from 4.36 to 3.90 Ga. In addition many of the zircons have discordant U–Pb systems and excess common Pb indicating a superimposed, relatively recent, reaction between radiation damaged zircon and low temperature fluids. The significance of oxygen isotope compositions for zircons with complex internal structures and U–Pb systems is complicated by uncertainty in the origin of the grains and the unknown effect of later reactions. However, a minority of grains with sharp oscillatory zoning, uniform and concordant U–Pb systems, igneous Th–U ratios and low common Pb contents, are interpreted as undisturbed primary magmatic zircons. The oldest identified, oscillatory zoned, magmatic grain, with an age 4363 ± 20 Ma, is one of a few reported magmatic grains with this age, which is interpreted as the oldest reliable age for Hadean magmatic zircons. Mantle δ 18 O values are reported for these zircons. Younger oscillatory zoned zircon, including oscillatory zoned cores in complex grains, have δ 18 O values lower than 6.5‰, which are within the range of ion microprobe analysed δ 18 O values for zircons in high temperature equilibrium with the normal mantle rocks of 5.3 ± 0.6‰ (2 standard deviations). These values are also within the range of δ 18 O values found in lunar zircons. The absence of heavy oxygen in the grains that can be interpreted as primary magmatic zircons and the complex history over the period from 4.36 to 3.9 Ga, seen in all other Jack Hills zircons and reflected in the internal structures and U–Pb isotopic systems, questions the model for the early Earth involving long intervals of relatively temperate conditions from 4.4 to 4.0 Ga that were conducive to oceans and possibly life.

We report oxygen isotopic compositions for 14 zircon grains from a sample of sawdust from lunar breccia 14321. The zircons range in age from approx.4.4 to 3.9 Ga and in U and Th content from a few to several hundred ppm. As such these grains represent a range of possible source rocks, from granophyric to mafic composition, and cover the total age range of the major initial lunar bombardment. Nevertheless, results show that the oxygen isotopic compositions of the zircons fall within a narrow range of (delta18)O of about 1 per mil and have (delta18)O values indistinguishable from those observed for terrestrial mid-ocean ridge basalts confirming the coincidence of lunar and Earth oxygen isotopic compositions. In the (delta17)O vs. (delta18)O, coordinates data form a tight group with a limited trend on the terrestrial fractionation line. The zircon oxygen isotopes show minimal evidence of the extreme and variable mineral differentiation and element fractionation that have contributed to the formation of their parent rocks.

Detrital SHRIMP U–Pb results from four samples of metasediment show that the Jack Hills metasedimentary belt, Narryer terrane, Yilgarn craton, Western Australia contains two lithologically similar siliciclastic associations with discrete age and source characteristics. An older association only contains zircons with ages greater than 3000 Ma and probably accumulated prior to 2700 Ma. Grains in the range 3600–3000 Ma are likely derived from granitic gneisses surrounding the metasedimentary belt. The older association was in part sourced from, and likely accumulated on, gneisses of the Narryer terrane, however, the source of the oldest (>4000 Ma) grains is unknown. The younger association contains zircons with the bulk of the ages between 2800 and 2600 Ma, and detrital grains as young as 1800 Ma. It also shows ages in the range 3600–3000 Ma and a few grains as old as 4100 Ma. The younger association has a significant contribution of zircons derived from Yilgarn craton and Capricorn orogen and was deposited after ∼1800 Ma, possibly in a foreland basin setting close to the older association with the two then tectonically interleaved.

The Eckergneiss Complex (EGC) is a geologically unique medium- to high-grade metamorphic unit within the Rhenohercynian domain of the Mid-European Variscides. A previously, poorly defined conventional lower U–Pb intercept age of about 560 Ma from detrital zircons of metasedimentary rocks has led to speculations about an East Avalonian affinity of the EGC. In order to unravel the provenance and to constrain the age of the sediment protolith, we carried out sensitive high-resolution ion microprobe U–Pb analyses on detrital zircons from five different EGC quartzite occurrences. The obtained age spectrum indicates a SW Baltica provenance of the detritus. Sveconorwegian ages between 0.9–1.2 Ga are particularly well represented by analyses from metamorphic recrystallization/alteration zones penetrating into igneous zircon. Cadomian (Pan-African) ages, which might reflect a metamorphic event, could not be substantiated. Instead, zircons of igneous origin yielded concordant Lower Devonian and Silurian ages of 410±10, 419±10, and 436±6 Ma (1σ), implying that sedimentation of the EG protolith must have taken place after 410±10 Ma. The lower age limit of the EGC metamorphism is constrained by 295 Ma intrusion ages of the adjacent, nonmetamorphosed Harzburg Gabbronorite and Brocken Granite. Sedimentation and metamorphism must thus have taken place between about 410 Ma and 295 Ma. Given that this time span coincides with most of the sedimentation within the virtually nonmetamorphosed (lowest grade) Rhenohercynian in the Harz Mountains, including the direct vicinity of the EGC, along with the high-grade metamorphism, the EGC can hardly be seen as uplifted local basement. A possible candidate for the root region is an easterly, concealed marginal segment of the Rhenohercynian domain of the Variscides, which is tectonically overridden and suppressed by the Mid-German Crystalline Rise during continent collision. However, based on the concept of strike-slip movement of Variscan terranes with different P–T–t histories as a result of postaccretion intraplate deformation, the EGC could also represent a fault-bounded complex with an origin located far east or south east of the present location.

(U+Th)–4He dates are presented for hematite/maghemite and hematite separates from pisolitic nodules from four rock specimens of lateritic duricrust sampled in an area of about 1 km2 in the Darling Range about 50 km northeast of Perth, where the duricrust forms a continuous cover over rocks of the Archaean Yilgarn Craton. Textures and compositions of the separates were checked by X-ray diffraction and scanning electron microscopy. Hematite/maghemite separates from three of the specimens yielded ages of about 10 Ma, identical within error (weighted mean, 9.9 ± 0.9 Ma, 2σ), whereas the hematite separate from the fourth specimen gave a U–He date of 7.5 Ma, all within the Late Miocene. While questions remain as to whether initial and boundary conditions of dating are adequately fulfilled, the iron oxide 4He dates are in good agreement with estimates by palaeomagnetic dating and other methods for the age of laterite formation in the Darling Range and other parts of south Western Australia. This study demonstrates the potential of (U+Th)–4He dating as a serviceable, directly applicable tool for dating lateritic duricrust.

The June Hill Volcanics occupy a central stratigraphic position in the tectonic evolution of the Capricorn Orogeny that occurred along the southwestern margin of the Pilbara Craton in Palaeoproterozoic time. The volcanic rocks have been interpreted alternatively as due to continental rifting, foreland‐basin development, or backarc extension. Previous multigrain zircon U–Pb results from these rocks, as well as from an unnamed rhyolitic porphyry that is interstratified in turbidites of the overlying Ashburton Formation, are influenced by the combined effects of Pb loss and xenocrystic inheritance. We report new SHRIMP zircon ages of 1799 ± 8 and 1786 ± 11 Ma, respectively from the June Hill Volcanics and the unnamed porphyry, both of which have been deformed during the Capricorn Orogeny. Close similarity between these ages and results from various late‐stage Capricorn granitoids (including our new SHRIMP result of 1795 ± 8 Ma for the Minnie Creek granite) imply rapid development of the western Ashburton Tro...

We present the results of a series of hydrothermal experiments on grains from two partially metamict zircon samples from Sri Lanka in the temperature range 350 to 650 °C and with different solutions (2 M AlCl 3 , 2 M CaCl 2 , pure H 2 O, and a multi-cation solution). Under these conditions, sharply bounded reaction fronts penetrated into the zircon grains and developed complex lobate and rim structures that resemble structures found in natural zircon systems. The reaction zones are characterized by a marked increase in the cathodoluminescence intensity, a decrease of the back-scattered electron emission, and an increased degree of structural order, as revealed by micro-Raman and infrared spectroscopy. Sensitive high-resolution ion microprobe and electron microprobe measurements revealed that the altered areas gained solvent cations (e.g., Ca 2 + , Ba 2 + , Mg 2 + , Al 3 + ) from the solution and lost variable amounts of Zr, Si, Hf, the REE, U, Th as well as radiogenic Pb. A comparison between "dry" and "hydrothermal" annealing trends shows that the kinetics of structural recovery, including recrystallization of the amorphous phase in metamict zircon, is strongly enhanced under hydrothermal conditions. This finding suggests that water "catalyzes" structural recovery processes in metamict zircon. We found that the structure of the reacted areas does not resemble that of crystalline zircon, i.e., is still characterized by a temperature-dependent degree of disorder, which would not be expected if the reaction is controlled by a coupled dissolution and re-precipitation process. Instead, the alteration process can be described best by a diffusion-reaction-recrystallization model. In this model, it is postulated that the diffusion of water into the metamict structure is the driving force for moving recrystallization fronts. We found that the rate and the extent of solid-state recrystallization of the amorphous phase is an important factor in determining the mobility of trace elements. This interpretation is indicated by the observation that trace elements, including U and Th, were preferentially lost during the reaction with a fluid at low temperatures, where recrystallization of the amorphous material was slow or not activated at all. The observed chemical alteration patterns are believed to reflect a competition between the kinetics of long-range diffusion and ion exchange and the kinetics of the short-range diffusion necessary for the recrystallization process.

High thorium euhedral, twinned and elongate zircons from the felsic part of a mafic dyke located in the Archaean Yilgarn Craton approximately 30 km northeast of Perth and approximately 2 km east of the Darling Fault, have consistent 207 Pb/ 206 Pb ages of 1214 ± 5 Ma. This age is interpreted as the age of dyke emplacement and is identical, within the uncertainties, with other U–Pb dyke ages reported for the southwest Yilgarn Craton. The present result extends the known occurrence of ca 1210 Ma dykes to the western margin of the Yilgarn Craton and confirms earlier conclusions that a major mafic dyke emplacement occurred throughout the southern Yilgarn Craton during a short‐lived magmatic pulse at ca 1210 Ma.

The chemical and structural alteration of metamict zircon crystals from a 619 ±17 (2σ) Ma old, posttectonic granite in the southern part of the Eastern Desert, Egypt was studied. The crystals show simple oscillatory growth zones with metamictization–induced fractures, which provided pathways for fluid infiltration. Electron and ion microprobe analyses reveal that metamict, i.e. U and Th–rich, areas are heavily enriched in Ca, Al, Fe, Mn, LREE, and a water species, and have lost Zr and Si as well as radiogenic Pb. These chemical changes are the result of an intensive reaction with a low–temperature (120—200°C) aqueous solution. The chemical reactions probably occurred within the amorphous regions of the metamict network. During the zircon–fluid interactions the metamict structure was partially recovered, as demonstrated by micro-Raman and -infrared measurements. A threshold degree of metamictization, as defined empirically by an α–decay dose, Dc, was necessary for zircons to undergo hydrothermal alteration. It is proposed that Dc marks the first percolation point, where the amorphous domains start to form percolating clusters in the metamict network and where bulk chemical diffusion is believed to increase dramatically. The time of the hydrothermal alteration is determined by a lower intercept age of a U-Pb SHRIMP discordia of 17.9 (2σ) Ma, which is in good agreement with an apatite fission track age of 22.2 (2σ) Ma. The hydrothermal alteration event occurred contemporaneously with the main rifting phase of the Red Sea and widespread low- temperature mineralizations along the Red Sea coast.

Understanding the stability of radiation-damaged zircon under low-temperature hydrothermal conditions is crucial to the application of zircon for U–Pb geochronology and as a host phase for the disposal of plutonium waste. We report the results of an investigation of the stability of partially metamict zircon by leaching experiments at 175 °C with a 2 M AlCl 3 and a 1 M HCl–CaCl 2 solution as hydrothermal fluids for 1340 h. Cathodoluminescence (CL) and backscattered electron (BSE) images show that the zircon grains have developed a reaction rim several micrometers thick or deeply penetrating reticulated alteration zones with sharp boundaries to unaltered metamict zircon. These zones have experienced severe loss of Si, U, Th, and Pb, and gain of Al or Ca, and a water species as revealed by electron microprobe, sensitive high-resolution ion microprobe (SHRIMP) analyses, and infrared spectroscopy. Micro-Raman and infrared measurements on the altered areas show that disordered crystalline remnants of the partially metamict zircon structure were partially recovered, whereas recrystallization of the embedding amorphous phase was not observed. No detectable structural or chemical changes were detected inside the unaltered areas. Intensive fracturing, which was most intense in the HCl–CaCl 2 experiment, occurred inside the altered areas due to the volume reduction associated with the recovery of the disordered crystalline material and probably with the leaching reactions. We explain the formation of deep penetrating alteration zones by a percolation-type diffusion model, which is based on the assumption that percolating interfaces or areas of low atomic density between crystalline and amorphous regions as well as between amorphous domains exist along which fast chemical transport is possible. The idea of the existence of fast diffusion interfaces is supported by the sharp chemical gradients at the margin to unreacted zircon. The model was used to estimate for the first time diffusion coefficients for U, Th, and Pb diffusion in amorphous zircon at 175 °C by assuming that volume diffusion inside the amorphous domains is the loss rate-limiting process. These estimates show that volume diffusion in metamict zircon can cause significant loss of U, Th, and especially loss of radiogenic Pb over geological time scales, even at temperatures as low as 175 °C. Our results show that recent Pb loss discordias can be generated (1) by predominate Pb loss from metamict zircon through volume diffusion at low temperatures where thermal healing of the structure is insignificant, and (2) by leaching of Pb (and U and Th) from metamict zircon through an external fluid.

In a recent paper, Nasdala et al. (2001) reported the results of a study of metamictization and the annealing process in natural zircons using micro-Raman spectroscopy. The main objective of this paper was to show that the linewidth (given as full width at half maximum) of the asymmetrical m3 Si–O stretching band of zircon near 1,008 cm and its radiation-dose dependence could be used to recognize zircons which have been annealed in their geological history. The authors demonstrated that a comparison of the line-width versus a-decay dose relationship obtained from natural, unannealed rhyolite zircons with those obtained from unknown samples provides a potential means of examining the low-temperature history of the host rock. This concept, which has previously been proposed by Pidgeon et al. (1995, 1998), opens new perspectives for the interpretation of discordant U–Pb ages and for the reconstruction of the thermal history. However, the main conclusion drawn by Nasdala et al. (2001) about the physical effect of annealing of radiation-damaged zircon rests upon a simplification of the physical meaning of the linewidth of the m3 Si–O band. The major purpose of this comment is (1) to show that the linewidth of this band is not only related to the short-range order as suggested by Nasdala et al. (2001), but that it is complexly dependent on the microstructure of metamict zircon, (2) to discuss their conclusions about the recovery process in metamict zircon during annealing, (3) to demonstrate that the physical significance of the linewidth combined with the phonon frequency – an aspect which was ignored by Nasdala et al. (2001) – opens new perspectives for the concept of radiation-damage ages as a geochronological tool, and (4) to further re-evaluate the high potential of radiation-damage ages, which contrasts with the rather cautious conclusions drawn by Nasdala et al. (2001).

Isothermal annealing of two partially metamict zircon from Sri Lanka were carried out at 870 K, 968 K, 1071 K, and 1166 K for 0.5 min up to ∼; 210 hours. Raman spectroscopy was used to monitor the amorphous-to-crystalline transformation. The evolution of the phonon frequency and the linewidth of the v 3 Si-O stretching band in zircon with annealing time clearly shows two recovery stages within the temperature and time ranges of the experiments. Both annealing stages form distinct linear segments in the frequency vs . linewidth plot, which are clearly separated from the trend defined by untreated metamict zircons. The first stage is characterized by the recovery of the short-range order, i.e . by the recovery of pre-existing, disordered crystalline domains as indicated by a fast recovery rate of the phonon frequency at the beginning of the transformation. This process dominates at temperature below ∼; 1000 K. In the case of the less metamict zircon, first stage recovery was activated after significant incubation periods, which follow an Arrhenius relationship. The second stage involves epitaxial recrystallization, which is activated within the first few minutes at temperatures > 1000 K ( e.g ., after ∼ 1–2 min at 1166 K). At this stage, the decrease of the linewidth is most probably related to the relaxation of phonon confinement associated with the growth of crystalline domains. We have estimated empirical activation energies of E A = 2.24 ± 0.04 eV and E A = 2.6 ± 0.2 eV for the first stage from the isothermal frequency and linewidth transformation curves. These activation energies are most likely related to recombination of point defects in the crystalline domains of partially metamict zircon. A single activation energy of E A = 3.8 ± 0.4 eV was obtained for epitaxial recrystallization by assuming Johnson-Mehl-Avrami growth kinetics as a first approximation. We suggest that a comparison of frequency versus linewidth relationships observed for natural zircons with experimental trends provides a potential means for recognizing an annealing history of natural zircons, provided that post-annealing radiation damage did not completely obscure the annealing effect.

A SHRIMP 207Pb/206Pb zircon age of 1204 ± 10 Ma is reported for an east west trending dolerite dyke from near York in the southwestern Yilgarn Craton. This age is identical within analytical uncertainty to previously reported ages of ca 1210 Ma for dykes from the central Wheatbelt and the Western and Eastern Goldfields. The consistency of the dyke ages and the wide areal extent of the dykes suggests that emplacement occurred as a single magmatic pulse at ca 1210 Ma throughout the southwestern Yilgarn Craton. The similarities between the age of the dykes and the ages of late events in the Albany Fraser Orogeny, and the approximate parallelism of the east west trending dykes to the margin of the orogen, raises the possibility that these events are related.

SHRIMP U–Pb micro-analyses are reported for parts of complex zircons from a granulite facies enderbite from the Pium Complex in the Carajas Metallogenic Province of the Amazon Craton of Brazil. Zircons from the granulite consist of two types of grains — (a) those with oscillatory zoned cores surrounded by rims composed of two or more curved, overlapping, nebulously zoned domains distinguished by differences in cathodoluminescence intensity, and (b) grains which are composed entirely of such domains and have no obvious cores. The SHRIMP U–Pb age of 3002±14 Ma, determined for oscillatory-zoned zircon cores is interpreted as dating the parent rock of the enderbite. This age is resolved from the U–Pb age of 2859±9 Ma, determined on zircon rims, which is interpreted as a time point within the evolving granulite facies metamorphism. SHRIMP U–Pb ages of cores and rim-type zircon are generally concordant to slightly discordant where uranium contents are less than about 820 ppm, but once this value is exceeded the zircon becomes strongly discordant suggesting that a threshold value of radiation damage exists above which zircon stability with respect to Pb loss is sharply reduced. The results provide the first substantial age determination of the granulite metamorphism in the Carajas Province. The zircon U–Pb ages have not been influenced by the Transamazonian metamorphism dated at ca. 2.0–1.85 Ga from Ar–Ar and Rb–Sr mineral ages.

Petrological and isotopic investigations were undertaken on high pressure granulites of granitic to mafic composition from the Prachatice and Blanský les granulite complexes of southern Bohemia, Czech Republic. The predominant felsic granulites are quartz + ternary feldspar (now mesoperthite)-rich rocks containing minor garnet, kyanite and rutile, and most show a characteristic mylonitic fabric formed during retrogression along the exhumation path. Three high temperature reaction stages at distinctly different pressures are recognized. Rare layers of intermediate to mafic composition, containing clinopyroxene, best record a primary high pressure–high temperature stage (>15 kbar, >900 °C), and a well-defined overprint at medium pressure granulite facies conditions (6–8 kbar, 700–800 °C) during which orthopyroxene (+plagioclase) formed from garnet and clinopyroxene. A further high temperature overprint at lower pressure (ca. 4 kbar) is reflected in the development of cordierite- and/or andalusite-bearing partial-melt patches in some felsic granulites. Conventionally separated zircons from the granulites were measured on a SHRIMP II ion microprobe. Near-spherical, multifaceted grains interpreted to be metamorphic, and short prismatic grains from the cordierite-bearing melt patch, are all concordant and yielded indistinguishable results producing an average age, for 83 individual grain spots, of 339.8 ± 2.6 Ma (2σ). Metamorphic grains from a meta-granodiorite associated with the granulites gave the same age (339.6 ± 3.1 Ma, mean of 9), whereas inherited magmatic grains of the same sample yielded 367.8 ± 1.4 Ma. A mean age of 469.3 ± 3.8 Ma was obtained for two short prismatic concordant grains in one of the granulites, whereas several of the rounded grains with ca. 340 Ma metamorphic zircon overgrowths had much older (207Pb/206Pb minimum ages up to 1771 Ma) discordant cores. In addition to analysis of conventionally separated grains, ion-microprobe measurements were also made on zircons extracted from thin sections (drilled-out, mounted and repolished) such that a direct relationship between the dated zircons and petrographic position could be made. Identical results were obtained from both preparation methods, thus showing that the considerable advantage in petrological control is not offset by any appreciable lack of precision when compared to conventionally prepared ion-microprobe samples. All these isotopic results are identical to those previously obtained by conventional multigrain and single-grain evaporation techniques, but rather than allowing a greater resolution of the age of the petrographically obvious different metamorphic stages the results document, for the first time, the apparent short time scale for high, medium and low pressure metamorphism in the granulites. The short time period between the 340 Ma age for the high pressure granulites, as derived here and from studies of similar rocks elsewhere in the European Variscides, and the 320–330 Ma ages for regional low pressure–high temperature metamorphism, migmatization and granite magmatism, strongly suggests an important link between these two high temperature processes.

Mapping carried out in the northern Murchison Terrane of the Archaean Yilgarn Craton, Western Australia, shows that correlation of units between isolated greenstone belts is very difficult and an informal stratigraphic subdivision is proposed where the greenstone sequences have been divided into a number of assemblages. The assemblages may not necessarily be time equivalent throughout the region. The lower units (Assemblages 1–3) consist of ultramafic, mafic and intermediate volcanic rocks deposited without significant breaks in volcanism. Felsic volcanic packages (Assemblage 4) are conformable with underlying units, but are spatially restricted. Discordant units of graphitic sedimentary rocks are developed along major crustal structures (Assemblage 5). SHRIMP and conventional U–Pb study of zircons reveal that felsic volcanic rocks of Assemblage 4 in the Dalgaranga Greenstone Belt were emplaced at 2747 ± 5 Ma, whereas those in the adjacent Meekatharra — Mt Magnet Greenstone Belt range in age from 2762 ± 6...