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The principal possibility of using high-uranium metamict zircon with a high self-irradiation α-dose for U–Pb geochronological studies (ID-TIMS) is demonstrated. The application of the optimal parameters of “chemical abrasion,” accompanied by preliminary high-temperature annealing, allowed us to estimate the age of Li–F granites of the Turga massif (Eastern Transbaikalia) (146 ± 4 Ma and 141 ± 1 Ma).

The structural and chemical properties of zircon inclusions in garnet megablasts from the Dora Maira Massif (Western Alps, Italy) were characterized in detail using charge contrast imaging, Raman spectroscopy, and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The aim of this work is to determine to what extent the degree of metamictization, metamorphic recrystallization, inherent structural heterogeneity, chemical composition, and zoning, along with the elastic stress imposed by the host mineral, can influence the Raman peak position of the zircon inclusion and hence, the residual pressure estimated via Raman geo-thermobarometry. We show and confirm that metamictization and inherent structural heterogeneity have a major influence in the Raman spectra of zircon in terms of peak position and peak width. We suggest that, for spectral resolution of 2 cm−1, the peak width of the B1g mode near 1008 cm−1 of reliable grains must be smaller than 5 cm−1. The method can be applied to both inherited igneous and newly formed Alpine metamorphic crystals. By coupling structural and chemical information, we demonstrate that there are no significant differences between the Raman spectra of zircon with oscillatory-zoned texture, formed during magmatic crystallization, and those formed by fluid-induced Alpine (re)crystallization. The discrimination between magmatic and metamorphic zircon based only on micro-textural constraints is not robust. Finally, our results allow establishing a protocol devoted to the selection of reliable buried zircon inclusions, relying only on Raman spectroscopic measurements, to use for elastic thermobarometry applications.

In situ U-Pb geochronology has been conducted using laser ablation inductively coupled mass spectrometry (LA-ICP-MS) on shocked and thermally metamorphosed apatite, titanite, and zircon grains from the Steen River impact structure, Canada. The dated relict mineral phases occur within impact melt-bearing breccias that underwent post-deposition sintering at 450 °C > T

The U–Pb isotopic system in zircon is the tool of choice to interrogate high-temperature geological processes, yet this system has potential to investigate lower temperature fluid–rock interaction as well. In some cases, removal of radiogenic Pb is incomplete, potentially allowing regression of discordant U–Pb data on a concordia diagram to determine both the age of crystallization and the timing of fluid-driven isotopic disturbance. However, in rocks preserving more complex histories, simple regression is not effective at resolving multiple Pb loss events. Here, we use a ‘concordant–discordant comparison’ (CDC) test to establish the times of U–Pb disturbance in the Acasta Gneiss Complex (AGC), Canada. AGC c. 4.03 to c. 3.40 Ga orthogneisses experienced a long and complex post-crystallization history, for which U–Pb zircon data reflects not only the heterogeneous nature of the rock, but also the varying degrees and duration of crustal reworking that inevitably involved open system processes. The CDC test calculates the similarity between the concordant age structure and a modelled age structure, the latter inferred from discordant analyses, over a wide range of potential disturbance times. Our analysis reveals concordant zircon components implying new growth and/or recrystallization at 3992 ± 5, 3501 ± 6, 3442 ± 5 and 3126 ± 6 Ma. In addition, we establish episodes of radiogenic-Pb loss driven by fluid–rock interaction at 3150 ± 50 Ma, and probably at 2875 ± 50 Ma and c. 2590 Ma. These Pb-loss episodes correlate with previously recognised events recording growth of zircon rims during metamorphism, granite emplacement, and unroofing. Pb-loss within the AGC shows an antithetic relationship in different samples that are in close geographic proximity. We suggest that zircon alteration and associated new growth effectively rendered those grains that underwent Pb-loss at a particular time less susceptible to alteration during the next episode of fluid interaction.

High-resolution electron backscattered diffraction (EBSD) and correlated in situ secondary ion mass spectrometry (SIMS) U–Pb geochronology have been conducted on impact-metamorphosed zircon, titanite, and apatite grains from the 453 Ma Lac La Moinerie impact structure of Quebec, Canada. Building on previous work, our new U–Pb results highlight the challenges associated with SIMS dating of low U, common Pb-rich accessory phases (apatite and titanite) within terrestrially shocked impact lithologies. Unlike zircon, microstructurally controlled Pb loss is limited in apatite and titanite, providing evidence that the mechanisms governing impact resetting in these phases are distinct from high U, low common Pb phases (zircon, monazite, baddeleyite). EBSD mapping reveals internal complexity within all three phases, providing new insights into their microstructural evolution during impact-related metamorphism. Correlated EBSD and Raman analysis of Former Reidite In Granular Neoblastic (FRIGN) zircon provides the first documented case of post-recrystallization radiation damage of individual zircon neoblasts. Two modes of recrystallization are recorded in apatite: systematic (Type I), wherein strain-free domains are preferentially oriented along specific crystallographic planes, and non-systematic (Type II), where strain-free domains exhibit no preferred orientation. A new shock twin is observed in titanite that has a disorientation relationship of 74°/ , interpreted to be the result of strain-induced misorientation of pre-existing $$\left\{ {1\overline{1}1} \right\}$$ shock twins. We document the first case of impact-recrystallized titanite, which is intergrown with granular rutile and partially preserves former $$\left\{ {1\overline{1}1} \right\}$$ shock twins along boundaries of strain-free subdomains. Based on our EBSD observations, we provide a microstructural framework outlining the sequential evolution of zircon, titanite, and apatite during shock and thermal metamorphism.

Obtaining reliable petrochronological and geochemical data from metamict zircon may be challenging. Metamict zircon and crystalline apatite from the Meiwu granodiorite and its microgranular enclaves from the Paleo-Tethys belt are examined to constrain their crystallization ages and the genetic mechanism of related skarn mineralization. The metamict zircon yields highly disturbed 206Pb/238U dates. Transmission electron microscopy shows that radiation damage forms nanoscale-banded damaged zones, leading to spurious dates. The coexisting apatite has not accumulated radiation damage, and apatite crystals from the granodiorite and its enclaves yield reasonably precise LA-ICPMS U–Pb Tera–Wasserburg concordia lower intercept dates of 240.2 ± 3.8 and 239.9 ± 4.0 Ma (2σ), with MSWDs of 1.0 and 2.1. Considering the fast cooling of the granite, the U–Pb dates effectively represent crystallization ages for these rocks. Compositional analysis shows that there are no Ce anomalies in apatite in either the granodiorite or enclave, indicating low oxygen fugacities. Apatite crystals from enclaves have weaker negative Eu anomalies, higher Sr, and lower HREE and Y contents than those in granodiorite. The compositions confirm enclaves as products of water-rich melts, resulting in amphibole fractionation and suppression of plagioclase crystallization. The hydrous magma induced production of hydrothermal-fluids that mobilized metals dispersed in dry magma and concentrated them into mineralization traps, which contributed to the formation of widespread skarns in Paleo-Tethys belt. This study demonstrates that apatite is effective in tracing the evolution of magmatic systems containing metamict zircon.

Cheongwon is well-known in South Korea for the abnormally high aqueous concentrations of U and Rn in the underlying Jurassic granite aquifer. This study reports on the chemistry and texture of a new U-host mineral to indicate the effective source of U in the granite aquifer, and discusses the implications of the occurrence of U near groundwater monitoring wells. To investigate the internal fabric and homogeneity, the mineral chemistry and texture were examined using field-emission scanning electron microscope and electron probe micro-analyzer, respectively. Uranopolycrase, a mineral of the euxenite group, occurred as a large subhedral grains in a pegmatite related to a Jurassic granite pluton. A significant U content indicated metamictization, which resulted in an optically isotropic body and generate cracks and voids. Elemental distribution maps revealed that uranopolycrase had relatively low in U and Y contents, but high in Ti and Pb contents near a micro-veinlet and void. These findings suggest that U could be preferentially leached out as a result of alteration and the loss of A-site cations in metamict uranopolycrase. The alteration of metamict uranopolycrase is an effective process for releasing radionuclides into the environment. Based on the U- and Ti-remobilized alteration texture, uranopolycrase is considered to be the most important host mineral of the interpreting the availability of U- and Rn-supplies in the granite aquifer of the study area in Cheongwon.

The Guangshigou deposit is the largest pegmatite-type uranium deposit in the Shangdan domain of the North Qinling Orogenic Belt, which is characterized by the enrichment of uraninite hosted in biotite granitic pegmatites. At Guangshigou, uraninite commonly occurs as mineral inclusions in quartz, K-feldspar and biotite or in interstices of these rock-forming minerals with magmatic characteristics (e.g., U/Th &lt, 100, high ThO2, Y2O3 and REE2O3 contents and low concentrations of CaO, FeO and SiO2). It crystallized at 407.6 ± 2.9 Ma from fractionated calc-alkaline high-K pegmatitic melts under conditions of 470–700 °C and 2.4–3.4 kbar as deduced by the compositions of coexisting peritectic biotite. The primary uranium mineralization took place during the Late Caledonian post-collisional extension in the North Qinling Orogen. After this magmatic event, uraninite has experienced multiple episodes of fluid-assisted metasomatism, which generated an alteration halo of mineral assemblages. The alteration halo (or radiohalo) was the result of the combined effects of metamictization and metasomatism characterized by an assemblage of goethite, coffinite and an unidentified aluminosilicate (probably clay minerals) around altered uraninite. This fluid-assisted alteration was concomitant with the albitization of K-feldspar subsequently followed by the coffinitization of uraninite during the major period of 84.9–143.6 Ma, as determined by U-Th-Pb chemical ages. Further investigations revealed that the metasomatic overprinting on uraninite initially and preferentially took place along microcracks or cavities induced by metamictization and promoted their amorphization, followed by the release of U and Pb from structure and the incorporation of K, Ca and Si from the fluids, finally resulting in various degrees of uraninite coffinitization. The released U and Pb were transported by alkali-rich, relatively oxidizing fluids and then re-precipitated locally as coffinite and an amorphous U-Pb-rich silicate under low to moderate temperature conditions (85–174 °C). The compositional changes in primary uraninite, its structure amorphization together with the paragenetic sequence of secondary phases, therefore, corroborate a combined result of intense metamictization of uraninite and an influx of alkali–metasomatic fluids during the Late Mesozoic Yanshanian magmatic event in the region. Hence, the remobilization and circulation of uranium in the North Qinling Orogen was most likely driven by post-Caledonian magmatism and hydrothermal activities related to large-scale tectonic events. In this regards, Paleozoic pegmatite-type uranium mineralization may represent a significant uranium source for Mesozoic hydrothermal mineralization identified in the Qinling Orogenic Belt.

This work presents a detailed investigation on zircon crystals of a Mesoproterozoic granite from the SW Amazonian Craton using a combination of back scattered electron (BSE) imaging, thermal ionisation mass spectrometry (TIMS) and Raman scattering spectroscopy. Six zircon grains were analysed. The results plotted in the Concordia diagram yielded an upper intercept age of 1423.0 ± 3.8 Ma, which is interpreted as the crystallization age of the rock. The scattering of the analyses in such diagram indicates that U-Pb isotopes are volume-dependent in the studied zircon grains. BSE reveals zonation in the zircon crystals, and Hf is the main element causing the variability in the BSE intensity and U has a secondary effect. Both elements have much higher atomic number than the principal constituents of zircon (Zr, Si and O), so the substitution of Zr by U and Hf results in increasing image brightness. BSE images from the zircon grains exhibit a euhedral external shape and fine-scale euhedral oscillatory zoning. The predominance of magmatic zoned crystals points out that the granite has not suffered metamorphic heating or any other processes that induce the formation of new phases. The results of the Raman scattering technique indicate that a SiO 4 tetrahedral internal vibrational structure is sufficiently sensitive to determine the increasing degree of metamictization. Furthermore, evidence for metamictization is given by the heterogeneity of the half-width values of the Raman scattering peaks, which exhibit a decreasing trend from the core to the rims of the analysed grains. We concluded that the combination of the three techniques provides information on the Pb loss and that the degree of U-Pb isotopic discordance correlates closely with the volume of the zircon grain. The data, in addition to the lateral degree of metamictization detected by the Raman scattering technique, indicate that the loss of radiogenic Pb may be linked to the continuous diffusion of this element. The correlation of the U-Pb discordance and metamictization emphasizes the importance of the Raman scattering spectroscopy analysis to performing zircon dating. Indeed, it is a helpful tool for geochronologists.

Two populations of zircons are present in the F-rich highly evolved 300 Ma Shuangji granites, Xinjiang, eastern Tianshan, China. Zircon I comprise a very small proportion of the population. They show characteristics of primary igneous zircons and yield an age of ca. 300 Ma. Zircon II are the dominant type and are weakly luminescent under cathodoluminescence (CL) but show a range of complex textures in back-scattered electron (BSE) images. Zircon II are characterized by Th-U-rich mineral inclusions not seen in zircon I and can be divided into zircon IIa and zircon IIb. Autometasomatism during the magmatic-hydrothermal phase of the highly evolved Shuangji granites, fluids rich in F interacted with zircon I through a coupled dissolution-reprecipitation process forming pores and cracks in the zircon grains. The simultaneous alteration of U-rich euxenite, released high amounts of U and Th into the fluids. Interaction of these fluids with porous zircon I resulted in the precipitation of U- and Th-rich inclusions in the zircon I grains. Radiation damage resulted in the formation of metamict zircons. Later hydrothermal alteration affected the metamict zircons, forming nanoscale baddeleyite in the amorphous zone. Subsequent radiation damage accumulated continuously resulting in the final textures of zircon II.

The beach sands of the Indian coast are bestowed with strategic minerals like ilmenite, monazite, rutile, sillimanite, garnet, and zircon. In order to bring out the importance of these heavy minerals, we present detailed studies on structure, surface chemistry, and absorption spectroscopy using advanced characterization techniques such as Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and UV–Visible-NIR spectroscopy. The study reveals the degree of metamictization in zircon and monazite and differentiates the isomorphous series in garnet, discrimination of opaque and non-opaque minerals, polymorphs, and the anisotropic changes in crystal symmetry due to their physical and chemical process. X-ray photoelectron spectroscopy illustrates the chemical composition, precise oxidation state, and chemical bonding of surface elements. UV–Visible-NIR spectroscopy reveals the electronic transition of elements and charge transfer spectra. This expansive dataset provides valuable information to the scientific community and mining industries to assist with determining the grade and potential uses of beach sands.

The ultrahigh-pressure (UHP) whiteschists of the Brossasco-Isasca unit (Dora-Maira Massif, Western Alps) provide a natural laboratory in which to compare results from classical pressure (P)–temperature (T) determinations through thermodynamic modelling with the emerging field of elastic thermobarometry. Phase equilibria and chemical composition of three garnet megablasts coupled with Zr-in-rutile thermometry of inclusions constrain garnet growth within a narrowP–Trange at 3–3.5 GPa and 675–720 °C. On the other hand, the zircon-in-garnet host-inclusion system combined with Zr-in-rutile thermometry would suggest inclusion entrapment conditions below 1.5 GPa and 650 °C that are inconsistent with the thermodynamic modelling and the occurrence of coesite as inclusion in the garnet rims. The observed distribution of inclusion pressures cannot be explained by either zircon metamictization, or by the presence of fluids in the inclusions. Comparison of the measured inclusion strains with numerical simulations shows that post-entrapment plastic relaxation of garnet from metamorphic peak conditions down to 0.5 GPa and 600–650 °C, on the retrograde path, best explains the measured inclusion pressures and their disagreement with the results of phase equilibria modelling. This study suggests that the zircon-garnet couple is more reliable at relatively low temperatures (P–Tpaths.

In the current study, different heavy minerals typical of gold placer deposits were identified by means of micro-Raman spectroscopy, and their chemical composition analyzed and discussed (garnet, kyanite, staurolite, zircon, allanite, monazite, xenotime, rutile, anatase, cassiterite, titanite, barite). Even complex solid solution series, such as those of garnets, can be deciphered with the aid of systematic trends observed in Raman line frequencies. The &nu, 1 mode in garnets will shift from high to low frequencies as a function of the ionic radius of the X2+ cation, from Mg2+, to Fe2+ and Mn2+, while the presence of Ca2+ will make the band to be shifted strongly to even lower wavenumbers. This approach has successfully been taken to differentiate between polymorph triplets such as kyanite-sillimanite-andalusite and rutile-anatase-brookite. Minerals under consideration with high contents of REE, U and Th are affected by intensive metamictization, particularly zircon and titanite. Raman peak features, such as shape, symmetry and intensity, respond to this radiation damage of the lattice and enable fine-tuning of these heavy minerals, such as in the case of fluorite (fetid fluorite).

This study investigates the variations of structural parameters and chemistry of a partially metamict and seven detrital zircon samples from different localities using single-crystal X-ray diffraction, synchrotron high-resolution powder X-ray diffraction, and electron-probe micro-analysis techniques. The unit-cell parameters for the eight zircon samples vary linearly with increasing unit-cell volume, V. A zircon sample from the Canadian Arctic Islands has the smallest unit-cell parameters, bond distances, ideal stoichiometric composition, unaffected by &alpha, radiation damage, and is chemically pure. A zircon sample from Jemaa, Nigeria has the largest unit-cell parameters because of the effect of &alpha, radiation doses received over a long time (2384 Ma). All the samples show good correlations between Zr and Si apfu (atom per formula unit) versus unit-cell volume, V. The &alpha, radiation doses in the samples are lower than ~3.5 &times, 1015 &alpha, decay events/mg. Substitutions of other cations at the Zr and Si sites control the variations of the structural parameters. Relatively large unit-cell parameters and bond distances occur because the Zr site accommodates other cations that have larger ionic radii than the Zr atom. Geological age increases the radiation doses in zircon and it is related to V.

U Pb zircon geochronology is one of the most widely used techniques in sedimentary provenance analysis. Unfortunately, the ability of this method to identify sediment sources is often degraded by sediment recycling and mixing of detritus from different source rocks sharing similar age signatures. These processes create non-unique zircon U Pb age signatures and thereby obscure the provenance signal. We here address this problem by combining detrital zircon U Pb geochronology with Raman spectroscopy. The position and width of the Raman signal in zircon scales with its degree of metamictization, which in turn is sensitive to temperature. Thus, combined U-Pb + Raman datasets encode information about the crystallization history of detrital zircons as well as their thermal history. Using three borehole samples from Mozambique as part of a source-to-sink study of interest for hydrocarbon exploration, we show that zircon populations with similar U Pb age distributions can exhibit different Raman signatures. The joint U-Pb + Raman analysis allowed us to identify three different annealing trends, which were linked to specific thermal events. Thus we were able to differentiate a dominant Pan-African U Pb age peak into several sub-populations and highlight the major effect of Karoo tectono-magmatic events. In our case study, we used Raman also as a means to systematically identify all zircon grains in heavy-mineral mounts, resulting in considerable time savings. Raman spectroscopy is a non-destructive and cost-effective method that is easily integrated in the zircon U Pb dating workflow to augment the resolution power of detrital zircon U Pb geochronology.

In situ laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been deployed to determine the U–Pb ages of impact metamorphosed apatite and zircon associated with the ∼12.5 km diameter Nicholson Lake impact structure, Northwest Territories, Canada. The dated phases occur within both impact melt-bearing breccias and clast-laden impact melts. A total of 84 laser ablation analyses from 57 apatite grains within seven rock samples yield a minimum refined lower intercept at 387 ± 5 Ma (MSWD = 0.87, 2σ, n = 26 ), and maximum age with lower intercept of ∼1740 Ma. A total of 90 laser ablation analyses on 52 zircon grains from two rock samples yield a minimum intercept age of 384 ± 8 Ma (MSWD = 1.3, 2σ, n = 22 ), with a maximum upper intercept age of 2679 ± 14 Ma, and a second discordia with a ∼1740 Ma upper intercept age. The results are consistent with the target rocks comprising Archean Snow Island Suite (∼2.7 Ga) and Paleoproterozoic Nueltin plutonic suite (∼1.74 Ga), with the impact event occurring at approximately 385 Ma. The degree of resetting of inherited apatite can be related to its proximity to impact melt (now partly devitrified glass) within the host impact melt-bearing breccias and clast-laden impact melt rocks. Those grains in direct contact with melt bodies are reset, while those occurring as inclusions in lithic or mineral clasts partly or wholly retain their original isotopic compositions. The youngest (impact-reset) apatite ages are most closely associated with the highest shock levels (i.e., granular textured and thermally dissociated zircons), which we relate to juxtaposition of apatite with superheated melt. Due to accumulated radiation damage prior to impact, many of the relic zircons are metamict, which facilitated enhanced Pb diffusion and their resetting to the impact age. Granular zircons record impact ages while those exhibiting planar fractures or experiencing negligible shock record basement ages. We link apatite and zircon geochronology to the textural and structural states of ZrSiO4 and its associated shock levels via field emission scanning electron microscopy and micro-Raman spectrometry.

The results of isotope U–Pb dating of zircons from lherzolite and vein olivine orthopyroxenite composing the Roseta ultramafic massif are presented. The zircons differ in their morphological, optical, and geochemical properties and in their age. Lherzolite samples that are almost deprived of cathodoluminescence are represented by two age clusters 788 ± 15 and 638.2 ± 5.4 Ma. The zircons from the first cluster are relict. A later event recorded in the zircons from the second cluster was manifested in an intense metamict mineral transformation. The age of the zircons from vein olivine orthopyroxenite conforms to 608.9 ± 3.4 Ma. These zircons are considered to be syngenetic; therefore, their age is determined by the time of crystallization of olivine orthopyroxenites.

The application of zircon and xenotime geochronometers requires knowledge of their potential and limitations related to possible disturbance of the age record. The alteration of the intergrown zircon and xenotime in pegmatite from the Gory Sowie Block (SW Poland) was studied using the electron microprobe analysis, X-ray WDS compositional mapping, micro-Raman analysis, and LA-ICP-MS U-Pb dating of zircon and xenotime, as well as the U-Th-total Pb dating of uraninite. These microanalytical techniques were applied to understand the formation mechanisms of the secondary textures related to post-magmatic processes in the zircon and xenotime intergrowth, and to constrain their timing. Textural and compositional features combined with U-Pb data indicate that the pegmatite-related crystallization of the zircon and xenotime intergrowth occurred ca. 2.09 Ga (2086 ± 35 Ma for zircon and 2093 ± 52 Ma for xenotime), followed by the re-equilibration of zircon and xenotime ca. 370 Ma (373 ± 18 Ma and 368 ± 6 Ma, respectively) during the formation of the younger pegmatite. The zircon and xenotime were most likely derived from Precambrian basement rocks and emplaced in the pegmatite as a restite. The zircon preserved textures related to diffusion-reaction processes that affected its high-U core (up to ca. 9.6 wt% UO2), which underwent further metamictization and amorphization due to self-radiation damage. The zircon rim and xenotime were affected by coupled dissolution-reprecipitation processes that resulted in patchy zoning, age disturbance and sponge-like textures. Xenotime was also partially replaced by fluorapatite or hingganite-(Y) and Y-enriched allanite-(Ce). The termination of the low-temperature alteration was constrained by the U-Th-total Pb age of the uraninite inclusions that crystallized in zircon at 281 ± 2 Ma, which is consistent with the age of 278 ± 15 Ma obtained from the youngest cluster of U-Pb ages in the re-equilibrated high-U zircon domains. This study demonstrates the importance of the careful examination of compositional, microtextural and geochronological data obtained using microanalytical techniques to reconstruct the complex thermal histories recorded by accessory minerals.

Broad variability in intrasample effective U concentration (eU) in zircon crystals is required to characterize zircon (U-Th)/He (zircon He) date-eU relationships that resolve thermal histories in ancient rocks. We describe a new protocol for selecting grains for zircon He thermochronometry that leverages visual crystal metamictization, a proxy for radiation damage accumulation, to generate a range in intrasample eU and zircon He date-eU/metamictization trends. Plane polarized light images, eU concentration, and zircon He data from 59 individual grains from six Proterozoic and three Archean North American granitoids reveal a progressive increase in crystal opacity and discoloration that correspond to increasing eU in each sample. Zircon eU ranges from 89 to 1885 ppm across the dataset and individual samples have eU variations of 538 ppm to 1579 ppm. Three Proterozoic samples yield distinct negative zircon He date-eU patterns with individual dates of ~908 to 20 Ma. Archean grains collectively define a negative date-eU trend from ~661 to 4 Ma. In contrast, three other Proterozoic samples yield uniform ~25 Ma zircon He dates over an 1800 ppm eU range, despite increasing eU with increasing metamictization. Simple thermal history models that account for coevolution of zircon radiation damage and He diffusion demonstrate visible metamictization and diffusivity are either coupled or decoupled depending on a sample's thermal history. Zircon He date-eU/metamictization pediments develop when variable but high eU grains with variable visual damage and closure temperature close with respect to He at the same time. Uniform dates with progressive increases in eU and visual damage, reflect decoupled He diffusion and visual damage, are associated with rapid cooling, and/or imply some forms of damage in zircon may not fully anneal.

Evidence for open-system magmatic processes related to wallrock assimilation accompanied by fractional crystallization (AFC) is present in the Guangshigou biotite pegmatites, North Qinling Orogen. The biotite pegmatite-gneiss contacts generally coincide with the greatest enrichment of U and Th. Zircon U Pb dating constrains the crystallization ages of the biotite pegmatite (rim zone-415 ± 2.6 Ma; internal zone-413.5 ± 2.5 Ma), in line with a pyrite Pb Pb isochron age (413 ± 22 Ma). Metamict areas in zircon show generally elevated concentrations of trace elements and expulsion of radioactive Pb. Internal zone samples, representing uncontaminated magma, have negative to positive zircon (~ 413 Ma) eHf(t) (− 1.53 − + 3.24), low eNd(t) values (− 2.4), and old Hf and Nd model ages (tDM2 = 1.5–1.19 Ga, T2DM = 1.35 Ga, respectively), indicating a dominantly recycled Mesoproterozoic lower crustal material with involvement of some juvenile materials in the source region. The magmatic oxygen fugacity (fO2) and crystallization temperatures ranges from − 24.81 to − 13.34 of log fO2 and 570 °C to 793 °C, respectively. Compared to the internal zone, pegmatite rim samples display a variable and lower eNd(t) values (− 3.9 to − 2.8) and T2DM (1.47–1.37 Ga), but similar Hf isotopic compositions, favouring a three-component isotopic mixing model (recycled Mesoproterozoic lower crust materials, juvenile materials, and host gneiss). Pronounced variations of Ti, Y, U, Th, Hf, and REE concentrations in zircon from grain to grain in individual samples and from area to area within individual grains suggest a fluctuating crystallization environment in hybridized magma from which the rim-hosted zircons crystallized. Variable and high radiogenic Pb ratios of pyrites forming in the hybridized magma were inherited from the matrix. Zircons from both zones exhibit similar Hf isotope patterns, indicating the rim-hosted zircons crystallized during the early stage of hybridization of magma. However, the heterogeneous Nd isotopic composition in individual pegmatites imply an incorporation of wallrock-derived melt with less radiogenic Nd.

The effect of selective preservation during transportation of zircon grains on the detrital age spectrum is difficult to quantify and could potentially lead to systematic bias in provenance analysis. Here we investigate whether the shape of detrital zircon grains holds provenance information and if the grain shape can assist in understanding preservation. We applied multiple linear regression analysis to identify significant shape properties in detrital zircons from Proterozoic metasediments of the Capricorn and Amadeus basins and their Archean and Proterozoic sources in the Yilgarn Craton and the Musgrave Province in Western Australia. Digital images and isotopic data from 819 SIMS U–Pb dated zircons were examined for correlation between grain shape, age, U and Th content. Out of twelve shape descriptors measured, Minor Axis , the width of zircon grains perpendicular to the crystallographic c-axis, consistently shows the most significant correlation with isotopic age. In the studied population Archean grains are narrower than Proterozoic grains: the probability that grains wider than 75 μm are Archean is less than 30%. Calculations of the proportions of source material in sedimentary rocks relative to the proportions of source material in the overall catchment area (erosion parameter ‘ K ’ calculated based on age spectra) produced values typical for mature river systems, with K = 6 for the Yilgarn-Capricorn and K = 5.5 for the Musgrave-Amadeus source-sink system. For the Yilgarn-Capricorn system, we also calculated ‘ K ’ based on Minor Axis , to determine whether grain width can be linked to age populations. Results of the shape-based K of 5.3 suggest a similarity between age-based and shape-based ‘ K ’ values, demonstrating that zircon grain width may be a useful discriminator of provenance. Contrary to commonly applied qualitative shape classifications, we found no consistent correlations between shape descriptors of magmatic zircons and the composition of their host rock. While metamict zircons were preferentially removed during transport, the similarities in grain shape and age distribution of magmatic and detrital populations suggest that hydraulic sorting did not have a significant effect. We conclude that transport of zircon grains from magmatic source to sedimentary sink affects their width less than their length.

Two baddeleyite megacrysts were evaluated as potential reference materials (RMs) for SIMS oxygen isotope analysis, and utilized to understand and calibrate instrumental mass fractionation (IMF). A baddeleyite crystal (S0045) from the Phalaborwa carbonatite, South Africa has a mean δ18OVSMOW=+4.6 ± 0.3‰(range 0.75‰) measured using laser fluorination gas source mass spectrometry (LF-GMS) and one (S0069) from the Mogok metamorphic belt, Myanmar has δ18OVSMOW=+22.2 ± 0.4‰ (range 0.89‰). SIMS standardization utilizing these inherently heterogeneous RMs is possible by analyzing a number of crystal fragments and utilizing one of them lying at the median of the range. Metamictization, lattice orientation, and chemical composition do not appear to be significant (< 0.5‰) variables in matrix matching of RMs and unknowns. Propagation of errors while utilizing the imperfect RMs results in 10 μm diameter spot uncertainties of about±0.3‰ (2σ). SIMS oxygen isotope analysis of co-crystalline zircon and baddeleyite from the 2.2 Ga Duck Lake sill (DLS) in the Northwest Territories, Canada, yield predominant δ18OVSMOW modes of +6.0‰ and +3.2‰, respectively. This difference is consistent with preserving high-temperature isotopic equilibrium between zircon and baddeleyite. DLS baddeleyite δ18O data as a whole are negatively skewed (to 0.0‰), and interpreted to reflect low temperature, open-system behaviour. Zircon δ18O are less affected, but also show hints of the same influences of secondary alteration and oxygen isotope exchange.

Zircon- and bulk-rock Zr-based thermometric parameters have become fundamental to petrogenetic models of magmatism, from which broader geochronological and tectonic implications are being made. In particular, petrogenetic models have become increasingly reliant on Ti concentration in zircon geothermometry (T ZircTi ) and zircon saturation temperature (T Zircsat ). A feature of many of these studies is an implicit assumption that all zircons present in the host igneous rock are autocrystic, that is, crystallised from the surrounding melt. However, it has long been recognised that zircons present in an igneous rock can be inherited either from the surrounding country rock or source region (xenocrysts), or from earlier phases of magmatism or the magmatic plumbing system (antecrysts). Distinguishing these different origins for zircon crystals or domains within crystals is not straightforward. Here, we first review the utility and reliability of zircon-based thermometers for petrogenetic studies and show that T Zircsat is a theoretical temperature and cannot be used to constrain magmatic or partial melting temperatures. It is a dynamic variable that changes during magma crystallisation, and essentially increases as fractional crystallisation proceeds, whereas true magmatic temperatures (T Magma ) decrease. Generally, in Temperature-SiO2 space, the cross-over point of these two temperatures is magmatic system dependent, and also affected by the type of calibration used for the T Zircsat calculations. Consequently, each magmatic system needs to be evaluated independently to assess the validity and usefulness of T Zircsat . A fundamental conclusion of T Zircsat and T Magma relationships assessed here is that new zircon generally only crystallises in silicic (granitic/rhyolitic) melt compositions, and thus autocrystic zircons should not be assumed to be present in igneous rocks with bulk compositions Zircsat and T Magma ) to estimate whether the magma was zircon-saturated or undersaturated. To test this new protocol, we use as examples, several Phanerozoic granitic rocks intersected by drilling in Queensland where contextual information is limited, and show how antecrystic and xenocrystic zircons and monazites can be distinguished. In contrast, where zircons are metamict (for example, high U and Th-rich zircons), much of the ability to discriminate is impacted because such zircons have suffered Pb loss and have modified compositions (e.g., higher T ZircTi ). We recommend an integrated approach incorporating whole-rock chemistry, independent geothermometric constraints, zircon composition, textures and ages obtained by routine cathodoluminescence and LA-ICP-MS or ion microprobe analysis to provide increased confidence for the discrimination of inherited zircons from autocrystic zircons and determination of the emplacement age.

A strongly altered zircon-xenotime intergrowth in pegmatite from the Pilawa Gorna (the Gory Sowie Block, SW Poland) was studied with transmission electron microscopy (TEM) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Distinct domains demonstrate features related to fluid-induced coupled dissolution-reprecipitation processes resulting in microscale to nanoscale porosity in the zircon and in xenotime, and diffusion-reaction processes in the metamict core of the zircon. The inclusions of secondary phases include fluorapatite, unknown layered Fe-silicate, fibrous Fe-oxides, solid solutions of coffinite-thorite and uraninite-thorianite, uraninite and secondary U-rich zircon. The fluid had high concentrations of Ca and Fe, transporting these nonformula elements through the zircon and xenotime structure while mobilizing U, Th and Pb even in robust xenotime, thus forming small inclusions in nanopores. Nanoinclusions of galena in the zircon represent major Pb mobilization that may cause disturbance during U Pb geochronological analysis. The trace element composition of zircon matches patterns typical of altered zircon. The differentiation of geochemical characteristics between the metamict core and the altered rim of zircon implies different alteration mechanisms, with a stronger role of fluids in the alteration of the rim. Nanoscale observations complement trace element microanalysis and serve as an important and necessary tool to further understand the alterations of geochronometers in the presence of alkaline-rich fluid, especially in the complex environments of pegmatites.

The major and trace element composition of the main HFSE-bearing phases from highly evolved miaskitic syenites has been investigated to assess their stability, an important control on HFSE retention and mobility during post-magmatic hydrothermal activity. The major HFSE carrier, abundant zircon (up to 5 vol%), has undergone intensive metamictization, caused by high initial U and Th along with the presence of early magmatic U-thorite inclusions. Subsequent to metamictization, zircon experienced pervasive fluid-driven alteration, as evidenced by strong depletion in Zr and Si, enrichment in non-formula elements (Ca, Fe, Al, P), deficient EMPA analytical totals, high porosity, and low BSE-intensities of strongly altered crystal interiors. Element maps suggest that extensive HFSE remobilization from altered zircon was controlled by interaction with oxidized aqueous solutions circulating through abundant microfractures that formed by volume expansion due to zircon metamictization. Enhanced HFSE mobility in hydrothermal fluids is reflected by the presence of a hydrated amorphous Zr-Th-U-Si-phase, filling microveinlets intimately associated with metamict zircons. In addition to HFSE remobilization from altered zircon, titanite released a significant amount of REE during interaction with the hydrothermal fluids that concurrently caused a fractionation of Eu in titanite, producing increased EuN/EuN* (4.16–22.2) in altered crystals. Extensively altered titanite grains with elevated EuN/EuN* are considerably depleted in ∑REE + Y compared to unaffected crystals, showing that degree of positive Eu anomalies, relating to post-magmatic metasomatic overprint, appears to be a sensitive indicator for an intensity of hydrothermal alteration and even the total amount of released incompatible elements. Pronounced LREE enrichment accompanied by HREE depletion in the strongly altered crystals indicates greater LREE retention in titanite and higher HREE mobility in the hydrothermal system probably caused by complexing with fluoride ligands. Fluorine was most likely supplied through amphibole and biotite chloritization, as suggested by notably low F in the mafic silicates along with the formation of secondary F-rich titanite at the expense of altered biotite. Moreover, the dissolution of zircon and titanite and resistance of apatite to pervasive alteration indicates that remobilization of HFSE and REE from these phases occurred under alkaline conditions (pH 8–12), presumably controlled by potassium-dominated complexes transporting HFSE along with REE over long distances, as indicated by a close spatial linkage of syenite outcrops with U-mineralization. Our results clearly demonstrate: (1) extensive chemical dissolution of zircon controlled by its self-induced radiation damage; (2) high solubility of titanite and metamict zircon under alkaline conditions; (3) enhanced mobility and long-distance transport of HFSE and REE in alkali- and F-rich hydrothermal systems.

Detrital zircon studies can suffer from selective loss of provenance information due to U-Pb age discordance, metamictization, metamorphic overprinting and fluviatile transport processes. The relationship between isotopic composition and zircon grain shape, and how grain shape is modified during transport, is largely unknown. We combine X-ray tomography with U-Pb geochronology to quantify how fluvial transport affects 3-D zircon shape, detrital age signature, and grain density along the Murchison River, whose catchment comprises Eoarchean to Early Paleozoic source rocks in Western Australia. We acquired tomographic volumes and isotopic data from 373 detrital zircons to document changes in size, shape and density in transport direction, and explore how grain shape, age spectra and the proportion of discordant material vary along the channel. Results show that shape characteristics are sensitive to transport distance, stream gradient, proximity to source material, and whether the source consists of primary or recycled zircons. With increasing transport distance, grain lengths decrease more than their widths. Furthermore, the loss of metamict grains occurs at a near constant rate, resulting in a linear increase of mean calculated zircon density by ca. 0.03 g/cm3 per 100 km transport distance. 3-D grain shape is therefore strongly linked to detrital age signature, and mean grain density is a function of the absolute transport distance. 3-D shape characteristics provide valuable information on detrital zircon populations, including the interaction between source materials with fluvial transport processes, which significantly affects preservation bias and, by inference, the representativeness of the sampled data.

The isotopic composition of lead ( 207 Pb/ 206 Pb, 208 Pb/ 206 Pb, and 210 Pb) in a recently formed galena from burning heaps after coal mining in Radvanice, Markousovice, and Rybnicek, the Lower Silesian basin, Czech Republic, was studied in detail. 210 Pb activity in galena varied from 135 ± 9 to 714 ± 22 Bq/g and calculated integral doses ranged from 2.21 × 10 11 to 6.11 × 10 11 α/g. The radioactivity of the galena causes micro-deformations in its crystal structure as indicated by the Williamson-Hall graphs, showing that the level of micro-strain depends on the length of time that galena samples were exposed to the radiation. However, the crystal structure of galena is affected very inhomogenously; according to TEM investigations there are domains of fully crystalline, polycrystalline, and fully metamict galena within one crystal. Inductively coupled plasma-mass spectrometry (ICP-MS) was used to determine the isotopic composition of the studied galena. The stable isotope ratios of Pb varied for 207 Pb/ 206 Pb from 0.8402 to 0.8435 and for 208 Pb/ 206 Pb from 2.0663 to 2.0836. The average ratios 207 Pb/ 206 Pb = 0.8312 and 208 Pb/ 206 Pb = 2.0421 were obtained for coal from the same localities. These isotope ratios show that there is no isotopic fractionation taking place during the coal burning and subsequent galena crystallization from hot gases.

We present a microstructural and Usingle bondPb systematics study comparing pristine, thermally annealed (TA) and chemically abraded (CA) ~ 3500 Ma zircon from a quartz-dioritic gneiss, with the aim to improve pre-analytical workflows for more accurate and precise LA-ICP-MS Usingle bondPb dating of ancient zircon. Four zircon domains are identified: i) low- to medium-U concentric-oscillatory zoned cores, ii-iii) two porous high-U outer alteration domains, and iv) low-U narrow inward growing recrystallization rims. Raman spectroscopy on the pristine zircon reveals a positive correlation between increasing structural damage and U content. The porous high-U outer domains show a drastic increase in non-formula Ca above estimated amorphous fractions of ~ 0.8, which we ascribe to hydrothermal alteration of high-damage zircon characterized by percolating networks of amorphous areas. Upon treatment (TA, CA), hyper-spectral CL and Raman spectroscopy suggest structural recovery of point defects, but not full repair of high-damage amorphous areas. Calculated Raman radiation damage ages suggest that natural annealing affected all domains at ~ 500 Ma, consistent with negligible laser ablation matrix effects comparing pristine and treated cores. We show that reverse discordance in pristine and TA cores is not an analytical artifact. High-U alteration domains are normal discordant and were partially reset at ca. 3410 Ma. Upon CA, Usingle bondPb discordance and scatter are reduced in the cores, yielding intercepts of 3503 ± 14 Ma and 560 ± 550 Ma (MSWD = 1.0). The lower intercept matches the timing of Pb-loss recorded in the alteration domains and the Raman radiation damage age. We argue that short distance Pb redistribution within the cores, which led to reverse discordance, was controlled by Usingle bondPb systematics recording both the crystallization age and the timing of Pb redistribution. Some excess Pb was redistributed from the partially re-set alteration domains into the cores, leading to mixed Usingle bondPb systematics and further reverse discordance. Removal of the latter excess Pb upon CA suggests that radiogenic Pb from the alteration domains accumulated within distinct damage sites accessible for CA leaching. We conclude that standardization of pre-analytical treatment is not recommended; we propose to investigate the structural state of unknown specimen by means of Raman spectroscopy, in combination with commonly applied CL imaging. During LA-ICP-MS analyses, co-measurement of non-formula and selected trace elements is deemed highly valuable in detecting ablations for use in reliable Usingle bondPb age determination.

In the Scotian Basin, offshore eastern Canada, an unusual combination of high heat flow in the Cretaceous and the abundance of halite has resulted in unusual diagenetic minerals such as sphalerite. The Newburn H-23 well is the most distal well in the basin with good core samples and has two previously unknown diagenetic mineral occurrences: fluorine-rich ferroan calcite and diagenetic zircon. This study uses SEM backscattered electron images and EDS analyses, EMP WDS mineral analyses and Raman spectroscopy to determine mineral chemistry and textures to investigate the diagenetic and thermal significance of these minerals. Late diagenetic Fe-calcite contains 1–2.5 wt% fluorine, mostly from adsorption, but rarely as small fluorite crystals. Fluoride is also adsorbed on the surfaces of some framework minerals and chlorite. Fluoride was transported in highly saline formation brines derived from the Argo salt Formation. Zircon grains, 20–40 μm in size, have crystal outlines that are straight adjacent to pores, partially lobate filling porosity, and cross cutting other grains: these may be diagenetic. Some zoned detrital zircon grains show 1–3 μm wide diagenetic outgrowths. Neoformation of diagenetic zircon requires temperatures of >250 °C. Transport of zirconium is favored by ligands in low-pH solution, principally fluoride and phosphate anions, with zirconium mobilized during the alteration of metamict detrital zircon under low-grade metamorphic conditions. The presence of diagenetic sphalerite and the documented mid-Cretaceous thermal event in the Scotian Basin indicate conditions that could have been suitable for the formation of diagenetic zircon in this well. Suitable geological conditions for such diagenetic formation of zircon will be found in a subsiding rift basin with early evaporites that are affected by a subsequent phase of volcanism due to new rifting or subduction.

This work was supported by National Science Centre, Poland, through grant no. PW-0415-003., The preliminary results of 57Fe Mössbauer spectroscopy and X-ray diffraction (XRD) of fully metamict samarskite dated at ~1500 Ma, which absorbed α-dose of 6.5 × 1017 α-decay mg-1, are reported after one-hour annealing at 673, 873, 1173 and 1373 K in argon atmosphere. Metamict minerals contain radioactive elements that degrade their crystal structures over geological time. All the Mössbauer spectra obtained can be fitted to two quadrupole doublets assigned to Fe2+ and Fe3+ in octahedral positions. The relative contribution of Fe2+ (Fe2+/Fe) reaches a minimum of 0.10 at 1173 K., NCN

The paper reports the results of mineralogical, geochemical, and geochronological (TIMS and SHRIMP) study of heterogeneous zircons from granites of the Mazara Massif, South Urals. Obtained data revealed the Mesoproterozoic age (1550–1390 Ma) of a granite protolith and the Neoproterozoic age of their formation (745–710 Ma). In the La–Sm/La diagram, the zircons of the massif occupy an intermediate position between the fields of magmatic and metasomatic (hydrothermal) zircons. This “intermediate” field is proposed to ascribe to the late magmatic zircons, which provides more reliable characterization of zircon formation throughout the entire crystallization history of a granite melt, up to the appearance of genetically metamict metasomatic hydrozircons.

Zircon (U–Th)/He (ZHe) data were acquired for 23 Proterozoic basement samples from an E–W transect through the Colorado Front Range to evaluate whether metamict zircons yield sensible (U–Th)/He data patterns and useful thermal history information. The 112 ZHe dates vary from 147 to 7 Ma, define positive and negative date–eU correlations, and are younger than titanite (U–Th)/He dates that range from 976 to 614 Ma. At moderate to high alpha dose of 10 18 – 10 19 α / g , zircons from the range core yield Laramide ( 52.5 ± 9.6 Ma) dates, whereas those within ∼15 km of the range front yield Miocene ( 21.6 ± 7.7 Ma) results. The He dates for the high alpha dose zircons are reproducible within each sample suite despite their visibly metamict character. The ∼20 Ma range front ZHe dates are younger than apatite (U–Th)/He (AHe) dates ( 66.5 ± 9.6 Ma) and published apatite fission-track data (65–45 Ma) for the same and nearby samples. Thermal history simulations can reproduce the first-order range front date–eU patterns and ZHe–AHe date inversion, but the high-damage zircons are more He retentive than predicted by the zircon damage He kinetic model. The ∼20 Ma ZHe dates may be explained by reheating from hydrothermal fluids along range front faults. The results demonstrate the promise of using He data for high-damage zircons to detect low-temperature (

Hafnium contents and Zr/Hf ratios were studied in zircons and their parent rocks from three magmatic suites associated with the Teplice caldera, Eastern Erzgebirge: rhyolite and dacite from the peraluminous Schonfeld Unit, relatively younger A-type Teplice rhyolite, and post-caldera A-type biotite and zinnwaldite granite and greisen. New data suggest that zircon crystallizing from a geochemically less evolved volatile- and water-poor melt is, compared to the host rock, relatively Hf-depleted, while zircon crystallizing from an evolved volatile- and water-rich melt has a Zr/Hf value approximately identical to that of the parental melt. Zr/Hf values in zircon did not change substantially either during greisenization, or during low-temperature alteration after metamictization. Zr/Hf values in the whole rock may serve as a sensitive indicator of magmatic fractionation of evolved granitic melts, as they are only negligibly influenced by the following hydrothermal processes. Zr/Hf values in individual cogenetic zircon grains are scattered but their general evolution trend in the rock series is consistent with the evolution of the whole-rock Zr/Hf values.

U-rich pyrochlore (UO2 up to 18.63%) occurs along the magmatic bands as well as disseminated grains within rauhaugites of the Newania complex. UO2 appears to be primary as it seems mostly evenly distributed all over the grains, though in one grain it does show concentration in parts. Ta is also an important element in some pyrochlore grains and its concentration reaches up to 17.15%. High U and Th are responsible for bringing metamictization in the Newania pyrochlore. Newania carbonatite has a complex emplacement history; rauhaugite seems to have been replaced at 2200 Ma years followed by emplacement of ankeritic carbonatite at around 1500 Ma. Later during tectonic event pyrochlore was involved in reaction with hydrothermal fluid and at this stage Fe and FeS were deposited on the rims of pyrochlore grains. At the same time pyrochlore was subjected to hydrothermal alteration resulting in removal of Na, Ca and F leaving large vacancy in its A-site. Very few grains have escaped such alteration.

Magmatic zircon from altered gabbros adjacent to the ∼1.07 Ga Lala Fe-Cu deposit, SW China was modified by NaCl-rich brines related to the Fe-Cu mineralization. The modified zircon grains are composed mostly of both inclusion-free and porous domains, and some grains also have overgrowth/rims. The inclusion-free domains, commonly overgrown by the porous domains, are roughly homogeneous under BSE imaging but display oscillatory or sector zoning under CL imaging. In contrast, the porous domains are distinctly mosaic-like under CL imaging, and contain abundant pores and mineral inclusions such as thorite, xenotime, REE-rich phases, actinolite, albite, biotite and calcite. The inclusion-free domains have concentrations of “non-formula” elements (for example Al, Ca, and Fe) much higher than the magmatic zircon, and are thus interpreted to be products of interaction between magmatic zircon (possibly metamictized) and the fluids via a diffusion-reaction process. However, these resultant domains have retained the Th and U contents, REE patterns, U-Pb ages and Hf isotopes of the precursor, magmatic zircon. On the other hand, the porous domains have stoichiometric end-member compositions (that is lowered Th, U, REE, Y, and P), and given that they are porous and inclusion-rich, we proposed that they have formed from the precursor, element-rich inclusion-free domains or magmatic zircon via a fluid-induced dissolution-reprecipitation process. It is notable that the porous domains retained the 177Hf/176Hf ratios of the precursors, but possess modified and meaningless U-Pb ages. Instead, a meaningful U-Pb age (1006 ± 62 Ma), similar to the timing of the Lala deposit, is well recorded by the overgrowth/rims with distinctly high LREEs (La = 50–700 ppm) and elevated Hf isotopic ratios. Our new results reveal that in the presence of the NaCl-rich brines, the nature of the precursor, magmatic zircon (that is high element budgets and/or metamictization) plays a key role on hydrothermal alteration of zircon.

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.

In situ U–Pb geochronology has been performed via laser ablation inductively coupled mass spectrometry on shocked apatite, titanite and zircon from the ~ 8-km-diameter Lac La Moinerie impact structure, Canada. The three analyzed phases are inherited from target rocks that were transformed to impact melt-bearing breccias and clast-laden impact melts. Apatite yields an array of U–Pb ratios populating a region between a younger regression with a refined age of 453 ± 5 Ma, and an older regression with a lower intercept age of 1708 ± 10 Ma. Titanite defines a younger regression with an age of 444 ± 15 Ma, and an older array with a lower intercept at 1844 ± 24 Ma. Zircon yields an upper intercept age of 1810 ± 13 Ma and a lower intercept age of 433 ± 21 Ma, within error of apatite and titanite. The oldest ages from all three phases define Paleoproterozoic igneous–metamorphic events in granitoid target rocks of the De Pas Suite. Isotopic resetting in apatite and titanite, with relatively high Pb-diffusion rates, was controlled by a combination of proximity to impact-generated superheated melt and the formation of fast diffusion pathways facilitated by shock effects and dynamic recrystallization. Zircon resetting was controlled by shock effects and metamictization, which resulted in significant Pb loss. We outline an approach for discriminating ‘true’ impact ages from metamict zircons with high common Pb that have experienced post-impact Pb loss. Lower intercept ages of all phases constrain the age of formation for the Lac La Moinerie impact structure, with apatite yielding the most precise age of 453 ± 5 Ma. With an age of 453 Ma, Lac La Moinerie joins a growing cluster of more than 12 terrestrial impact structures formed in the Middle-to-Late Ordovician, with potential connection to the L-chondrite parent body breakup event and a period of enhanced bombardment on Earth.

At Arvogno, Vigezzo valley in the Central Alps, Italy, pegmatite dikes are unique in the scenario of a tertiary alpine pegmatite field because they show marked geochemical and mineralogical niobium&ndash, yttrium&ndash, fluorine features. These pegmatites contain AB2O6 aeschynite group minerals and ABX2O8 euxenite group minerals as typical accessory minerals including aeschynite-(Y), polycrase-(Y), and samarskite-(Y). They are associated with additional typical minerals such as fluorite, Y-dominant silicates, and xenotime-(Y). The Y&ndash, Nb&ndash, Ti&ndash, Ta AB2O6 and ABX2O8 oxides at the Arvogno pegmatites did not exhibit any textural and compositional features of oxidation or weathering. They are characterized by low self-radiation-induced structural damage, leading to the acquisition of unit-cell data for aeschynite-(Y), polycrase-(Y), and samarskite-(Y) by single-crystal X-ray diffraction. Aeschynite-(Y) and polycrase-(Y) crystals allowed for both to provide space groups whereas samarskite-(Y) was the first crystal from pegmatites for which cell-data were obtained at room temperature but did not allow for the accurate determination of the space group. According to the chemical compositions defined by Ti-dominant content at the B-site, the cell parameters, respectively, corresponded to polycrase-(Y), aeschynite-(Y), and the monoclinic cell of samarskite-(Y). Emplacement of Alpine pegmatites can be related to the progressive regional metamorphic rejuvenation from east to west in the Central Alps, considering the progressive cooling of the thermal Lepontine Barrovian metamorphic dome. Previous studies considered magmatic pulses that led to emplace the pegmatite field in the Central Alps. As an example, the pegmatites that intruded the Bergell massif were aged at 28&ndash, 25 millions of years or younger, around 20&ndash, 22 m.y.

International audience; The zircon U-Pb system is one of the most robust geochronometers, but during an impact event individual crystals can be affected differently by the passage of the shock wave and impact generated heat. Unraveling the potentially complex thermal history recorded by zircon crystals that experienced variable levels of shock and heating, as well as additioanl pre-and post-impact thermal events, has been difficult using classical geochronological methods. The existing high-precision 40 Ar/ 39 Ar age constraints for the K-Pg Chicxulub event, and the previous U-Pb dating of the basement rocks from the impact site, make Chicxulub an ideal location to study impact-induced effects on the zircon U-Pb systematics and to evaluate potential 'memory effects' of pre-impact U-Pb signatures preserved within those individual zircon crystals. Recent IODP-ICDP drilling of the Chicxulub impact structure recovered 580 m of uplifted shocked granitoid and 130 m of melt and suevite, providing an unprecedented opportunity to study zircon crystals subjected to a range of shock pressures, thermal, and deformational histories. Zircon morphologies were classified using scanning electron microscopy (SEM) imaging and then samples were depth profiled using laser ablation inductively coupled plasma mass-spectrometry (LA-ICP-MS) to document the range of preserved age domains from rim-to-center within individual crystals. The results show U-Pb ages range from 66 to 472 Ma, which are consistent with both inherited Carboniferous and Late Paleozoic basement ages as well as Pb loss ages in response to the K-Pg impact event. While the bulk of the zircon grains preserve Paleozoic ages, high U (metamict) zones within fractured zircon crystals exhibited an age within uncertainty (66 ± 6.2 Ma) of the impact age (66.038 ± 0.049 Ma), indicating that inherited intragrain U-Pb kinetics and/or hydrothermal fluid flow may have controlled age resetting those zircon crystals rather than impact-induced shock and heating alone. Moreover, the calculated α-decay doses suggest that the zircon crystals experienced Stage 1 or early Stage 2 radiation damage accumulation. Therefore, we suggest that the lowered crystal annealing temperature in crystals that previoulsy experienced radiation damage make the zircon U-Pb clock either more susceptible to the relatively short heat pulse of the impact event, the moderate pressure and temperature conditions in the peak ring, and/or to hot-fluid flow in the long-lasting post impact hydrothermal system.

Carbonatite represents a major host rock for niobium (Nb) resources worldwide. Both magmatic and post-magmatic metasomatic processes are crucial for Nb mineralization in carbonatites. However, the roles of these metasomatic processes are difficult to be evaluated due to their multiple origins and complexity of the physico-chemical conditions. In this study, we present detailed mineralogical investigations of pyrochlore group minerals and chemical U-Th-Pb geochronology of uraninite within the Miaoya carbonatite complex, aiming to better characterize the role of post-magmatic metasomatic events. The Miaoya complex (ca. 420–440 Ma) hosts the second largest carbonatite-related Nb deposit in China, mainly in the form of pyrochlore group minerals, ferrocolumbite and Nb-bearing rutile. Primary pyrochlore group minerals evolved from pyrochlore to uranpyrochlore, and ultimately reaching the betafite end-member during the magmatic stage. They have then experienced an episode of metasomatic events at 235.4 ± 4.1 Ma, as determined by U-Th-Pb chemical ages of secondary uraninite. Fluids activity for uranpyrochlore alteration was concomitant with the hydrothermal reworking of REE mineralization, which was probably related to tectono-thermal events that occurred during the Triassic closure of the ancient Mianlue Ocean. During this process, hydration and decomposition of uranpyrochlore were characterized by the leaching of Na, Ca and F from its structure, the incorporation of Fe, Si, Sr and Ba from the fluids, and the final in situ replacement by secondary ferrocolumbite, uraninite and Nb-bearing rutile. In addition, parts of Nb and U liberated from uranpyrochlore by metamictization were then transported over distances of several hundreds of microns in relatively reducing (Fe, Si, S, CO2)-bearing fluids under high temperature, and were ultimately re-precipitated in amorphous Fe-Si-U-Nb-bearing oxide veins and poorly crystallized Nb-Ti-Ca-Fe-rich oxides. The relatively weak fluids activity failed to efficiently promote the Nb re-enrichment.

Direct dating of mafic dykes/sills is crucial for understanding mantle geodynamic evolution and crust-mantle interaction, but is also challenging, especially in ancient samples. Here, we provide a reliable approach for dating Proterozoic mafic dykes/sills through an integrated investigation of U–Pb isotopes and elemental distribution maps of the coexisting baddeleyite, zircon and apatite. This study focuses on Paleo- to Neo-Proterozoic mafic dykes/sills in the North China Craton. In the studied samples, baddeleyite is undoubtedly magmatic, with sensitive high resolution ion microprobe (SHRIMP) 207Pb/206Pb ages that may record crystallization ages of the dykes/sills. Common lead incursion along rims and fractures of baddeleyite is identified via laser ablation quadrupole inductively coupled plasma mass spectrometry (LA-Q-ICP-MS) elemental mapping as the likely origin of age uncertainties. In contrast, magmatic zircons from the Proterozoic mafic intrusions are somewhat affected by metamictization as roughly indicated by high alpha dose (Dα), and thus show intricate U–Pb isotopic features. Intensely metamict zircons are susceptible to Pb loss due to fluid infiltration, as clearly illustrated by opposing enrichment trends of Pb and U in zircon maps. Where metamict zircons are unaffected by fluid alteration, they are able to preserve the original 207Pb/206Pb ratios and thus give high precision age constraints on emplacement of the ancient dykes/sills. As for apatites, abundant euhedral coarse-grained crystals were separated from the mafic rocks, rendering them suitable for LA-Q-ICP-MS measurement. U–Pb data define Tera-Wasserburg isochrons with lower intercept ages that match crystallization of the host rocks. Age uncertainties of this method lie in instrumental analysis errors caused by low concentrations of U, Pb and a low proportion of radiogenic Pb in the total Pb, with these parameters commonly showing consistent enrichment trends from crystal cores to rims. By combining U–Pb dating and elemental mapping, this study provides a novel approach to the geochronology of mafic rocks, by highlighting the potential of ubiquitous apatite, offering additional means for error analysis and age interpretation of baddeleyite and zircon.

The Garies Granite is a mesocratic to leucocratic, porphyritic post-tectonic member of the Spektakel Suite in the Mesoproterozoic Namaqua-Natal Belt of western Namaqualand. It is a composite unit, showing a continuum of rock types from mesocratic porphyritic biotite granite with characteristic slender phenocrysts (Rooiberg-type) to coarse-grained equigranular leucocratic granite (Karkams-type) with few or no phenocrysts at all. Metamict zircons prevented accurate dating, but field relationships suggest the Garies Granite is synchronous to slightly younger than the spatially associated Kliphoek Granite, which has recently been dated at 1078 ± 5 Ma and 1060 ± 9 Ma. The acidic, potassic and weakly peraluminous granite yielded ɛ Nd values of between −1.39 and 0.61 and T DM values of between 1579 and 1710 Ma indicating a significant contribution of older crustal material to the source magma.

Zircon geochronology is a critical tool for establishing geologic ages and time scales of processes in the Earth's crust. However, for zircons compromised by open system behavior, achieving robust dates can be difficult. Chemical abrasion (CA) is a routine step prior to thermal ionization mass spectrometry (TIMS) dating of zircon to remove radiation-damaged parts of grains that may have experienced open system behavior and loss of radiogenic Pb. While this technique has been shown to improve the accuracy and precision of TIMS dating, its application to high-spatial resolution dating methods, such as secondary ion mass spectrometry (SIMS), is relatively uncommon. In our efforts to U-Pb date zircons from the late Eocene Caetano caldera by SIMS (SHRIMP-RG: sensitive high resolution ion microprobe, reverse geometry), some grains yielded anomalously young U-Pb ages that implicated Pb-loss and motivated us to investigate with a comparative CA and non-CA dating study. We present CA and non-CA 206 Pb/ 238 U ages and trace elements determined by SHRIMP-RG for zircons from three Caetano samples (Caetano Tuff, Redrock Canyon porphyry, and a silicic ring-fracture intrusion) and for R33 and TEMORA-2 reference zircons. We find that non-CA Caetano zircons have weighted mean or bimodal U-Pb ages that are 2–4% younger than CA zircons for the same samples. CA Caetano zircons have mean U-Pb ages that are 0.4–0.6 Myr older than the 40 Ar/ 39 Ar sanidine eruption age (34.00 ± 0.03 Ma; error-weighted mean, 2σ), whereas non-CA zircons have ages that are 0.7–1.3 Myr younger. U-Pb ages do not correlate with U (~ 100–800 ppm), Th (~ 50–300 ppm) or any other measured zircon trace elements (Y, Hf, REE), and CA and non-CA Caetano zircons define identical trace element ranges. No statistically significant difference in U-Pb age is observed for CA versus non-CA R33 or TEMORA-2 zircons. Optical profiler measurements of ion microprobe pits demonstrate consistent depths of ~ 1.6 μm for CA and non-CA Caetano, R33 and TEMORA-2 zircons, and do not indicate variations in secondary ion sputtering rates due to chemical or structural changes from the CA treatment. Our new data underscore the potential for cryptic Pb-loss to go unrecognized in other geologically young magmatic centers that do not have zircons with high U, statistically discordant isotope ratios, high common Pb, or metamict textures.

This study aims to improve our understanding of the current limitations to high-precision U–Pb analysis of zircon by LA-ICP-MS by investigating the underlying causes of variation in ablation behaviour between different zircon matrices. Multiple factors such as: the degree of accumulated radiation damage; trace element composition; crystal colour; and crystallographic orientation are all systematically investigated. Due to the marked decrease in elastic moduli of natural zircon crystals with increasing radiation damage, the accumulation of this damage is the dominant factor controlling the rate of ablation for partially damaged to highly metamict zircon samples. There are slight differences, however, in ablation behaviour between highly crystalline matrices that cannot be attributed solely to differences in the degree of accumulated radiation damage. These differences are associated with structural weakening (i.e., decrease in elastic moduli and overall lower mechanical resistance) caused by an increasing degree of cation substitution in some of the zircon samples. Effects of crystallographic orientation and of crystal opacity (i.e., colour) on ablation behaviour are negligible compared to the combined influences of accumulated radiation damage and trace element substitution into the zircon structure. Experiments performed on natural and annealed zircon grains reveal that the reduction in ablation rates observed for the treated samples compared to the untreated grains is proportional to the degree of structural reconstitution achieved after annealing. Thermal annealing of natural zircon at temperatures > 1000 °C results in much more uniform ablation characteristics. This ‘homogenisation’ of ablation behaviour between zircon matrices produces a decrease in the laser-induced matrix effects and subsequent improvement in the accuracy of 206 Pb/ 238 U ratio determinations by LA-ICP-MS.

Understanding how radon escapes from minerals is important for many fields in Earth science, yet few studies have focused on the mechanisms for radon escape. We measured radon emanation rate and radon loss upon heating for crushed aliquots of three large zircon crystals from three localities: Mud Tank (Australia), Bancroft (Canada), and Malawi (Africa). Our study, in conjunction with published data, shows that the room temperature radon emanation coefficient (REC) varies over 5 orders of magnitude in zircon. For low U zircon, Mud Tank, there are variations in REC that appear to be related to annealing at different temperatures, possibly due to annealing of fission tracks, however, all REC values for Mud Tank zircon are within error of one another. Bancroft and Malawi zircons have higher U content and do not show any systematic relationship of REC to annealing temperature. Results from Mud Tank zircon suggest that partial annealing of fission tracks decreases REC, but when all fission tracks are annealed REC reaches a maximum. REC in zircons with high U content, Bancroft and Malawi, is slightly higher than in zircon with lower U, although results are within error. Results of measurements of radon loss upon heating suggest that radon diffusion is slow, ∼30% of the radon is lost during heating at 975 °C for 48 h. Samples heated a second time yield less fractional radon loss, ∼10%, suggesting that diffusion parameters are changed during heating at temperatures ⩾975 °C, which is likely the result of annealing of radiation damage. Diffusion parameters calculated from the fractional loss experiments reflect diffusion in highly radiation damaged or metamict zircons. Our results indicate that internal microstructures in zircon, such as fission tracks and alpha-radiation damage, influence radon escape for diffusion and recoil mechanisms, and hence if these effects can be further characterized, measurements of 222Rn escape have the potential to be useful for probing the internal structure of zircon, and other U-bearing minerals.

The chemical variability, degree of radiation damage, and alteration of xenotime from the Pisek granitic pegmatites (Czech Republic) were investigated by micro-chemical analysis and Raman spectroscopy. Dominant large xenotime–(Y) grains enriched in U, Th and Zr crystallized from a melt almost simultaneously with zircon, monazite and tourmaline. Xenotime is well to poorly crystalline depending on its U and Th contents. It shows complex secondary textures cutting magmatic growth zones as a result of its interaction with F,Ca,alkali-rich fluids during the hydrothermal stage of the pegmatite evolution. The magmatic xenotime underwent intense secondary alteration, from rims inwards, resulting in the formation of inclusion-rich well crystalline xenotime domains of near end-member composition. Two types of recrystallization were distinguished in relation to the type of inclusions: i) xenotime with coffinite-thorite, cheralite and monazite inclusions and ii) xenotime with zirconcheralite and zircon inclusions. Additionally, inner poorly crystalline U,Th-rich xenotime domains were locally altered, hydrated, depleted in P, Y, HREE, U, Si and radiogenic Pb, and enriched in fluid‐borne cations (mainly Ca, F, Th, Zr, Fe). Interaction of radiation-damaged xenotime with hydrothermal fluids resulted in the disturbance of the U–Th–Pb system. Alteration of radiation-damaged xenotime was followed by intensive recrystallization indicating the presence of fluids >200 °C. Subsequently other types of xenotime formed as a consequence of fluid-driven alteration of magmatic monazite, and Y,REE,Ti,Nb-oxides or crystallized from hydrothermal fluids along cracks in magmatic monazite and xenotime.

Monazite within a granite intruding the Kalak Nappe Complex (Norway) provides an informative example of a complex age spectrum in which U–Th–Pb data scatters for ˜300 Ma along the Concordia curve. SIMS analyses yield 207 Pb/ 235 U ages (1σ) of 876 ± 18 to 633 ± 15 Ma, and petrographically constrained age groupings suggest dates of 856 ± 16 Ma for oscillatory zoned cores, 761 ± 32 Ma for patchy domains, and 647 ± 21 Ma for rims. A grid of LA-ICPMS spots across a single grain resolve 207 Pb/ 235 U ages (1σ) of 884 ± 23 to 564 ± 14 Ma, corroborating the spread in the SIMS dataset and highlighting its spatial relationship to BSE textures. Such Concordia patterns have led to diverse interpretations including prolonged growth or the influence of a variety of radiogenic-Pb mobility processes. In combination with U–Pb analyses, detailed chemical, EBSD, and Raman imaging are used to resolve the primary mechanism for this protracted age spread. The spread in monazite ages is not the result of deformation-induced radiogenic Pb loss because EBSD reveals that the grains are only weakly deformed and have no discernible microstructures. The age spread is not the result of thermally induced radiogenic Pb mobility either, as thermal diffusion time–temperature models fail to reproduce the observed age pattern, and even simplifications indicate diffusion domains that are vastly below the observed scale of dated domains. The age spread is not the result of metamictization as well-defined Raman peaks and the strong EBSPs indicate a well-ordered crystal structure. Younger monazite domains have smaller negative Eu/Eu* anomalies, elevated La N /Yb N ratios, and enhanced Th and U. The age distribution is primarily attributed to fluid-mediated element mass transfer driven by coupled substitution in the altered parts of monazite, consistent with the geochemical signatures in these domains. This process left the P–O framework of the original c. 850 Ma magmatic crystal intact, as confirmed by EBSD, but variably purged of its radiogenic-Pb cargo, as demonstrated by spatial interpolation of LA-ICPMS U–Pb data. In some instances, removal of radiogenic Pb appears complete, consistent with the correlation between texturally-defined age domains and well-known tectonothermal events, as inferred from dated intrusive rocks in the region. These results indicate the susceptibility of monazite to fluid alteration, which allows even a single monazite grain to record several tectonothermal events and potentially chart much of an orogens history.

For the first time we report alluaudite from India, which is metamict and is hosted in a zoned pegmatite, near Pisangan, Ajmer district, Rajasthan. Alluaudites known till date, all over the world, are non-metamict type. Therefore, the alluaudite reported from the area is the first locality in the world for the metamict-type of alluaudite. The most conspicuous features exhibited by the alluaudite are various types of cracks in different directions and shapes, including its isotropic nature. The calculated crystallographic parameters of the reported alluaudite are: a0 = 11.9874 A, b0 = 12.5144 A, and c0 = 6.4136 A, β = 114.240 with unit-cell volume (V) = 877.31 A3, which are in agreement with the values of alluaudite standard. Geochemical data indicates high content of P (32.30% P2O5), Fe (30.2% Fe2O3), Mn (10.62% MnO), besides Mg (7.71% MgO), Ca (5.60% CaO), Na (3.40% Na2O) and Si (2.30% SiO2), and appreciable amount of water of hydration (3.50% LOI). It is highly radioactive due to uranium (2.28% U3O8) and thorium (185 ppm Th). Calculated structural formula of the alluaudite is Na1+0.59Ca2+0.54Mn2+0.80Mg2+1.02Fe3+2.03Al3+0.037U4+0.043P5+2.45O12. The chondrite-normalised plot shows enrichment of HREE relative to LREE with pronounced negative Eu-anomaly (Eu/Eu* = 0.46). Such a high negative Eu-anomaly suggests extremely fractionated nature of the host pegmatite.