Radiation-damaged Zircon Research Articles

Detrital zircon in Pleistocene aeolianite of the Isipingo Formation at Cape Vidal, KwaZulu-Natal, South Africa, gives age and Hf isotope signatures without provenance significance

Abstract Pleistocene (50 to 70 ka) aeolianite of the Isipingo Formation (Maputaland Group) at Cape Vidal, northern KwaZulu-Natal province, South Africa, contains a combination of three detrital zircon age fractions (A: 940 to 1150 Ma, B: 470 to 720 Ma, C: 230 to 280 Ma) that are also known from Holocene sediments in eastern South Africa, Mesozoic – Cenozoic sandstones in southern Mozambique and from the Carboniferous to Jurassic Karoo Supergroup. Archaean and Palaeoproterozoic bedrock of the Kaapvaal Craton, which is exposed in the drainage basins of rivers that have provided detritus to coastal sedimentary basins, is represented by one single Archaean zircon. Combined laser Raman micro-spectroscopy and estimates of accumulated alpha radiation dose from U and Th concentrations indicate that the virtual absence of zircon older than late Mesoproterozoic cannot be attributed to selective removal of radiation-damaged zircon grains by abrasion during erosion and transport. The Isipingo Formation sandstone at Cape Vidal is a product of sedimentary recycling, potentially involving river transport from the continental hinterland, water- and wind-borne drift parallel to the coast and local recycling. Because of the similarity in detrital zircon distribution patterns of the sandstone and all of its potential Palaeozoic to Cretaceous sedimentary precursors, detrital zircon data cannot provide useful information on the relative importance of these processes, or on the routing of detritus to its final site of deposition.

The role of zircon in hydrothermal heavy REE mineralisation: The case for unconformity-related ore deposits of north-west Australia

Zircon is hailed for its chemical and physical durability, but can undergo extensive chemical and structural modification due to radiation damage via the emission of alpha (α) particles, and subsequent low-temperature hydrothermal alteration. Here, we investigate Archean zircons from arkosic metasediments of the Browns Range Metamorphics (BRM) to evaluate their role in the formation of local unconformity-related heavy rare earth element (REE) ore deposits, within the Browns Range Dome, Western Australia. We determine that the heavy REE inventory of the BRM are primarily hosted in zircon, and that these zircons have a wide range of major element totals (77 to ~100 wt%, including low SiO2 and ZrO2 contents), and high and variable ‘non-formula’ components (U, Th, Y, REE, Nb, P, Al, Ca, Fe, Ti, F and OH− or H2O). Concentrations of Y + REE in some cases exceed 8 wt%. Extensive radiation damage (metamictisation) is confirmed by structural features including porous and amorphous domains, cavities, and voids. The lack of regional thermal events over an extended period likely prevented thermal annealing of these radiation-damaged zircons. Uptake of non-formula elements in metamict zircon, most likely during sedimentation in the late Archean, promoted further radiation damage, such that these grains remained highly susceptible to alteration by subsequent hydrothermal fluid circulation. We propose that the unconformity-related REE mineralisation was formed by saline fluids leaching Y + REE (and possibly P) from metamict zircon in the BRM, followed by ore mineral precipitation in fault zones near, and along the regional unconformity. More broadly, this model of ore formation may be relevant to other basin-hosted mineral systems, and could be used to guide exploration for unconformity-related REE deposits in Australia, and globally.

Probing structural disorder in zircon by electron backscatter diffraction (EBSD): Radiation damage and Kikuchi pattern

Electron backscatter diffraction (EBSD) was employed to probe the structural order of a zoned radiation-damaged zircon (ZrSiO4) on the sub-micron scale. The amorphous fraction of the growth-zones is in the range of ∼45–80%, due to variations in the amount of incorporated uranium and thorium (∼0.22–0.43 wt% UO2 and ∼0.02–0.08 wt% ThO2) and the resulting alpha-decay events over time. The obtained Kikuchi patterns’ band contrast (bc) and band slope (bs) are indicative of the degree of atomic-scale order. The excellent correlation of both parameters with the evolution of the elastic modulus validates the methods reliability.

Setting and formation of the earliest Neoproterozoic rifted arc Pingshui VMS deposit, South China

The Neoproterozoic Pingshui volcanogenic massive sulfide (VMS) deposit (Cu and Zn metals of 0.40 Mt) represents one of the best preserved VMS deposits in the northeastern margin of the Jiangnan Orogen, South China. This study reconstructs its magmatic and metallogenetic history and geodynamic evolution using new geological, whole-rock geochemical, and zircon U–Pb–Lu–Hf isotopic analyses. Two lithotectonic units are identified: the ore-hosting Pingshui Formation composed of a bimodal basalt-rhyolite suite and pyroclastic rocks, and the post-ore extrusive-intrusive assemblage including high-Mg basalt, Nb-enriched basalt, high-Mg diorite and felsic granitoids. The formation age of Pingshui Formation basalt to andesite is newly constrained at ∼977 ± 15 Ma by the least radiation-damaged zircon. The new and compiled data suggest that these post-ore rocks were generated during ∼932–904 Ma after a possible magmatic quiescence. In terms of geochemical characteristics, both the Pingshui Formation basalt to andesite (∼977 Ma) and late high-Mg basalt (∼921 Ma) are enriched in light rare earth elements (LREEs) and depleted in high field strength elements (HFSEs, e.g., Nb, Ta, P, Ti, Zr and Hf). The late high-Mg diorite (∼932 Ma, MgO = 5.84–6.91%) has moderate (La/Yb)N ratios (13.7–14.1), resembling those of high-Mg andesites (HMA). These geochemical signatures indicate that they originated from a heterogeneous mantle wedge metasomatized by slab-derived fluids and melts. The Nb-enriched basalt (∼916 Ma) was derived from a mixture of OIB- and arc-like mantle sources as evidenced by relatively high Ti/V, Ti/Zr and Zr/Y ratios. The geochemical changes from a dominant subduction influence to asthenospheric involvement, corresponding to the mafic-intermediate rocks (977–921 Ma) and the Nb-enriched basalt (916 Ma) respectively, is indicative of a possible slab roll-back that triggered asthenospheric upwelling. Furthermore, the felsic rocks originated from partial melting of juvenile mafic lower crust or fractional crystallization of parental mafic melts. Their anomalously high temperatures of formation (over 950 °C), which are indicated by zircon saturation thermometry, suggest a long-lasting high heat flow environment. In summary, subduction of young oceanic crust and intra-arc rifting are likely mechanisms to account for the formation of the high temperature magmatic rocks and massive sulfide ores at Pingshui.

Open-system behaviour of detrital zircon during weathering: an example from the Palaeoproterozoic Pretoria Group, South Africa

AbstractDetrital zircon in six surface samples of sandstone and contact metamorphic quartzite of the Magaliesberg and Rayton formations of the Pretoria Group (depositional age c. 2.20–2.06 Ga) show a major age fraction at 2.35–2.20 Ga, and minor early Palaeoproterozoic – Neoarchaean fractions. Trace-element concentrations vary widely, with Ti, Y and light rare earth elements (LREEs) spanning over three orders of magnitude. REE distribution patterns range from typical zircon patterns (LREE depletion, heavy REE enrichment, well-developed positive Ce and negative Eu anomalies) to patterns that are flat to concave downwards, with indistinct Ce and Eu anomalies. The change in REE pattern correlates with increases in alteration-sensitive parameters such as Ti concentration and (Dy/Sm) + (Dy/Nd), U–Pb discordance and content of common lead, and with a gradual washing-out of oscillatory zoning in cathodoluminescence images. U and Th concentrations also increase, but Th/U behaves erratically. Discordant zircon scatters along lead-loss lines to zero-age lower intercepts, suggesting that the isotopic and chemical variations are the results of disturbance long after deposition. The rocks sampled have been in a surface-near position (at least) since Late Cretaceous time, and exposed to deep weathering under intermittently hot and humid conditions. In this environment, even elements commonly considered as relatively insoluble could be mobilized locally, and taken up by radiation-damaged zircon. Such secondary alteration effects on U–Pb and trace elements can be expected in zircon in any ancient sedimentary rock that has been exposed to tropical–subtropical weathering, which needs to be considered when interpreting detrital zircon data.

Fracture toughness of radiation-damaged zircon studied by nanoindentation pillar-splitting

Nanoindentation micro-pillar splitting was employed to measure the fracture toughness (KC) of growth-zones in radiation-damaged zircon with varying degrees of disorder (∼45%–80% amorphous fraction). The radiation-induced amorphization is caused by α-decay events from incorporated U and Th (∼0.22–0.43 wt. % UO2 and ∼0.02–0.08 wt. % ThO2). KC has been found to increase with the increase in the amorphous fraction (∼2.39 to 3.15 MPa*m1/2). There is a good correlation with the modulus/hardness (E/H) ratio evolution over the investigated zones. As zircon has been proposed as a nuclear waste form for the incorporation and disposal of Pu, a deeper knowledge of KC as a function of radiation damage is important, as radiation-induced cracking provides diffusion paths for the release of incorporated actinides. Zoned zircon provides a model for the development of multilayer coatings and complex ceramics that can be designed to be resistant to crack propagation.

Trace-element segregation to dislocation loops in experimentally heated zircon

AbstractTo evaluate the mechanisms driving nanoscale trace element mobility in radiation-damaged zircon, we analyzed two well-characterized Archean zircons from the Kaapvaal Craton (southern Africa): one zircon remained untreated and the other was experimentally heated in the laboratory at 1450 °C for 24 h. Atom probe tomography (APT) of the untreated zircon reveals homogeneously distributed trace elements. In contrast, APT of the experimentally heated zircon shows that Y, Mg, Al, and Pb+Yb segregate to a set of two morphologically and crystallographically distinct cluster populations that range from 5 nm tori to 25 nm toroidal polyhedra, which are confirmed to be dislocation loops by transmission electron microscopy (TEM). The dislocation loops lie in {100} and {001} planes; the edges are aligned with <100>, <101>, and <001>. The largest loops (up to 25 nm diameter) are located in {100} and characterized by high concentrations of Mg and Al, which are aligned with <001>. The 207Pb/206Pb measured from Pb atoms located within all of the loops (0.264 ± 0.025; 1σ) is consistent with present-day segregation and confirms that the dislocation loops formed during our experimental treatment. These experimentally induced loops are similar to clusters observed in zircon affected by natural geologic processes. We interpret that differences in cluster distribution, density, and composition between experimentally heated and geologically affected zircon are a function of the radiation dose, the pressure-temperature-time history, and the original composition of the zircon. These findings provide a framework for interpreting the significance of clustered trace elements and their isotopic characteristics in zircon. Our findings also suggest that the processes driving cluster formation in zircon can be replicated under laboratory conditions over human timescales, which may have practical implications for the mineralogical entrapment of significant nuclear elements.

Comparison of reidite formation between zircon bulk and nanoparticles

Although modifying high-pressure behavior through the particle-size of a material is well recognized, a clear mechanism, underlying the start and subsequent growth of a high-pressure phase, remains elusive. Here, we investigate the effects of particle-size on the formation of reidite (ZrSiO4, I41/a), a high-pressure phase of zircon (ZrSiO4, I41/amd), by comparing zircon nanoparticles with bulk. This is done by high pressure Raman scattering and synchrotron X-ray diffraction experiments on zircons pressurized in diamond anvil cells and subsequent transmission electron microscopy analysis of quenched samples. As compared to bulk, the larger surface energy of nanoparticles is the cause of a higher critical pressure required to start the transition to reidite. However, after passing the critical pressures, the similar growth trends between nanoparticles and bulk indicate that the reidite growth is dependent on the core, rather than the surface. These results are important to identify craters caused by meteorite impacts using reidite as a high-pressure indicator, as nanoparticles are formed in naturally-occurring, highly radiation-damaged zircon.

Dry annealing of radiation-damaged zircon: Single-crystal X-ray and Raman spectroscopy study

Structural reconstitution upon dry thermal annealing of mildly to strongly radiation-damaged, gem-quality zircon from Sri Lanka has been studied by single-crystal X-ray diffraction and Raman spectroscopy. Results of structure refinement of a strongly radiation-damaged zircon (sample GZ5, calculated alpha dose ~4 × 1018 g−1) indicate the existence of an interstitial oxygen site that is sparsely occupied (about 4% of all O atoms). Annealing of this sample at Ta (annealing temperature) = 700 °C has resulted in nearly complete recrystallization of its amorphous volume fraction and significant decrease in the occupation of O-interstitial sites. For all samples studied, annealing up to Ta ≤ 650–700 °C is characterised by preferred recovery of Raman shifts (compared to Raman FWHMs; full width at half band maximum) and extensive contraction of the unit-cell volume, in particular along unit-cell dimension a. This low-T annealing is dominated by epitaxial growth of the crystalline volume fraction at the expense of the amorphous volume fraction, and general recovery of low-energy defects. During annealing at Ta = 700–1400 °C there is preferred recovery of Raman FWHMs (compared to Raman shifts) and only mild unit-cell contraction. High-T annealing is dominated by the recovery of high-energy defects such as recombination of cation Frenkel pairs. Here, unit-cell parameter a shows a remarkable behaviour (namely, mild re-increase at Ta = 700–1150 °C and mild final shrinking at Ta = 1000–1400 °C), which is attributed to enhanced contortion of ZrO8 polyhedrons due to cation repulsion. The combined data set of Raman band and unit-cell parameter presented herein will help analysts to assign Raman spectra of annealed unknowns to certain recovery stages.

Alteration and elements migration of detrital zircons from the Daying uranium deposit in the Ordos Basin, China

To study the alteration and elements migration characteristics of detrital zircon in sandstone-hosted uranium deposits, we analyzed three groups of zircon samples from the Jurassic Zhiluo Formation of the Daying uranium deposit in the northern Ordos Basin, China. One group of zircons was selected from the uranium metallogenic belt, while the other two groups were obtained from the non-metallogenic belt. According to the back-scattered electron (BSE) images and energy dispersive spectrometer (EDS) elemental maps, zircon can be divided into altered and unaltered zircon, and alteration types include oscillatory zoning alteration and rim alteration. The rare earth element (REE) pattern of unaltered zircon is characterized by positive Ce anomalies and negative Eu anomalies, similar with those of the Early Precambrian metamorphic rocks of the Khondalite Belt in the North China Craton. The results of the trace element analysis showed that REEs, uranium, and non-formula elements (e.g., Al, Fe, and Ca) are abundant in the altered area, specifically observable in the BSE images, and along with the EDS elemental maps of altered zircon in the uranium metallogenic belt, exhibited higher uranium concentrations and more developed cracks. Interaction of fluids with the radiation-damaged zircon lattice can provide a favorable conditions for fluid infiltration and element migration. The action of uranium-bearing fluids and the radiation of uranium minerals can induce zircon alteration and crack formation, which is instructive in uranium prospecting.

The closure temperature(s) of zircon Raman dating

Abstract. Zircon Raman dating based on irradiation damage is a debated concept but not an established geo-/thermochronological method. One issue is the temperature range of radiation-damage annealing over geological timescales. We conducted isochronal and isothermal annealing experiments on radiation-damaged zircons between 500 and 1000 ∘C for durations between 10 min and 5 d to describe the annealing kinetics. We measured the widths (Γ) and positions (ω) of the ν1(SiO4), ν2(SiO4), and ν3(SiO4) internal Raman bands, and the external rotation Raman band at ∼974, 438, 1008, and 356 cm−1 after each annealing step. We fitted a Johnson–Mehl–Avrami–Kolmogorov and a distributed activation energy model to the fractional annealing data, calculated from the widths of the ν2(SiO4), ν3(SiO4), and external rotation bands. From the kinetic models, we determined closure temperatures Tc for damage accumulation for each Raman band. Tc ranges from 330 to 370 ∘C for the internal ν2(SiO4) and ν3(SiO4) bands; the external rotation band is more sensitive to thermal annealing (Tc∼260 to 310 ∘C). Our estimates are in general agreement with previous ones, but more geological evidence is needed to validate the results. The Tc difference for the different Raman bands offers the prospect of a multi-closure-temperature zircon Raman thermochronometer.

Effect of water on δ18O in zircon

The mineral zircon is stable across a wide range of temperature and pressure conditions, and the most widely used geochronometer in felsic rocks. The oxygen isotope ratio recorded by zircon crystals is a sensitive tracer for crustal recycling in magmatic rocks and is a commonly used tool to address zircon petrogenetic questions (e.g. in studies on the evolution of geodynamics and continents). However, secondary processes (i.e. water uptake facilitated by radiation damage) can alter the oxygen isotopic composition of zircon. We present in-situ oxygen isotopic and 16O1H/16O data of natural zircon samples in combination with zircon trace element concentrations, and parameters that quantify crystal damage (i.e. Raman spectral parameters and alpha dose). In agreement with previous studies, our results demonstrate that the uptake of water into the zircon crystal structure strongly influences its recorded oxygen isotope ratio. Two distinct secondary processes are recorded which shift zircon δ18O values towards isotopically heavier and lighter values, respectively. Lower δ18O values associated with broadening of the zircon Raman bands and increasing 16O1H/16O are the result of a local charge-balance process during the interaction of radiation-damaged zircon with meteoric water. In contrast, an equilibrium fractionation process between zircon and percolating water leads to higher δ18O values with increasing 16O1H/16O. The disturbance of the oxygen isotopic system in zircon can be assessed through monitoring zircon 16O1H/16O; a parameter that is highly sensitive to the influx of water into radiation-damaged areas of the zircon grain, providing a powerful tool to access the validity of primary δ18O signatures.

The effect of low-temperature annealing on discordance of U\u2013Pb zircon ages

Discordant U–Pb data of zircon are commonly attributed to Pb loss from domains with variable degree of radiation damage that resulted from α-decay of U and Th, which often complicates the correct age interpretation of the sample. Here we present U–Pb zircon data from 23 samples of ca. 1.7–1.9 Ga granitoid rocks in and around the Siljan impact structure in central Sweden. Our results show that zircon from rocks within the structure that form an uplifted central plateau lost significantly less radiogenic Pb compared to zircon grains in rocks outside the plateau. We hypothesize that zircon in rocks within the central plateau remained crystalline through continuous annealing of crystal structure damages induced from decay of U and Th until uplifted to the surface by the impact event ca. 380 Ma ago. In contrast, zircon grains distal to the impact have accumulated radiation damage at shallow and cool conditions since at least 1.26 Ga, making them vulnerable to fluid-induced Pb-loss. Our data are consistent with studies on alpha recoil and fission tracks, showing that annealing in zircon occurs at temperatures as low as 200–250 °C. Zircon grains from these samples are texturally simple, i.e., neither xenocrysts nor metamorphic overgrowths have been observed. Therefore, the lower intercepts obtained from regression of variably discordant zircon data are more likely recording the age of fluid-assisted Pb-loss from radiation-damaged zircon at shallow levels rather than linked to regional magmatic or tectonic events.

Short-range order and electronic structure of radiation-damaged zircon according to X-ray photoelectron spectroscopy

Core-level and valence-band X-ray photoelectron spectroscopy was employed to study the dose-dependent radiation effects in the short-range order and the electronic structure of natural U, Th-bearing zircon near-surface layers. Single crystals from different localities (Ratanakiri, Cambodia; Mud Tank, Australia; Highlands, Sri Lanka) exhibiting wide variations in the accumulated radiation dose D≈(0 ÷ 9.2)·1018 α-decays/g was investigated. The dose values obtained by electron probe microanalysis and Raman micro-spectroscopy were used to correlate the samples with the two percolation transitions (p1, p2) in the amorphous-crystalline structure of damaged zircon. The dose-dependent variations in Eb (530.9–531.3, 101.7–102.4, 182.8- 183.3 eV) and FWHM (1.32–2.57, 1.47–1.77, 1.16 -1.55 eV) of the O1s, Si2p, and Zr3d5/2 core levels, respectively, were attributed to changes in the ensemble of non-equivalent short-range order structures. An increase in the dose resulted in the complication of the oxygen sublattice, with the following nearest environments of O atoms: (1) O (Si, [8]Zr, [8]Zr), Eb = 530.8–531.2 eV, the amount of > ~3.5 apfu (at D p2). For the first time, under an increase in the radiation dose, the oppositely directed changes in the effective charges of Si and Zr cations were detected in damaged zircon. This phenomenon was assigned to an increase in the content of the short-range order fragments characteristic of pure oxides SiO2 (namely, Si-O-Si) and ZrO2 (namely, [7]Zr) as well as to the influence of the anions O (Si, Si, [8]Zr), and the assignment was independently confirmed by the valence band analysis. The sequence of transformations in the Si-O and Zr-O sublattices was shown to be not concurrent: a partial polymerization of SiO4 tetrahedra occurs mainly at low and medium doses (D p2) in the amorphous fraction.

Diffusion of helium in radiation-damaged zircon

Diffusion of helium was characterized in natural zircon that had been implanted with Kr at a range of energies to simulate the effects of alpha recoil in natural radiation damage. Polished slabs of zircon, oriented either normal or parallel to c, were implanted with Kr+ ions at a series of energies to produce a damaged region ∼ 1μm in thickness, then implanted with 100keV 3He at a dose of 1×1015 3He/cm2, which placed the 3He within the region damaged by the Kr ion implantation. The implanted zircons were annealed isothermally in Pt capsules in 1-atm furnaces at temperatures ranging from 51 to 252°C and times ranging from 15min to 3 weeks. 3He distributions following experiments were measured with Nuclear Reaction Analysis using the reaction 3He(d,p)4He. For diffusion in zircon normal to c, we obtain the following Arrhenius relation:D=1.7×10−8 exp(−71±2kJ mol−1/RT) m2sec−1.This activation energy for diffusion is about half of the value for He diffusion in zircon from the same sample locality but without Kr implantation, measured with an otherwise similar experimental and analytical approach (Cherniak et al., 2009). He diffusivities in the Kr-implanted material are also significantly faster. Further, He diffusivities normal and parallel to c in the Kr-implanted zircon are similar, in contrast to the marked diffusional anisotropy (with differences of two orders of magnitude for diffusion normal and parallel to c) observed for He diffusion in this zircon in samples not implanted with Kr.These data indicate that heavily damaged zircon will have very limited retentivity of helium. Only those zircons larger than a few hundred μm will have mean closure temperatures exceeding typical earth surface temperatures; mean closure temperatures for He in highly damaged zircon will be about ∼200°C lower than those for relatively undamaged zircon. At 200°C, equivalent amounts of He will be lost from severely damaged zircon at a rate about a million times faster than from relatively undamaged zircon. For retentivity of He comparable to that for low-damage zircon at 200°C, the severely damaged zircon would require residence temperatures of ∼ -10°C.

Minta előszűrési vizsgálati módszer cirkonon végzett U–Pb kormeghatározás pontosságának javítására

Habár mind a mai napig az U-Pb geokronológia legmegbízhatóbb ásványa a cirkon, mégis a belső, szöveti heterogenitása a kellő megbízhatóságú és időfelbontású korolás legfőbb akadálya lehet. Kutatási munkánk eredményeképpen e korlát leküzdésére négylépcsős elővizsgálati eljárást alakítottunk ki, mely általánosságban véve bármely olyan esetben hatékonyan alkalmazható, ahol a geológiai kormeghatározás alapját a cirkon ásvány képezi. A négylépcsős elővizsgálati módszer a következő lépéseket tartalmazza: 1. A cirkonkristályok morfológiai típusainak meghatározása. 2. A cirkonkristályokban található egy- és többfázisú ásványzárványok azonosítása elektronsugaras mikronanalízis alapján. 3. A cirkonkristályok (elsődleges és másodlagos) szöveti bélyegeinek nyomozása pásztázó elektronmikroszkóppal (SEM) készített katódlumineszcens (CL) és visszaszórtelektron-képek (BSE) alapján, 4. A cirkonkristályokban lévő zónák szerkezeti állapotának meghatározása Raman-spektroszkópiai vizsgálatok segítségével a ν3(SiO4) rezgési sáv félértékszélessége (FWHM) alapján. Jelen cikkben a módszer hatékonyságát bizonyítandó, hazánk területéről (Mórágy környéke) és Ausztriából (Rastenberg környéke) származó variszkuszi granitoid kőzetek járulékos elegyrészeként megjelenő cirkont vizsgáltunk. Választásunk olyan területekre esett, melyek előzetes megfigyelések alapján geokémiailag és kőzettanilag egyaránt szoros rokonságot mutatnak, így az azonosságok továbberősítése mellett a különbségek kimutatására is lehetőségünk nyílt. A négylépcsős elővizsgálati módszert alkalmazva, a szeparált cirkonkristályok részletes szöveti térképének elkészítése során lehatároltuk az elsődleges (magmás) és másodlagos (utómagmás) geológiai folyamatok által hátrahagyott szöveti bélyegeket, továbbá kizártuk az összes szerkezetileg roncsolt (metamikt) zónát, elkerülve ezzel az ólomvesztés lehetőségét és a felülbélyegzett koradatok esélyét. Végül az összegyűjtött adatok együttes értelmezése nyomán kijelöltük a cirkonkristályokon belül azokat a néhány tíz mikrométeres, kémiailag és szerkezetileg közel homogén területeket, melyek megbízhatóan felhasználhatók az U-Pb korhatározás során, egyúttal megkaptuk a kulcsot is, mellyel a mért koradatokat geológiai folyamatokhoz köthetjük. Ezen négylépcsős módszer segítségével a cirkon magok esetében 80%-os, növekedési és szektorzónáknál 94%-os, konvolút zónák kormeghatározása során 100%-os kihozatallal tudtuk hasznosítani koradatainkat.

The importance of cation–cation repulsion in the zircon–reidite phase transition and radiation-damaged zircon

AbstractSingle crystals of synthetic reidite and natural radiation-damaged zircon from Okueyama, Japan were investigated using X-ray diffraction. The pressure-induced zircon–reidite transition is described by the twisting and translations of SiO4 tetrahedra with disappearance of the SiO4–ZrO8 shared edges. The lattice of radiation-damaged zircons expands mainly from α-decays of radioactive elements such as U and Th. Although old radiation-damaged zircons show anomolous lattice distortion, young radiation-damaged zircons do not show such distortions. These distortions are caused by thermal recovery that suppresses the Si4+–Zr4+ repulsion between the SiO4 tetrahedron and ZrO8 dodecahedron. These changes in structure can be understood by considering the cation–cation repulsion between the SiO4–ZrO8 shared edges.

Secondary magnetite in ancient zircon precludes analysis of a Hadean geodynamo

Zircon crystals from the Jack Hills, Western Australia, are one of the few surviving mineralogical records of Earth's first 500 million years and have been proposed to contain a paleomagnetic record of the Hadean geodynamo. A prerequisite for the preservation of Hadean magnetization is the presence of primary magnetic inclusions within pristine igneous zircon. To date no images of the magnetic recorders within ancient zircon have been presented. Here we use high-resolution transmission electron microscopy to demonstrate that all observed inclusions are secondary features formed via two distinct mechanisms. Magnetite is produced via a pipe-diffusion mechanism whereby iron diffuses into radiation-damaged zircon along the cores of dislocations and is precipitated inside nanopores and also during low-temperature recrystallization of radiation-damaged zircon in the presence of an aqueous fluid. Although these magnetites can be recognized as secondary using transmission electron microscopy, they otherwise occur in regions that are indistinguishable from pristine igneous zircon and carry remanent magnetization that postdates the crystallization age by at least several hundred million years. Without microscopic evidence ruling out secondary magnetite, the paleomagnetic case for a Hadean-Eoarchean geodynamo cannot yet been made.

Radiation-damaged zircon under high pressures

Polarized Raman spectroscopy and single-crystal synchrotron X-ray diffraction were applied to three representative zircon samples exhibiting a negligible, intermediate, and high degree of radiation damage to analyze the pressure-induced structural response up to 10 GPa. It is shown that pressure does not change the overall amorphous fraction, but induces atomic rearrangements at pressures of ~ 2.5 and ~ 6.5 GPa. The first threshold pressure is related to weakening of the Si–O bonds in the amorphous matrix. The second threshold pressure marks the correlated response of the coexisting amorphous and crystalline nanoregions, namely, the beginning of irreversible densification of the amorphous material and reduction of inhomogeneity of radiation-induced strain in the crystallites. The latter process occurs abruptly in the crystalline regions of moderately metamict zircon (amorphous fraction ~ 54%) and more smoothly for heavily metamict zircon (amorphous fraction ~ 84%) due to the different pathways of release of the local strains. The dynamic and static compressibilities as well as the isotropic and anisotropic Gruneisen parameters are considered in detail. The radiation damage increases the volume compressibility of the crystalline fraction as well as the crystal phonon compressibilities and decreases the Gruneisen parameters.

Radiation-damage-induced transitions in zircon: Percolation theory applied to hardness and elastic moduli as a function of density

Two in literature predicted percolation transitions in radiation-damaged zircon (ZrSiO4) were observed experimentally by measurement of the indentation hardness as a function of density and their correlation with the elastic moduli. Percolations occur near 30% and 70% amorphous fractions, where hardness deviates from its linear correlation with the elastic modulus (E), the shear modulus (G) and the bulk modulus (K). The first percolation point pc1 generates a cusp in the hardness versus density evolution, while the second percolation point is seen as a change of slope.