Nanogeochronology of discordant zircon measured by atom probe microscopy of Pb-enriched dislocation loops.
ABSTRACT: Isotopic discordance is a common feature in zircon that can lead to an erroneous age determination, and it is attributed to the mobilization and escape of radiogenic Pb during its post-crystallization geological evolution. The degree of isotopic discordance measured at analytical scales of ~10 ?m often differs among adjacent analysis locations, indicating heterogeneous distributions of Pb at shorter length scales. We use atom probe microscopy to establish the nature of these sites and the mechanisms by which they form. We show that the nanoscale distribution of Pb in a ~2.1 billion year old discordant zircon that was metamorphosed c. 150 million years ago is defined by two distinct Pb reservoirs. Despite overall Pb loss during peak metamorphic conditions, the atom probe data indicate that a component of radiogenic Pb was trapped in 10-nm dislocation loops that formed during the annealing of radiation damage associated with the metamorphic event. A second Pb component, found outside the dislocation loops, represents homogeneous accumulation of radiogenic Pb in the zircon matrix after metamorphism. The (207)Pb/(206)Pb ratios measured from eight dislocation loops are equivalent within uncertainty and yield an age consistent with the original crystallization age of the zircon, as determined by laser ablation spot analysis. Our results provide a specific mechanism for the trapping and retention of radiogenic Pb during metamorphism and confirm that isotopic discordance in this zircon is characterized by discrete nanoscale reservoirs of Pb that record different isotopic compositions and yield age data consistent with distinct geological events. These data may provide a framework for interpreting discordance in zircon as the heterogeneous distribution of discrete radiogenic Pb populations, each yielding geologically meaningful ages.
Project description: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.
Project description:Trace elements diffuse negligible distances through the pristine crystal lattice in minerals: this is a fundamental assumption when using them to decipher geological processes. For example, the reliable use of the mineral zircon (ZrSiO4) as a U-Th-Pb geochronometer and trace element monitor requires minimal radiogenic isotope and trace element mobility. Here, using atom probe tomography, we document the effects of crystal-plastic deformation on atomic-scale elemental distributions in zircon revealing sub-micrometre-scale mechanisms of trace element mobility. Dislocations that move through the lattice accumulate U and other trace elements. Pipe diffusion along dislocation arrays connected to a chemical or structural sink results in continuous removal of selected elements (for example, Pb), even after deformation has ceased. However, in disconnected dislocations, trace elements remain locked. Our findings have important implications for the use of zircon as a geochronometer, and highlight the importance of deformation on trace element redistribution in minerals and engineering materials.
Project description:Nanospheres of lead (Pb) have recently been identified in zircon (ZrSiO4) with the potential to compromise the veracity of U-Pb age determinations. The key assumption that the determined age is robust against the effects of Pb mobility, as long as Pb is not lost from the zircon during subsequent geological events, is now in question. To determine the effect of nanosphere formation on age determination, and whether analysis of nanospheres can yield additional information about the timing of both zircon growth and nanosphere formation, zircons from the Napier Complex in Enderby Land, East Antarctica, were investigated by high-spatial resolution NanoSIMS (Secondary Ion Mass Spectrometry) mapping. Conventional SIMS analyses with >µm resolution potentially mixes Pb from multiple nanospheres with the zircon host, yielding variable average values and therefore unreliable ages. NanoSIMS analyses were obtained of 207Pb/206Pb in nanospheres a few nanometres in diameter that were resolved from 207Pb/206Pb measurements in the zircon host. We demonstrate that analysis for 207Pb/206Pb in multiple individual Pb nanospheres, along with separate analysis of 207Pb/206Pb in the zircon host, can not only accurately yield the age of zircon crystallization, but also the time of nanosphere formation resulting from Pb mobilization during metamorphism. Model ages for both events can be derived that are correlated due to the limited range of possible solutions that can be satisfied by the measured 207Pb/206Pb ratios of nanospheres and zircon host. For the Napier Complex zircons, this yields a model age of ca 3110 Ma for zircon formation and a late Archean model age of 2610 Ma for the metamorphism that produced the nanospheres. The Nanosphere Model Age (NMA) method constrains both the crystallization age and age of the metamorphism to ~±135 Ma, a significant improvement on errors derived from counting statistics.
Project description:Metamorphic zircon from a hornblendite in the South China Block (SCB) yield U-Pb age of 533?±?7?Ma and Hf model ages from 900 to 1200?Ma. Geochemical and isotopic characteristics indicate that primary magma of the hornblendites was probably derived from an enriched asthenospheric mantle source. This Late Neoproterozoic-Cambrian (Pan-African) metamorphic event provides the first direct evidence that the SCB was an integral part of the Gondwana assembly. Combined with available geological data which show that the SCB has great affinity with India or Australia, the Pan-African metamorphic event most likely belongs to the eastern Kuunga orogeny. We propose that the SCB was located at the nexus between India, Antarctica and Australia along the northern margin of East Gondwana, with the Cathaysia Block connecting western Australia whereas the Yangtze Block facing northern India at ca. 533?Ma.
Project description:Zircon of crustal origin found in mantle-derived rocks is of great interest because of the information it may provide about crust recycling and mantle dynamics. Consideration of this requires understanding of how mantle temperatures, notably higher than zircon crystallization temperatures, affected the recycled zircon grains, particularly their isotopic clocks. Since Pb2+ diffuses faster than U4+ and Th+4, it is generally believed that recycled zircon grains lose all radiogenic Pb after a few million years, thus limiting the time range over which they can be detected. Nonetheless, this might not be the case for zircon included in mantle minerals with low Pb2+ diffusivity and partitioning such as olivine and orthopyroxene because these may act as zircon sealants. Annealing experiments with natural zircon embedded in cristobalite (an effective zircon sealant) show that zircon grains do not lose Pb to their surroundings, although they may lose some Pb to molten inclusions. Diffusion tends to homogenize the Pb concentration in each grain changing the U-Pb and Th-Pb isotope ratios proportionally to the initial 206Pb, 207Pb and 208Pb concentration gradients (no gradient-no change) but in most cases the original age is still recognizable. It seems, therefore, that recycled crustal zircon grains can be detected, and even accurately dated, no matter how long they have dwelled in the mantle.
Project description:Wilkes Land in East Antarctica remains one of the last geological exploration frontiers on Earth. Hidden beneath kilometres of ice, its bedrock preserves a poorly-understood tectonic history that mirrors that of southern Australia and holds critical insights into past supercontinent cycles. Here, we use new and recently published Australian and Antarctic geological and geophysical data to present a novel interpretation of the age and character of crystalline basement and sedimentary cover of interior Wilkes Land. We combine new zircon U-Pb and Hf isotopic data from remote Antarctic outcrops with aeromagnetic data observations from the conjugate Australian-Antarctic margins to identify two new Antarctic Mesoproterozoic basement provinces corresponding to the continuation of the Coompana and Madura provinces of southern Australia into Wilkes Land. Using both detrital zircon U-Pb-Hf and authigenic monazite U-Th-Pb isotopic data from glacial erratic sandstone samples, we identify the presence of Neoproterozoic sedimentary rocks covering Mesoproterozoic basement. Together, these new geological insights into the ice-covered bedrock of Wilkes Land substantially improve correlations of Antarctic and Australian geological elements and provide key constraints on the tectonic architecture of this sector of the East Antarctic Shield and its role in supercontinent reconstructions.
Project description:Zircons are crucial to understanding the first 500?Myr of crustal evolution of Earth. Very few zircons of this age (>4050?Ma) have been found other than from a ~300?km diameter domain of the Yilgarn Craton, Western Australia. Here we report SIMS U-Pb and O isotope ratios and trace element analyses for two ~4100?Ma detrital zircons from a Paleozoic quartzite at the Longquan area of the Cathaysia Block. One zircon ((207)Pb/(206)Pb age of 4127 ± 4?Ma) shows normal oscillatory zonation and constant oxygen isotope ratios (?(18)O = 5.8 to 6.0‰). The other zircon grain has a ~4100?Ma magmatic core surrounded by a ~4070?Ma metamorphic mantle. The magmatic core has elevated ?(18)O (7.2 ± 0.2‰), high titanium concentration (53 ± 3.4?ppm) and a positive cerium anomaly, yielding anomalously high calculated oxygen fugacity (FMQ + 5) and a high crystallization temperature (910°C). These results are unique among Hadean zircons and suggest a granitoid source generated from dry remelting of partly oxidizing supracrustal sediments altered by surface waters. The ~4100?Ma dry melting and subsequent ~4070?Ma metamorphism provide new evidence for the diversity of the Earth's earliest crust.
Project description:The mineral zircon through its isotopic and elemental signatures comprises the greatest archive recording the evolution of Earth's continental crust. Recognising primary from secondary zircon compositional signatures is thus important for the accurate interpretation of this archive. We report two examples of metasedimentary rocks from high-grade shear zones within the Southern Granulite Belt of India, where anomalously high and homogeneous oxygen isotope signatures indicate disturbance of this isotopic system. Utilising the combined U-Pb-Hf-O and trace element signatures from these zircon grains, we postulate that fluid-assisted alteration has led to complete resetting of the oxygen isotope signatures. This case study presents a rarely observed natural example of potentially fast diffusion of oxygen under hydrous conditions. Given the pervasive nature of fluid interaction within high-grade and highly deformed rocks, we expect that such isotopic disturbance might be more common to nature than is currently reported. A lack of correlation between isotopic disturbance with cathodoluminescence or Th/U values, suggests that these altered zircon grains would not clearly be classified as metamorphic, in which case they would be expected to yield primary compositions. Caution is therefore advised when using detrital ?18O zircon compilations without a high level of scrutiny for primary versus secondary compositions.
Project description:This study presents boron (B) concentration and isotope data for white mica from (ultra)high-pressure (UHP), subduction-related metamorphic rocks from Lago di Cignana (Western Alps, Italy). These rocks are of specific geological interest, because they comprise the most deeply subducted rocks of oceanic origin worldwide. Boron geochemistry can track fluid-rock interaction during their metamorphic evolution and provide important insights into mass transfer processes in subduction zones. The highest B contents (up to 345 ?g/g B) occur in peak metamorphic phengite from a garnet-phengite quartzite. The B isotopic composition is variable (?11B?=?-?10.3 to?-?3.6%) and correlates positively with B concentrations. Based on similar textures and major element mica composition, neither textural differences, prograde growth zoning, diffusion nor a retrograde overprint can explain this correlation. Modelling shows that B devolatilization during metamorphism can explain the general trend, but fails to account for the wide compositional and isotopic variability in a single, well-equilibrated sample. We, therefore, argue that this trend represents fluid-rock interaction during peak metamorphic conditions. This interpretation is supported by fluid-rock interaction modelling of boron leaching and boron addition that can successfully reproduce the observed spread in ?11B and [B]. Taking into account the local availability of serpentinites as potential source rocks of the fluids, the temperatures reached during peak metamorphism that allow for serpentine dehydration, and the high positive ?11B values (?11B?=?20?±?5) modelled for the fluids, an influx of serpentinite-derived fluid appears likely. Paragonite in lawsonite pseudomorphs in an eclogite and phengite from a retrogressed metabasite have B contents between 12 and 68 ?g/g and ?11B values that cluster around 0% (?11B?=?-?5.0 to?+?3.5). White mica in both samples is related to distinct stages of retrograde metamorphism during exhumation of the rocks. The variable B geochemistry can be successfully modelled as fluid-rock interaction with low-to-moderate (<?3) fluid/rock ratios, where mica equilibrates with a fluid into which B preferentially partitions, causing leaching of B from the rock. The metamorphic rocks from Lago di Cignana show variable retention of B in white mica during subduction-related metamorphism and exhumation. The variability in the B geochemical signature in white mica is significant and enhances our understanding of metamorphic processes and their role in element transfer in subduction zones.
Project description:The absolute crystallization ages of minerals from hydrothermal fluids measured in situ can unravel the timing of key events leading to the formation of, for instance, ore deposits and hydrothermally derived geological terrains. In this study, a skarn iron deposit from northwest (NW) China is shown to have U-Pb garnet and U-Pb zircon ages of 254.2 ± 1.7 Ma and 255.5 ± 1.0 Ma, respectively, which are both significantly younger than magmatism and metamorphism of the region. This skarn age instead correlates with the occurrence of strike-slip and thrust faulting in the region. The water/rock mass ratio of 0.065~0.115 suggests the δ18O garnet composition is ~1‰ at temperatures ranging from 250-450 °C. The low oxygen isotopic composition indicates the role of meteoric water in the garnet formation. These measurements can be interpreted as the shear along faults circulating meteoric water ~10 km below the hanging wall of meta-volcanic sedimentary rock. Meteoric water in this hydrothermal system would leach cations from the meta-volcano-sedimentary rocks necessary for mineralization. Silica-rich hydrothermal fluid reacts with calcic-rich materials in the meta-volcano-sedimentary rocks, depositing the garnet and magnetite. Our work suggests that the shear zone is rich in ores, rendering this deposit for NW China a prospective source for future mineral resource exploration.