Monika A. Kusiak

Mobilization of radiogenic Pb in zircon revealed by ion imaging: Implications for early Earth geochronology

Zircon is arguably the most commonly used geochronometer, but the reliability of ages obtained requires a full understanding of processes that might compromise the integrity of its U-Pb systematics. Here we present the results of a multifaceted ion microprobe study of zircon grains from the Napier Complex, East Antarctica, a region affected by pervasive high-temperature metamorphism at 2.5 Ga, and from which previous zircon geochronological interpretations have been problematic. Both U-Pb spot analysis (∼15 μm) and high spatial resolution (∼2 μm) scanning ion imaging of Pb isotopes have been applied in an attempt to quantify the effects of metamorphism. Spot analyses spread along concordia yielding 207 Pb/ 206 Pb ages from 2.5 Ga to 3.9 Ga, with the oldest grains reversely discordant. Ion images of uranogenic Pb reveal a surprising micrometer-scale patchy distribution that is unrelated to crystal morphology or damage. The 207 Pb/ 206 Pb ratios within these subdomains correspond to apparent zircon ages as old as 4.2 Ga. These are interpreted as artifacts of ancient redistribution of radiogenic Pb, a process that can generate meaningless ages, and are not relicts of ancient (including Hadean) zircon. Scanning ion imaging thus facilitates identification of unsupported radiogenic Pb and enables testing of the validity of old ages from zircon known to have a long and complicated history.

Sensitive high-resolution ion microprobe analysis of zircon reequilibrated by late magmatic fluids in a hybridized pluton

Zircon from a microgranular enclave in the ca. 315 Ma postcollisional Karkonosze pluton (Western Sudetes, northeastern Bohemian Massif) is characterized by unusual morphologies and reequilibration textures. Blocky, clustered, and skeletal Th-U–rich zircon grains are internally corroded along discrete boundary zones, and subsequently replaced by porous microgranular aggregates of zircon and various other minerals, including thorite. The boundary zones have textures and compositions characteristic of diffusion-controlled chemical reaction fronts, including enrichment in Ca, Ba, and light rare earth elements, whereas microgranular domains are typical of zircon replacement and regrowth by coupled dissolution and precipitation. Initial zircon crystallization occurred with the mingling of mafic magma into a cooler granitic melt, whereas zircon modification is attributed to the reaction of late magmatic fluids from the host granite with the enclave. Precise dating of reequilibrated zircon as 304 ± 2 Ma indicates that fluid activity, which is also responsible for scheelite mineralization, postdates the emplacement of the main part of the pluton by several millions of years.

Changes in zircon chemistry during archean UHT metamorphism in the Napier complex, Antarctica

Zircons from two paragneisses (from Mount Sones and Dallwitz Nunatak) and one orthogneiss (from Gage Ridge) in the Tula Mountains, Napier Complex (East Antarctica) were analyzed for U-Pb age, oxygen isotopes, REEs and by scanning ion imaging. A large number of zircons from all samples are reversely discordant. Mount Sones zircons show an age range from 3.0 Ga to 2.5 Ga and underwent high-grade metamorphism at both ∼2.8 Ga and 2.5 Ga. Zircons from Dallwitz Nunatak record detrital ages between 3.5 Ga and 2.5 Ga. Zircons from Gage Ridge record multiple age groups, with concordant data between 3.6 Ga and 3.3 Ga and reversely discordant data that form a discrete ∼3.8 Ga population. All of the grains show evidence of Pb mobility during metamorphism. Ion imaging of zircons reveals Y and U zonation, characteristic of magmatic zircon, together with a micro-scale patchy distribution of 206Pb and 207Pb that does not correspond to either growth zonation or crystal imperfections. Some of these patches yield 207Pb/206Pb ages >4 Ga, whereas others yield ages younger than the magmatic crystallization age. Reversely discordant data are the result of ancient Pb mobilization, which is independent of the degree of metamictisation, oxygen isotope and REE content of the zircons. This mobilization can result in spurious ages and was most likely caused by polymetamorphism under anhydrous conditions; that is two high-grade events; one poorly defined at ∼2.8 Ga and the other ultra-high temperature (UHT) metamorphism at 2.5 Ga.

Metallic lead nanospheres discovered in ancient zircons

Significance Metallic lead nanospheres have been discovered in ancient (>3.4 Ga) zircon grains from an Archean (2.5 Ga) high-grade metamorphic terrain in East Antarctica. Native Pb is present as 5–30 nm nanospheres, commonly in association with an amorphous silica-rich phase, along with titanium and aluminium-bearing phases. Together, these phases form nanoinclusions generated during the recovery of crystallinity in radiation-damaged zircon under high-grade metamorphic conditions. Once formed, the entrapment of nanospheres in annealed zircon effectively arrests Pb loss, explaining why zircon that has experienced such extreme conditions is not completely reset to its metamorphic age. The heterogeneous distribution of Pb can, however, affect isotopic measurement by microbeam techniques, leading to spurious age estimates. Metallic Pb is extremely rare in nature and has never previously been observed in high temperature rocks. Zircon (ZrSiO4) is the most commonly used geochronometer, preserving age and geochemical information through a wide range of geological processes. However, zircon U–Pb geochronology can be affected by redistribution of radiogenic Pb, which is incompatible in the crystal structure. This phenomenon is particularly common in zircon that has experienced ultra-high temperature metamorphism, where ion imaging has revealed submicrometer domains that are sufficiently heterogeneously distributed to severely perturb ages, in some cases yielding apparent Hadean (>4 Ga) ages from younger zircons. Documenting the composition and mineralogy of these Pb-enriched domains is essential for understanding the processes of Pb redistribution in zircon and its effects on geochronology. Using high-resolution scanning transmission electron microscopy, we show that Pb-rich domains previously identified in zircons from East Antarctic granulites are 5–30 nm nanospheres of metallic Pb. They are randomly distributed with respect to zircon crystallinity, and their association with a Ti- and Al-rich silica melt suggests that they represent melt inclusions generated during ultra-high temperature metamorphism. Metallic Pb is exceedingly rare in nature and previously has not been reported in association with high-grade metamorphism. Formation of these metallic nanospheres within annealed zircon effectively halts the loss of radiogenic Pb from zircon. Both the redistribution and phase separation of radiogenic Pb in this manner can compromise the precision and accuracy of U–Pb ages obtained by high spatial resolution methods.

Age determination of monazites using the new experimental chamber of the Cracow proton microprobe

Abstract The Cracow microprobe was applied to determine the age of small detritalmonazite crystals extracted from the uppermost carboniferous sandstone of Upper Silesia Coal Basin (southern Poland). The method applied follows the technique of chemical dating of U–Th minerals: assuming that the monazite crystal is a closed system and all Pb within grain is radiogenic, it is possible to determine the age of a specimen by solving an equilibrium equation which includes as computational factors the elemental contents of U, Th and Pb and decay times of uranium and thorium. Using this approach, thanks to rather fast Pb accumulation in a crystal, monazite older than 100 My may be dated with relative ease. The investigated specimens were clusters of crystals, 30–100 μm in size, polished and mounted in Epoxy resin. Due to different geological history, the age of individual crystals from one sample may differ significantly, therefore the application of a microprobe has been necessary to extract information concerning single monazite grains. Two age groups were identified: small cluster, connected with Cadomian tectonothermal event (579±30 My) and dominating cluster, connected with Variscan tectonothermal event (329±19 My, 353±41 My). After successful preliminary measurements carried out in a provisory experimental chamber, an optimized chamber was constructed and set into operation for regular studies. Together with results of these investigations, the constructional details of the new chamber are presented.