Nanoscale records of ancient shock deformation: Reidite (ZrSiO4) in sandstone at the Ordovician Rock Elm impact crater

The terrestrial record of meteorite impacts is difficult to decipher because unequivocal evidence of impact is increasingly destroyed with time by erosion, burial, and tectonics. Zircon survives these processes as a shocked mineral, and above 20 GPa transforms to reidite, a high-pressure ZrSiO4 polymorph diagnostic of impact. However, the utility of reidite has been limited by its occurrence; it has only been reported from three relatively young (<36 Ma) impact craters globally. Here we report a new occurrence of reidite in brecciated sandstone from the Ordovician Rock Elm impact crater in Wisconsin, United States. Electron backscatter diffraction mapping was used to identify reidite and microtwins within shocked zircons smaller than 50 µm in diameter. Reidite occurs both as 200–500-nm-wide lamellar intergrowths and as nanoparticulate grains, and not only provides the first diagnostic evidence for ultrahigh-pressure shock metamorphism at Rock Elm, but is also the oldest reported occurrence of reidite. Considering its small size, and the ubiquitous presence of detrital zircon in siliciclastic rocks, reidite may be more common in the rock record than has been reported but has potentially gone undetected. The recognition that nanoscale reidite can be preserved over deep time within zircon in shock-metamorphosed sandstone presents new opportunities for investigating Earth’s impact record, as it could potentially preserve nanoscopic evidence of impact events much older than the one that formed Rock Elm. Given that shocked zircons have been shown to survive sedimentary cycling, the identification of reidite within zircons in siliciclastic rocks could facilitate investigating the impact chronology over much of the geological time scale, as the oldest terrestrial minerals known are detrital zircons

The origin of high δ18O zircons: marbles, megacrysts, and metamorphism

The oxygen isotope ratios (δ18O) of most igneous zircons range from 5 to 8‰, with 99% of published values from 1345 rocks below 10‰. Metamorphic zircons from quartzite, metapelite, metabasite, and eclogite record δ18O values from 5 to 17‰, with 99% below 15‰. However, zircons with anomalously high δ18O, up to 23‰, have been reported in detrital suites; source rocks for these unusual zircons have not been identified. We report data for zircons from Sri Lanka and Myanmar that constrain a metamorphic petrogenesis for anomalously high δ18O in zircon. A suite of 28 large detrital zircon megacrysts from Mogok (Myanmar) analyzed by laser fluorination yields δ18O from 9.4 to 25.5‰. The U–Pb standard, CZ3, a large detrital zircon megacryst from Sri Lanka, yields δ18O = 15.4 ± 0.1‰ (2 SE) by ion microprobe. A euhedral unzoned zircon in a thin section of Sri Lanka granulite facies calcite marble yields δ18O = 19.4‰ by ion microprobe and confirms a metamorphic petrogenesis of zircon in marble. Small oxygen isotope fractionations between zircon and most minerals require a high δ18O source for the high δ18O zircons. Predicted equilibrium values of Δ18O(calcite-zircon) = 2–3‰ from 800 to 600°C show that metamorphic zircon crystallizing in a high δ18O marble will have high δ18O. The high δ18O zircons (>15‰) from both Sri Lanka and Mogok overlap the values of primary marine carbonates, and marbles are known detrital gemstone sources in both localities.The high δ18O zircons are thus metamorphic; the 15–25‰ zircon values are consistent with a marble origin in a rock-dominated system (i.e., low fluid(external)/rock); the lower δ18O zircon values (9–15‰) are consistent with an origin in an external fluid-dominated system, such as skarn derived from marble, although many non-metasomatized marbles also fall in this range of δ18O. High δ18O (>15‰) and the absence of zoning can thus be used as a tracer to identify a marble source for high δ18O detrital zircons; this recognition can aid provenance studies in complex metamorphic terranes where age determinations alone may not allow discrimination of coeval source rocks. Metamorphic zircon megacrysts have not been reported previously and appear to be associated with high-grade marble. Identification of high δ18O zircons can also aid geochronology studies that seek to date high-grade metamorphic events due to the ability to distinguish metamorphic from detrital zircons in marble

Shocked Quartz in Polymict Impact Breccia from the Upper Cretaceous Yallalie Impact Structure in Western Australia

Yallalie is a ~12 km diameter circular structure located ~200 km north of Perth, Australia. Previous studies have proposed that the buried structure is a complex impact crater based on geophysical data. Allochthonous breccia exposed near the structure has previously been interpreted as proximal impact ejecta; however, no diagnostic indicators of shock metamorphism have been found. Here we report multiple (27) shocked quartz grains containing planar fractures (PFs) and planar deformation features (PDFs) in the breccia. The PFs occur in up to five sets per grain, while the PDFs occur in up to four sets per grain. Universal stage measurements of all 27 shocked quartz grains confirms that the planar microstructures occur in known crystallographic orientations in quartz corresponding to shock compression from 5 to 20 GPa. Proximity to the buried structure (~4 km) and occurrence of shocked quartz indicates that the breccia represents either primary or reworked ejecta. Ejecta distribution simulated using iSALE hydrocode predicts the same distribution of shock levels at the site as those found in the breccia, which supports a primary ejecta interpretation, although local reworking cannot be excluded. The Yallalie impact event is stratigraphically constrained to have occurred in the interval from 89.8 to 83.6 Ma based on the occurrence of Coniacian clasts in the breccia and undisturbed overlying Santonian to Campanian sedimentary rocks. Yallalie is thus the first confirmed Upper Cretaceous impact structure in Australia

Dendritic reidite from the Chesapeake Bay impact horizon, Ocean Drilling Program Site 1073 (offshore northeastern USA): A fingerprint of distal ejecta?

High-pressure minerals provide records of processes not normally preserved in Earth’s crust. Reidite, a quenchable polymorph of zircon, forms at pressures &gt;20 GPa during shock compression. However, there is no broad consensus among empirical, experimental, and theoretical studies on the nature of the polymorphic transformation. Here we decipher a multistage history of reidite growth recorded in a zircon grain in distal impact ejecta (offshore northeastern United States) from the ca. 35 Ma Chesapeake Bay impact event which, remarkably, experienced near-complete conversion (89%) to reidite. The grain displays two distinctive reidite habits: (1) intersecting sets of planar lamellae that are dark in cathodoluminescence (CL); and (2) dendritic epitaxial overgrowths on the lamellae that are luminescent in CL. While the former is similar to that described in literature, the latter has not been previously reported. A two-stage growth model is proposed for reidite formation at &gt;40 GPa in Chesapeake Bay impact ejecta: formation of lamellar reidite by shearing during shock compression, followed by dendrite growth, also at high pressure, via recrystallization. The dendritic reidite is interpreted to nucleate on lamellae and replace damaged zircon adjacent to lamellae, which may be amorphous ZrSiO4 or possibly an intermediate phase, all before quenching. These results provide new insights on the microstructural evolution of the highpressure polymorphic transformation over the microseconds-long interval of reidite stability during meteorite impact. Given the formation conditions, dendritic reidite may be a unique indicator of distal ejecta

Iron projectile fractionation processes in siliceous glass from small impact craters

Detection of extra-terrestrial geochemical components in melt generated during meteorite impact provides diagnostic evidence that can be used to confirm a hypervelocity impact event, and in some cases, classify the projectile. However, projectile contamination is often present at sub-percent levels, and can be difficult to detect. In contrast, meteoritic abundances in glass from small impact craters (&lt;1 km diameter) formed by iron meteorites can be anomalously high, which has been attributed to glass originating from the projectile-target interface. Emulsion textures, immiscible liquids, metal spherules, and non-meteoritic siderophile element ratios have been cited as evidence that the projectile component is typically fractionated in impact glass. Here we present compositional data for impact glass from the Henbury crater field in Australia, where the largest crater is 145 m in diameter and the subgreywacke target rock and IIIAB iron projectile are geochemically distinct. Mixing models (Fe-Si, Ni-Co, Cr-Ir) and high platinum group element abundances indicate average projectile contributions ranging from 3 to 13 % in Henbury glass, comparable to ranges reported in glass from the Kamil (Egypt) and Wabar (Saudi Arabia) impact craters. However meteoritic siderophile element ratios (Fe:Ni, Fe:Co, Ni:Co) in Henbury glass appear nearly unfractionated, whereas Wabar and Kamil glasses have more fractionated ratios. Observed variations are attributed to fractionation of meteoritic Ni by formation of immiscible Ni-rich spherules during oxidation of meteoritic iron, and subsequent separation of Ni-rich spherules from glass during ejection. The Henbury glass sample analyzed is interpreted as an example of an interface melt that quenched prior to extensive oxidation and phase separation, and thus may represent one of the least fractionated samples of melt from the projectile-target interface described thus far, whereas Wabar and Kamil glasses record more evidence of fractionation processes. These results further highlight the influence of metal spherule formation on the composition of ejected glass from small impact structures formed by iron meteorites and provide new insights that explain textural features observed in natural impact glasses

Stirred not shaken; critical evaluation of a proposed Archean meteorite impact in West Greenland

Funding Information: The Ministry of Mineral Resources and Labour, Greenland Government supported field and analytical work.Large meteorite impacts have a profound effect on the Earth's geosphere, atmosphere, hydrosphere and biosphere. It is widely accepted that the early Earth was subject to intense bombardment from 4.5 to 3.8 Ga, yet evidence for subsequent bolide impacts during the Archean Eon (4.0 to 2.5 Ga) is sparse. However, understanding the timing and magnitude of these early events is important, as they may have triggered significant change points to global geochemical cycles. The Maniitsoq region of southern West Greenland has been proposed to record a ∼3.0 Ga meteorite impact, which, if confirmed, would be the oldest and only known impact structure to have survived from the Archean. Such an ancient structure would provide the first insight into the style, setting, and possible environmental effects of impact bombardment continuing into the late Archean. Here, using field mapping, geochronology, isotope geochemistry, and electron backscatter diffraction mapping of 5,587 zircon grains from the Maniitsoq region (rock and fluvial sediment samples), we test the hypothesis that the Maniitsoq structure represents Earth's earliest known impact structure. Our comprehensive survey shows that previously proposed impact-related geological features, ranging from microscopic structures at the mineral scale to macroscopic structures at the terrane scale, as well as the age and geochemistry of the rocks in the Maniitsoq region, can be explained through endogenic (non-impact) processes. Despite the higher impact flux, intact craters from the Archean Eon remain elusive on Earth.Publisher PDFPeer reviewe

Phase Heritage: Deciphering Evidence of Pre-Existing Phases via Inherited Crystallographic Orientations

The concept of 'phase heritage' (e.g., Timms et al., 2017a) involves microstructural recognition of the former presence of a phase that has since transformed to another via evidence encoded in crystallographic orientations. Phase heritage relies on the phenomenon that newly grown (daughter) phases nucleate with particular crystallographic orientation relationships with the preceding (parent) phase. This phenomenon is common for displacive (i.e., shear or martensitic) transformations, well documented in the metals and ceramics literature, but is relatively uncommon in geosciences. This presentation outlines the concepts behind this approach, showcases results from software for automated analysis of EBSD data, and illustrates examples of polymorphic and dissociation phase transformations in the ZrSiO4-ZrO2-SiO2 system, which has particularly useful applications for 'extreme thermobarometry' in impact environments (Timms et al., 2017a)

Melting mud in Earth's mantle

Melting of subducted sediment remains controversial, as direct observation of sediment melt generation at mantle depths is not possible. Geochemical fingerprints provide indirect evidence for subduction delivery of sediment to the mantle; however, sediment abundance in mantle-derived melt is generally low (0%–2%), and difficult to detect. Here we provide evidence for melting of subducted sediment in granite sampled from an exhumed mantle section. Peraluminous granite dikes that intrude peridotite in the Oman–United Arab Emirates ophiolite have U-Pb ages of 99.8 ± 3.3 Ma that predate obduction. The dikes have unusually high oxygen isotope (δ18O) values for whole rock (14–23‰) and quartz (20–22‰), and yield the highest δ18O zircon values known (14–28‰; values relative to Vienna standard mean ocean water [VSMOW]). The extremely high oxygen isotope ratios uniquely identify the melt source as high-δ18O marine sediment (pelitic and/or siliciceous mud), as no other source could produce granite with such anomalously high δ18O. Formation of high-δ18O sediment-derived (S-type) granite within peridotite requires subduction of sediment to the mantle, where it melted and intruded overlying mantle wedge. The granite suite described here contains the highest oxygen isotope ratios reported for igneous rocks, yet intruded mantle peridotite below the Mohorovičić seismic discontinuity, the most primitive oxygen isotope reservoir in the silicate Earth. Identifying the presence and quantifying the extent of sediment melting within the mantle has important implications for understanding subduction recycling of supracrustal material and effects on mantle heterogeneity over time.National Geographi